ML20083J299
| ML20083J299 | |
| Person / Time | |
|---|---|
| Site: | Harris  |
| Issue date: | 12/19/1983 |
| From: | Eddleman W EDDLEMAN, W. |
| To: | Atomic Safety and Licensing Board Panel |
| References | |
| NUDOCS 8401050209 | |
| Download: ML20083J299 (138) | |
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** DOCKETED U%c Health Effects of the Gas-Aero661C me Compley m. -.m :
Report to Special Committee on Health and Ecological Effects of Increased Coal Utilization by Bernard D. Goldstein* Con.bmtion products derised from the burning of coal are dennitely capable of producing adierse human health effects. No single compmnnt of the combustion product niisture is solely responsible. se Itat hcr, efrnis are due to a group of comp >unds, both gases and acrosoh, in the efnuents of stationar) sour combustion procem. Although incompletely denned, the indisidual componenh of the gas-acro.cl corn-pies appear to be capable ofinteracting both in termsof atmosp'.eric chemistry and health cffects. The thrn primary air quality standards pertinent to regul.iting coal combustion all represent to some e tent indirect, a!though reasonahk, measures of this gas-aerowl comples. As a group, these standards appear te he adequate to protect human health. Comentional tosicological considerations suggest that the adserse heaf th effects of any necewar) increase in coal combustion emuents would be greatest per unit of coalin thme areas which are most heasily populated and base the highest preeshting lesels of the gas-serosol comples. In order to decrease the degree of uncertaint) for fut ure decisions of this t3 p,it is important that prusp ctise epidemiological arid air monitoring studies be initiated in conjuMion mth any large scale intmduction of coal use. tiple eminion point sources arising from goa1 com-Introduction bustion. Coal was used for heatmg of mdividital t Combustion products derived from the burning of homes as well as for power generation and industry. coal are clearly deleterious to human health. The in December 1952 weather conditions produced a causal relationship between coal emissions from four-day inversion period, which resulted in a combustion and disease, particularly of the iespira- marked increase in air po!!utant levels. During the tory tract, has been inferred for centuries. Modern smog, and a few days subsequent to it. more than y i appraisal of this relationship can be considered to 3000 excess deaths were estimated to have occurred. have begun at the time of the London smog episode This galvanized medical authorities in 13ritain and i elsewhere to look very closely into the causes and of 1952, although a few antecedent studies and local air pollution disasters (e.g.. Donora. Pennsy lvania in consequences of air pollution, particularly in relation
; to coal combustion. The pollutants that were mea-1948: Meuse Valley in 1937) can be cited.
; sured weres quite obs iously, those that 'A cre amena-In 1952 London was characterized as having mul-ble to analysis with the available technology. This led to a focus on sulfur dioxide and particulate-i
> 'New York Unisersity Medical Center. New Yoik. New York. (measured as smokeshade in Great Britain and total This report w as prepared w hde the author mis on sabbaticalicas e suspended paniculates in the U.S.I. While many at the Department of Ilioctiemistry. Unmel Um ersit). and the g g Department of Community Medicine.St. Thomas s Hospitat and late with observed health effects, it was recognized f Medical School. England.
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. s at about the time of the 1952 London disaster that
( proaches. A number ofieviews describing the heanh I sulfur dioxide and smokeshade were somewhat,indi- effects of air pollutants have bee n pubikhed in recent I re'cfindicators of the agents responsible for human years. These should be consulted for detailed infor-effects. Since that time, much evidence has ac- ! mation beyond the scope of this document t/-.JL ( cumulated demonstrating that it is a complex of The subject of health effects of photochemical I atmospheric products and mixtures of emitted pol- oxidants will not be discussed in this review. al-lutants which play the major causative role in ad- though one of the precursors of these pollutants. verse health effects due to fossil ft.el combustion oxides of nitrogen (NO,), will be increased by the products. The group of compounds participating in proposed switch from oil to coal. It is dif0 cult to this process, which will be discussed in more detail assess the effect of increased NO, emis, ions on l below, will be described as the gas-aerosol c omplex. photochemicaloxidant levels because of the compli- j Although the nature of the available information re- cated time-dependent set of reaction mechanisms : quires this document to treat this complex in its leading to the formation of oxidants. individual components,it should be kept in mind that ( it is the interplay of these many components which j result in the deleterious human health effects as-Constituents Of the Gas-Aerosol i sociated with fossil fuel combustion. gOmpgeX i Inasmuch as the focus is on coal. this document The constituents of the gas-aerosol complex de- t will stress studies in Great Britain where control of rived from st#oncry source fossil fuel combustion I c coal combustion effluents has led to a marked im-provement in air quality, as wcil as American are usually subdivided ir.to particles and gases (the [ majorgases being sulfui oxides and nitrogen o xides L studies. Unfortunately, in neither country was there The subject of airborne particles has recently been
/
I a ricorous attempt to study prospectively the health resiewed by a p mel of the National Academy of i consequences of the major changes in fuci consump- Sciences (1). Of importanee is that ihe particles I tion and emission control that led to the presence of fomied as a result of fossil fuel combustion tend to be cleaner air. This lack ofinformation is most unfortn- in the respirable size range (i.e., <l m). The maior nate. It is possible to construct a graph depicting the anionic components of toxicological importance are decrease in atmospheric pollution les cls in the recent sulfate 3 and nitrates, and pei haps sulfires and nitiites past. Were one able to construct a similar curve as well. These are piedorainantly products formed in g e showing changes in community health associated the atmosphere from reactions of the emitted gases I with the previous decrease in level of pollutants, it would now be a much simpler proposition to predict ti.e., secondary products). More information about j the levels of the associateti cations is becoming g what effect, if any. would occur due to increased available. These cations include trace levels of vari- 5 pollutant levels attendant upon conversion to coal. Il ous metal elements, ammonium ion 3, and protons is unlikely that retrospective studies in the United (hydrogen ions). The effects arising from trace ele- fg States will rectify this serious omission in view of our ments are considered in a separate document. generally inadequate health statistics base. There is. Sulfur in fossil fuel is converted mainly into so! fur I however, the possibility, worthy of exploration, that dioxide during ccmhustion, although a smal! per-pertinent information concerning the effect of de- centage is emitted directly as sulfate. Sulfur dioxide creasing coal use on human health could be obtained is a highly soluble gas which exists in solution. either by a study of the more complete British health rec- as hydrated SO2 or as the sulfite or bisulGre ion. ords. As an obvious corollary, a careful study of the depending upon pH. Two general processes as-kf effect of reinstitution of coal use should begin as sociated with polluted atmospheres act to conser {
; soon as possible before the actual switchover oc- sulfur dioxide to sulfate aerosols. In the p'esence 01
! curs, and continue for some time afterwards. While various trace elements, SO: absorbed into aqueous
! such. a sady wou;d t e relatively expensive relative aerosols is catalytically oxidized to H:SO (sulfurie
- to the current funding level for studies of environ- acid). This process is highly dependent upon humid- l j mentally caused health effects, it is extcemely cheap ity, temperature, the type and quantity of trace cle- l compared to the multibillion dollar impacts arising ments present, and the pH of the aerosol.The second from decisions concerning the energy program. [
general pathway for the formation of atmospheric I It is assumed tnat those reading this review are reasonably knowledgeable concernir.g the biomedi-sulfates is through a photochemical process in w hich the action of sunlight on hyth ocarbons and oxides of (I cal effects of pollutants, the inherent limitations of nitrogen generates species capable of oxidizing SO the various types of toxicological studies, and the { The ecmplexity of both of these processes requucs e need for conGrmatory information from differing ap- emphasis. There is a potentially large variety of dit.- p 4 1 192 Environmental llcalth Perspectim t k
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sulfur dioxide. Pollutant removal within the nose fen ni sulfates formed depending upon the cations. does not compiciely preclude pulmonary effects, as I These sulfates have a wide range of physicochernical there is some evidence which suggests that vagal l properties end, presumably, toxicity. Mostreflexes, are in the leading to bronchoconstriction, may be ini. respirable size range. Further information concern- tiated by nasal receptors. Breathing through the { mouth also cffectively removes soluble gases and ing the mechanisms of formation, larger the reaction particulates, rates,the but to atmospher a lesser extent than the k' sulfur oxides is necessary in order to better under- nose. Smaller particulates, including most an-stand the toxic properties of the aerosols, andthropogenic in sulfates and nitrates, as well as less sol-d order to attempt to construct successful. control uble gases such as NO: and Oa, more readily pene-strategies. Of particular value would be a determina- 1: ate deeply into the respiratory tiact. In normal tion of the chemical speciation of sulfates present adults, in mouth breathing usually occcrs during
' amSient air. This would allow epidemiologicalperiods and of high minute volume when the dme deliv-controlled human exposure studies to focus on those cred to the lower airways uould tend to be highest.
sulfates most likely to be responsible for toxicity.Such At considerations presumably play a role in the present, however, there is little reason to expect susceptibility that of children and individuals with pre-existing cardiorespiratory disease to pollution. any one sulfur oxide will be solely Mouth or breathing mainlyandrespon-sible high minute volumes for the effe occur ,#' should be kept in min 6 that sulfur in fuel and the relatively frequently in these population segments. Acute Expmure. Muccciliary clearance is a
#" resultant sulfur dioxide, are the precursors of essen-cleansing process which results in a flow of mucoid
- tially all anthropogenic sulfur oxide acrosols.The material upwards toward the mirogen oxides pharynx. There is un- ha separately from sulfur oxides and particulates fortunately in dis- relatively little information conceining d cussion of health effects of air pollutants.This in part the basic determinants of musociliary clearance is due to the fact that buh statiney source andrates or the effects of pollutants on this process.
## automative fossil fuel combustion contribute Although some sub-studies have obtained indircct evi-stantially to atmospheric NO, emissions. In the past. dence of altered pulmonary clearance ratc 3 following f '# # the toxicity of nitiogen oxides has been considered almost solely in terms of ni'rogen dioxide. (Nitric exposure to components of the gas-aerosol complex there is r.o evidence that usual ambient lesels $ oxide, the other major gaseous oxide of nitrogen, an effect on this process. Of potential interest are does not appear to be toxic at ambient concen- recent animal studies uggesting that repetitive acute
,'[ ,$ trations). Recent information has suggested thatexposure to sulfuric acid acrosol during a perio acrosols containing nitric acid. organic and inorganic months may lead to an alteration in baseline pulmo-y,, nitrates and nitrites are present in the atmospherenary clearance LD. Also of interest is the ability
, , .p, and may contribute to the observed toxicity of the mucosal secretions to buffer inhaled acid 3., pas-acrosol complex. The evolving evidence sug- This has been highlighted by recent studies suggest-gests a situation analogous to that descobed ing abovethat ammonia may be a constituent of the re-
,ig i.e., ne presence of nitrates concen- spiratory tract M). If neutralization of acid aero for sulfater
- g. , . trated in the respirable size range. and being derived does prevent toxicity, then it is conceivable that t 1,y4 from atmospheric transformation of gaseous NO, bufTering capacity of the respiratory tract is the b whe, precursors. There is, however, far less information for a tme threshold for the acute effect n,n, concerning nitrate air chemistry and toxicology than aerosols. although possibly mbject to individual or
, ,. there is for sulfate The subject of nitrogen oxidetemporal variability. This is, of course, speculat ..m e n formation and toxicity has recently been thoroughly but represents an intriguing area of potential s nee g . reviewed by an N AS panel W. cance. sucous The alveolar macrophage is an important compo-stune ' nent of pulmonary defense. There is some evidence i numid-ee cie. Bas.c i B.omed. i ic al Cons.derations suggesting that the basis for the potentiation o spiratory tract infections by nitrogen droude m
' " "" d Respiratory Tract Response to Inhaled an interference in the ability of alveolar macrophag t hene Irritants to kill inhaled microorganisms (7. A r. Such esiden awhkh The human respiratory tract contains a number is not of available for sulfur oxides. More udesof relatively effective defenses against inhaled irritants. concerning the effect of inhaled particulates o nest) ' The nose is particularly efficient in removing those veolar macrophage function is needed. A better un-equaes 4arger particles which impinge upon the nasal derstanding turbi- of the mechanism of the bacteno
. of dir. nates, and also in sembbing out soluble gases such as 193
'In ti* 1)ecember 1979 .
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! mechanisms employed by the macrophage is aho Individual Variability ijor physiological response to sulfur oxides The concept of individual variability in the sus-i in controlled short-term human and animal exposure ceptibikty to poHutants is important for understand-studies is an increase in airway resistance. In animal ing the health impact of the gas-acrosol complex.
l Such vanability must 1;c considered to be operative i studies, sulfuric acid aerosol has been shown to be a
' stionger potentiator of bronchoconstriction than both anwng ditTerent mdividuals, leading to some
! ammonium sulfate aerosol which is stronger than members of the population bemg mherently more SO: gas (9). The pathways mediating bron- XulneraNc. and withm a smgle mdividual at different
; choconstriction, which is generally believed to be tune penoA Intenindividual differences represent I the basis for this response, include vagal reflexes set '.nherited titetors, includmg presumably the reactis-1 -oft by receptors located in various parts of the re- tty of the bronchial tract to external agents, and spiratory tract. However, studies have shown that acquurd factors, such as preexisting cardiorespira-bronchoconstriction can occur even when the vagus tory disease. Intra-individual variabihty includes nerve has been inactivated. It is hypothesized that such temporal factors as the presence of microbial I humoral factors are capable of acting on airway respiratory tract infection and age. Contiolled ex-
, smooth muscle, or may potentiate the efTect of such posure studies have clearly demonstrated widely difTering responses in groups of ammals to bron-l factors. In ritro studies have shown that acid salts I are enhancers of histamine release from cells (10). chocqnstrictive pollutants. Inasmuch as ammals
! This bronchoconstrictive response could account for used m these studies generally have a common ge-many of the adverse health consequences associated netic and environmental heritage, it is not surprising l in epidemiological studies with the gas-acrosol com- that, based on the few available studies, there ap-i ,
! plex. Controlled human studies on asthmatics have pears to be at ! cast as great a variabihty m human I shown that short-term NO: exposure potentiated IFe response. A marked variabih,ty m human response is ako suggested by some epidenuological studies.
'j bronchoconstrictive efTect of carbachol (11).
Unfortimately, there are as of yet madequate data t hmg-Term upmure. Studies of the effects of , I long-term exposure of animals to sulfate aerosol to statistically characterize the degree of human
' variabihty m response to pollutants. This w oulJ be of have produced evidence of some effects, out in gen-eral, the findings have not been dramatic. Slight value m detemunmg the valichty of extrapolatmg
! bronchi d epithelial proliferation, edema and ah eo- mults of controlled human exposure studies (w hich
} lar w:dl thickening in animals exposed to at least 500 EC"C'"IIYutilize a small number of healthy subjects) pg/m' of sulfuric acid has been reported, as has a to @ M. populatmns
{ decrease in CO lung ditrusion capacity in beagles continually exposed to H2SO4 for up to two years Physicochernical Characteristics of O PolIltttants in Relation to Respiratorv l
, Monkeys con!!nually exposed to H2SO levels of -
100 g/m' for one year have shown no evident lung D"* l - abnormalities. At 112S04 exposure levels c,f about Studies in anim:,ls exposed to defined components I 1t00 g/m2 in conjunction with about 500 g/m' th of the gas-aerosol complex have clearly demon-I ash particles. bronchio!ar wall thickening was ob- strated that there is a marked difference in the ability served (13). Occupptional studies of workers chroni- ofindividual pollutants or combinations Io elicit an cally exposed to 112SO4 levels above 10,000 gg/m' acute bronchoconstrictive iesponse. This is par-l has e not indicated excess chronic disease incidence, ticularly evident in the series of studies perfor med by but have indicated an excess numberof acute attacks Amdur and her colleagues on guir.ea pigs W.14. The I
- in those individuals already suffering from chronic physicochemical characteristics which appear to be respimtory disease, such as bronchitis. These results particularly significant are si7c, solubility. pH. and j
yield nn unclear picture of rossible long-term acid chemical reactivity. For example, particles in the sulfate acrosol exposurc effects. The real problem is respirable (< l pm) size range appear to exert a that the underlying biochemistry of the disease etiol- greater bronchoconstrictive respcuse than larger j ogy is not well understood for sulfates. particles given a similar mass concentration. Many Considerably more research is required to defini- aerosols of the appropriate size are. bowever. inert tively pin down the role of individual coa!-derived with respect to bronchoconstriction. In some cases 3 pollutants in the causation of chronic disease. The the absence of response appears to be due to lack of biomelecular mechanisms must be elucidated as well " chemical reactivit y" (e.g., NaCh. in others it is due as the dose-response relationships. to the relative insolubility of the compound whkh
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presumably allows clearance before any chemical that is explainable by pollution levels. There is, how-reaction can occur. The pli of the aerosol also is of eser, a lack of consensus concerning whether the hportance. In general, Ihe greater Ihe acidity. the effect coirelates more strongly with sulfur dioxide or higher the likelihood of a bronchoconstrictive re- total suspended particulates. This is not surpiising in sponse. More information is needed on the sole of view of the interrelationship of these two measures particle shape and hygroscopielty in determining re- of the gas-aerosol complex. There is also con-gional airway deposition and subsequent bron- troversy concerning the interpretation of these choconstrictive impact (15). , studies; tiie iesults of one investigation suggesting ^ Knowledge concerning the role of these physico- little or no threshold for the association of mortality chemical characteristics in mediating airway re- with sulfur dioxide levels (20), while a more recen't sponse to aerosols has been of great value iu under- analysis Cl) reports no change in the excess mortal-starding pollution effects and predicting response. ity associated with pollution during a period in w hich Simple manipulations of these parameters does not- there was substantial improvement in ambient sulfur however, totally explain the response of guinea pig dioxide levels. ainvays to inhaled irritants. A better basic under- A deficiency in most of these investigations, as standmg of the biochemistry uNerlying the physiol- well as air pollution-related epidemiological studies
. ogy of airway response wouid be of great value. in general,is the use ofonly one monitoring station to Another research area of related importance is the characterize the pollutant exposure of a large popu-determination of the responsiveness of the human lation. This adds to the t,acertainty of the resulis. It
! respiratory tract to these pollutants. Such studies should be noted that studies of daily mortality in would consist of short-term acute exposures w ith the relation to daily air pollution levels are unlikely to aim of establishing a hierarchy of responsiveness to discover a life-shortening effect that is due to the individual components of the gas-aerosol complex, causation of a chronic disease by these air pollutants. as well as determining appropriate no-effect levels'. In addition, mor e information is required concerning potealial synergistic interactions of these air contam- Morbidity
- inants. In particular. animal studies of sulfur dioxide A rnte Effects. .There are 1 erally dozens of1ypes effects in the presence of inert respirab!c particles of adverse health effects wh,ich have been reported and photochemical pollutants includiug ozone. NO;. to be awociated with mhalation of the gus-aerosol and organic irritants such as acrolein should be cv c mplex or it . componcats. For many of these ef-tended to man, fccts (e.g., behavioral. immune) the mformation is inconclusive or at best, peripheral. Epidemiologic studies of respiratory tract effects of these pollutants base utihied a sariety of different measmed param-eters. These studies have tended to focus on popula-Observed Health Effocis of thO ti n gmups believed t b at high risk forpulmonary Gas-Aerosol Complex in Humans elTects, including children, asthmatics, the elderly, and individuals with pre-existing cardiorespiratory Mortality disease.
4 There is no question that exposure to past ambient The impact of air pollutants on children has been levels of the gas-aerosol complex has led to in- studied extensively [sce for example ieviews by the creased mortality during acute air pollution American Academy of Pediatrics 02), Wehrle and eiwsodes. Those individuals who died during such llammer 03), and N AS (nj. A relation between the episodes were mainly the elderly, the infirm, and, in gas-acrosol complex and lower respiratory illness some episodes, the very young. Controsersy does has been established. Epidemiological studies in exist concerning the extent,if any, to which current Great Ilritain, including evaluation ef up to 10,000 pollutant levels are responsible for daily variations in individuals, have reasonably clearly demonstrated mortality. To study this problem it is necessary to an effect of air po!!ution on bronchitis incidence carefully adjust for many variables, inchiding C4-26). meteorological and seasonal effects. Of particular interest are two studies in which in recent years a number of investigators have cohorts w cre evaluated at varying time intervals. In a evaluated New York City mortality data in sclation study of 5-year-olds lEcing in four different areas, the to' air pollution levels (16-2/1. inciden'cc of chronic cough correlated well with ex ~ The studies are in general agreement as to the isting air pollution levels, and there was a significant existen:e of a residual variation in daily mcrtality decrease in pulmonary function in the residents of 195 Decen$hcr 1979 ret t
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the most polluted area during the first study period. sensitive to inhaled air contaminants.1 here are a l'our years later,in 1969, these same children were number of epidemiological studies which appear to
.rgstudied. During this period there had .been a support this contention as well as the iccent con-marked improvement in air pollution levels $45-8tr4 trolled human study on NO and carbachol 1// L The decrease in smokeshade: 10-259 decrease in sulfur epidemiological studies are, however open to vari-dioxide) with an abolition of the pollutant gradient ous degrees of criticism which appear to rencet the between the fom areas. Appreciable decreases in fact that asthmatics are a particul.uly difHeuh group observed respiratory effects were observed and to study. It is dif6 cult to obtain a large study popula-there were no longer differences between the areas tion, and there me numerous confounding variaNes. .
(27,28). Another study of a cohort of children bon. in particularly meteorological and seasonal factors. 1946 noted an association of the history of lower which complicate interpretation of the effects of air
- respiratory tract infection with air pollution (25). pollutants.
When this group was thoroughly evaluated at age 20, The retrospectiv, abservation that 87.69 of asth-cigarette smoking was found to be the dominant matics ieported respiratory symptoms during the factor in the presence of respiratory symptoms, Donora air pollution disaster (36), as compared to while air pollution had at most a minimal effect. 42.79 of the general population, indicates that asth-
. Other British and American studies have reported a matics do respond adsersely to air pollution. The lesser prevalence of respiratory problems in awoci- question at present, which is similar for other sus-ation with improvement of air quality (29-3/). ceptible population s. is to u hat extent do current or Studies in the United States and elsewhere, in- foreseeaNe pollutant levels proJuee ast hma attacks.
cluding the CHESS studies (32), have evaluated the Relatively low level effects were reported in the association of sulfur oxides and particulates with CHESS studies and in an EPA study performed in childhood respiratory tract illness. With some c6 New Cumberland, West Virginia 137). The latter is ceptions, lower respiratory tract illness has been one of the few U.S. studies of effects due to an positively correlated with those pollutants at lesels uncontrolled coal-fired power plant. These studies somewhat above the current U.S. standards, but not hase been heavily criticized. mainly on the basis of at lower levels. Studies of childhood pulmonary the data collection and analysis techniques which function in relation to sulfur oxides and particulates were used GN). At piesent, it would app"ar wm-have shown less consistent results. ranted to place a relatisely wide error band around Ambient levels of nitrogen dioxide have been im- any extrapolation relating potentiation of asthma plicated in the potentiation of upper respiratory tract attacks to cmrent or projected levels of stationary infection in children and their f.anilies. This is in source fossil fuel combustion products. l contrast to sulfur oxides which, while clearly as- It should be emphasized that asthma attacks rep-l sociated with lower respiratory tract bacterial ill- resent an acute effect, and are therefore particularly l ness, have not been consistently found to be as- significant during high short-term peak levels of sociated .vith upper respiratory viral infections, pollutants. The causation of the basic underlying Epidemiological evidence of a relationship between efTect leading to classical allergic asthma does not NO and respiratory infection was noted in school appear to be related to chronic pollutant exposure. children and their families in a study performed in The relation of air po!!ution to asthma attacks has Chattanooga G3 ). This took advantage of a relatis ely been the subject of a number of reviews (4,39,40). unique point source of nitrogen dioxide. Replication Exacerbation of pre-esisting cardiorespiratory of this study, which is a major base of the U.S. air disease has been clearly demonstrated to be a con-quality standard, would be of pieat value, but is sequence of exposme to the gas-aerosol complex. dilTicult due to the entanglement of nitrogen dioxide Controlled anirnal and human exposure studies have with other pol!utants in most areas. Recent studies suggested that bronchoconstriction is the basis for demonstrau;ig relatively high nitrogen dioxide levels the observed acute effects. There trav also be an in kitchens with gas as compared to electric stoves element of pollutant induced increa' sed mucous (34,35) may provide a basis fe. re-evaluation of the production leading to worsening of disease, particu-epidemiological association of nitrogen dioxide with larly in the chronic bronchitic. respiratory tract infection. Numerous epidemiological studies have focused There is some controversy concerning the sus- on individuals with chronic pulmonary disease ceptibility of asthmatics to the gas-aerosol complex. (chronic bronchitis, emphysema, and nomenclature Basic b omedical considerations lead to a strong variams thereof). Diary studies of this group tin suspicion th : individuals with a hyperactive bron- liritain) readily demonstrated an awoeiation of choconstrictisc response should be particularly worsening symptoms with short-term po!!ution 196 Ensironmental IIcalth Perspectises t k e.
(
. \
l .
.I
{ ,. chni- levels. This has recently been less esident following onstrated a higher prevalence of chronic respiratory w the I institution of control measures leading to a marked disease in polluted areas. When originally studied in =,"[. abatement in particulate levels and lesser decreases the 1950's, air pollution appeared to account for a 1 in sulfur dioxide (29,30,41,42). . substantial propor1 ion of the totalincidence and dh-sutwi- Similar studiesin the United States hase produced ability 4 eto chronic bronchitisin iltitain. A relation naer, somewhat contradictory results. For example, Ilur-of air Nilution to the prevalence of respiratory dis- [tc and rows et al. (43), found littie or no correlation of sulfu r case has also been acted in American and CanaJian
. dioxide levels in Chicago with daily symptoms of studies.The hirgest American study of this ty pe was N'[:
LorEn patients with chronic respiratory disease, although performed by CllESS in various pm ts of the country
- 6. M Carnow et al. (44), using a similar, but somewhat by use of a self-administered questionnaire (32).
A id8 more extensive approach in Chicago, reported that There was a reasonable consistent finding of a higher
' 2 and symptoms wuc Mated io suk dioxide levels ex- prevalence of chronic l espiratory disease in t he more racite tending dow n to the range of the current air quality polluted communities. This is among the least con-1.utin standard. The CH ESS program has utilized panels of trosersial of the CilESS findings. Howescr inas-c AP- ,
elderly subjects, with and without chronic car- much as the observed effect presumably represent-ad the
- di0 pulmonary disease, to study daily pollution ef- long-term expo 4ure to air pollution, including the fects (32). While a positive correlation with current much higher levels of the past, the data can not be Snuoi ambient sulfate levels was reported, the high dropout readily used Io estimate efrects due to current am-reao or rate and other technical difGculties complicated in- bient levels. It would be useful to analyze sub-terpretation of these results. sequent years of the CHliSS studies to deterraine
' d* "-
Chnmic Effects. The bulk of the studies dis- whether there was a decrease in the pievalence ot Un", cussed above deal with the ability of the inhaled chronic respiratory disease which parallels the pre-univ gas-aerosol complex to produce acute disease or an vious fall in air pollution levels. entor accelemtion of an already existing chronic disorder. A study comparing the prevalence of histolog.-
*N' The present section focusses on the possibility that cally determined emphrema prevalence on autopsy nuol. long-teim inhalation of these pollutants may act to subjects showed that the disease was three times as ytics, cause the production of chronie disease, particularly prevalen: among nonsmokers in St. l.ouis as in Win-com- chronic sespiratory disease. The potential impact of n! peg, Canada (43). The variable used to exp!ain the "* a role for aii pollutants in the causation of chronic difference was fossil-fuel combustion product de-respiratory disease may peihaps be greater than that rived air pollution. No speciGe substances were cor- ". to the of acute disease. It is. however, a more difficult related with the disease, rather only total emissions kmy or problem to study. Evaluation of day-to-day varia- of SO2, particulates, and NO,.
tions of pollutants in relation to health effects does There is the possibility that components of the y'* not provide any direct information. Nor are usual gas-acrosol complex might play a causative role in Q prospective studies of value in a situation where it may require many decades of exposure for the de-the increased les cis oflung cancer observed in urban areas. BisuiGte has been show n to be mutagenic in a velopment of measurable chronic damage. number of systems, presumably by deaminating Studies approaching this problem have generally cytosine (46, 47). It is, however, questionable utilized a geographie comparison in which the prev- w hcther this scaction can occur at physiological pH. alence orchronic sespiratory disease among a popu- Tumor formation in animals exposed to sulfur lation in a polluted area is compared to the preva- dioxide has been reported, most notably in a study lence in a nonpolluted area, in order to make such a demonstrating higher levels of lung tumors in ani-
-comparison successfully it is necessary that the mais exposed to sulfur dioxide and benzpyrene as I populations in the study areas be as similar as posci- compared to benzpyrene alone (48). In conjunction )
ble in other respects. The major confounding vari- with arsenic exposure, sulfur dioxide exposure ap- l able in such studies is the cxtent of cigarette smok- peared to increase the risk oflung cancer in smelter l ing, which is the most important causative factor in workers 140). Nitrogen oxides have also been sug-chronic respiratory disease. Other factors, particu- gested to be potential carcinogens, mainly based on
. larly occupation, but also life style and social class, reactions with other agents w hich might form nitro-could conceivably play a role in the causation of samines which are known to be very potent carc;..o-chronic re piratory disease and should be evaluated gens (30). Recent studies base demonstrated that in the study design. these reactions can take place in polluted atmo-
; 'Using such measures as death rates, reason for spheres, especially during the nighttime hours.
( disability, and questionnaires concerning cough and While further research concerning the possible
't sputum production, many studies have clearly dem- mutagenic effects of components of the gas-aciosol 3 tis es December 1979 197 1
s The above caveats should be kept in min.1 o..
. . complex would be ofinterest,it is unlikely to provide information in the near future specifically applicable considering the available literature coneem.,
eflicts of the gas-acrosel complex. Among ti., to human exposure, frequently quoted studies is that of 1.ase an i se l Dose-Response Analyses *all" mban h" i". mr ' 97" "'d *"'*d 'h"' " 5" ) Pr"J ' ~ pollution would result m a 2W l . rement in the exces,s urban mortalitj and n.m The estimation of human dose response to the from bronchitis, 25% of hm; cancers. :V n: gas-aerosol is an arcane art. The major difGculties are derived from the dose side of this equation. The spimtory disease.1001 of cardiovascular n., and mortality. as well as a 15ri deesemm . -
, most commcaly measured pollutant, sulfur dioxide, is an indicator of varying reliability of the entire overall prevalence rate. These figures but N 5
utilized by a number of other authois as t he b + gas-aerosol comp lcx. To complicate the problem, funher calculations. It should I e emphasized sulfur dioxide is also a major precursor of more toxic the analysis refers to all air pollutants and is gph, components and its own toxicity can vary depending on its combination with other pollutants. This multi- ble to the increment of these effects obsencd l urban areas. 1 ple role for sulfur dioxide is the basis for t he apparent discrepancy between epidemiological studies and A frequently emp!oyed data set for extrapet.ci, controlled human and animai exposure experiments. the effects of various levels of stationary som ce 6, the latter requiring much higher levels of sulfur sit fuel combustion products is deiised nom use e-the CHESS studies U2). These studies bas e i cen u . dioxide in clean air in order to observe effects. The common methods of particulate measurement are subject of much controversy, ineluding.a r.nen , 1 also only indiactly related to those agents actually critical congressional resicv; as well as fwnc: causing adverse effects in addition, one must care- criticism by other researchers. The CH!!M d%
,l i fully disentangle the effects of other variables (e.g., res[vnse estimations w ere based on measm ed te .c:
of atmospheric sulfates. As pointed out b) the .m cigarette smoking, weather, and occupation) from f those due to pollution. There is accordingly an es- thors, they clearly represent a first approsimaw containing a large degree of uncertaint) . It sbould ! . sentially inherent degree of uncertainty in the as-noted that the major reason for estrapolatin : Jo-
. signed dose for each ievel of response. There m e also difGculties in the raeasurement of response, includ- response curve from the original CHESS dat . " a- a need for making segulatory decisions based en r:c-ing adequate characterization of populations, the validity of measuring techniques, and the selcetion ently availabic evidence. This remains true toda .
6f subjects for study.- These problems are com-Among the subsequent analyses. u Jog th, ' CHESS extrapolations, is a report b. the N.dior pounded by the requirement for multiple points in the plotting of a dose-response cave. Academy of Science to the U.S. Senate pan , l There are a number of complex statistical tech. Works Subcommittee NI in which the impact o ^ 4 ternate fuel use strategies was evaluated. Tim m mques which hpe been developed or re0ned in re- cludes estimates for the health impacts assow ! cent years to handle the variables in individual studies and to formulate dose-response curves. with individual plants depending on siting \ sem ' of studies of a similar nature have been peria wd . There is, however, a crowover point at which the Brookhaven National 1.aboratory includin : c-o . uncertainty cam.ed by the multiplicity of pollutants and other variables is replaced by uncertainty about tion of mortality due to coal utilization. I h as I the validity of the complex statistical procedures clearly indicate that their mede!is great?) e.* l used to disentangle these variables. Furthermore, due to the lack of solid baseline data hom ui b~ n : therr is to concensus in the scientific community calculate the health effects of coal combust on ered concerning where this crossover point is located. ucts. Specific criticisms of their approach iociude i Dose-response information can be more simply use of a non-threshold model (based on I .ne derived from controlled human exposure ex- Seskin) which employs an annual as eraec po'hu dose to impute mortality rather than shoit ter m p; " periments involving de6ned responses to measured les els: the lack of characterization of porn' anon' doses. The major drawback of this approach, as is evident in the case of sulfur dioxide, is that the ex- riskt and assumed constant sulfur diosiJe ed - mtes. In order to impiove the validd) of the F~ posure does not replicate the complex mixture pres- dictive models it is necessary to des elop mxe w cnt in urban air. In addition, it is difGeolt to study the
. response of susceptible populations. Animal ex- rate dose response function based on apprC averaging times for the pollutant dose. In addo '
, posure experiments, ahhough advantageous in other better means of predict;ng the lesels of w"nd o ways, suffer the same limitations with the added drawback of interspecies differer.ces. formed pollutants would be of value.
Emironmentr' llealth Pcl 198 4 E _ _ _ . - - -._, . ~ . - - . - - - - i . . . . _
I' ' Summnry Cf lSSUBS that nonorganic coal combustion products may i it does not appear possible to readily subdivide the cause cancer. Such a hy pothess, is supported pu-issues concerning health effects of the gavaerosol. maril, by basic research indicating that derisatives l complex into those for w hich there is a consensus of of sulfm dioxide and nitrogen dioxide could produce l opinion and those for w hich there eust uncertamtics , mutagenic elTects and by epidemiological evidence (; indicatine a higher incidence oflung cancer in urban or controversy. There is no conciete borderline I where reasonable men may or may not differ. Rather meas. Mitch more research is required to assess the
$ there is a continuum ranging from questions for iciation of the basic research fmdings concerning a which the answer appears certain, to where there is mutagenesis to human cancer. In respect to the i disagreement as to even how to phrase the question- epidemiological esidence, if it in fact ieflects a Following are a pa 1ial list ofissues that appear per- causatise role of air pollution in urban lung cancer.
tinent to the problem of health effects due to the the es idence at present mor e strongly supports a role gas-aerosol complex. Inherent in such an exercise is for org nie fossil fuel combusdon products. the t.uthor'> judgment concerning w hat are Ihe issues To What Extent 1)oes the Aruitable lufonnation of particular importance, what are the bounds of pe,mit .1cru.ute l'icdiction of tire .idrerac licohh reasonable differences in interpretation of existing cony,juences Jane to Giren Lewis ofCoal Comhus. rion? There is amf le historical evidence that am-data, and which are the areas w here further informa-bient levels of stationary source fossil fuel combus-tion, in the relatively near future, is likely to be of crucial importance. tion products bas e produced serions health effects in Can the Gun.lcrowl Compics 1)crired from the exposed populations. This is particularly true for Cambustion of Coal Produce Acutely liarmful Ef- situations ir which there were ichitisely high polhi-fccts in 3 fan? The answer to this question is a def- tant concentrations. In recent years theie has gener-inite yes. Past experience in the United States, Great ally been a decrease in ambient levels of most of these pollutants, exclum of nitrogen osides whose Britain, aad elsewhere, provides more than ample evidence that atmospheric sulfur osides and par- emissions have continued to increase. The extent to ticulates are causally related to adverse health which present ambient levels of the gas-acrosol comples produce adserse health consequences is a efTects. These include increased mortality, particu-larly during prolonged periods of atmospheric inver- m.. iter of controvers y. Reasonable interpietations of sion. This situation affects mainly the very young, the data range from tio, or negligible, pollutant ef-fccts at present. to the position that any level of the the old and the ill. Also included is an increased pas-aerosol compkx is capable of producing harm. morbidity inclusive of exacerbation of preexisting These widely differing interpretaticos reflect cardiorespiratory disease and potentiation oflower re ,piratory tract infection, and, more than likely, the uncertainties concerning the validity of the existing data. As described abm e, there have been a number production of asthmatic attacks in susceptible indi-viduals. of dose. response estimations performed in recent years. They have been based for the most part on can the Gon .tcrosol Complex f)crired from the data developed by the* CHESS program. This con-Com6ussion of Cool Produce Chronic IJisenac ire troversial program contains Ihe most comprehensive 3 fan? There is reasonaoly good evidence that attempt to establish the les els of measurah!e compo-long-term exposure to these po!!utants can play a nents of the gas-aeiosol com,!ex which produce ad-causative role in the production of chionic respira-tory disease. Supporting this hypothesis is esidence verse health effects. There are other studies w hich provide information useful for approximating a indicating a higher prevalence of chronic respiratory dose-response curve. These, however, are few in disease in polluted areas that does not appear to be number and are derived from ditTerent countries, accounted for by differences in cigarette smoking laboratories, scientific approaches, and circum-rates, occupational exposure or other confounding stances. This greatly complicates the problems of
.! variables. There are, however, diffeiences of opin-ion conceming the interpretation of these data and it extrapolation and leads to the necessity of assigaing a ietatively high degree of uncertainty to any derived would not be unreasonable to state that the dose-response curve. Accordingly, if the CHESS hypothesis is unproven. In thejudgment of this au- data are interpr eted as being meaningless, one is left thor, the scientific evidence that long-term exposure with a very wide range of poss ible interpietations, to stationary source fossil fuel combustion products particularly conceining the effects of current am-can be involved in the causation of chronic respira- bient pollutant levels and those likely to be achiesed tory disease appears compelling. This assumption with the proposed consersion of power plants to would also appear to be in keeping with a prudent co.1 public health point of view. There is far less evidence If the CHliSS data are accepted as being per tiner.t.
Ikcember 197'I 199 i
, I
. 1+
there are then a number of analyses bamron these this subject has been obtained in epidemiological data which can provide dose response estimations studies, although this is sery oftca complicated by l u<.eful for estimating health effects due to the gav problems in obtaining sufficient numbers of indi-i aerosol complex. One of the more extensive viduals for study and for appropriate control groups.
- analyses is that of the Natural Academy of Science Controlled human exposure studies of susceptible j
discussed above. It has the advantage of providing indisiduals have only rarely been performed. This is data for individual power plants located at various in part due to ethical considerations. Even when distances from mban populations. This author par- ethically appropriate, the performance of these ticipated in the health effects aspects of the NAS studies is often hampered by the spectre oflitigation analysis and estimated that a reasonable error-band which makes university review boards reluctant to for the dose-response curve for sulfate used in the permit such stud:es. Unless some answer to this computations ranged from an underestimatioa by a problem is forthcoming, peihaps through feder.dly factor of two to an overestimation by a factor of 10. guaranteed insurance, it is unlikely that information
, There appears to be no new informationjustifying a peninent to the understanding of human variability change in this conclusion. will be attained in the near future.
l It is also unlikely that any newly instituted re- Short-term peak pollutant levels are obviously scarch effort will provide information which will most important in reference to causation of acute substantially change the boundaries of this analysis effects. It should be emphasiicd that prolonged j or Ghc certainty of.any prediction of dose-response meteorological inversions which have the capacity j before the anticipated switchos er of utilities from oil for deseloping highest pollution icvels may occur at and gas to coal. There is, however, every reason to intervals of onI3escry few years. Inasmuch as these begin such further studies as soon as possible, and episodes represent the greatest potential for acute preferably in conjunction with any fuel conversion eficcts, these infrequent occurrences should be con-
! efforts, so as to provide information pertinent to sideied a . a major basis for determination of appro-determining the extent to w hich further conversion priate control strategies. Such an arproach does not affects air quality and public health. substantially differ from that of assignation of Good There is one saurce ofinformation pertinent to this plain areas based on the concert of the "100 year pmblem which could be available within the near Good.'
. future. This is Ihe remaining unanalyzed omtions of What is the fielutire Impuet on llenfth ofI' e Cus.
- the CIIUSS program. Only 1he first. and part af1he Aerosa! 11ixture Presen t in the Incal.1ren of a Pou er second year of this Gve-yem program have been Plant Fueled by Coni. Cornpured to the Cus- terosol completely analyzed. h1any, although not all. of the 11ixture Present after I.or:pliange Transport of criticisms of this program renceted prcblems inher- Pmrer Plant unissions? A number of;.rocesses act 3 ent in the instititution of a complex epidemiological to modify the components of power plant emissions
} study. Some of th se were rectiGed in subsequent as thev travel downwind. These are discussed in study years. If the Gndings in the latter years of the des above. In general. the emitted gases are CHESS study replicate the initial findings, this oxidized to acidic aerosols which appear to be of would lend a great deal of credence to the derived greater potential harm then the parent compounds.
dose-response formulations. The conveise would Presumably buffering substances, such as NH4, are also be true. Accordingly, a rapid and thorough also added over time and these may alter the poten-analysis of the remaining CH ESS data, preferably by tial tosicity of the gas-acrosol complex. Obviousl> . those not intimately connected with the study or its dispersal of the plume over distance leads to a dilu-criticism, could be of great value. tion in pollu' ant concentrations. In areas such as the To What Estent Are Average Pollution Lercis and Northeast there may, however, be additive effects Awruge Iluman ltesponse Predictors of the llenith from multiple point sources. Impact of the Cos. Aerosol Complex in n Popula- The importance of this issue lies in its pertinence tion? It is misleading to consider average pollution to decisions concerning which electric power plants levels and average response in the formulation of should be converted from oil to coal. If, as has gener-control stmtegies. There is a large degree of variabil- ally been assumed, the local etTects predominate by ity in the response of humans to air pollutants. In virtue of higher concentrations, then clearly the ex-general, regulatory actions in this country have tent of the adverse health impact of a given les el of l specified that the most sensitive groups should be coal combustion would be proportional to the den-protected. Accordingly. there in a particular need for sity of the local population. This effect uould be information concerning the effect of the gas-aerosol magniGed by t he fact that existing air pollution les el-complex on susceptible individuals. Information on tend to be highest in dense urban areas. Therefore. 200 Emironmental IIcalth I'ersp.'cti es
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' 0966L 47. Shapiro. R., Servh. R. E., and Welcher. M. Reaenm et
- 26. llolland. W. W., liabt. T.. Dennett. A. E., and Elliott. A. uracil and cytosine derivathes with sodmm biwMe. s Factors influencing the onset of chronie respiratory dhease.
specitic deamination method. J. Am. Chem. Soc. < C. 0970L Brit. Med. J. 2:205 0969L .
- 48. I.askin. S.. Ku v .r . hte ..
- 27. Iwnn.J. E.. Knowelden. J.. and Handyside. A.J. Patterns of 4 nary carcinogem h I, b. 2. a C.no w ene e
- u respiraton illnew in Sheffield infant schoelchildren. luit. J.
Prev. Med. 21: 7 (1%7L Ss mp. Series 18L M. G. Hanna.Jr. P. Nettesheim. .md J R
- 28. Lunn, J. E., linowc!Jen. J., anJ Roe, J. W. Patterns of Gdbert. Eds. U.S. Atomic Energy Commiuion Deioa o.
' respiratory illnew in Sheffield junior schoolchildren. A Technic.d information. Oak Ridge. Tenn.p ut rp. 321 *"
follow.up study. Brit. J. Prev. Soc. Med. 24: 223 (1970L 49. I.ee. A. M., and Fraumeni. J. I'. Jr.. Arserne and respir o m
- 29. Emerson. P. A. Air pollution, atmospheric conditions and cancer in man: An occupational stud). J. Nat. Cancer Ino 42: Im5 (1969L chronic airwa> obstruction. J. Occup. Med.14: 635 fl973t
- 50. Fhhbein. I. Atmospheric mutagens. I. Sulf r ouJes c.J I 30. Lawther. P. J., Waller. R. E. and lienderson, M. Air pollu. nitrogen osides. Mutat. Res. 32: 309 0976L tion and exacerbations of bronchith. T horas 25: $25 (1970L 51. Lase.' l.. B., and Seskin. E. P. Air pollution and hum a
{ 31. Ferrk. H. G., Jr.. Higeins. I. T. T. liiggirw. M. W., and heahh. 'i he qu.mtitatis e effect. uilh an estimate of the d#
- Peters. J. Chronic nonspecific respiratory dhease in Berhn.
New Harceshire.1%I to I%7 A follow.up study. Am. Rev. benefit off ollution aratement hconsidered. Science im > Respir. Da. 107:110 0973L (1970L E Emironmental IIcalth Persi>ecthes __,,,e*~~"^* "
Q.- H Co z t Envi onmental llca!!In l'e rspa tis cs -
,, , vor. n. re. 3000KETED USMC
'84 5 -3 A0 03 i Healtil Effects of Coal Min!nc and. -
I ( Combustion: Oarcinepas and Cofactors { by Hans L. Falk* and William Jurge! ski, Jr.* 4 8 j Some poly aucicar ernmaticqPN A) has c han Ibund te I e pttcnt c arcinoce..s for all tiwue and errans of nperimental animah that hase been eywl to them,la t different dow le.e h are ncuted for these eth cts. 1hty base been kr.own for decades to canw cancer at tbe 5:tc of appliustir.a t.ut uho at t tridin sites di. tant { from the atea of conhct. Althount. some hy di os arhons are r.r.u.t and conspf t tecercir.onns. Ihe majority of a a related hydrocarhom was orspina!!y found to be inacthc. .s.nce they generally appear together it was in.partant to know morc ahout tlwir interactian. paitin:1 rly w het her they would sy nergire,ur ant..nor. lie,
'1hc polycyclic l.3d rocarbons hase been st Aied by cubcmsprousinjedion,w here they prose ury potent f carcinogens. They are aho ser nethe on the skin of n. ice whcie they product cancer on prolonged application. Inh 11atiim studin, re.guire tar r doses yiclAd regaue rnulb until particutaic ma'ta r un I introduced which Iicititats d the doctopnicnt r.f bne tumors. Althr.a.:h iron oside du t w as used imtially.
ether dets were aho capabic of < nhancir.g the response ofIbe tiwuc to bor. iota) py rene can cinogenesis. ~l his j peint is ofimportance. particuhrly since the inhalat.oa of I .M in situatious of air tvilution or cual mir.in;t imuhes p-erticulates, although of a dinest at type. Not is not a hunogen3us substante and sneral factur<. determine its propertin. Scots will fos some of l . the chsorbed themicah dudra simr iesidence in air, tmt they retain their PNAs for lung periods of time when they reach iter soil. Th carcinogenichy eif PN As in the adsorheel state may he c omplete1 3 absent, dept ndine un partictoire of ( the et and asailability of clutir.g capabibty of the tiwan er celh in conteet with the soot. Whcnner the c.trt hiogenic poly nucicar aromatics c n be clated they w ill be actis e la producing cancer if their rnidence h l adequate.
'lhere seems to he no reason to a.sunse th78 a I.or,:e incre ase in coal sembmtion in the future will by twcessify ! cad to greater risks of cancer tr, the coa mincrs or (Sc gcaerat urban dwcHer. htrause atthides to l he started now can take into consia ration tt.c rquirerr.eah neccuary f or controf of nir pollutmn in mino as well as in citi es. If new uws of coal will I,e deselcrid it will be n con.pletely different sitention, and I stakments alwmt the carcinogenic risk from coal utdirati:.n do not apply there. Althouhh some of the samc carringenic PN k are insobed in the . mith hazards num those procoscs. other carcinorens and cho j cocarcinogens will f.c prnent, and the eyinwd worke rs vill, at base the apparent benefih of ads.,rpt;un of PNAs on snot,
, Intf0 duction becomes impossible to predict the range of activity w hen alkyl derivatives are involved. Carcinogenicity 4
Pel) nuclear aromatics (PN A) have been know n as
. of alks i derivatives may be far greater t ian t hat ot the
( uqnocens for many laboratory species since the - - thnties. and efforts have been e xpanded to correlate p;ulnt compound, depending on the location on the E*"b I 't'wture and calcinogenic activity for many mem-Ntwf that gtoup. It was not completely successful. l f:t cettain conclWons are still accepted about the Carcinogenic Polycyclic and nits of structtfr This allowsl.13terocyclic Aromatic t ;c rese.treher m tne , e4.tivity coirelations. field to make educated guesses l i 8ti 1hlhe the possible carcinogenicity of polycyclics Compounds
- h. pecitic arrangement of the ring system. but it giresence in Coal and Soot "s th ml Insutote of Environmental llealth Sciences. P.O. ' Coals have not been analyzed very often for their f.
t
""' 1:2 44. Research Triangle P.uk. North Carohna 7709. composition it . far as organic constatt.ents are con-lhtmher 1979 203
{ l
- i t
1 l 1 I
.i cerned. There are data on the atomic mtio of hydro- ken and free radicals are formed. Under conditions gen to carbon which for a sample of coal tillinois # 6) ofincomplete combustion soot is liberated toge:her was found to be 0.86. A highly imaginative structure with a collection of adsorbed polynuc! car aromatics was given by Wadden (1)(Fig.1). It allows fi le cren- consistingof the same structures that were present in t' ion of an image of what variety of structures may be coal.but not necessarily the same molecules. During j present in coal. Completely realistic, however, is the the process of combustion the polycyclic aromatics
, analysis of an extrai.1 of powdered bituminous coal are broken down or may lose their alkyl sidechain so i which identifies the polycyclic aromatic hydro- that the chemicals that can be recovered from the
, carbons by means of absorption spectroscopy and soot are more generally the parent substances. i.e.,
{ the degree of alkylation by mass spectrometry. This those without alkyl groups belonging preferentially
, analysis gives a quantitative picture of the various to the peri-condensed group of aromatics. Some data groups present. Ofinterest with regard to potential on the pyrolytic process will be given later in this
. carcinogenicity are the groups: benzota) pyrene, paper. So far no mention was made of heterocyclic chrysene, cyclopentanochrysene, and benz (ahn- compounds, but independent of the presence of thmeene derivatives (2). It is cicar that t he process of these compounds in coal the pyrolytic process dur-pulverization and extraction would not have con- ing combusti on will allow the form:ition of nitrogen-tributed to the formation of these compounds which containing polycyclic compounds and a number of therefore must be assumed to be present as such in them have been found in air pollution particulate coat (Table 1). matter (Table 2) (3). Their carcinogenicity al'a de-When coal is burned, many changes occur in the pends on structure, but diffcrent niles seem to gov-composition of these polynuclear aromatics. At the em structure and carcinogenicity in this case. Some high temperature reached, chemical bonds are bro- are quite potent; but an increase in the number of H H l 1 H O S g i l 1 O H Hg fH l ;
H - H , N/ N' H H \ f
- 1 l I_ I I
-C - / N-O- A S \
. H/ I l
~H"H' l
' '"2 C =O l l S'
/ -C -C H I
HH'-(O )'C I
'H H
O l NH p H g, *O O
' l H 2 Hp H' g lNH t4 S H e H-C-H l 2' N 'HHC-H H H H H l H H Hg H l2 l / ,CH3 Hp, s
'H
-O- N 'N H H '2 If pH' 'M" H' l
# Ns / O y H H
j'H H"H / '/ 'N H- c-H H-E-H 2 2 O H f H Hp l l H' #\ H- C-H "' / '" H-C-H H i H-C-H H' I b H - C-H l;l H I
H O N / O
's 'o# j H H H H H O I
- s/
/
% g H Hp Hs /*C ' N.O \, \ \ /
H' H H H # \ # \ l H'C'H H H H H f N f Hp O 1 i H' H/ H H g, N 2 H
/ %g 2 OH Fictitt t. A representathe bituminous coal structure (1).
; 248 -
Environmental llealth Perspectises i i
*"r * ' * * ' "
.,,g... ..e ...e
t
. . I,
! derstanding of what kind of structures we could es.-
' n .n s ..u'open atoms in the ring system tends to decrease t pect to be present in coal, which might be formed r.e e
' Menev ahntptly. subsequently on tar formation. and w hich might lead
. ,: c s *lbe Enalysis of coal mentioned above did not ex-
. .y h yond the polycyclic aromatic hydrocarbons. to new structures on combustion. Structures ccn-u.m taining a thiophene ring instead of an aromatic ring in D em.- I brudies on coal tar revealed the presence of many the polycyclic structure may also be quite car.
~%e s i ..tct heterocyclic compounds where nitrogen. oxy-cinogenic.
m . -.* l w n, or sulfur is built into the ring systems. It is Table 3 shows the concentrations of some poly-
- oe l x;essary to dissociate these f mdings from both, the cguposition of coal and the composition of mt. cyclic aromatic hydrocarbons and related com-
,e.
h eause these compounds may be formed under dif- pounds found in coal and in urban air. The concen-
.:c ,
tration range of some of these compounds in city air
.* *a l 'terent conditions. However, they help us to an un- has been determined by Sawicki et al. (4h Figure 2
) "" o por-
' " 9U i uae i comper.iiion of the part of coal estract not reae*he with tant FN As One group of polycycn.e hydroembons f : mateie anhydride. which was not mentioned in the ceal analy sis is that i
~/ -
concentration. of benzfluoranthenes. These compounds are present
- a. m #
W of estract in soot and in air pollution and may contribute to the
. . .g sian Powible nuclei carcinogenic burden of urban populat!;ms. Figure 3
^'"
- p2 Benienes o.30 ,
shows seasonal vanat on m air polluuon. based on "e g,, o.33 0.44 the presence of benzo (alpyrene. u 2"- * :o o.30 v te M4 0.13
'**'f O' I p.8 Cyclopent.inonaphthalenes o.24 Inorganic Compoumis 32
* % 0.26 Some inorganic carcinogens exist in coal and
' 2 "' 0 38 reach the atmosphere following combustion. The 13 Phenanthrenes o.16 concentration of these elements in coal are given in Table 4 (5). They are mentioned here only for the
[ @ sake of completeness. As most of them will be re-0.13 220 0.03 moved before reaching the air by electiostatic pre-l 234 j .2a 0.02 cipitatbn. the carcinogenic risk may not be very o.05 great. however, elements such as arsenic. cadmium. 2tM C lopentanophenanthrenes (.* 2'2 0.08 0 07 lead. and selenium may pass the precipitator and
thus reach the environment as fallout from the air.
( Others may reprenent a disposal problem of fly ash l['$ $$ and clinkers. This topic will be dealt with in another 202 Pyrenes 0.03
' o.oS PUPCE' 216 .
210 0.12 l 0.00 N-Nitrosamines 1 244 I 258 o.% The last group of carcinogens to be mentioned are o.o4 g 4 272 0.01 the N-nitrosamines.They are not present in coal, but l 36 i o.04 it might be anticipated that they would be formed l 22x chrysenes s" 8 242 0.04 during the process of combustion of coal under spe-256 0.06 cial conditions. An analysis of the problem has been
. l made by Henschler and Ross (6). who exposed mice l
I
$ Op;-
o o2 to 40 ppm NO2 for various time intervals observing 29s pm Mation d ahedar ceh but no suggo,bn[
- 26N C)clopentanochrysenes o.04 development of cancer. The report was an intenm f 32 o.o3 o.m mport as many of the animals were still alive, but it 2% enabled the authors to conclude that a carcinogenie 380 0.03 j
252 11 ento (alpyrenes o.06 risk from N-nitrosamine formation from osides of I nitrogen in the air and amines present in the tissues of 2"> o.M
-(
l 2$ y the mice seemed unlikely. lly contrast. Pitts th ob-servell N nitrosamme formation on allowing a reac-MM o.ot tion to occur between secondary amines added to air [ o.o 122 I l containing 0.3 ppm NO, in darkness, while nitra-( *Ibia of he ei at. ei. mines were fomied in daylight. The amine concen-205 thember 1979 s I i E 1 e ~ - --
..m
^ A /N A/N WAA/. A/vV AA/
'VVV VV vv Benz (a) anthracene Chrysene Pyrene S
A
/N ,
AA A/NA A/N/V /v\/N I V V N/vV VN/N/ V Fluoranthene Benzo (a) pyrene Benzo (e) pyrene A
^ A A AAA !
syvv A/vNA N/VN/N I vv v v v v Perylene Benzo (b)fluoranthene Benzo (j)fluoranthene
/N AA AAA AAA/ /VVN A/vV s vv v vvy vvd 1
v l Benzo (k)fluoranthene Benzo (ghi) perylene Anthanthrene
^^
^^ A/NA AA'A/N vv5/
v VV VV Indeno(1,2,3-cd) pyrene Coronene FtGrut 2. PNA components of air potiution. 206 Environmental IIcalth Perspectim T
~ - ~ - - - , . . . . - _ _ _ _ _ _ _ _
3,t,.te 2. Approshnair concentrations of uia heterocyclic compounds in benicuc-soluble fration of sciccted urban atmmphercs *
'~
Conen. pfp
' .o s New
. mJ Atlant.: Cincinnati Angeles Nashs i'le Orleans Philadelphu
- q. r.;, . ; .qnmoh ne 200 b0 b 100 7 2(,
ur 'o hs.nnaLne 20 20 1 30 1 7 , ver .o iendine 200 80 3 70 20 30 I wr.f'a us ndme 30 10 I H 2 6 l l til Imk noa 1.2.b4 qi:n.ee 30 40 4 20 8 10 g Wrau j tiendine S 2 a 6 0.6 6 I l*t data f 4
*t nJetect able in the amount of sample ana!)ied.
Tah!e 3. Four to sis-ring PW and it:rir actisitics in carcinura nc is. Coea r cinoge n Complet e A nti-g ,,,vund initiator uith ItaP s arcir. ogen car cinogen t .. rfi .o..nt b rac c r.e +++ + i t 3 wne +++ + ++ s.c. I N ene ? +4 -
+
s.c. g I * ..unthene - - Pen. .i..cru e ne +++ +4+ N nav e tpp ene -
++4 -
+ ++
li f)te')e - s.c. 4 4
' skin e ho Mluorant hene ++
t- nei*j.qi.oranthene ++ ( t .. ne.= L uluorant hene -
++
s.c. hcr .welmper)lene 1 44 - - s.c. f eihuahie'ne - - -
- . . c .
! .kw t.2.3-cdlp) rene + -
s.c. c.senene 2 _ _ s .c .
'labic 4. Tabulation of carcinogenic elemental tration was high, i.e. 50 ppb. for the reaction to concentrati,.n, in coat.a occur and these les els may not generally be found in t &cnt concentration, ppm Mass now, g/m.in uiban air, but may esist at certain locations. The formation of NO, during combustion has been Wne 3.8 . ix 4.7 - 21 studied and quanCtated and the evidence for N-I'< n :hn nt 0.3 - <5 0 4 - <6.3 nitrosamine formation in the air or in the organism i %um- 0.44- 0.50a 0.55- 0.63 needs further clan 0 cation.
t h wam* 21 - 23 26 - 29
- r. u - 3.3 I c ar
<5 - 30 3 4.i . 6.3
<6.3 - 37 COcarcinocens Associated with wer <100 -150 < t 30 -190 Coal Combustion vemum' 2.6 - 3.2 3.3 - 4.0 L ' in um' i.67 1.3 2.09- 4.1 I_ately the problem of syncigism between chemi-cals in their toxicologic effect has been emphasized.
,"tS ta ot stotton et at. m.
cunon actis.iiion analysn.. and some weight has been attached to its possible
%L source mass spectrometry. contnbution to cancer induction, but as yet no er
'l tope dilution sssts.
haustive s:adies of the effect have been made. Oiigi-themhef 1979 207 r --..._._.._ ., e
, _ l l I I I _
30 - ALTOONA,PA. l 20
! 10 -
ASHLAND,KY. 9 - l 4 - -
]7 s j /
5 _
.' E 4 _
In CHICAGO, ILL. I ti g 3 - o
~, w 4
' h2 E
-\-
\
! 3 \
'N 2 \ / s 5 \ / N
- = 1 / N 0.9 -
\ CtARION COUNTY, F'A. N / '
0.8 - \' ' f \ /
< ^
0.7 - \ / - 06 - N f - 0.5 - (/ -
~
j URBAN $lTE 0.4 -
---- NONURBAN 31TE -
0.3 - j ;l 02 - CURRY COUNTY - s ORE. % s s f' \
% NOT DETECTABLE 0.1 -' ' ' ' -
1 2 3 4 1 2 3 4 1969 1970 Ilft,E, quarter of year 1%uat 3. Seasonal variations of berro(a) pyrene concentrations in ambient air at selected NASN stations (3). I i nally it was considered a tool for the study of mecha the synergistic effect have not been identified in must nisms of carcinogenesis, but soon was recognized as being involved in human career, such as the inci- situations. It is reali/ed that it is not necewary th.it the agent responsible for the synergistic effect is dence of skin cancer in the oil industry, and lung cancerin heavy smokers particularly those who also present at the same time, but may be separated by live in urban areas, work with asbestos, or carn their time intervals of several days which makes ibeir living as uranium miners. study more difficult.There seem to be definite limit s l to this cocarcinogenic effect as observed in amm.J In all these cases there is a greater than expec'ed [ cancerincidence. but an understanding of the mech-studies. If we can extrapolate to humans on thn t ani:,m is stilliacking. Even the agents responsible for basis, it may be possible to describe many of the specific synergistic situations as only applicable m 208 ' Ensironmental liculth li rspectis es S
-==.-=---.*w - - - = = -
- e * *^ ' ' ~ ' ~
c.- 1
r egg. cme occupational situations which have been plus the adJitional 6 hr/ day on the high concentration remedied as soon as they were discovered, but we of SO2. These experiments used too few anim.ds for 1 wpi,be left with one perfect example: the habit of the evaluation of the effect of SO. alone. Two other cigarette smoking 2 packs or more perday. As will be studies are ofinterest also. In one study, rats were i discussed under Ihe heading of epidemiology, esposed cht onically to 4-8 ppm SO No lung tumor s . smoking cigarettes may be considered a cocar-cinogenic hazard in association with coal combus- were obsened in these animals. (9). Howes er. in a study by Peacock and Spence, on mice of a strain j tion. highly susceptible to long tumor formation (LN)Ihe ( lung tumor incidence was doubled in males exposed i Initiators or Incomplete Carcinogens 1o 500 ppm SO2 forjust 5 min / day. 5 days!w eek for a I - q period of 300 days. In females of that strain who do Recently some of the "inactsve,', policych.e com-c pounds were retested m combm, atmn with a syner- not show lung tumors spontaneously. lung tumors gist, or promoter of carcinogenesis, useally croton were also observed (10). 6 i resin or one of its components in pure form, i.e., it may be ofinterest to note that soJium bisulfite phoibol myristate acetate. The species ofchaice was was fo.2nd to be mutagenic to lambda phage. ;md the d the mouse, and the polycylic hydrocarbon was mechanism of action has been studied showing that bisulfite ieacts with uracil-and cytosine-forming f applied to the skin with subsequent treatment with the promoter. as will be described in some detail later addition compounds ill). h another study it was t
-f on. Some became effective initiators of car- found that bisulfite leads to the deamination of cytosine. lligh concentrations or bisulfite were used a cinogenesis under these condn.ons while without promotion treatment they had been inactive or w cre in these studies (/2).
P er b d ares. Partical ites plav an important role ( yery weakly carcinogenic. They were then called meomplete carcinogens or initiato:s of carcino- in all aspects of air pollution's adherse cifeets. They geresis. However, not all previously " inactive" may help to carry adsoibed gasc s to greater depth for [g compounds were active under these conditions, deposition in the lung, or they may overuhelm the mu:ociliary defenses of the reipiraiorv tract leadine g Although it is not to be implied that those incom- ' to longer ' residence of toxic materdds in critical g plete carcinogens should be weighted the same way as the complete carcinogens, nonetheless they may areas. Howeser, tLey may also seive to prevent g esposure of tissue to some carcinogenic chemicals if play an important role towards understanding of the i carcinogenic process. Table 3 ghes the chemicals these can be adscrbed stiongly on particul.stes such as soots. i , that have been identified this way as incomplete l in our concern about coal dust and soot as con- [ carcinogens, but they tion to hmg tumor induction have never in animals. It shouldbeen ah tested tiibutorsin to re!".o- human long cancer, w e need to be eware p be noted that the compounds studied are only the of the impoi tance of surface area to Iheir capacity for major polycyclic hydrocar'oons on soot, and do not adsorption. It has been fcund that particle size is a repiesent all of the adsoibed PNAs. controlling factor in determining whether adsorbed polvcyclic aiomatic hydrocarbons will be cluted or k There is little evidence for the presence of pro- ' I nioters in coal or soots. Promoters found in peti"- not. In a study of different particle size caibon I leum fractions are long-cham saturated or blacks, c was found that the critical average particle I unsaturated hydrocarbons and sulfur-containing size was 40 nm. below w hich even the best solvent compounds. Although they are absent from coal it- would not ehne any PN A, but at a particle size of 80 nm clution was effective. In a study in which DaP self, they could be formed during its liquefaction.
! was added at increasine concentrations to 100 me of 41 f cach carbon black in 6'ml benzene it was found l' hat it . b Cocarcinogens Associated with Coal Com- up to 200 y hap could be completely adsorbed to s
yd *." partrcles with 10 nm diameter and only I g hap remained in solution when 500 pg BaP was added to y Sulfur IExide, Sulfur dioside was found to be a that solution. As the particle size was increased to 30
! promoter of carcinogenesis by Laskin et al., who nm adsorption was no longer complete even with k't I exposed rats for 6 hr/ day to 10 ppm SO or to clean
.t the lowest concentration (5 g hap) added and 107 l air and also for I hr/ day to air containing 10 mg remained in solution. With a carbon black sample of n I BaP/m' and 3.5 ppm SO2 for i days / week (N). The
.e 80 nm no adsorption took place, but the originally
! experimcats werc continued for 98 weeks and pro- hekl BaP and other PNA were cluted (13).
n- I duced no lung cancers in the animals exposed to L
!!is also true that in mixtures of carbon blacks of clean air, compared to 5 rats of 21 with squamous cell ditTerent particle size the smaller pa 1ieles will a i-3 carrinomas on exposure to the carcinogen and SO: sorb readily what has been cluted from the larger lhecember 1979 t
209 t
- E T
p _ . _ . . _ _.
f particles so that none can be deteved. quarry workers in slate and igneous rock and la co.d These findmss .,crve to suggest an explanation for workers suggesting that direct contact with soil in the ditTerent observations made in laboratory es- areas with high mor tality might have been an impor-periments as well as on humans exposed to sooror tant factoriTabie 5). Another puzzling finding in the carbon blacks. When soot is allowed to come in study was the excess mottahty of about 50% from contact with skin and its sebaceous secretion. it may stomach cancer in wives of coal miners as compar ed give rise to cancer if contact is allow ed to persist and with all married women in England and Wales. !n the the particle size is large enough. The same soot may coal fields as a whole when the rates for nhnminer s not have any effect on inhalation in the lung. How- were weighted by the miners' population, the ever all ever,if a solvent system were available in the lung- rate of stomach cancer was 294 per million. This and it is likely that cigarette smoke condensate may mortality in meh aged 20-64. was about 10 percent serve this puipose - clution may take place in the aime that of all males in England and Wales. It was . Iung. This theory would need experimenta! confir- speculated that the excess rate of carcinoma of the mation of the capabilities of tobacco condensates, stomach in the wives of miners might be due to some but clution of PNA from soot also occurs under codaminant in the home such as coal dust. normal conditions by serum proteins. specifically Similar conclusions on coal mincts derive from the lipoprotein fraction, w hich may account for the one recent American paper. Matoio et al. (17) found observation that carbon deposits in human lungs that the age- and su-adjusted incidence of gastrie when recovered at autopsy are des o;d of most poly- cancer from January 1965 to January 1969 in the only cyclic aromatic hydroccibons (14). Additional esi- two coal mining regions in Utah was four times that dence will be given below on the importance of of the Statc of Utah:thice times that in iesidents u bo adsorption of carcinogens on soot. were not coal miners lising in counties with coal it is also ofimportance ta note that adsorption on mining and at least cicht times that of males in coun-particulate matter such as soot will protect PNA ties with no coal mining. It was furth.t found that from quick destruction by light and air (15), $90 of the male patknts with gastric cancer were coal miners. Mi homes of patients affected with pas-Epidemioiogic Evidence of tric cancer werc heated w ith coal and in some of the CarCinO0enic Risks in Coal Minin9 h '"*' ""' *"' "d f"' '"9ng. Ah hough A meri-can wises of miners.1;ke English miner's wises, and Combustion showed an excess raic of gasiric carcinoma. ihe ex-Cuel Minirig cess rate for Americ m females was not found to be smmficant. Neither diet, socioecono'nic class dr-Corcinomu of alw Stomach. Several epidemi- dbution, nor ethnic. religious. or social background ological stud:,es imply that the m, en, fence of gastric
, appeared to be telated to the increased cancer inci-carcinoma m coal mmers is elevated abo ~c that of dence.
comparable segments of the general population not engaged in mining cf coal. Thus, Stocks (/6) found that the death rates from Tahie 5. Arc. adjusted mcan annual death rates per miHion rrom cancer of the stomach in nine mining areas in En- '""* "I "'# """"' h i" '*' """"' ""d gland and Wales among coal miners of w orking age in ""' " " # " # "d """ " ' ' ' ' ""?"*""""' ""d 244 i" the period 1949-1953 exceeded that of nonminers in Arc-adjusted Mes yer miUbni the same counties with the L.mc distribution by age and urbanization of place of residence. In es erv area county ams y the rate of stomach cancer in coal miners edeeded '""'^"U"*'"*d' ""'#" "*"*"'"" that of nonminers but the excess incidence showed Breetnock cammthen. 53s 312 + 226 pronounced geograph,i cal differences, the average W.nbroke difference being 125 per million with a range from 65 Glamorpn 520 325 + M5 to 226 per million. It is high in mountainous areas of Monnmuth 412 255 +157 a 3 heavy rainfall. The greatest excess in the rate shown by miners over nonmmets occurred m W, ales m c ibh nubnland yo,Lshire tweu Ridin.9 . 34e 230 + 1:4 Brecknock, Carmarthen, and Pembroke, where it sianord. Shiophire arid 384 319 4 65 was 226 per million. It was ofinterest that 829 of the worcester miners in the area were engaged in the mining of anthracite at Ihe time of the censa. However. it was y,;'(( w,;eg
; g 3[ fj
. y also found that in North Wales mortality from stomach cancer was particularly high in farmers. Data or stoci m.
210 Ensironmental IIca!th Perspectises
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data in the liegistrar Generars Ikcennial Nupph g gjer American study by Creapei. et al. (18) ! a gates an awociation between mining and an in- ment on Occupat;onal Mortality for 194%Io53 i2/ t
', u.aerrate of cancer of the stomach and suggests I)oll (22) found a similai association in the dem i records of l5,000 men w ho had been iesident s in f ow bt the correlation is with socioeconomic class districts of South Wales during 1948-56. The ratio e'
( r .ther than with occupation. In this uork, mortality i.vm castric cancer in 23 coal mining counties in deaths from lung cancer to deaths from othei causes sewn states ofh t e United States during the period was calculated for several occupational gioups aoJ i
. 3930 to 1969 was compared with other counties. found to be particularly low foi coal mincis. It w as lupulations weic carefully matched by educational shown that if cancer had accounted for the same
[ proportion of all deaths in coal miners as it did in
; lesel and median income. While obsened deaths othei men. that 152 deaths nom hmg cainer would t tun pastric cancer were 209 to 3W7 greater than expected for men and women (statistically highly hase been expceted in coal min u s u heie.n only 73
&mticant) a similar excess was noted for lung md were recorded, a deficit of 52G .
Se', eral studies of neciopsy incidence of lung I dnical cancer, tumors related to low socio-cancer in coal miness hase been reported. Of these.
! ccenomic class. Izewer deaths occurred as a result of t leukemia, and breast and colon cancers, tumors the best controlled is that of James C3 L v lo com-
! which are associated with higher social claw. pared the resuhs of neciopsies on 1827 co.d miners and 1531 male nonminers of similar age from South The authors dismiwed the excew stomach cancer
, rate on the basis of a socioeconomic awociation; yet Wales. Lung cances was present in 3.3G of the min-ers and in 5#; of the nonminers. Howeser, it was i thes stiewed that the miners and nonminers were in Det closely matched on the basis of schooling com- suggested that pneumoconiosis was a competing i
pteted and median family income, cause ordeath leading to t he lou necrops) incidence in a recent moitality study, Rockette (19) found a oflong cancer among these woikeis. In mo:e reecut 150 exct w of stomach cancer among a population of papers. Goldman CO has presented foiIher surport
! 22.WS coal miness, representing a IW; probability for these earlier obsen ations He icported that the
! sample of all coal miners eligible for benefits fr om the standaidized mortality ratios foi cancer of the lune of
$ United Mine Workers of American Welfare and Re- underground miners and ex-miners employ ed by the tirement Funds as of January 1,1959. The sample National Coal Board of lingland w as 74 in comrari-i I population was traced through the year 1971, and son to 100 expected deaths trom this cause. The j was contpared to all males in the U.S. for 1959-71 as a mortality in surface woikers was found to be hiehes cont rol.
(Table 6). Moitality rates foi cancer of the lang for a t
! A definitise conclusion on the awociation be- small coal mining salley and the mortality tirmcs foi tween coal mining and incr eased risk of cancer of the long cancer in several towns which are situated in l
stomach is not possible from the published mining and nonmining m eas surported these Egm es. l epidemiological data. However, when the available The authoi also summarized the data avaibHe on t he ( relationship between smoking and lung cancer in data are taken on balance, it would appear that the excess rate of cancer of the stomach in coal miners coal miners. He concluded that numerous inses- { oser nonminers cannot be dismissed wholly on a tigators have found littie dit ference in smoking habits g oeioeconomic basis. While the existing data imply between coal miners and nonminers and found no l indication that the low incidence of lung cancer
]
that an increase in coal mining might result in an incicased incidence of cance of the vomach among among coal miners resuhed from unusually low [ cigarette consumption. He speculated that a reduced I coal miners and perhaps their immediate families, fmther work to identify the effects. of connieting f sariables is requiicd before such an association can Table A standardised mnriar;i3 ratim intn, or miners and te g sninm en1pimd h Hic Briibh Nauun.d Coal Board. feo canu r of he either confirmed or denied, the lung and for other neoplasm ,1955." k C.uremomo of tiw Img. Available epidem.iolog.ic g studies suggest that the death rate of coal miners enacrponna somee j fiom cancer of the lung is appreciably lower than the w oiken woaen l rate for nonminers of comparable age in Ihe earliest ' repoiled study, Kennaw ay and Kennaway et al. 00) c,'sr n ne n, E ne t ms esamined the death certiheates of men aged 20 ) cars and over who died in England and Wales during observed ac.obs 216 359 54 93 304 150 59 82 1921-32 of cancer of the tune and larynx. They cal- threcicJ deaths S R' 70 3 3 "2 " 93 3 3 3 b8 culated age-standardized death rates for 63 oc'c upa-lf j tions and noted specifically low rates in agricultuie and coalminers. This finding was corroborated by
.g u , g g m n a Tngland and Wales. mies = 100 m i Ikcember 1979 211 I .
.~
b
cration. 'I he Standard Mmtality Ratio obtained in risk of equiring lung cancer is a speciGe effect of working in a coal mine, and that an occupational this study was 67. a 6pme w hich agreed well with factor such as inhalation of coal dust may block the liritish figuies and coiroboiated the association re-induction of pulmonary malignant change. Imrted in the llritish literature between coal mining l and a decreased fung cancei incidence (Table 7). One of two initial studies in the United States Again no relationship between amount of cig.neues failed to corroborate the liritish findings. Thus En-teiline W). using occupational data from the Na- smoked and the decre.ned rate of lung cancer was found, tional Office of Vital Statistics of the U.S. Public llealth Service for 1950, calculated standardized The asailable data strongly suggest that an un-known tactor in the co.d mine environment, powihh mortality ratios for seseral selected causes of death in coal miners aged 20-64 and 20-59. In the age group coal dust. exerts a protective effect with reg.oJ to 20 M there were 161 observed deaths caused by cance of the lung Accoidmgly,it would be antici-cancer of the trachea, bronchus, and long with 84 pated that an increase in the scale of co.d mining would not increase ihe incidence of long cancer in espected deat hs giving a S M R of 192;i.e.,192 deaths coal miners. Flowes er, if co.d dust is in fact beneti-compared to 100 espected. In the 20-59 age pioups the SMR was IM. This viudy can be attacked on the cial w ith iegard to long cancer, it is also a causatise a factor in black lung Thus w hile long cancer rates grounds that the espected deaths are based on might not increase as a result of an espansion of coal populations reported in the 1950 census estimates which recorded the last occupation preceeding the production. black long and other tespirato:y dis-date the census was taken: i.e., men w ho once mined cases would probably become more pievalent. coal but changed occupations weie not classified as
. coal miners. Coal Combustion in the positive American study. S.carano c: al. (26 )
found that cances of the hmp was diagnosed in 7G of .tir l'olhainn umf Cuncer. 'I his ieport considers cancer only; effects of ait pollution on respiratory anthracosilicoties and in 1.0SG of nonanthracosili-cotics.this diffeience being highly significant. How - disease aie not diseuwed. ISidence for an associa-eset , no data on Ihe ages of minet s s ersus noaminers tion betu een air po!!ution and car er sie na from tw o were published, again rendering the conclusion sus-type of studies. In tric first. urbaa, and rural popo-lations base been compared for in:idence of lung pect. in the most recent study of mortality from lung cancer. Sescra! small European studies by Stocks and cancer in U.S. coal miners. Costello et al. (2h fol- Campbell CN h I)aly CW. and Stocks Uu) and a num-lowed up a cohott of Appalachi.m co.d minets who were included in a 1 % 2-1963 U.S, Public Ileahh ber of laige-scale American studies standardifed Sersice prevalence study and compared the long with revect to both smoking habits and to age by cancer mortality of this sample with the 195S death flammond and Horn 6/). and Haenvel ct al. U2) indica!e that these is approximately a tw o fold higher rate of the United S:ates males as a who!e. Smoking habits were recorded in ihe population undei consid- inciJence oflung cancer in m ban t han in rural areas. In the second type of study attempts have been 'l Ta!.le ?.otncrud and espected deaths and staniird nuo tanty rati" made to correlate caneer moitalitv data w ith indices
}
in a group of 451 Appalathian cual minery w ho died on or befon- of air pollution. Howeser, the e{idence linking air knuao I.19L. - pollution and more specifically ben /otalpyiene 1% pecied tilap) duectly to lung or other cancers is inconsis-Ape Obsen ed lent. Ihus Menck et al. d.4 found a coirelation be-2 0 tween the concentration of ben /ola)p) rene in air and 0 sod and the lung cancer moitality excess of 40'; in
,33 39 _
i south central 1.os Angeles County. The highest au.4a o 4 t49 s o 3 ben /o(a) pyrene concemration found was five times 50 54 2 6 greater than would base been espected fiom auto-j j mobile exhaust alone and the escess syas thought to result f rom the petroleum and chenucal mdustries g, , 33 39 70 74 1 o conecotrated in the area. 'l his association is consis-1 75-79 0 0 tent with eather findines of Stocks tM) from En-Total 24 36 gland. It was postulated that the increased rate of lung cancer in the 1.os Angeles area resulted f rom a asstR - c4 TM s 100 = C hom a cohed of 1726 nunen N> nergistic action between smoking and neigh-r.uwfomty selecied by ihe t LN. Pubbe lteahh sen ke in 196249nt boihood air pollution.
- Data of coelio e7t Ensirenmental llealth perspectises 232 i
1
- *sm=w aseeve. --e. -- - , sWT ' P' ---=- - , .. _ _ , _ .
.~
g.i.m extension of the above studies.11enderson et smoke. l'or 26 areas in northern England and W: des, i.: there appeared to be httie relationship between !
" [43measuied actual lesels aromatic h3drocarbons (PNA) ofinathe number suw of poly-noniespiratory tract cancers and a smoke mdes.
I
, , acd airbo:ne particulate matter in South Central 'lhe sing!c exception occurred in males w hen the
- . .wceles County. Four PN As were found in e.s- s.oeioeconomic vmiable w as social class: heie the i t ben /ote)pyr ene ( hep). ben /ota pp> iene ( hap). smoke indes esplained a signiticant amount of tiie
! k,aforchi)per>lene (GEE). and coronene (CORL A variation in the cancer mortality rate. Repressions
! .. I through 5 imp l> that if the qu.dity of air of all b,o:ie' nhotion anon of lungwas apparent cancer between cases and the generalthe geographie twough . were impiosed to that of the borough with
( w.gion of industries which emitted these PN As. the best air, the rate of death fr om lung cancer w ou!J
, Io the en: ire county, occupation was an impor- fa!! by beta een 1I and 44 percent. Repressions 5 and t in: detenninant of a male's lung cancer risk but 6 indicate a relationship between air pollution and mtlun the limits of proportionalincidence statistics. long cancer u hich is either insieniticant or iin erse.
.t al not explain the excess male tisk in the region. Winkelstein et al (73L using as a measure of pol-sugecesting that oecupational risk may not e splain Ihe lotion an indes of suspended p.aticulates aseraged esee s long cancer in south central 1.os Angeles. oser a two yea: period. found the iate of mortality
%cher did smoking habits appear to be a salid ex- fiom stemach cancei in Itof falo. New Yor k, and the
;% nation for the increased lung cancer rate since immedime environs to be mor e ihan tw ice as gr eat in i
en;> one (esophageal) of the five 13 pe of cancers areas of high pollution as in areas of low pollution. aeoci.ded with cigarette consumption was in excess liones er. the authors recogni/ed the necessity of ar,J since the picatest excew rate was of adenocar- fuither woik which would peimit an independent emoma of the long. a histological type which does awessment of the powible effects of cigarette
.at appear to be related to smoking. smoking. air pollution. and ceonomic or occupa-k lane S which summari/es the evidence for an tional status.
association between air pollution and long cances is Hagstrom et al. tf9L using four measmes of air f tat en f rom a paper by Lase Lf6) and is based on the pollution. found the cancer muitahty rate to be 25G l wmk of Huell and Dunn Lf 7L For smokeis, death higher in pailuted meas than in meas of relatisely t rates (adjusted for age and smoking) ranged from 25 clean air among middle class residents of Nashsille.
! to 123 peicent higher in uiban areas than in rural Tennessee, between 1949 and 1960. They also found
{ areas. For nonsmokers, all dilferences exceeded significant mortality r.de increases awoeiated with j 12LN . indisidual categories of cancer such as stomach
! The incidence of nonrespiratory tract caneers has cancer, cancer of the esophagus and cancer of the also been related to air pollution. In a f eworking of NadJer.
d.da 6om England on rates of death from non- I evin et al. (41) eported for all types of cancer the respuatory tract cancer. I as e and Seskin L17)( l able fo!!owii<g relationships: the age adjusted cancer esi-i % found that the esidence of stomach caneer was dence iates for uiban males was 24 percent higher sieniticantly related to a paiticulate deposit indes than foi rural males in New York State tesclusis e of { and a smoke indes with nearly identical effects for New York City) (1949-51 L 367 higher in Con-3 j' males and females. Intestinal cancer appeared to be necticut I1947 51L and 407 higher in lowa (1950n only marginally related to indices of either deposit or the incidence for urb.m females w as 149 higher than i I Table H. A eomparison of puhtished lung t ancer mnriaht3 data from rural and urban areas. Number of deaths from h:ng c.mcer pt r 10(1,W pnpulation.'
\ No. of deaon standanbred for No. of deaths age and smokmg in nonsmoken f' --
l l's barv Urban { l'iban Rur.d rural Urban Rural rural StuJ) I
- g 10I 80 1.26 36 ti 3.27 Cahtorma men: death rates by coundes
{ 52 39 f 31 15 0 x Amer tean men l IW 85 2 23 50 22 2.27 1:ngland .. id Wa les 3 3x In OO Neithe'n tretand 149 (n 2.15 23 29 .79 I~ ngl.md: no adjustment for smokmg lon 50 2.00 16 5 1.20 Amencan men
*D.da of 1.ase un i
December 1979 213 { - 1 ( .t a. t
1 l l 1 l 1 Table
- 9. twueiations twtween cancer, air palution, aml vuionmmmic status. N!ultiple rrriewit ns based on data from Ent .md. f Sunnbers in parenthe es are the i st.itisti(.- e Indev' !
R Air Soc io. Categor) pollusion econonuc 1.ung cancer mortahty rate l 53 County huourb O. m 0 041 0.154 (demnit indet per ons'asre t 2 09) 14.2 h i 28 Count) boroughd 0.576 0 h64 0.!61 hmoke, persons'aere: M.de. 26 are.is' 1409 a ly0 O.7x ! (i.I17 0.Il5 A bmoke, personGesel (2 h4 il '03 Male. 26 areae 0305 O.161 0.1 '2 hmoke, social cl.m) , f5.62) ( 2. 4 7, 53 Urban are.n* O 144 -00% bmoke, pensonnere) 0 184 1--2 42) e4 bh j Si thban are.n 0.378 0.105 ($O2. penons acre 1 0197
- 1 tm (5.2h Other cancen e Stomach. mate. 51 county boroughs 0.167 0.070 0 005 ddepinit inde t renons 'as se) (304 0).123 6 Stom..ch. female 0.175 0 070 _0.03 (3 HM t - 0 4r0 Stomach, male. 28 county boroudn 0.257 0.714 0 065 hmoke. penonvaere) l t 2.57) 41.21) ; Stomach. Iem.de 0.454 0 hx1 OfM g
(4. l h ( t wo Intestinal. 51 (ount> huoughs 0 041 00m -00 2 (degnit inden penoniaciel (1.44 (_0.52, Intestm.d. 28 county bomughs l 0.129 0.174 0 016 bmo(c. pei sonVacre) (1.24 (l.15) Other cancer, m.de. 26 areas 0 as4 0.019 l 0 073 hmoke, renonnere) ( 0. 5 'h t i 6ni Othei cancer, female. 26 areas 0 044 0 019 -0 062 ( hmoke, personaere t to 9h 1- 1.01: Other cancer male. 26 areas 01% 0(M 0.017
. hmoke. wsial claw) 12.75) (034 I ) Other cancer. fem.de. 26 areas 0 002 0.on5 - 0.013 bmoke, social cLm)
(0.17: ( - O 19i i l i
- Data of 1.ase (3%
j Ihc coeffkient of detelnunation. a wJue of 0.h6 indicates a multiple cor relanon coef6cient of 0 62, and indicates that 39G of the I sariation in the &ath rate is "esplamed" b) the regicwon. rihe r statistic; for a one-tailed t-test with 23 devices of treeJom. a s alue of 1.71 indicates significance at the 0.05 lesel, for 25 or 50 l ! degrees of freedom, the critic / s aiues are 1.71 and I>>X 3 dPenons per acie (multirhed by Ini: the sauge h (W to IM. and it.e sacan n If i. Dcath rates.ne meaund as mJes numben with the , mean for all huoughs m I.nyland and W.de., equal to 100 Ranres withm thn s.unple are .n fodoa s I ronctins im.do h 7 4 to 259: ~ bronchitis afem.ded. 72 to 268: lung cancer. 70 to 159 stomach cancer (malesi. 67 to 168. stomah cances ifcmaleu. 54 to 161 mtestinal cancer. 87 to 121 l
' Data for 2h country huoughs m England and Wafes equal to 100 Ranges withm thn sample are as follow e bronchitis tmaleu. 73 to 259. bronchitis tremaleu. 72 to 26X: lung cancer. 70 to 159. stomach cancer s maleq. 67 to 16S. stomach cancer ifema!co. 84 to 161; intestinal cancer. E7 to 121 I
' Data for 28 counthhiroughs m England and Wales as reponed by Stocks. Air po!!ution h me.nuied by a smoke indes asuspended matter,in mg'l00 m'); the range h 6 to 49. Again. the soooecononuc indes h espicwed in numben of perwns per acte t > 10); the iange n g 83 to 342.
' Data for 26 areas in not thern England and Wales as reported in Stoci s Air pollution h measured by a smoke indes; the r.mge is !$ to 562 mg/ lou 0 m'and the mean h 260 One wooet onomic sanaNe is the number of renons pei atre lot the range n I to 342 and the '
mean h l02. t he other weioctonomic buiable n socialelaw: the range is 611o 294. Death rates are me.nureJ as for cateror y 1;withm thn Nunple the range for lung cancer h 21t o 165; for other cancer.6 to 122 f malco and b5 to I54 femalea.for bronehais. Ih to 259imaleu and i 12 to 240 tfem.. leo: for pneumonia. 61 to 227 Imaley and 40 to 245 s temales:
" Data for 53 areas as reported by Ashfe) . Au pollunon n measured by a smoke indes las for categor) 3L with a range of 21t o 261 pg m' and a mesm of 124.or by an NO: inde s t app. rcnil) m the ume unit L w n h a range of 11 to 277 and a mean of 124. Death Iares are measured I as for carefory 1; within this umple, the range for lung cancer n 70 to 144. and for bronchitis. M to 186. '
i i 214
- Emironmental llealth Perspectises t
i
,m,, , , , , -w e
- T"P F'N W ** ' ~ - N'*lh*'**** - aus v .m.. . , . . .
h
,t for rmal females in New York State. 2E; higher in incicased with are at time of migration. Unfouu-q Connecticut, and 3E; higher in Iowa. Foi botii nately most of the studies lack data reg.irding the e males and females the incidence for each of 16 cate- elrect of the smoking tactor.110wes er. in ses etal
[ gories of cancer was higher in urban than in rural areas. . ' studies such as that of Eastcott (JA an es ahiation of migrants from the t'nited Kingdom to New ZeakmJ
- 1. ave and Seskin 07) speculated that approxi- showed that the migrants had a 35'; higher to.L of i mately 25G of mortality from fung cancer and 159 jung cancer than m oure New 7e. danders if they i mortality from all cancer can be climinated b 1 Str; came from the l'nited Kingdom before the ace of 30 i reduction in air pollution. In monetary teri.. . these This was true regardless of the fact tlut the migiants decreases in cancer rates woulJ serresent $33 mil. generall) incicaseJ the number of cigarettes smoked
' lion and $390 million respectisely. af ter anising in New Zealand.
, On the other hand, iiiggins (4/ ) founJ little con e- Dean's studies 444. J5 ) me also impor tant in this
., lation between ben /o(alp > rene or total suspended regard. lie compared lung cancer rates in lhithh
; pare urate levels and lungcancer death rates in some subjects w ho mipated to South \friea and Austi.dia 50 standard Metropolitan Statistical Areas. liow-with those in natis e bor n South Afiicans and Austra-ever, a significant coirelation with sulfate lesels ap- lians.
pemed to exist (Table 10). Austr.dians bas e beas ier smoking habit s th.m pei-A stiong relationship of llaP to long cancer was sons in the United Kingdom and South Vucans me
- Jso absent in a study by Waller (42). He reported among the heaviest cig.o ette smokers in the wor h!.
that the incidence oflung cancer in gas w orker s w as lhitish migrants to South Afiiea tended to increase only about 1.5 times that expeeted in spite of a If ni- to their consumption of cip.n ettes m.o Ledly. While the U 10.000-fold excess of ben /otalpyiene in the air butt lengths of cip.ucttes smoked by lhitish and i breathed by those woikers in compmisen with air to South African smokers weie closely comparable, p which a normal mhan population i,. esposeJ. (25.3 s s. 25.2. tespectis c!)) a cicaici percentage of g Peihaps the most consineing support fm a ie. South Africans inhaled deeply .mJ some South ifn-
- g. lationship between air pollution and lung cancer cans took more puffs per cig.uctte. In spite of this, stems from migrant studies. In this approach, hmg rnigrants fiom the Umted Kmpdom h.uf a signifi-cancer death rates in mipants from one counti> to cantly lower lang caneci death rate than persons another weie compmed with those in their home remaining in England but a hipber rate than natis e populations and with those in populations in the South Africans or Australiarr flables 11 and 12).
f{- countries to w hich they had immigrated. If such mi-grants can be consideied as equis alent to random or The lung cancer death rates in merants to Australia from the United Kingdom (45) w eie also highei than ( ' representa:ive samples of the populations of the in natis e Australians but low er than in a cohort yn.up home countries, differences in death rates fr om in the United Kingdom. those in the home countries can be ascribed to Simika findings v.cre reported by Reid (46) for I changes in ensironmental conditions, since concen. migrants fiom the United Kmpdom and Norway to trations of pollutants including ben / ora) pyrene s ary the United States as compared with reisons ie-considerably worldwide. maining in the home country and with natise-bm n
'I he results of these studies indicated that persons Americans. Again, hmg caneci death intes of mi-migrating from a more polluted ens ironment to a less pants weie intermediate between those of natise polluted ensironment had an increased risk 'of long RS. tesidents anJ those of nonmip ants in the home cancer compared to the native population. but a countries Gab!e 13).
loner risk than their home populations. The risk A recent study selevant to both the urban-tural Table 10. I piderointo o of lung unur in the l niied Narev i Ibah rates fro ti lung ca icer l'*$9- 1%I
,i ,
Ntates i emales l Stcasure of pottunon ' Whde Nonw hac Whde Nonu hde F kal suspenJed pamcul. des -o ot o.25 --o 09 .oo
%! fares o 42 039 o.19 - o o<
tien/otory rene 0.17 o Ou 0.10
- O.ll
- ?
- Data oflhpginW/ i Cor relanon cocmacni beiw een measur ewfir po!!unon and age 4tanJxJucJ Jc.dh ra'e, trom leup cancei dC D i
e 162164 in approumaict) 50 sr.indarJ rnetropoto in siansucat .nen of U.S. u . i ikccmher 1979 A 215 I s
Table 11. I ung cancer death rates for white male nathes or l'n-d.n sulfation rate). The data support the hs pothesis gland, M ales, and South .itrica and I nited hinplom mi;*r.mts to South Af r.& 1987 19 % ? - {t th de h of moki@ Md N Idhb m . additise. An important consideration ;uismg from Annual lung unter death rate these data which is ielesant to migration studies is iper 100.000 persono the hypothesis that immigr ants to a polluted commu-lbMaion rroup 45M 3 ears eta (I5 + > ears otd nity aie a self-selected unusualls healths eroup These factors require further e' amination'. 'l he s Nathe whitt South Afncans 50 112 above findings pros ide a strong b. isis for concludio
- United Kegdom ndgrants to that diffeiences in jung cancer death rates in differ ent South Afnca ll' l uy ons a Nga to nm than cigaiene Natise white United Kmrdom 135 21 smoking i.e., to an mban factor.
%Dataof Dean uts. 1%ilric LJhet os.%<suscer lanci<lcun e <>f f racreau,c,I C,wil Consrunpriors. Among the po!) nuclear hy dro-carbons pzoduced by coal combustion is ben /o-Tahte 12. Age-adjusted 90 + 3 ears oldt luna oncer drath raies.
3*'* NWiene. a c;ucinogenic hydrocarbon under es-perimental cond;tions. Concentrations of ben /o-I ung e.meer death i.ne copyrene ben /o(c)p> rene. and ben /(alanthiacene Poput.aior, group per 100.om penons in the Atle gases from coal-fired installations base Nathe Auqraluns n pubhshed by Diehlet al.bih)(Tables 14 and 15i. 33 Unned KinWom m@ ants These resuhs indicate that poly nuclear hydmearbon to Au n.Ju 94 concentrations in Due gases fiom coal combustion United Kingdom cohon gioup 154 can be highly variable and that the sariation cannot
%ta of Dean a3' normal l) be related to identifiable operating param-eters.
While hap cannot be assumed to be the cause of Table 13. Age-adjusted death rates fa om tane uncer in Great long or nonlespiratory cancer in man. it can be used liritain. Norway, and the t nited States? as an indes of air pollution since its concentration is correlated with other hs drocarbons and sulfur
$"$ r s f dioside, and since it appears in solid form in air.
usually :.dsorbed on particles. Ibrutation troup M. des l'em. des A quantitative estimate of the tela ionship be-tween lung cancer death rates and ainmspherie hap Great Itntam resident, i31.2 i93 , Great lintain born U.S. residents 9u Ip concentrahons was attempted by the Committee on Nanm> iesidents 30.3 31 HiologICal EffeCis of Atmospheric Pollutants of the Norwagorn U S residents 47.5 10.7 National Academy of Sciences 6191.1 hi .committec Nath e U.S. residents 72.2 9E used the comparison betw een m han and rural cancer tales (i.e. a male urban lung cancer death rate ap-
*D.da of Reid ei at. w.
prosimately twice that found in corresponding rural comparison studies and migrant studies is that of measl and the m ban (6.6 g'1000 m' Hapt and rural Moriis et al. 617). In this woik moitality esperience (0.4 gg/1000 m' hap) concentrations of Sawiki (59L was determined over a 13-3 ear period (1960-1972) for On this basis, approximately a 1000 increase in long sample populations in tuo small Pennsylvania com- cancer rate is associated with a 6.2 enit tone unit of munities with widely different air pollution levels. A hap = 1 pg/lood m')inercase in hap or an ineicase relationship was suggested between mortality rate of arproximately 159 in deaths per unit increase in and length of residence in the polluted community hap. Ilowever, since the 1007 increase represents (age adjusted) but not in the control community. An the difference between the most heasily urban and inDuence of smoking on mortahty was elemly evi- the most rural environments, the pollution effect ! dent. While a small (volunteer) population size pre- estimated from these studies should be somen hat l cluded definitive conclusions. (socioeconomic pat- less than 15G. Using the difference in lung cancer tems were also not determined) it appeared that death rates of 13 per 100.000 of population reported those with oser 20 years esposure to aii pollution in between urban and iural areas in a study by Ham-the polluted community (151 pg/m'su pended par- mond and Hom(52 L there is a chance of about 59 in ticulate:3.7 mg'100 cm 2/ day sulfation rate) had about the lung cancer death rate per unit of hap. one-tenth the excess mortality of1 hose smoking one The committee also utilized Iegression anal) sis to pack of cigarettes a day in the control community separate the effect s of factors that diffeientiate ui ban (109 pg,'m' suspended particulates; 0.6 mg'l00 cm;/ and rural ensironments. using the assumption that 216 Emironmental ifealth Perspectists
*~- , . ~ . . . ._ - , , m. ..
lahte IJ. Concentration of three pr,1>nudcar hy drocarl.ma in the flue gas of coal. fired installation,.*
' Ilenio(alppcne llenios e lp) re ne lleni(anant' racenc
. I oad _
Capacit y , factor pg1000 pg10' g 100 pg lo" pg:1000 pg'10* f ,. g s pe of bui ner Ib steant hr sampled m' 1L1 li mg hr m' 11f li mg/hr m' IITll mg'br
! Ch.un grate 33,000 0.61 '50 !!9 3.5 - - -
' Ch.un pate 35J100 0.45 9 4 01 91 42 1.0 44 20 0.4
, i Ch.un grate 40.000 0.47 110 75 2.8 440 300 1I _ _ _
4 Ch.un prate 52.000 0.41 850 500 20 $30 310 12 1.400 b20 32 4 Ch.on graic $5.000 0.b 1' - - - - - _ _ _ _
- e. L'nJeitted 1 N).000 0.74 240 120 11 140 72 7.7 3h0 200 21
! - l'ndeif eel 25.000 0 40' 53 31 1.1 590 350 l' s spreaJci 24,000 0.75 120 f,5 1.3 820 470 9.1 - _ -
9 It hanny grate 2,470 1.00 650 330 1.3 1,3to 670 2.7 1.tCo 670 2.7 ei ibben/cd coal 40.000 0. b0 420 230 9.1 d60 470 19 400 220 8.7
;I 1% hen /cd coal 240.000 0 58 180 120 45 1,100 bu 310 - - _
Ithers/cJ coal 600.000 1.10 - - - 160 64 Ab - - - l'ah eri/cd coal h10J)00 1.05 66 21 31 110 34 50 - - - u Itheo/d coal 1.060.000 1 00 IN 6 10 380 110 220 - - - I4 1% hen /cd coal 1,250.lMO I 02 80 32 59 68 27 50 - - -
- 1, Ithen/cd coal 2.010,0'80 0 76 59 20 54 130 44 120 - - -
l l' lbheri/cJ coal 2.100.000 0 F6 56 17 28 120 37 62 - - -
, b Cglone 2.2003100 0.99 43 16 49 140 55 170 - --- -
li ., el lhehl iAl. 1.,hte 15. l'oly nmlear hydrusartmns in the flue gas produud by ddierens ty pcs of wal(puhatis.;: grate stokerL* llenrot.Op> rene lienzoielpy r e ne llenit al e nt hracene Finng rate, pg'1000 p g 10' g 1000 p gs 10" p g' l000 pp 10'
. Co.J 10' illlLhr m' 11I U pght m' irl li pg hr m' It i U pghr
, I- No. 5 3.87 1500 840 3.2 3S00 2l00 8. I 5700 3200 12 3.45 - - -
64 30 0.1 24 11 0.04 ii ' '- m .ihh 3 4.4 % $40 210 1.0 1200 480 2.1 770 100 1.3 lt :No 5 4.29 1700 820 3.5 2600 1200 5.1 1000 450 2.1
No b 3.29 120 71 0.2 2FO 160 0.5 - - -
I c,v: t 3.52 54 25 .09 bb 41 0.1 190 58 0.3
- i. 650 330 1.1 1300 670 2.7 1300 670 2.7
*ii , of thch! NR I.sh!c 16. Slultir.le regression analysis of lurg cancer death rates for males in 19 countries and cigars-tte and schJ. foci consumption.*
Regiession coefficients r Sohd fuel. Asciage Cigarettes. metric tons death rate 1,0$Ys per person per person
\ge troup. per rr.ilhon Constant per ) car per year
)c.u s person s (C,) (avg. = 1.76) (a g = 1.55:
Age.adjustcJ 749.3 310.0 110.0 144.0 25-34 10 0 2.8 2.0 2.0
' 35 44 7.1.2 9.7 23.0 15.0 45 54 427.6 !(4.0 78 0 80 0
, 55-(4 s I.377.2 704.6 13h.0 276.0 65-74 1.939.1 810.0 321 0 361.0
*\ W Jata M7L the lung cancer death rate is related both to cigarette lung cancer death rate. This suggests an increment in wnsumption and to solid fuel consumption and that male long cancer deaths of 20Cf per metric ton of coal the ellects are at least approximately addithe. With burned per year per capita (Table 16).
tins approach the regression coefficient for solid fuel The conclusion sugcested by these results is that ,., g mnsumption is approximately 2001 of the average the products of solid-fuel combustion or of some 1%tmber 1979 217 b.,
+ ! vadables highly correlated with solid fuel may be an Effect of Tetuperature on Formation of PN A l important etiologic factor m lung cancer. Ilowever, h,ennaway made the impoitant observation that
! as' discussed elsewhere in this paper, an estnipola, tlon based on BaP levels appears to be a gross os er-on pyrolysis of isoprene polycyclic hydrocarbons
' were pnly formed at temperatures abose 750 C. lie simplification considering the importance of ad- identihed ben 7ene. naphthalene, anthracene.
! sorptise properties of soots and the synergistic phenantluene. and chrysene. The tar thus formed
! capabilities of air pollutants, particulatly those in wm highly carcinogenic anti probably contained
'{ tobacco smoke. higher condensed systems of PN A as well (Sn. A "I'k"I *P""'"ie for the formation of carcino-
! Carbon Illack Manufacture genic polycyclic hydrocarbons was also poquiated
' Commercial soot pioduction has become a sizable by Dickens :md Weildlatherbe w ho produced a noa-r I industry and it is of interest to learn that a car. carcinogenie soot extract fmni wooJ tha? had been
; cinogenic ha7 aid has not been detected in the wwL- heated to 400-450'C (SR These data support the
' ers due to the presence of carbon black in the air. OnJings on lung cancer incidence amone woikers Although it is not clear what particle si/c carbon employed near caiboni/ation chambeis ai show n in t blacks weie prepared in the factory under study. Table 17 (59h Ingalls could not demonstrate any cancer risk for .. Taue t u immure mnge acag7nmnukuni,en and esum a
- i. that group (52). Similar GndinFs were reported for luna canni n poriid.
1 workers in a 12rench caibon black manufacturing facility (53). A plausible explanation was offered by Te nira amic t.sceu
'"' m M lung Ingalls in the low content of acetone-estractable C" """' "E d'""" T '"' P'* ' # 4 ! matter from the carbon blacks manufactured in the ~
!! plant undet study compared to the soots that w ere in venie,,i ,emn s .;oo 3m 7, i contact with the llritish chimney sweeps
- skin. kivontat remos wi no m Joke osens 1.W f *
- i 255',
bip.lDf %C fa% FCnCla:Ol% 1 fin butI E Laboratory Studies Which Support m a.l a nenna w m
; or Contradict Epideraiologic Data carcinogenicity of selected PNA and A few data are given in this section to orient the Ileterocyclics Found in Air Pollution
' reader on some background information which may Few of these compounds were studied for their be helpfulin the cancer usk esaluation of mereased ability to induce lune tumors. There are also few esposure to coal dust and soot. Iloweser, none of uudih on their emeinocenicits on oral administia-
~
thc esperime'nts are adequate to answ er questions on tion but each and esen'one has been tested for car-
~
human nsks quantitatisely. cinogenicity to the skin by painting the back of mice. Howeser. by repeated appheation of the solation. it l is dif6 cult to estimate the total dose required for a
' Fortnation of Polynuclear Aroinatics (PNA) i carcinogenic response and for,that ieason the sub.
l Ellis (54) pave an esplanation for the formation of cutaneous injection route in mice is chosen here for
' largely pericondensed aromatic hydroembon from comparison of potency. It is realized that relatise organie materiais on ppolysis. At 1100'C. methane. potency necd not be the same foi other organs or for instance. would break down to methylene radi- tissue and for other species. It may seive the pm ro'e cals and hydrogen, the fice radical would dimeri7e to of icfieshing one's memory on the diffeient con-ethylene w hich on losing additional atoms of hydro- stituents of soot belonging to the PN A and hetero-i gen would give rise to w hat was ret, erred to by Groll cycijes, (55) as " nascent acetylene" from which by pol)- ' Benzo (alpyrene injected in a 1:9 cholesterol:ohse merization aromatic hydrocarbons would be l,ormed. oil misture, produced sarcomas in C57 mice. When 4 The simpler structures w ould t hen break dow n losing the dose was 40,4, or 0.4 gg sarcomas were pro-hydrogen to gise rise to carbon hydrogen and more duced in 23. 5. or I mouse in each group of 50 A.
comples aromatie hydiocarbons. The same products Hen /(a) anthracene, dissob ed in tricapnlin pio-were obtained by p> rolysis of natural gas, containing duced sarcomas in C57 black mice on subc'utanuu-l hydrocarbons with two and more carbons in the injection. With a single injection of 50 gg thet e w eie molecule. From these findings one can understand the sarcoma-bearing animals among 43 mice, with the' observations of Kennaway that pyroly sis of or- 200 pg 11/43. with 1000 pg 15!31, with 5.00a pp ganic.materiah might lead to caremogeme tars (56 L 49/145, and with 10.000 pg 5/16 (6/ L 218 Emironmental llcalth Perspertises (s. .
" "~
.+,p. ,s w- y . ,w ,
s Chroene in tricaprylin at a dose of 5000 pg pro- the abose esperiments using iom oside m partien lates it was found that ?O instillations 001.5 mg each ( d;.eef foui saicomas in 39 mice (fi2): in a similar of ben /Loanthracene produced no iespiratory tract l . ep.Quent aho on C57 black mice, of 20 mice. two ges eloped s:ncomas on subcut.meous injection of 10 tumors in 47 h.unstei s: 30 insti!!ations of 3 my ps t ene [ r asses of l000 pg each o chrysene in arachis oil 63). produce l one tumoi m as animals: 0.5 mg ben /tb)0uoranthene gis en 30 times pioduced oae
) Hen /lb)Duoranthene was gis en subcutaneously to tumor in 47 animah; and 30 instillations of 0.25 mc
! a NYli nc// mice in thice injections of fa) pg each.
)
diben/ta.hbanthracene produced two inmon in 46 [ind 18 out of 24 survisors had sarcomas (64).
. I Indenoti.2.3-cd) pyrene in olive oil was injected hamsters (74 L into XVil nel/ mice and produced 10 saicomas in 14 in contiast to these lareel> necatise resuhs the l hamsters responded to four insti!!ations of 2 mg eac h t m.de and I sarcoma in 14 female mice on thice do'es of diben7ta.ilp>iene with the pioduction et ici ie-l of wo up each to4L Dibenzia.h)aciidine, at a dose of 1000 pg in snicatory nact tumois in 34 anim.ds and in anothei j esperiment with the same carcinogen ghen in 24 ses;une oil injected subcutaneously into 19 mice, i doses of 0.5 mg each with induction of W tumois in
; poJaceJ 8 wircomas in 13 survhors (65) w hile the same dose in A strain mice w ith tricarrylin as soh ent 44 ani:nah. Ileie, then. is a highh notent e.u cinocen
{ i pioduced no sarcomas at the injection site but muhi- for that s> stem 174 ).
! pie long t umors (fA ). Dibe n/(a,j)aciidine dissolved in Feron (75 i aho used instillation of a s: dine suspen-i
.uachis oil and injected in three doses of from 500 to sion of ben /onopy seae innanwheolh in Ssiin hm pp each into strain XVil mice produerd no golden hamsters to study the iespiratory traellesions
' { inJueed without the use ordost but with hiitants hle
; s.u comas in the few sun h on at 4.5 months m7).
t 0:her esperiments with better survival aho had fmfural When onh ben /otalpy rene at a dose of I mg
! nepth e resuhs. At repeated injections of 5000 pp of each was administened toi 3h tects 41 out of 62 the compound into 10 mice, lladger et al. obsei sed h.unsters had iespiiatory tumois (in connast to the j lindines abos e), but the introduction of a 1.5'i fm-
, tuo sarcomas (fd).
, 'I here is good evidence that all the specific chemi- fural ' solution instead of s. aline made onh minor cah mentioned above me carcinerenic aho when changes:i.e.. not so much in epithclial tumoi mdac-j applied to the skin of mice (fWL Esperiments have tion. but in shortening the I:itent peiioJ and in canv i been carried out with specific PN A to attempt the inginduction of pciit racheal saicomas in 20 hamsters I indaction of cancers of the respiratory tract. The out of 61 as comp.ned to 2 sanomas in the bun /a
.. ! Sp ian' golden hamster was used foi these studies and pyrene treated gioup of 62 animah (75L Similar
! the chemicah were gh en by intratrac heal instillation studies usine ben /op>iene as the carcinogen anJ l as a suspension in saline with an equ.d weight et iion aciolein as cofactor did not show any cocarcinogenie oxide (Fe: Oil Without the line suspension of the actisits u hen the h imsters weie esposed to air con-
- j. iion oxide. the carcinogen failed to induce tumors. taining 4 ppm aciolein for 7 hr/ day. 5 day cweek for i One study gave 30 weekly doses of 2.1.0.5 m 0.25 one year Ro.
I mg' dose of ben /of a)pyicne and the same dose of iion
} oxide to 30 hamsters of each ses and obser ed 34.42 i 19. and 10 tumor-bearing animals, respectisely. Cocarcinnaenicity of PSA and Compounds equally distubuted between the sexes. I he locanon Related to Coal Combustion of the tumors was mainh in the bronchi, aho ,m d the nachea but less in the lungs (70L Incicasing the incomplete carcinogens weie identified by Van quantity ofiron oxide administered with the ben /o- Douren et ah i771 in e s peiim:nts in w hich t he chemi-3.)
cal was applied in a single dose to the skin ofICleila talp> rene suspension to tuice and thrice the quan-
- tity of carcinogen did not aher the tumor tesponse Swiss mice and with repeated application of phoibol myristate acetate. one of the aerne principles of
,,y 171). Iteplacing the dust by magnesium oxide gas e a similar result although the location of tumors croton resin. to the skin foi a year or longer. With l ,j ben 7(a) anthracene he obsened benign tumors in 10 l m was diffet ent 172); choosing titanium dioxide as dust pioJueed the'same response in the hamster out of 20 animals atter appheation of t mg total dose. Lm " tracheo bronchial trec as with iion oxide. Aluminum I'or perylene and ben /tg.h.iipei>lene. the dose l applied was 0.S mg and the tumm induction was of i ., oxide and exhon were less effectis e. howes er. The can bon was identified only as a cai bon black w ithout borderline significance. but the shortened latent
.n detaih on particle size and the few tumors produced period definitely suggests initiating aethity. In a p
were lat eelv benien (73 L separate' study coionene at 0.5 mg total dose was P When'a n' umber'of different PN A, present in typi- found to be a weak initiator, while two othe PNA cal sooty atmospheres were compared with llaP in not encountered in soot namely diben/ta. clan-
" 219 liecember 1979 I
1
~ . . ,
4
-t -
n l , l tijracene and 6-methylanthanthrene, weie potent in- perylene reduced the incidence of tumoi.be ring j itiators lienzo(c) pyrene was inactive, as was an- animals to 339 (N/ ).
! thanthrene (78). Turning now from skin painting to subcutar.cous Cocarcinogenicity was also tested by Van Duuren injection into C57 b!AL mice, antie.ucinogesne er et al. (79) by application of a low dose of ben /of a)p3 - fectswere oNened fm a numbei of PN T inn oJuced rene to mouse skin (5 g, three times a week) to- at a ratio of PN A to llaP as encountered ia tonacco i gether with 15 g benzo (elpyrene for one year. In tar. The carcinogen ben /otalpyiene was given at a i ditTerent experiments 45-48 mice sunised in each dose of 400 gg in tricarrylin. The other PN T were group and the above treatment produced 34 tumor- ben /ota)Duorene, ben /un.n.o)nuoranthene. ren l-bearing mice with a total of 70. papillomas an) 27 ene. perinaphthoxanthene. ben /(alearba/ Ac. ,
carcinomas The painting of the skin with 12 Fg chry sene. ben /otk)0notanthene and a mistme of pyrene and 5 pg ben 7o(alp 3 rene produced 27 phenanthrene. anthracene and py rene. Onh those j tumor-bearing animah with 40 papillomas and 19 mentioned abose inhibited c.uemogenesh in ILP
; carcinomas: and 21 pg benro(p.h.iiperylene with signilicantly W2 L Moie detail is not ph en Iveause j benzo (alppene produced 20 tumor-bearing animals the subcutaneous route is often considered too f ar with 33 papillomas and 17 caneers. Painting ben /o- removed from the actual tarret in human cancer j (a) pyrene alone produced only 13 tumor-bearing induction.
I animah with 14 papillon.as and 10 carcinomas. Thus . j the PN A on test show ed a cocarcinogenie effect with E,xperintents on Soot + benio(alpyrene (70 L 1 citch (N3) attempted to pioduce scrotal canect s - In a different type of experiment, Horton and in rats and iabbits by the app!ie..@n of oot.b u ;. iter
; Christian applied some of the PNA of relevance to one y ear's time observed none. Seelig ,u.d i:empros a this report on coal combustion to t he backs of micc in IM) replaced the shaving in capes of Ito Hultc.lo decalin t non-promoting)or a 50:50 mixtuic of decalin strain mice with ceal soot and obseis ed E lung l and dodecane (promoting). C311 male mice were tumors comp.ned with I in 50 control anana's. W 8
treated for 80 weeks and tumor induction was moni- skin tumors weie repor ted for these anim..h ik in : m tored. A 60 pg dose containing 0.159 chrysene was coal soot (M L Campbell (A5) exposed 75 mice to a f cloud of chimucy soot 30 times a wcek foi ono yea 1 applied twice a week and yielded 13 carcinoma-
! bearirp mice and two with papillomas-only out of 17 and got a long tumor yield of 2tri. Ilowes ei in his mice. The aserage latent period was 45 weeks. connot groups he aho obsened lung tumor inci-g Pyrene, similmly tested at a 0.59 concentralien. dence as high as 20';. Feeding cad on blad to mice j produced two carcinoma-bearing mice and two with proJuced no tumors in the ammah and f eeding i papillomas. The latent period was 56 weeks. methyl cholanthrene adsorbed on carbon b!ack aho I Fluoranthenc and rery!cne were negative. The vehi- produced no tumors in mice. When the exuact ot cle alone produced only two papilloma-bearing ani- carbon black. on the other hand, was fed to mice in
{ mais with a latent period of 75 weeks. All the abose their diet. tumors appeared in the stomach N. results were obtained with the schent system con- Extracts of soot were known to be carcinegenie taining the promoter dodecane. Without the pro- since the studies by Passey WA in 1922. w ho panned moter the equivalent studies with 100'; decatin as ether extracts of hensehold soot from bi:nminous solvent wcre largely negative FO). coal on the skin and obsen ed nine malignant t omor - In contrast to the cocarcinogenic effects described in 18 mice sunising eue 3 car. Passe) ani C.' a above another type of experimentation was used Braine fractionated the extract by datillaQn m by Finzi et al. glh A 0.3G benzene solution of obtained an active dhtillate abos e 190 C and an ae benzo (a)psrene or dibenz(a.c) anthracene (alternat- lise residue WNL . ing every second day) was painted on the backs 0140 Chimney sooi extiacts pas e a 407 3,ielJ of ur. Swiss mice for 25 weeks. This group was compared comas in C3H mice on subcutaneous mjecten m to two other gioups painted with hap and benzene Aho, an estiact of wood soot painted on the skm q only or diben/(a.c) anthracene and ben /ene esery mice proJueed three neoplasms m 10 mice anei - second day. The percentage of tumor-bearing ani- years (Vot Theie is little doubt that caremogens mais after 25 weeks reached 90"; for hap painting PN A are present in those soots wluch goes EAh compared to 459 tumor-bearing animal. with the very early findings of Sir Percha!! Pott on tb 1:c-combined painting. A comparable study using quent occunence of chimney sweep eance: Wii perylene instead of diben/(a.c) anthracene with a Davis et al. iecently studied inu a-tiacheal ms ' slightly dilferent protocol produced similar results. tion of ben /oralpyrene in infusine at ditten n' o"c Inste'ad of the 90G tumor-bearing animals with lesch with andextractabfe without carbon bent (a) pyrene alone, the combination of BaP and black contained py rene,black. but no t he {^ ' 220 Ensironmental IIcalth Per po on -
~
l
~
4 could be accounted for 100";. so that metabolism or i N \. In these experiments on Wistar SPF rats the degradation of some of the PN A represents a possi-
' meacgators found squamous neoplasms of tbc
( bility (/5). (Fig. 41 k ..r..s in proportion to thd e ose of benzo (alpyrene but 3,ersed only half as many cancers when carbon
~
J Proj.ections of Carcinogenic cnd
* .. ek w as also present in the infusate (9.?).
j \ll these experiments taken together suggest that Cocarcinogenic Risk Due to Ccal ( ynuclear aromatics adsorbed on soot me not j .c..ui.a.ie for carcinogenic action unless a proper Utilization with Achievable , e schiele is avadable for clution from soot. % hereSafeguardo the Due to Technologicai
.npunt of adsorbing carbon black or soot is inade.
, qd:e to remose the carcinogen from solution some Developments j cancen may develop. - In order to assess the potential carcinogenic ri L of In this connection it may be ofinterest to note that greally incica sed coal utilization for combu stion. it is I. : Jees not icquire a lipid soh ent to clute polycyclie necessary to assume the imposition of safety mea-hdroembons from soots above a certain partich. sures, controls, and safeguards v.hich can cun ently i me, but that plasma will suffice to extract them. be formulated. Coal mining w ould be better and saf er
': hough le s rapidly and efficiently. The rate of clu- if it were done by surface mining. except for the i nen has been studied for 48-hr exposure to saline, enhanced destruction of agiicuhural land and the
' ahh eluted none of the PN A on soot, and up to ecologie imp: cl of the disturbance of the land. As a muun esposme to plasma which cluted several compromise will hase to be woiked out, the adsan-
[ iW.\ completely including benio(alpyrene and
; tages and disadvantages must be compmed and e:t.eis to more than 507;. Not all of the compounds l
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i l W~_7- ' = 2 = .'_2 fintn 4. Flution of Pil A from oot b3 pbsmai/.D. 221 IWmber 1979 l
.---,,-m,r,,_m.--.-m,..--.,,-,..%, , . , . - , . . - _ . . , .
wciphed and possible he.ilth elfects must be included i in the assessment. Depending on the location of the Removal of Particulate Matter coal seam % underground mining will undoubtedly be necessus , but the new mines will hase to h.ne the B'enostatic piecipitators base been emptosed i o successfully for many y ears for the rcmond of p.
! be.neGis ' f technoloric aJumees such as ifieh ticuhde
' aii matter and they can be ser> etliciem R; circulation to reduce the accumulation of coal dus,
! and gases in the air. Also the use of powerful diesel : ud or niosuracc element s as u en as soot ha s ecomplished. One problem remains. i .e . th; ,
5 machines will eany out much of the um-L so that the mining population'will be small. posM of the waste. For Ihe trace elements w h, PO?C7 carcinogenic or other toue piopetties. tL unh/ation of wage mate ial wdl produce proHeu. i Remouil of Sulfur Dioxide Simihuly the soot may carty carcinogenic pN i which may persist. j t On the other side of the energ) proJuetion pr?
; gram is the pollution f om coal combustten w hich is already under c ' Mrdion of N in Soil j- "rable controh Removal of oxides of sultur has xen accomplished by a sariety Soil will not readily decompose many poly nuc:ca; ofmeans some leading to usable product s. other s to aromatics ahbough speciGc organisms h;n; bc ,
waste materi:ds but idl able to remose the SO, pro. identified that can destroy polycyche by dr oe m bons. 3 duced with rather high efHeiene) . T his technology is Most sod organkms do rot seem to h.a e that cap . j bihty N L Uptabe of the pN A by plants has been obligatory and will be included in any new phmt g development. The efficiency at this stage of ac- documented. l hese uudies used the hphocaibm
; selopment in iemoval of SO, is estimated to be 90;; without soot as car rier w hieh must ch.mg. the ca . o:
awJ needs upral.e considerably. It wiu probably be beu to s o% Mill fmther improsement. Other pio. cesses u hich w ould lead to the a ccos ery of sulfur and bust the mateiial co!!eeted on the elecnostatic p:e. avoid some problems of disposal of waste materials cipitator to desnoy the PN A that vca). are aho on the drawing boards (9M. UndoubtedP, under other conditions of coal utdi/ation completely Destruction of PNA in Air dMerent pro;eesses uiH be deseloped. such as the H wme soot passes through the elechosta:ie pre. estraction of morgame sulGdes (iron sulfide) I,mm cipitMorit wiH May in the atmosphere for some th: s j puberi/ed coal and removal of organic sulfur com. i Nta mi4 on the dmadAion of po% eUc 4'ni-pounds by treatment uith bydiogen and a catal)st- c.ubons by Ught and air v. hen adsoded or not aa These proecsses will be considered under coal sorbed a soot pM. m The r ate is different for e, . h gasification and liquefactmn w hen these teclunques member of the pNA encountered in air po!L < a me up for heahh assessment. Hen /oMpyrene is nm one of the more n - -tu . i hydroem bons. In the free state benMmp3 rene L l Remout! of Chlorine destrosed or pone to 20'; in 24 hr esposuie to h ! *
} and aib When adsorbed on sool. it is oNy 104 to th The presence of chlorine in coal may be handled during a hr in h;*ht. When esposed. adsorbed on by the same process as described above. i.e., using *l time scrubbine desicew but hvdrogen chiaiide i. I" "O N hhC'M o sidant atmospheic. pter aey l quite corrosi[e to the equipment. Oom mac and s apori/ed ga sohne. tu ic> as mus h n
{ i gone in I hr. Ihpo'an e to an osidant atmosphe.e has Reduction in Oside of Nitrogen Formation aho a far greater effect on many other poly nut le r aromatics enconniered on soot.4 p to m is de Osides of nitrogen are formed partly by the oxida- Mf0FCd tion of organie ninoren-containing components of coal and partiv in t oxygen with nibogen.he interaction of atmosphene m l the lauer accounts for most of L.ncerhu.
' wehn Needs
- k. for Resolution of the osides of nitrogen formed. Reduction of the tem-remture of combustion is the beu wa3 af reducing On the assumption that neither the min- nor H e urban dweller wiH ha'.e to be esposed to the ha/.m s
' oxide of nitrogen formation fiom air constituents. It is not effectis e in preventing the oxidation oforganic ofincreased coal production m combustion anJ ti.
nitrogen-containing components of coah lioweser. technological impms ements over today N inJ+t i senibbing desiees can remose some of the esides of techniques will fmther reduce mining hom A .
? nitiogen and cataly tic reduction or decomposition pothnion of mban areas it is stdl seiy desnaia '
techniques can neduce NO, emission from stationar y underuand better some of the functiom of le i somces (94L cyclie hydrocaibons in producing their be.dth ci
- l. fects.
222 4 Dnironmental llealth l'crspectho ( {
applied and diffeient modes of administration tim-lN \ Carcinogenicity for the Linig ing, and aninutl strains or species were used. A
- I> njoii the carcinogenicit3 of PN A w ere obtained clearer picture coukt be obt;uned it a systematie g ;g
- ..i the beginning by skin painting on mice, sub-j . qaently by subcutaneous injection into mice. ~lhe wenes of these chemicals m relationship to each Gnet.te b.usceptibility
[ .be: is 1.ugely based on these Gnding,. It wouki be Species that cannot activate PN A seem to suffer ' mential to get a similar comparison of actisity for no ill effects from then presence. Recent studies on l re trachco-bronchial tree. Knowing the difGeulties mice and man suggest that genetic variation in in- ' d mducing tumor s in the respirator y tract compared ducible mixed function oxidaWs mas nnke the indi-t, the skin or the connectne Ilssue. It should be s idual morc or less susceptible to the' des clopmeut of 8 Atenniued how the various PN A compare in car- lung cances (VR 11 may be w orthw hile to understand
, enogenicity for the respiratory tract. this relationship better and ultimately to be in a posi-i tion to seicen those to be esposed to PN A at their ' 1%\ Synergisin with Particulate Matter woikplace for their inducible en/s me capal-ihtv. -
i in esperiments on rats and hamsters, inti.at racheal , mtubation with llaP has produced negative results t II3^",'b OI h,oal l,lih./at. ion by G,as,h,,eation
' which led insestigators to introduce dusts, com- or LHltiefaction posed of sarious metal oxides leading to enhance _ An entirely different problem will te encountered ment of tumor production. Replacement of the dusts j if these piocesses are introduced on a large seale in t., soors may make the esperiments somew hat mme the U.S. 'Ihe processes and the products will repre-comp.uable to te.d life and may clatily the picture of g
' a.fsorption of the PN A on soot, leading to unavail- sent a different decree of carcinocenic risk which shoukt be rectyni/ed before thes[ approaches are Khty of cateinogens and thus presenting cancer eduction. The particle of the general air pollution is activated,
' of the si/e that would relcee the PN A af ter phago-Epidemiological Studies I c y t osis.
Further epidemiological studies w hich adth ess the l IN \ Synergism with Cominunuls Present in 4"'.s@ms unw J by the atmlable data on as.-
> l'olluted Air socut ons between coal mining and cancer and mr g pollution and caneci are uigently needed. Specific Some groups of chemicals base been tested for areas uhich need to be esplored are: the appateut weaicinogenic activity, mostly on mouse skin. and g
not sery many were active. Phenol itself and excess of stomach cancei in coal minen and their g wises; the possil'le role of tobacco consumption eab hol were two actis e promoters. Aldehy des tsmoking and chewingt air pollution, and occupa- { were also espected to act as promoteis. Furfural in tiona! status in the etiology of stomach cancer in coal conjunction with llaP was found inactis e for t he skin mina s and their famihes: prospectis c epidemiologi-f of mice but active as promoter for the long of cal studies of the role of air pollution and mo:e speci-h.unsters (75 ). Another important aldehsde. acro-f: fically the efnuents of coal combustion,in the etiol-lein. was inactise as a cocarcinogen for the hamster ogy of cancer with emphasis on more independent lung in conjunction with BaP (74). It mas be worth- and quantitatise assessments of the ettects of ciga-l whde to undeitake a more systematic study of 13 pi-rette consumption. air pollution tbeed on analy tie u! air pollutants that could act as cocarcinogens g w uh the PN A particularly w hen applied to the lung of ensironmental suneil!anceI and economic or occu-hamsters. Similatly, it would be most desirable to pational status; and a re-evaluation of migrant { studies uith specific regard to self-seleciion of the le.u n more about incomplete carcinogens, those that j act only as mitiators of carcinogenesis for mouse immigrants, y a skm. but may base importaut properties for the long pyyygg gs in the presence of appropriate promoters. f, I W"dd#" R ^ C "I hid'"F#" "i"" ""d C "U '""
- C "'"'
I AnticarcinoSens heahh. I ndron. If c.dth Per rect. IJ .'Of i F'N t 1 he. R.. Hoaon. A. w araf Rarien. I Heniowr> rene and Some studies on anticarcinogenic properties of otha aninuue hydiocart ons estuctabfe from tutonanous PN A have been carried out by subcutaneous injec, coat. Am. Ind. Ih g. Awoc. J. . . J ilmi.
- i. tion into mice $2), others by skm. pamang. Ihe A n EPA. seiensric and techmc.a Awemment Herwt en ramculate roheghe orgamc mner dett 1.Puoo6 t
results at times were quite contradictory, w hich was 74 oni, Wrth 1971
', rut surprising because ditferent dose lesels were
?
223 lhember 1979 I a
a I i s
- 4. Sawicki. E., llauser. T. R., Elbert. W. C.. Fos. F. T.. and workers with pncomoconiosit Hrit l Meeker, J. E. Po!) nuclear aromatie hn'rocarbon cemross- (l
- 54 J. Ind \ led 12 s-1
' hon of the atmosphere in some 1.uge Ameisean citiet Am Ind. flyg. Assoc. J. 23: 137 (t%2L 24. Goldman. K. P. Mortahty of coalmmers f om urem ,.
! the long. Hnt. J. Ind. McJ. 22. 72119et
- 5. Holton. N. E., Van liook. R. .. Folkes wn. W.. Ly on. W. S.,
} Andren. A. W., Carter.J. A.. and Emery.J. F. Trace element 25. Enter;.ne. P. E. A review of mor t.dd > d..ta for Wen, ,e measurements at the coal. fired AHen Stearn Plant. Progrew m.new Ann. N.Y. Acad. Set 200 2m i19'2l Report June 1971.Januar) 1973. ORNL-NSF.EP 43. March 26. Sear.mo. D., I adoh. A. M. A., anJ 1 enmh . G. M C.m r.
1 1973. of the lung and .inthracosibcosis. Cheu 62: 251 i10
- 27. CostePo. J., Ortrney er. C. l.., and Moigan. W. K. C.
- 6. lienschler, D., and Ross. W. Zur i rage der Bddung can-ceroger.er Nitrosamine aus Gewebs.uninen undy.h.dierten it) fromlung canees m U.S. coal minert Am J. Pult t h ..
M 222(1974L Stickstoflouden. Naturwiw $0 503 (196h 28
-l 7. Pdts. J. N., Jr., Grosjcan. D., Wmer A. M.. Van C;.uw t n- Stocks. P. and Campbd! J. M. I ung cans ei deeh i m j berghe. K., Tua/on. L C.. Graham. R. A. 5,:hmid. J. P .and among non-smoker and pipe and ciga.ci'e smolci 3
Fitz. D. R. Photos hemhti) of amme.NO, mistures in simu- es ahutionin relatmn to.or pohunon b) bene) rene and v:.t t.
'l substances thit. Med. 3, 2: 93 t 1955L lated urban atmospheies: formation of rutroununew mua.
1 minew arnides and photet hemical oudant. Presented at the 29. Daly . C. Air potiution and cmnes of death Hnt. J. h es . So, l Med 13.14 (1959t 13th Informal Photoshemistry Conference. Cleaiu ste Itcach. Florida. ' nuai > 44,191 10. Stock % P. I.ung c.mccr and Nonehitis in reldoo to cic "c:*e
- 8. laskin. S.. Kus .ncr. M , anJ Diew . R. T. Studies in pulmo- snuskmg and for! consumpnon m twent> countnes im: J.
nary caremogenesis. In: Inhalation Carcmogenesis ( AEC hev. Soc. Mel 21: 1 Ai i1967L Symp. Ser. No.10. M G. lianna. Jr.. P. Nettesheim, and 31. llammond, h C . and Horn. D. Smoking and death r..te,- J. R. Gilbert. Eds. US AEC. Washmgton. D.C.. ITO. pp. relwt en44 montinofioMooupof IF 31:acn P.ct I. io: 321-350. mert..ht> . J. A m McJ %.e. IW 1294 t i9M
'l 9. Marik. J., Kemeny. T., and Kertai. P. I frects of the Sf b 32. llaenwl. W. I os el.md. D. It and Sn ken, M (L i e content of the air on normal rats and rats with mjured heart cancer mortuly as re!AcJ to sedlen.c. and wd m D
{ muscle in long. term espenments Fgstseptudoman) 8- 27 tones. I White n.a'es. J. Nat t ancer luu. 2m 9.! .19 2 j (19641
- 33. Menck. IL R., ('augranJe. J.1. and licoderson. It i j 10. Peacock P. R., and Spence. J. H. Incident e oflung tumors in Industual air pdh:aon: pmible effect on hmg camci Sen
; LX rnice eywed to (16 f r ce radicab. (2) soc !!nt. J. Cancei ence in: 210 t1974t i
21: 606 (1967L M. Stosks. P. On the iclahons bs twcen atmospheric po!ha:, u n l 11. Ilayatsu. II.. and Miura, A Tbc mutagenic action of wJiu n urbaa and rural holaics aad mortaht) from caneci rwn-bhuffite. Biochem. Hiophy t Ret Con.mun.19.156 (l9NL chith and pneu%uu s ith pasutai reference to (4 ts
; ioryrene, bery thum, nad> bdentmi. sanadmm. anJ .awm
- 12. Shapiro R. Di Fate. V.. and Welcher. M. Deamin.aion of cytosine derivanvcs by bi ulfi:e. Mechamsm ef the react.on. Bot. Med. J.14: N7(19'm 4
J. Am. Chem. Soc. % 906 (1974 L 15. llenJcison, it I. . Gordon. R. J.. Menc!.. I!.. Sodor J .
- 13. Falk,11. L., and Steiner. P. E. ihe adwmtion ef 3.4- M;u tm. S P., and P.ke. M. C.1.ung cances and air po:h .
3 sm l benirytene an.1 pyrene by carbon blackt Cancer Ret 12: 40 south central I.os Angeles Count > . .\m. J. I ride nm lu: 0952h 477 (1975L
' 36. I ase, l..
- 14. Falk.11. L., Kotin. P., and Markul.1. 'l14e dharpe.can e of D.. and Ses!.in. I . P. .\ir adNnon and I.unan carcinogens f rom wot in Imman lunp. Canect i I:482 0955) beahh. Science Ifn. 721 i19 %
- 15. Kotin P., and Falk. fl. l.. Atmospheric factors in 37. Bucil. P. j.. and Danr. J- ).. Relathe impas t of staokm; mJ pathogenesis of lung cancer. In: Adsances in Cancer Re- air poMution on lung c.mccr. Arch. Enuron fleshh 15. 31 3 OWL search. A. lladdow and S. Weinhouse. Eds.. Acadenuc 38. Wmkehtein. W.. Jr., and Kantor. S. Stomach cancer rosun e
' Prew, New York.1963. Vol. 7, pp 475-513. asweiation with se pended p.atis ulate air pdunot Wh
- 16. Stocks P. On the death rates from caacer of the stomash and Ensiron. Heahh Ib 544 (19 SOL respiratory diseases in 1949 - 53 among coal rniners and 19. If agstrom. R M., sprance,11.
other male residents in counties of England and Wales. Bnt. \.. and I.andaa. I The J. Caricer l& 50 (1962f Nashsille air pollu: ion uudp Vll Mortaht) f:om cames m
- 17. Matolo. N. M.. Klauber. M. R,.Gonshek. W. M.. and ikon. relation to air po!!intion. Arc h i.rn iren fic Ath 15. 2 U t Id ~'
- 40. Lesin. M 1. Iloenvel. W., Canod. B 1: . 6c Au A k J. A. High incidence of gastnc caremorna in a coal mm:ng liandy. V.11. and Irq uhan S. C.11. Canscr mejJerac : .
region. Cancer 29. 733 81972L .
- 18. Creagan. E. T.. lioo cr, R. N., and Fraumeni. J. F. Mortahty urtian and ruralareas of New York State. J. Nat. Car.ect in t.
24: 1241(1960L fiom stomach cancer in coal mming regions. Arch. Ensimn. 11ca!!h 28: 28 09741 41. liiggint 1. T. T. Eridemndogy oflung cancer m the United
- 19. Rockette.11. Mortality among coal miners cosered by the Statet In: Air Po!!unon and Cancer m Man. U. Moh.
UMWA flealth 2nd Retirement FunJs NIOSit Research D. Schinah1. and 1.. Tom:ai .1 dt. Interranon.d Acene) f or Report. Morgantow n. W. Va. USDif EW. CDC. NIOSil. Research on Cancer (I ARC Sci. Publ. No.16h Lyon. IC , pp.191 203. ALOSif. March 1977.
- 20. Kennaway. N. M.. and Kenn may. E. L. A study ef the 42. Wai'er R. E. '1he combined effects of smoking and occup -
incidence of cancer of the lung and lar>nt J. Il>g. 3& 216 tionat or erban factors in relanon to lung c.mccr. Ann. Oep (1936h li>p. Is: 67 (1972 L
- 21. Reghter GeneralN Decennb! Supplement - England and 41. Eastcott. D. F. The ephlemiolog> of lung cancer in New ,
7ealanl 1.ancet 1: 37 0956' Wales.1951. Part II. Vol 1. 0ccurational Mortaht) . ll M SO. 44 Dean. G. Lung cancer arnong w hite South Afneant Pot London.1958 pp. 9.18. 35, and 96. I ' 22. Do!!.R.Cancerof the lungand nosein nickel workers Bnt.J. Med. J. 2. 85211959: ', Ind. Med. !$: 217 (195N 45. Dean. G.1.ung cancer in South Africans and Bnthh imnu-grants Proc. Roy See. Med. 57: 984 i19ML
- 23. James." W. R. L. himary lung cancer m South Wales coal r
- 46. Reid. D. C.. CornGeld. J., Mar kush, R. E., Seige!. D . Peder -
224 . Emironmental IIcalth l'erspeclis es f
- 6
, s sen. E., and lisensiet. W. Studies of dncase among migrant , cancer by pure huhocarbons V. Proc. Ro, . Soc. Il nadoni i and natne populations in Gicat lintam. Nor w a>. anJ the 11129 439 il9mL 1 i2: 07 Cnned States. Ill. Pres atance ofcardiorespiratoi > sy mptems f.9 %ionograrhs on the lhaluanon of Caremogenk IM ef the
.asnong migrants and natne born in the l'nited Mates Chemica! to M.m Cert.nn l'o!gg hc .bom itic fly eo
, ,,nu of , I pidemiolopkal study of cancor and other thronie dneases. c.uhms and Iktewyhc Compoundt Vol 1. I \RC. In l Natl. Cancer inst. Monogr.19: .121 I!96N. 70. Sattio:ti. U.. hieuno. R., Scilakum.ir. A. R. and K..af ' s..n coal 41 Morrn. S. C.. Shapiro. M. A.. and Waller. J. II. Adult mor- m.m. D. G. Respir nor) tract carcmogenesis mduceJ in f taht) in two commumties with widel) ddTerent ;ui pollutmn hamster s by J.ftocni dose les ch of ben /oi. opp ene arat f o d
.,,n,,,,, l lesch. Arch. Environ. Ile.dth 31: 24x (IC6L eside. J. Na!. ( ance lost. 4+ 1199 IIG P2, 4A. Diehl. E. K., du llreuil. F. and Glenn. R. A. Po! nuclear3
- 71. Sellakomar. A R Montesano. R., Nathotn.1] . ar J Kant.
w n.4 , bidrocarbon emiuion from coahlired inst.dlationt J.1:ngr. rnan. D. G. Itamster resfi ratorv carcmaenesn mJm J % He.d:h j Power W.2t 2'6 41967L ben /ohopy rene and dolerent dose leu h of ferne od g 49. Committee on !bolog: cal I.fTect of Atmosphenc Po!!u:.mts. J. Nat. Cancer in-t 50 507 t1971L s rares Particulate Po!>ciche Organic %!atter. Dniuon of McJul 72. Sienhas k. l . Neil iktunar. A., and NhnNL. P N1. a , an gn f' Sciences. National Research Co.med Nanona! Ac iJemy of osiJe as can ar dmt in ben /otal-ppene.m lucs d L.r.3 c.e- 'Jether i Sciences hhington. D C. 1972 rp. 205 226 einog nesis m S, nan hamsters. J . N..t Ca.a.ei inst. 5.: M1
/ So. Sawicki,1:.. Elbert W. C., llauser. 'I . R.,1-os. I'. T. and (1975L we i Stan!cy JI . W. llenrot a)p3 rene conten: of the air of Ameris an 73. Stenh5cl.. l . Rouland. J. and Selh.kum:n . A Cm I communitics Am. Ind. Il> e. Awoe. J. 21. 4414 tNH cmogeniaty of Fcn/inaf rs rt ne and Justs ia the h e te r 1:.t
.rene I, 31. llammond. I:. C and llorn. D. Smokine and Jeath rates - tm ti' led inn a ta as he.dl> w nh t:tannen ouJc. almmnu u
%.J report on 44 menths of follow-up of l.C.43 men. Part i. Total oside. caiMu and lenic osiJei Onso;or 33 29 a Irra. Moriahty. J. Ar" Med. Auoe. If4 1159 (195n 74. Selukumar. A.. :md ShuNk. P. Carcmoa mcity of d lu ent ae s - l 52. Inpfh.1.11. Incidence of cancer in the carben b!ack mdus. po!ycghe hy d.oc e bons ir the re'rii.dtm tract of hwiers T o; ' l try. Arch. Ind. Ily g.1: 66211950t J. Nat. C:.ncei inst. 50 1711eIC4L 3 St. Tara. S. Noir h carbunc. Res. Pathol. Gen. 60. t il t 19mL 75. I'cion. V. J. Re pu atory tract tunun s in hamuers af ter mua. I ong ) 54. Elin. C. The Chemistry of Petroleum Derivatnes. Vol. 2. trathcal mstil ation of ben /oi mp> iene alone and s.ith h r.
- l. i s. ( Reinho!J. New York.1917. fural. Cancer I:t s. 12 28t1072
<2: 55. Gro!! IL P. A. Vapor-phase crackmp ind.1 ng. Chem. 25: 76. l'eron. V. J.. . nd Kruy ue. A. I tt: cts of e spo m e to .w ..!c;n l
it 1.. g 7h4 ( 1933L sapor in hamster s sin.nli a nt oml> t r eat ed with So. t $6 Kennaway. L L. Lspeiiments on cancer-producmp sub. ben /oeap>iene et d.ethylminuamme. J loucot I.ns m
! st.nces. lhit. Med. J. 2: Ii1925L llealth 1. 379 t19M
- 57. Kennaway. I:. l . ~1he formation of cancer-pioduemp sob 77. Van llouren.11. l ... Sn ak. A. . f soidschm: D. It ', . Kat/. C.
. n in l nron. stances from imprene (2.n.ethy l butad.enet J. P.nl.ol. liac and Me!Jm.nv S inmat mg ictiuty of .comati, hsJ o ben. l teno!. 27: 2M i1924r caibons in tuo stage c.ucinoge- s v J. N.<t Car.cei Iw 44: eme. ! $( Didens l .. and Weil M.dherbe.11. Insestiptron into t! c 116 i 19^th l puible carcinogenic actn ary of wood smoke. Ca:her Res. ' 78. Van Dem s n. Il I .. Sn ak. A . I anysne:h. l . GoIJstbmdr
.J.. 680(1942L IL M.. .md Scyal. A. linti ds .s and p.omoter s m t.6aan am
( 59. Criteria Document. Rwmmendations for an Occupanon.d cah mogenesis Nat. Cancer Ine Monograph No > 17t lot. Esposuie StanJard for Coke Osen 1: missions.1(SM Puhkea- tP m tion No. 73 11016 U. S. Depanms ni of Ilea:th. I.ducanon. 79. Van Dum en. IL 1... K at t. C. ar.d Goldshmidt.14. M.10 icf 't in l and Welf me. Washmgton. D.C.: 197 2. p Vll-l. Communit at ion Coe.n cmovemc agents m tobacco car-l 60. Ilieger I. Casemogenesis by cholesterol !!nt. J Cances !) cinogeneus. J NY. Cancer inst. 51: 701(197 4 tJ 1 439 (1959L KL llodon. A. W. and Chrisaan. G M. Cocaremegeme ser sm .' 4 61. Stemer. P. E. and I:dgecomb. J.11 Carcinovemcity of I. mcomplete c..rcmogenie acinits among momanc h3 Jiu-
, ben / anthracene Cancer Res. 12: 657Il952p carbonv Contr.ut between chr) sere md ben 7m benrhe-ne l 62 Steiner. P. E., and I afk.11. L. Sumnution and inh:bition nylene. J. Nat. Cancer Inst R 1017 il974L
- h. cfTects of weak and strong caremogenic h>Jrocarbons- 1:2 81. I inn. C.. Daudel. P.. and Piodi. G. Inter fo ence amone poi > -
l benz. anthracene, chrysene.1.2:5 6.d. ben / anthracene, and c he h> dmc.u bons in espenmental skm carunogenesn g N j 20-methylcholanthrene. Cancer Res. I1: 56 4195iL Eur. J. Canser 3. .ro a Ivhu m l 61. Ilo>lanJ. E., and Sims. P. ~1 he carcinepenic actiunes in mict b2. I aik.11. l... Kotm. P.. and T hompson. S. Inhibeion of car-l of compounds related to beniManthratene. Int. J. Cancer 2: cinogenesis. Arch I:nuton Heal th V IfN (19Mi g 5 0 ) (1 % 71. 81. Lent i.. A. Tt.e cs penmenta! mquu 3 mtu be ran-es dcancer m . M. I .acawayne, A.. I?uu-II.n. N. P., /a.tdel.i. l ., I as it-! amy. Ilot. Mcd. J. ? I s l92tp ? l D., and Chahet. O. Actisite cancerogene d'hy diocarbun s M. Seehg. M. G. and lienignus. E. l.. Coal smoke sooi and l aromatiques polycgliques a noyau fluoranthene. Un. Int. tumors ( f the long in rnice. Am J. Caneci 2x: 961194L J Cancer. Acta 19: 490 (IW). M5 Campbell. J. A. Caremogenic agents piesent in the atmo-l
- 65. llachmann W. E. . Cook. J. W.. Dar.si. A., de Worms. sphere and mcidence of riimar) fung tumors m mice. lint. J.
C. G. M., llastewood. G. A. D.. Ilew ett. C. l... and Re5m- Espt!. Pathol 2n 122119391 son. A. M. '1hcTroduction of cancer by pure bydroc.ubens b6. Nau. C. A.. Neat. J., and StembriJge. V. A stud > of the IV. Proc. Roy. Soc. (Londoni H123: tiill937L phy sio!ogical elkcts of carl on black.1. Ingest on Arc h. Ind. E Andersont, it 11.. and Shimkm. M. It ihological testine of Ilealth 17 21#195% l carcinorens. II. Pulmonary turnor mJuction technique. F7. Pawey . R. D. la renmental soot t ancer. llot Med. J. 2: lll2 l J. Nat. Cancer inst. I: 225 (1940L i1422) 07.12cawagne. A.. Iluu. Hoi. N. P., /ajdela. I'.. Roy er. R., and M8. Pa we). R. D., and Carter.llrame. J. Ihrernnental soot Huberi-itabart. M. Actiute cancerogene des dWennetidmes cancer. J. Pathol. ILictenol. 2x IH 1925L his-angulaires. Ilull. Cancer 42.186 i1955L F9 Shunkm. M lt, and I eiter. J. Indi eed pu!monary tumois m
- 68. Iladger G. M., Cook. J. W. llewett. C. l . Kennaw ay. micc. lit. T he role of chronic erritahon m the product!on of F N. M., M.utin. R.11..and Robinson. A. M.1he productson of pulmonary tumors m strain A mice. J. Nat. Cans er inst. I: 24i q
. (1940L December 1979 225 i
k
}
V
. J s
- 2. Sulman. E.. and sulman. F. The carcinorenicit) of w ocd soot nitrecen oudes f ro" Mationar y socit es 1: N IA;t Ita from the chimney of a moked aus. ire f actoin Caneci Res. I dus : lion .md \\ e! Lee. N \P( \ rabhcar.on it' r. . I'ro
- 6: 366. 367 (1946).
- 95. Shat..id. l . \1 Ceh ir., S . l... Ilnc/i> . \. l' . K be- i. \ Y.
- 91. Pott, l'. Cancer Scrot: In Chuinpcal obsersations. llawes. Shcherbak. N. P. and Santnos . G. .\. ~lhe t.eunoes C). uke & Colhns, landon.1775.
hulrocarboa t-en/o:aip> rene in the sed. J. Lt. Cance; in t
- 92. Dasis.11. R., Whitehead. J. K.. G:ll. M. L.. I ec. P. N.,
47: il'> t iu?ll. Ilutterworth. A. D.. and Roe 11 J. R. Response of rat hm, to 3.4 ben /py rene administered by ictratr.icheal insD!L *io i m % Kotin. P. and l'a'k. II.1. f be ro'c an) . s tion e' en . c o . mental aper >ts in the pattiorenesis of 10 g t..nset. I -\ u p,, ' inf usine with or without can bon bl.isk lint. J. Cancer 11. f 41 lutants. Canse 12 14 (1959L
, (1975).
97 Kurat sunc. M.. and finobat.i. 1. lieson.posino i of ro*3 -
- 93. Anony mous. Nulfur diosiJe remos al pio css passes test. be- c y che . iomanc h> Jroc.o bon unJer I.e' orator y in., m i.
rins demonstration s un. 'l echno!. New . l.citti.-Cheni. Wect Nat C.meer Inst Monoct.arh 9,11 i M2s 121: 35 t Nov. 2.1977L 9s. Ktl'ermana. G., I u> tt n-Kenenn.:nn. M anJ v .n . C. R
- 48. Ilarris. R. L.. Ch. ir man. Nation d Air Po:iution Conhol Geneac s.uianon of.o y l b dioc.u bon tpf os la se ir han Techniques Adsisor y Comnnitee. Control tcchmques for ly mpho( > tes Am J. Ilum :n Ger%I. 25: 327 (19 3 )
l i i i 1. 1 s i 226 1:mironmental IIcalth l'erspectis es fs r
a 7
$'~ %Dd 2 114 D. F. S. Natusch.
Ta co e5 Fue _F
;5
% Co y JK on Characterization of Atmospheric =1 ~E
*E Pollutants Em
~5 from Power Plants
- fr.
D. F. S. Natusch bu wi Professor of Chemistry, Colorndo Siale University, Fort Collins, su Colorado na Ri fo Al Fossil. air pollutants fueled power plants in most constitute developed a ubiquitous countries. In the Unitedsource of pe States they have the dubious distinction of ranking third to motor lo' vehicles and industry in total emissions and contribute approximately 25 percent of the particulates, 45 percent of tne oxides of sulfur, and 25 tii percent of the oxides of nitrogen emitted nationwice.i S, At the present time approximately 80 permnt of the electHc do power generated in the United States is derived frei.. the combustion of re fossil fuels. Of this total, coal combustion accounts for approximately 70 percent-the balance being made up by natural gas and oil. It is now apparent, however, that increased coal utilization will be the main source ca
. of the nation's electrical energy for the next several decades and that er much of the coal may come_from-:ddwet^m fields. te While particulates, sulfur oxides, nitrogen oxides, carbon w monoxide, and a variety of aliphatic organic compounds constitute the r:
major atmospheric emissions from fossil-fueled power plants frable 1), tc significant amounts of trace metals and metalloids, acid mists, and T polycyclic organic species are also produced. Most of these so-called al minor pollutants are ernitted in particulate form and many are highly V: toxic to living organisms. In-discussing the characteristics of pollutant cl emissions, therefore, emphasis is placed not only on the amounts emit-ted, but also on the manner in which both major and minor pollutants st attain their final form and on the physical and chemical nature of the ai emitted material. w l
-q
. u t
l
^$
fi
.Q Atmospheric Pollutants from Power Plants 115 Tab e 1. Average Air Pollution Emisalons From Power Plants Ac-f cording to Fuel Type (pounds per 1000 pounds of fuel)'
~
g L 1g . I Fuet Particles
- CO HC NO, SO," HCOH ( l Las 85 (1-E) 0.25 0.1 to 19 S 0.002 .l'
... 1.7 (1-E) 0.07 0.5 17 19 S 0.1 00 Spheric "'r~ c - 2 7 ('-e> a a- a a- 7a 'a s a2 i o the mass collection efficiency of the control equipment. ,
"S a tne percent suffur content of the fuel by weight. V '
h ! i}S ,
.suttur Oxides f ll li I In the absence of controls the amount of sulfur oxides emitted @e from a power plant is directly related to the sulfur content of the fuel [
i orned. The average sulfur content of U.S. coals is about 2.5 percent
. '. w:th about one-third of current production having less than 1 percent [pl lity, Fort Collins, s.:! fur and thereby classifying as low sulfur coal. The sulfur is present E
.t. aurally both as pyrite (metal sulfides) and as organic sulfur compounds. hp Residual fuel oils contain between 0.7 and 5.5 percent' of sulfur in the
. . form of dissolved H,S, elemental sulfur, and organic sulfur compounds. I !
ubiquitous source of About one-quarter of the United States supply contains less than 1
- 3 tries. In the United p,.rcent sulfur. Natural gas used for power generation is typically very
- ng thini to motor M law in sulfur (which is present primarily as H,S).* p te approximately 25 While reducing conditions occur in parts of the fuel combus- ll jl f sulfur, and 25 tion zone of a power plant so that sulfur may initially be gasified as H,S or , ;i i nt of the electric S rapid high temperature oxidation of these species to SO, occurs both $[
the combustion of during and immediately following combustion. In addition, the reversible %M l reaction trapproximately 70
- cnd oil. It is now 2SO, + 0, c 2SO, (1)
]
' be the main source decades and that can take place, so that between 1 and 10 percent of the sulfur may be emitted as SO,." The actual amount of SO, emitted depends upon the
;f ,
temperature profile in an individual plant. The reaction rates associated n oxides, carbon with Reaction 1 are fairly slow so that high temperatures promote more ,h] nds constitute the rapid attainment of equilibrium and thus SO, production. However, high ; [ (r plants (Table 1), temperatures also drive the equilibrium to the left (i.e., towards SO,).
, acid nusts, and The net result is that fossil-fueled power plants most commonly emit d;q' '
of these so-called about 1 to 2 percent of the sulfur as SO,, which rapidly reacts with water ; i ' h many am highly vapor to produce sulfuric acid. A small amount of the SO, is also j !, tics of pollutant chemisorbed by fly ash particles to form metallic sulfates l primarily iron. - ' i I the amounts emit- Overall, it is estimated that approximately 95 percent of the *
', minor pollutants sulfur present in fossil fuels is emitted ir. the form of sulfur oxides. This ( l l ucal nature of the amounts to 19 S pounds of SO, per 1000 pounds of fuel where S is the y(l!
weight percentage of sulfur in the fuel. The actual SO, concentrations ,6 , ii i !
]- Wi n
.cgl>
)
116 D. F. S. Natusch appearing at the stack exit depend, of course, on the ratio of feed air to o g-q fuel consumption as well as on the sulfur content of the fuel. Typical . ,4 values lie in the range 500 to 3000 ppm with 1000 to 2000 ppm being most commonly encountered in the absence of control. i=- 1 Nitrogen Oxides 8 By contrast with sulfur oxides, which are derived from sulfur present in the fuel, nitrogen oxides produced by fossil-fueled power .
'" ~
plants are dedved prunarily from fixation (oxidation) of atmospheric I." . nitrogen present in the combustion feed air according to the reactions' Figure 1. Net NC N,+0,a2NO (2) a Function of Ter and 2N + 0, a 2NO, (3) Consequently, nitrogen oxides cannot be effectively contmlled by selec-tion or pretreatment of fuel. '"l g The extent of nitric oxide forrr.ation depends primarily on the tu,- - O, and N, contents of the feed air, the combustion temperature, and the i I ,, average residence time of the oxygen and nitrogen molecules in the ? combustion zone." These dependences, which are reproduced from ref- , erence 8, are indicated in Figures 1 through 4 and are summarued by the experimental equation' . ,'i [N01, - 5.2 x 10' t exp (-72.300 Tl Po,' PN, (D
. . Figure 3. Effec where t is the residence time m seconds, T is the absolute temperature, Pressure on NO F and Po, and PN are, respectively, the partial pressures of oxygen and nitrogen in the feed air.
The amount of nitrogen dioxide (NO,) formed during com-bustion is generally much less than than that of NO, and its rate of tions of NOx are formation depends upon the 0, and N, concentrations according to the emissions. Sigmfics relation ral gas combustion It is int d[NO:] ppm oc (P.y . Po, (II) involved in many dt elevated pressures The temperature dependence of NO, formation by Reaction 3 is analo- is essentially indep gous to that of SO, formation by Reaction 1. Thus, high temperatures cati n Processes op promote attainment of equilibrium and hence NO, formation, but they ve) have been p move the position of equilibrium in Reaction 3 to the left. In practical even elunmated, s situations, therefore, the amount of NO, formed depends primarily on (Figure 1) due to tl the amount of NO forrned and thus on the comtustion temperature. Reaction 2. Repres.antative emission factors for NO and NO, combined are given in Table 1 although it should be recognized that NOs emissions Carbon Monoxide are not directly related to the amount of fuel consumed. Rather, they As can depend on the feed rate of air supporting combustion. Actual concentra- emissions from foss
m -
,d
$ I' li Il:
Atmospheric Pollutants from Power Plants 11 7 l ! ratio of feed air to
,,, u,l uu 'xu -
.1, ,_~ ,l l
$ the fuel. Typical ' , j ,! ppm being most 9 *' ' p
*i m
}l' tl L i 2 i 8 .
~ '**' '
'I "f '
. m=c tw n *ll
.lerived from sulfur ,,,,,,..m.,,,,, .i ssd fueled power n) of atmospheric
, , A 4 4' ,,,
v -- e
, i, ,,
- a' e
,, n, ,j 3 * #**# "* ,.;
Figure 1. Net NO Production as Figure 2. Effect of Oxygen (2) l l .
.1 Function of Temperature Pressure on NO Formation '
(3) ntrolled by selec- ' '~ }
'"l ' ' '
?
. primarily on the mo'- 1
'sN ~ ~'- k )
perature, and the i== -
'""" ;O,4 -
f
!l ,,,,,..,,,.,_ 1 molecules in the i I 2 y,
uced from ref-j 'i
'l, f manzed by the l y , , , , ,
ij 1 ! o as no is too o Lo nao iso ano y"g m .. -~ w l
, (D '
Figure 3. Effect of Nitrogen Figure 4. Effect of Residence hl l lute temperature, *, i < Pressure on NO Formation Time at Temperature on NO For. ps of oxygen and h mation i ' i rmed during com- h(1l ), and its rate of tions of NO, are normally m. the range 300 to 1300 ppm m. stack i 1 i according to the emissions. Significantly higher concentrations are produced during natu-ral gas combustion than during combustion of coal or oil (Table 1). It is interesting to note that the relatively low temperatures j (" r (II) involved in many proposed coal gasificatiori processes
- operating at M eaction 3 is analo-elevated pressures will markedly reduce NOx formation since Reaction 2 is essentially independent of pressure. On the other hand, a few gasifi-hj.
tigh temperatures cation processes operating at extremely high temperatures (-2000*C and g, rmation, but they above) have been proposed. Here also NOx formation may be reduced, or U1 8 eft. In practical even eliminated, since NO production rapidly falls off above 1900*C ends primarily on gum 1) due to the onset of NO dissociation by the reverse process of [(l , , temperature. eaction 2. . ;J . , nd NO, combir.ed iat NOs emissions Carbon Monoxide jdh l. p e ied. Rather, tLey As can be seen from the data in Table 1, carbon monoxide I b. , Actual concentra-emissions from fossil-fueled power plants are negligible where the fuel is l , [f I I c, y
'dI
- A L. _.
118 D. F. S. Natusch natural gas. The higher emission factors given for oil and coal-fired power howeve plants are directly related to the efficiency with which high temperature quite d-oxidation of CO takes place in the combustion region." ing con r In general terms fossil fuel combustion can be thought of as taking place in three distinct zones. In the first, or oxidation zone, the Bulk P. reaction C + 0, -. CO, ganicir occurs. The CO,is then exposed to a reduction zone where the reaction "8*[ CO, + C -+ 2CO (4) natural i have m takes place. Finally, at the periphery of the combustion region, CO is , tion of oxidized by secondary air such that 2CO + 0, -+ 2CO, (5) Fe,K, At normal combustion temperatures Reaction 4 is about ten times faster than Reaction 5 so that complete oxidation of CO is strongly dependent on the availability of oxygen at a sufficiently high temperature content [ for Reaction 5 to take place. This requirement is achieved for gaseous fuels and, to a lesser extent, for liquid fuels, both of which are well dispersed with respect to the oxygen supply. Combustion of coal, how- Table : ever, takes place in a bed where the efficiency of CO oxidation depends Coali more sensitively on the amount and configuration of the secondary air supply.
-3 As pointed ou' reeviously, CO emissions from fossil-fueled power plants do not contribute greatly (~2 parcent) to the anthropoFenic CO inventory. Stack concentrations are normally in the range 200-700
- ppm but can vary greatly depending on operating conditions. u,o
~*
Padicles Particulate emissions from coal-fired power plants constitute a major air pollution control problem. By comparison oil- and gas-fired
- plants emit relatively small amounts of particles (Table 1). Consequently current emphasis is on the charactenzation of fly ash from coal-fired impur panic power plants.
Fly ash from coal combustion constitutes a nuch more com _ many sition plex physi _ cal and_ chemical system than do thepeous._ pollutants pre-viously discussed. Not only do the physicochemical characteristics of the-partic bulk particles influence their environmental impact, but these particles impur also contain a wide variety of more or less toxic trace constituents ent. I including metals,'r' n
~
etalloids, and nepmew It is appropriate, ferror therefore, to consider fly ash in terms of its bulk propenies, its trace mass element constituents, and its organic constituents. It should be stressed, magn s_
" - _ -- _ ---- L -
m y l
> r 1 i '
i i
- Atmospheric Pollutants from Power Plants 119 1
~
i [ciland coal-find power imwever, that fly ash is heterogeneous and that its composition can vary ' yhich high temperature i ouite dramatically between different coal types and power plant operat- , egion."
~
F ing conditions. 1 on can be thought of as r ^
, or oxidation zone, the Bulk Properties i
Pqt,icles emitted from coal enmkm+E-. = p u -e ny_w - , { l Jani_c in nature beine derived frguunid u..p"d'Ec gmm. m O.++eal . l
;one where the reaction u.nseque@e gmnunt _ofjnW ~*ar _ne -n ; pmi coal r !
v.rongly influences the particle _e, mission b+nrw>f that coal. Oil and ;, j. (4) r.atural gE wTliictrimari~only'small amounts of inorganic impurities, I mbustion region' CO is have much lower particle emission factors than coal and a larger propor- [ '} don of these particles are carbonaceous as compared to coal fly ash I, The major elemental constituents of coal fly ash are Si, Al, I (5) Fe, K, and Ca. Some typical composition ranges representative of both ! m 4 is about ten times the eastern and western U.S. coal fly ashes are presented as the weight f l tion of CO is strongly percent of the oxides in Table 22In general, western U.S. coals have a j - Intly high temperature higher ash content and exhibit higher alkali and alkaline earth metal , j - e ntents than eastern coals, which are typically high m sulfur. h cchi:ved for gaseous _ soth of which are well I J .' mbustion of coal, how- Table 2. Typical Matrix Element Composition Ranges of Some U.S. . ;
' CO oxidation depends Coat Fly Ashes Expressed as Weight Percentages of the Oxides." d I @ of the secondary air d e Mejor Constitu.nts j ,
i:ns from fossil-fueled g' gg,o, - Sica F.103 K0 Ca0 ,
- 3) to the anthropogenic ' 22-60 3-21 0.2-3.s 0.5-31.0 s
i4-;,0 , - Q 'I j f in tha range 200-700 ,,,,,e,,,,,,,,n,, i & conditions, , j I U0 Na:O MgO TiO: P Os SO.* 'g 0.01-0.07 0.2-2.3 0.7-12.7 0.6-2.6 0.1-1.1 0.1 -2.2 Q i H)wZr phnts constitute soiuni. .un.t. M d rison oil- and gas-fired m ? pble 1). Consequently During comhustan-in a powr plant tha mnjor'(aluminosilicate 1,' / Ry ash from coal-fired impurities in coal melt forming.ama11gngstly scherical particles._These 1 , particles exNsignificant X-ray diffractiori patterns anii are, in Dj l ' ( ps e much mom com- many cases, traisparent under an optical migoscope. In fact the compo-4l raous pollutants pre- sition of fly ash is closely similar to that of siggwith individual l. characteristics of the particles containing widely different amounts _of. tron andarians trace
, but th:se particles impurities;"In addition some elemental carbon (soot) particles are pres- '
trace constituents ent. It is interesting to note thaCmuch of the iron present occurs as . l
. It is appropriate, ferromagnetic Fe.O., and for some fly ashes as much as 95 percent of the '
properties, its trace mass cr. be separated magnetically." This suggests the possibility of f+ It should be stressed, magnetic collection of fly ash, although such collection could not be b 0 ____ JL _ _ _ _ _ _ _ _ _ _ -- .- _ A _
120 D. F. S. Natusch
- universally applied since the proportion of ferromsgnetic mass varies A widely between different fly ashes.
The aerodynamic equivalent mass median diameters of coal
}
i fly ashes emitted from uncontrolled power plants typica'ly lie in the range 8 to 30 m" and the mass is, to a reasonable approximation, log-normally 6stributed."" The mi.ss median diameters of fly eshes emitted from control devices are considerably smaller than indicated above and depend largely on the collection efficiency of the control devices. In the case of electrostatic precipita'. ion, removal efficiencies as high as 98 percent by *
- weight are claimed" and mass median diameters of fly ashes emitted from these devices are typically in the range 0.5 to 2.0 m. The efficiency of essentially all currently operating particle control devices falls off with decreasing aerodynamic particle size below about 1 to 2 m, however, and it is these submicrometer size particles which are of primary concern since they have long atmospheric residence times, provide large specific surface areas for heterogeneous reactions, contribute greatly to visibility reduction, and are deposited mamly in the innermost (pulmonary) region of the human respiratory system when inhaled."
The morphological characteristics of coal fly ash can be clas-sified into four types." The first consists of non-spherical " clinkers" which occur mostly as very large particles and are rarely emitted to the atmosphere. The second' type involves solid spheres. Essentially all fly ash particles having physical diameters less than about 5 to 10 m are
~
solid with densities close to 2.7 gm em". The third type consists of hollow
- spheres. These may have either quite thick or extremely thin (<1 m) shells, and they predominate in the physical size range 20 to 60 m. The most intriguing particles are the fourth type, which consists of hollow particles filled with large numbers (10-200) of small solid particles r
7n, -. (Figure 5). These occur primarily in the physical size range 20 to 60 m
-- and preliminary studies indicate that between 20 and 40 percent of the Figt mass of particles smaller than about 5 to 10 m may be present as encapsulated particles in fly ashes emitted from coal-fired power plants.
Pre'
^
The occurrence of hollow and encapsulating particles may be insa of considerable significance from an environmental standpoint. In the natt case of hollow particles the low density, and thus small aerodynamic ticic diameter, will enhance the probability of their emission compared with solid particles having the same physical diameter. In addition, these p ' particles tend to behave like ping pong balls on impaction so that they t 1- may bounce off collection surfaces. This is particularly important in
~
determining particle size distributions using cascade impactors."" esse 7
~ ~
^
The phenomenon of particle encapsulation may, however, Zr, represent a very positive factor in particle control. Thus the aerodyn- mat amic size range of the encapsulating particles (22 to 66 m) ensures that mar they will be efficiently collected by most particle control devices thus orgt Rh_ ~ - x . . ~ _
y l.N r q i Atmospheric Pollutants from Power Plants 121 ' l
~
i .i l i
- t, iramagnetic mass varies
~;%_+ . .: r~. .
.,.a.. <
; ,' t I
n diameters of coal 1. :j" ' ,[M b A - [! j ji ( typically lie in the range -2 7,~ & *e4' h.t_
, I 9 - .
%ximation, log-normally W. ],! fly ashes emitted from - ,:. b Y
. . .~-
cated above and depend - .?? -i 1,, -
,z' 'f I; devices. In the case of 1,y~ 7. ri
.U
_ NC - .I 1 high as 98 percent by ' f fly ashes emitted from . F. cf.,,,:8' c 1 - ( '. i!: W if. _ 5" {
.0 m. The efficiency of I devices falls off with
..f
'.t e ..
E U a _. (~-W $ t 1 to 2 m, however, ' 'a -. lt : M, ' Gd "L.U* h are of primary concern I e ., ~ h s, provide large specific ; U, ,- > 4 . i ', ! bute greatly to visibility ; ,. g - *
;{% p 4... ; ( ,' E ? !'
ost (pulmonary) region '. @p *
- f , ,
h
..,-.,:a '
E
*~ i coal fly ash can be clas- .T % .
' i. 5# - .
f 'i i i Dherical" clinkers" which Ii i1 '/ 7 *" /- ' rarely emitted to the a;1 - h( i, eres. Essentially all fly ' 'M - c
..~'
. hj about 5 to 10 m are M 'py9~%. : ;
type consists of hollow
*m
; f"-
# ,j!j
-xtremely thin (<1 m) ^ V ' ' ,' '.. '. ' '
T.' , I, range 20 to 60 m. The (, f 3 ~ ~ N -(*c
+
q3
' .' , f"5 '
j
- 4 - -
hich consists of hollow % ,
~;
" ~
l'" .'" 1,[, i
~~ -
f small solid particles .c c r.. N: ' in size range 20 to 60 m d Figure 5. A 10 m Fly Ash Particle Showing Encapsulated Spheres and 40 percent of the I! Nn may be present as ~ coal-fired power plants. ?g preventing emission of the small, less easily collected, particles encased lating particles may be inside them. In short, particle encapsulation may represent a significant ,y ntal standpoint. In the natural process for the control of undesirable submicrometer size par-p us small aerodynamic ., j mission compared with ticles." f
.ter. In addition, these i "{ p Particulate Trace Elements impaction so that they [3 As a result of their geological orir , coal and oil contain . !
'cularly important in ants. The elements Hg, k,I de i,mpactors."'" essentially all known stable elements in trace a i - 'i lation may, however, Zr, 2n, Cd, As, Pb, Mn, and Mo occur in association with inorganic '
l i
- 1. Thus, the aerodyn- material in coal-mainly in the' pyritic fraction. Ge, Be, and B show
! .L to 66 m) ensures that marked organic association. P, Ga, Ti, Sb, and V are associated with both i 1 r.
sie control devices thus organic and inorgame material in coal but show a preference for organie *n :>
..! l. '
9 3 i
.. i l l A .
12? D. F. S. Natusch association whereas Co, Ni, Cr, Se, and Cu tend to be associated more me with inorganic impurities. Trace element concentrations in oil are much als 7 lower than in coal with the notable exception of vanadium which is in { present as organic porphyrin complexes. During combustion these trace inc elements are partitioned between bottom ash and fly ash although most are of the Hg, Br, and Se are emitted as elemental vapors." ag: The specific cancan ~*~ (polem) of individual trace ele-ments found in coat ~and oil fiv ashes depend primarily on the trace elemelit content of the nricinal fueLin general, a fly ash wIiich EihtainT- - Ta! Trz hig'frToiicentrations of one trace element will also have high concentra. tions of most others as well. However, the relative concentrations may ser differ markedly between fly ash and fuel due to the different partitioning characteristics of individual trace elements between bottom ash and fly ash. Table 3 lists some representative specific concentrations and volume [g concentrations ( g/m') of particulate trace elements emitted from coal-and oil-fired power plants. Volume concentrations will, of course, vary 7$ greatly with plant operating parameters as well as with fuel type. 4,7_ One partitioning mechanism thought to be of importance in 3.s-power plants involves high temperature volatilization of certain trace 2.1-11-elements (or their compounds) followed by their condensation onto the surface of entrained f'y ash particles as the temperature falls.'"' This behavior would account for the observation that volatilimble trace ele- - size Table 3. Specific Concentrations ( g/gm) and Volume Concentra- m ei tions ( g/m') of Trace Elements in Coal and Oil Ry Ashe i bul Coal Fly Ash Oil Fly Ash g Element pggm pg/m' pg'gm a m* coll As (10 Mb 60-90 30 5 Pa 1070-000 30-110 9000 1600 det Be 1-10 - - - low Cd 10-100 - - m e-Co 10-100 1-5 90 16 12 8Pe Cr 10-1000 6-20 66 Cu 10-1000 - - - Par Hg 0.1 -1.0 - - Mn 100-1000 12-40 45 8 par Mo 10-100 - - - in ( Ni 10-1000 10-25 - - pg Pb 100-5000 10-15 - - Sb 1-100 1 -2 5 1 Se 10-100 "8-18 5 1 the Sn 1-10 - - - dia: V 50-5000 5-60 100-100,000 1000-1200 tha Zn 1000-10,000 20-70 3500 640 der.
-, . , Q
f N I l l ' E i l
~
Atmospheric Pollutants from Potter Plants 123 1 ! s a . h ,n 1 6 to be associated more nents are preferentially enriched in fly ash as compared to bottom ash. It l 3 i i Itrations in oil are much also accounts for the fact that some elements exhibit a noticeable iner ease ,, 1 { 1 of vanadium which is in specific concentration with decreasing particle size (Table 4). The I I y combustion these trace increase, which is a direct result of the dependence of specific surface j~ Ed fly ash although most area on particle size, is very marked when concentrations are plotted ' j vapors." ugainst the BET surface area of fly ash particles.":' L {j of individual trace ele- 4 primarily on the trace Dependences of Specific Concentrations ( g/gm) of Some l' [L . a fly ash which contains Table 4. 1 m have high concentra. Trace Elements on the Aerodynamic Particle Diameter in a Repre- ji li Mve concentrations may sensative Coal Fly Ash'* f ke different partitioning a Jeen bottom ash and fly (([ j . Ecentrations and volume (pm) As Cd Cr Ni Pb Sb Se T1 V Zn it ants emitted from coal- ~$ gg try
> 11.3 680 13 740 460 1100 17 13 29 150 8100 y i 7.3-11.3 800 15 290 400 1200 27 11 40 240 9000 *r I'
! as with fuel type. 4.7- 7.3 1000 is 460 440 1500 34 1s s2 420 s000 '?
. j j
- to be of importance in 3.3- 4.7 900 22 470 540 1550 34 16 67 230 3800 i lization of certain trace IP condensation onto the 2.1- 3.3 1.1- 2.1 pig qqp 26 1500 900 1500 35 3300 1600 1600 37 53 19 59 65 76 310 15000 480 13000 ifI i sperature falls.'"' This l,k [
S volatilizable trace ele- M' l +i This dependence of trace element cencentration on particle lfj l size has the net effect of decreasing the aerodynamic equivalent mass r . t0 Vclume Concentra- median diameters of volatilimble trace elements with respect to that of I' L El Fly Ach" ij bulk fly ash."' Therefore the following is true: (1) Many toxic trace elements tend to be most concentrated (/ , Oil Fly Ash +I '4 - in small, lung depositing fly ash particles which are least efficiently y
,e em nym' collected by existing particle control devices. l 5 (2) Specific concentrations of volatilinble trace elema-- ;@[
5 1acc
. de.termined by anal _ynn ash retained in control devices are very much lower than_tha enneentrations in particles actually emitted. Trnea ele _
h) ' ment emission factors cannot, therefore, be obtained bv multinivimr tha - N specifa i,gritThTration of an aWx: ' etnin M Ry n=h hy_tha %!k - 12 p _ partic@on_f_act_or._ p - (3) Thqtential toxicities of trace elements depos,i,tdon t l 8 particle surfaces are enhanceo singeA is.we panietesurfacewhichmmeC7 : E -
~
in direT:t-'Eiiitact with_hngJissues whera. efficient absorption 3.an take _ Pl ace-
'I 3
~XHfie.. ... .present time there is little definitive information about 1 the chemical forms of trace elements in fly ash and about the mass median diameters of emitted trace elements. It has, however, been established ; -
[ 00.000 q 1000-1200 that selenium occurs as the element in fly ash." It has also been reliably : l demonstrated 2'that the elements AsJe 1Sb. and Pb are enriched at least a
-- __-_--.-____._-_AL .
~
124 D. F. S. Natusch fivefold in emitted fly ash as compared to the coal burned, and that V, Ni, Zn, As, Pb, Se, Sb, Br, and I are enriched at least fiftyfold in emitted partiel fly ash as compared to crustal dusts.** tially ; aggiorr Particulate Polycyclic Organic Matter (POM) ash par The exact nature and extent of emissions of particulate in extr pressm organic species.from fossil-fueled power plants is not well established. tures er However the highly carcinogenic nature of polycyclic organic species e nden: (notably benzo-a-pyrene) has stimulated a number of studies of the class pected of organics known as POM.= Combustion of any carbonaceous fuel, whether it be pure m e nt methane or coal, leads to the formation of a large number of species containing two or more aromatic rings. The actual mechanism of POM formation is not fully understood although the available evidencea sug-gests that high temperature vapor phase formation of carbon-carbon is stron bonds takes place, probably via a free radical mechanism. In any event, the forr essentially the same several hundred compounds are formed in similar _POM. relative amounts irrespective of the type of fuel." PO M,,, POM emission factors for fossil-fueled power plants are gen-erally small," but they show a remarkable apparent donondence nn the where 1
^C^nev d 'nenace operation (Table 5). Total annual emission estimates mean P; species for residential heating and power generation in the U.S. amount to 500 adsorpt:,
tons expressed as benzo-a-pyrene."IfemHy hald that tha vo Inw POM (missions fre.m nawaArts result from their efficient breakdown - - glass-lik to carbon dioxide and water at theliig h tem ratures involved. How-plant sh.
+ ever, the extraordinary ditMisnees obse between emissions from power plant furnaces and less efficient combustion operations leads one to tively o experim suspect the validity of the numbers. In this regard it should be noted that emission factors are generally based on analyses of fly ash retained in .
control dervices and it is by no means clear that this material has similar slderab!<
* "I" POM content to emitted fly ash.
_ posed. "
.. ineffectis
( operatin) Table 5. POM Emission Factors for Coal Fired Furnaces
- In inate in (pounds / ton of coal) X 10* , observat
-
- phere.
Pulvertzed Ctusin Grate Hand factors o specks riring Stoker Fired analysis ; A% . Benzo-e-pyrene 0.2-4.52 0.3 552o , .t Pyrene 0.8-1.6 3.5 5260 ported b Benzo e-pyrene o-2.3 1.1 880 cancer,8 Perytene 0-0.6 - 526 Fluoranthene - 6.0 88oo Sions of u - importan __ A
I' M s Atmospheric Pollutants from Potcer Plants 125 4 ixt that V, Ni, , The way in which POM vapors become associated with fly ash " Did in emitted l particles is not well understood." It has been suggested" that essen-tially pure POM particlec may form by self-micleation followed by agglomeration. POM may also adsorb onto the surface of entrained fly ash particles. Both mechanisms would lead to the predominance of POM of particulate in extremely small particles (~0.1 m). Consideration of the vapor 3 established. pressures of representative polycyclic aromatic species at the tempera- a ganic species tures enecantered in a power plant shows that neither self-nucleation nor l es of the class condensation would be likely to occur. POM would, therefore, be ex- 3 pected to exist in the vapor phase at all points within the plant. Con- j ., er it be pure sequently it is appropriate to think in terms of an adsorption mechanism. 3 i nr of species The equilibrium for the process js nism of POM POM., + Particle n (Particle) (POMa.,m) ' ' ddence'* sug-
- arbon-carbon En any event, is strongly dependent on temperature T, and is given by an equation of the form' [k I" "I""I*# k( ,
= (Const) (N,) (o,8) exP (AE/ RT) (III)
PO I 2dRT ! Ws are gen-mdence on the where N, is the number of fly ash particles per unit volume, o, is the son estimates mean particle diameter, M is the molecular weight of the adsorbing species and AE is the difference between the activation energies for if[ 9, mount to 500 !
- the very low adsorption and desorption. , b '
mt breakdown Evaluation of Equation III for adsorption of POM onto ' soled. How- glass-like fly ash spheres of the size distribution encountered in a power d: !1 insions from plant shows (Figure 6) that POM would be expected to adsorb quantita- k 'I sleads ene t tively onto fly ash at, or close to, the stack exit. Preliminary field $ be noted that experiments substantiate this prediction.= The consequences of this adsorption mechanism are of con- & retamed m Mas sinular siderable importance since they suggest that POM emissions from fos- P sil-fueled power plants may be very much greater than hitherto sup- h posed. They further show that particle control devices would be , j]l ineffective in removing POM which is present as vapor at precipitator . T, operating temperatures, and that after adsorption, POM would predom- h Furnaces
- In inate in very small particles. This prediction is in accord with the Ld observation of small mass median diameters for POM in the atmos- i!
phere." Finally the mechanism would account for the large emission Hand factors observed for small furnaces from which fly ash is collected for
) '
i F1md analysis after it is emitted and Reaction III ha's approached equilibrium. ss20 In view of the disquieting correlations which have been re-5260 ported between atmospheric POM levels and the incidence of lung sao cancer," it is of considerable importance to reevaluate the actual emis-y sions of POM from fossil-fueled power plants. In this regard it is also j important to establish whether POM is decomposed within the plant, as - j i t[ *
'S,, 1
1% D. F. S. Natusch 20 currently sup presence in th I8 - Other Emissi In 16 - power plants e amounts. Fon and sulfuric ai w I4 - Th. gaseous organ F determined b3 3 12 - low (Table 1). y for POM" can bons, mecham p 10 - 3,j en z near the exit t I * * "U
- IO~
b8 d Some metal-es W takes place in x Indeed, samp! 6 - due to the pre: e o mists. Quantit. J 4 - so the relative unknown. 2 - donclusions In
= emissions fron o _.
approximate e involve POM
~ '
1600 spuriously low O 400 800 1200 TEMPERATURE,'K are known m 9' investigation < Figure 6. Theoretical Ratio of POM Adsorbed on Fly Ash to that in mtrogen, of pa the Vapor Phase as a Function of Temperature. Particle diameters of
- """*U"""
2 m and an activation energy [,1E in Equation 111] of 8 kcal are , standing of for
,,, g ,
t References I
; 1. R. F. Sav Starkman l
_ _ _ _ _ _ _ _ _ _ _ __ h 1
}. .
;; .. 7 . % E ---
)
c > 4; ' ^ 2 . fg , 1 1 I
. t l l Atmospheric Pollutants from Power Plants 127 hl 5 -
I currently supposed, or whether it has simply evaded detection by its t .l presence in the vapor phase. t, l 1 . Other Emissions ';
!. l In addition to the pollutants already discussed, fossil-fueled 2 i power plants emit a very wide variety of pollutants in more or less minor .3 l amounts. Foremost among these are gaseous hydrocarbons, aldehydes, f and sulfuric and hydrochloric acid mists. 'I The nature of the various hydrocarbons, aldehydes, and other l' gaseous organics is not well known as these compounds are generally ]j.
determined by nonspecific techniques. The actual emission factors are ,,, low (Table 1). While mechanisms of formation similar to those proposed kji for POM8' can be invoked to explain the formation of certain hydrocar- I 1; bons, mechanistic pathways are, for the most part, unknown. Sulfuric and sulfurous acid mists are formed in small amounts , near the exit to power plant stacks where the temperature is sufficiently pi ' ' low to allow formation of liquid water droplets which absorb SO, and SO . l . Some metal-catalyzed oxidation of sulphite to sulphate almost certainly - p l l takes place in these droplets, which are extremely acidic and corrosive. u , l Indeed, sampling equipment is often rapidly corroded near a stack exit f]il , : due to the presence of sulfurie and, to a lesser extent, hydrochloric acid ;! mists. Quantitative information on emissions is apparently not available, .: e : so the relative importance of acid mist emissions from power plants is e jL h unknown. . f' j j [; a : i Conclusions 'L L
- . e :~
In overview, it appears that the most important pollutant emissions from fossil-fueled power plants have been identified and that
~
approximate emission factors are known. An important exception may ' involve POM for which currently accepted emission factors may be 1600 spuriously low. hj ,, The basic processes giving rise to each major pollutant species i are known in outline, although there is need for much more detailed ;. Fly Ash to that in investigation of mechanisms. In particular, control of the oxides of nitrogen, of particles, and of POM may be facilitated by modification of i _rticia diameters of combustion and post-combustion conditions based on a detailed under- i lil] cf 8 kcal are standing of formation mechanisms. I
.J References ajl :
fg! I T
- 1. R. F. Sawyer, in Combustion Genemted Air Pollution, ed., E. S. y ,
Starkman, Plenum Press, New York, p. 275, 1971. ! Ml ,
@o !-
.s
123 D. F. S. Natusch
- 2. R. F. Goldstein and A. L. Waddams, The Petroleum Chemicals l' Industry,3rd ed., E. and F. Spon Ltd., London,1967.
. 3. A. F. Wilhams and W. L. Lom, "H,S in Natural Gas: Tolerance of Some National Acceptance Tests," J. Appl. Chem. (London),17 p. It 179, 1967.
- 4. A. Levy, E. L. Merryman, and W. T. Reid, " Mechanisms of For-mation of Sulfur Oxides in Combustion," Environ. Sci. Technol.,4: 1!
- p. 653,1970.
- 5. J. B. Edwards, Combustion: Formation and Emission of Tmee Species, Ann Arbor Science Publishers Inc., Ann Arbor, Mich., p. 2t 58, 1974.
- 6. M. Feldstein, in Combustion Genented Air Pollution, ed., E. S.
Starkman, Plenum Press, New York, p. 307,1971.
- 7. T. R. Ingraham and D. J. MacKinnon, " Equilibria in the N-0 System 21 at Steam Boiler Temperatures," Extraction Metallurgy Report IR 70-58, Mines Branch, Ottawa, Oct. 5,1970.
- 8. D. J. MacKinnon, " Nitric Oxide Formation at High Temperatures," 22 J. Air Pollution Control Aesoc.,24: p. 237,1974.
- 9. E. D. Ermenc, " Controlling Nitric Oxide Emissions," Chem. Eng.,
77: p.193, June 1970.
- 10. L. G. Massey, " Coal Gssification," Advances in Chemistry, Series No.131, American Chemical Society, Washington, D.C.,1974. , 34
- 11. Ref. 5, p.155 et seg.
- 12. R. E. Bickelhaupt, " Surface Resistivity and the Chemical Composi-tion of Fly Ash," J. Air Pollution Control Assoc.,25: p.148,1975. 25
- 13. A. Loh and D. F. S. Natusch, unpublished results,1975.
26
- 14. R. L. Davison, D. F. S. Natusch, J. R. Wallace, and C. A. Evans, Jr., arrace Elements in Fly Ash: Dependence of Concentration on Particle Size," Environ. Sci. Technol.,8: p.1107,1974.
27
- 15. G. B. Nichols, " Theoretical and Practical Aspects of Fine Particle Collection by Electrostatic Precipitators," Pme. U.S. - U. S. S. R. 25 Working Gmup Symposium on Control of Fine Particulate Emis-sions fmm Industdal Sources, San Francisco, Calif., p. 137, 1974.
- 16. D. F. S. Natusch and J. R.'Wallace, " Urban Aerosol Toxicity: The Influence of Particle Size," Science,186: p. 695,1974.
.,u
""" ^
. _ _ _ - -w -
S.
, lI I j ,
Atmospheric Pollutants fmm Power Plants 129 l; 1: Petroleum Chemicals 17. D. A. Lundgren,"An Aerosol Sampler for Determination of Particle don,1937. Concentraticn as a Function of Size and Time," J. Air Pollution "J ' l Control Assoc.,17: p. 225,1967. - i' l 0: ural Gas: Tolerance of l Chem. (London),17: p. 18. D. F. S. Natusch and J. R. Wallace, " Determination of Particle Size l 'f ' l' Distributions: The Influence of Cascade Impactor Characteristics," ; Alm 8 Ent'im" , in Press,1975. l
, " Mechanisms of For-
- 19. R. R. Ruch, H. J. Gluskoter, and N. F. Shimp, " Occurrence and gf viron. Sci. Technol.,4:
Distribution of Potentially Volatile Trace Elements in Coal," 111inois if .
'*
- Y ' P*" *' ' '#
nd Emission of Tmee jh
> Ann Arbor, Mich., p. 20. N. E. Bolton, W. S. Lyon, R. I. van Hook, A. W. Andren, W.
Fulkerson, J. A. Carter, and J. F. Emery, " Trace Element Mea- !J P Pollution, ed.' E~ S-3uMmen 8 a e a en eam 8n , MEMS8 ePod !I June 1971 to January 1973, Oak Ridge National Laboratory, Oak j[ }
,1971. Ridge, Tennessee. g. i H- '
ib 21. D. F. S. Natusch, J. R. Wallace, and C. A. Evans, Jr., "Toxie Trace da' / riain the N-0 SIste* uTY ePon IR Elements: Prefenntial Concentration in Respirable Particles," Science,183: p. 202,1974. i.
-(
emma uns," 22. J. Kaarkinen and R. E. Jordan, private communication,1975. . g
- 23. A. W. Andren, Y. Talmi, D. H. Klein, and N. E. Bolton, " Physical {'
assions,,, Chem. Eng.' and Chemical Characterization of Selenium in Coal Fired Steam Plant Emissions," Pme. 2nd Annual NSF-RANN Trace Contamin-I. {SlI j p in Chemistry Series ants Confennce, Asilomar, Calif.,1974. I" , kgton, D.C.' 1974~ 24. G. E. Gortion, " Study of the Emissions from Major Air Pollution [d ! Sources and their Interactions," Progress Report November 1972 to y r d , vers y ary , ge M, Mar %ani .; j fhe Chemical Composi- ,j ' scoc., 25: p.148,1975. 25. G. E. Gordon and E. Mroz, Department of Chemistry, University of l bsults,1975. Maryland, private communication,1975. l-[
- 26. " Particulate Polycyclie Organic Matter," Report of the Committee j0 e and C. A. Evans n Biological Effects of Atmospheric Pollutants, National Academy 'g ;
h o,f Concentration on of Sciences,1972. g 2107, 1974, j
- 27. Ref. 5, p. 65 et seg.
pects of Fine Particle ! !
- 28. H. Kim, A. H. Miguel, D. F. S. Natusch, and B. Tomkins, un-
) Pme. U. 9. - U. S.S. R. - ,. I j ine Particulate Emis- published results,1975. ' ' o, Calif., p. 137, 1974. Aerosol Toxicity: The - 1 25, 1974.
~
kl !
, e I
L a {4 nl 4
@- Mod h e
1.nrunnmental licollh l'er y*s's *n r s
- . Vol .U. lcp. : ? :4!. LYN j ,
00CKETED UMC W JY:-3 im 23 Potential Hea!th and Environmentef ( EiTects c7 Trace Elemento and < i Radianuclides from increased Coat Uti!!zation i by R.1. Van Hoch* i i
} ! i
'lhis report 3 tdtens the efhets of cua!-d.rbed trace and ra,finacthe el.ments. A umtmas 3 of our cunent undrewediae of heatth and eminonmental criests of trece and radioettne clorerts rel phumnena MI.h are importar t in ds termirJ+: orcani m esposuir are ah tration and transformation as steH as $3rcitMe and ant. gor.istic actio:*s a. Tion; trace coat m inst'ts are j
diowed fra tosns cf their im;urtance in m Ai6ty, ts rcteace. asabbility, :md .ultiraale i Ibe tosirity nn wiuences of fm;!cmentire the Prrshicet'< Mtie n.ill.rrir> Plan urt ronsideredin iernw s.f ttt impace r f
, n.e M Pin ICM 4:nd 2(ulon the pAential elTi tts of trace and radioadhe elementdrem the cual f u.! cyc Arras of newicd reverth are inlentified i.: Sg ecific recotamentiaticas.
1 ' (P,1fCduClion j The President's Natiomd Energy Plan (NEl1 ( ombustion ofcoal for the production of electrical .
.n d thennal energy n not without attendant heahh contains assumptions w hich bear directl) on ques-tions about health and ensironmental impacts of and emironmental effects. Numerous reports has e trace elements and radionuclides from increased i
been piepared in recent 3 ears concerning these ef- cd utilization. The most important assumptions are ' fest urlatwe to ourcunent pattern orcoal utilization that anmmi coal production will grow from 650 mil- ' 4 apptosimately 650 mi!! ion tons per year. Most lion tons (15.3 quads)in 1975 through I.200 million ebo h ne dealt with specific parameters of coal tons (28.2 quads)in 1985 to 1.910 million tons (44.9 wh/ation such as health effects ofcoal combustion quads)in 2000.ar.d that by 19S5.allemission ources th. tosicity of coal-derived trace elements C), ef- will be in full compliance with environmental re leets of coabdern ed trace elements on water quality Imiom promulgated by tne U.S. Environmen'eu- tal
- m. anJ ettects of coal derived radionuclides (1). Pmtection Agency (EPA) and by individual states.
Recently Jeseral reports base appeaied addressmg The NEP is based on application of the Ikst Avail-a mteri ned assessment ofcoal utilization (5-8)and able Contml Technology (ll AC f) being applied to all these teports have been utilized extensively m de- new or espanded utility and industrial boilers. As sch* ping the following materials. Specifically, outlined in Public Law 95-95. the 1977 amendments I RD \ ~7 M "F.ffects of Trace Contaminants From to the Clean Air Act of 1970. II ACFis to replace the (;od Combustion"(5) has been used as a basis for New Source Performance Standards (NSPS). Al-the piesent analysis and sections of that report have though not directly addressed in the NEP, fly ash and been icpeated ve batum with new information m- scrubber sludge may be defined as hazardous sub-setted in appropriate locations. stances under the Resource Conservation and Re-covery Act of 1976. This will base a significant im-pact on allowable release rates from landf:lls and
'l ninonmental sciences thision. oak Rike Liional 1.
W. Ibk Redg. Tennessee 37MO. abo _ponds used in fly ash disposal. The Surface settling Miningand Reclamation Act of1977%illplaya major Ihrmher 1979 227 t l s. _ ,_, g. , _ , , _ _ , , _ _ -
f role in determining coal availability by placing raore pathways in aquatic and tenestri.d ensironments. j stringent regulations on lesels of mine drainage and oprottunities exist for interactions of trace clements on reclamation practices for both existing and new with hie toims. Organisms. es pecially mietooi-mines. The NEP awumes no adsanced coal com- ganisms in aquatic ensiionments. can absot h, con-bustion or coalliquefaction before 2000. Coal gasiG- centiate, and transform tiace and radioactise cle-cation is awumed to contribute 1.2 quads by 1985 ments into mme concentiated foims or moie toxie and 3.8 quaJ s by 20N with altendant solid waste and compounds. lliotransformation of trace and water use pioblems. radioactive elements is paiticulatly irapo: tant in de-The objectis e of the piesent paperis to discuw the termining etrects on man and ether organisms. siace current status of our undeistanding of health and it is the moleen!at fmm of the e contam'nants that determines their persistem.c. andlabiht) . bioae-environmental effects of trace elements and cumulation. and toxicity . liioaccumulation is of pas radionuclides from coal utili/ation and to estimate ticular concern hu elements such as Cd. lip. ;md Pb the probable impacts ofincreasing coat utili/ation as envisioned in the NEP. A discuwion of ensiron- bec.mse cuitent intake les els for these substances mental mid biologic;d transpmt is included because are near loferable human he.dth hmits. transpmt and transformations of ha/aidons ele. Ecological effects of trace and radioactis e cle-ments detcimine organism exposure and ultimate ments fr om Ihe coal fuc t e) cle are pr esently or w ill be toxicity. It should be pointed out early that accurate, awociated piimarily with mining, cleaning, and solid inexpensise analy ticed techniques for determining w aste (ash, sludge) disposal. The acidic natme of mine drainage fiom eastein coal fields tends to hold amounts and chemical forms of trace contaminant . are ewential to understanding and evaluating trans- metalions in solution and promotes their tiauspoit to port and effects of these materials. With the excep- smface and pound w ateis. Acid m'ne J.amage from tion of transportation, w hich is coscied elsew here, inactise mines in the eastern United States is t!.e the complete coal fuel cycle is addiewed in this greatest single source of drainage and transport to study, aquatic enti:onments, and is seiy dif0 cult to con- , tro!. Western coal gencially laels acid-for ming sub- L stanus, althonyh increa ed sahnity of surface and Summary ground w ateis m a estem coal regions could become Trace elements and radionuclides potentially a problem due to soluble salts in mine spoils. Dming overbuiden iemos al im strip mining, giound water haiardous to human health and ecos) stems are piewnt in coal. Trace elements of concern include aquifers ate commonly intticer'ed; hazaidons ele-among others. As. lie, Cd. Cr F. Hg. Ni, and ph. ments may enter these disturbed aquifeis. Impacts , Concentrations of these elements vary considerably aweeiated with elements in runoff; .d teachate tiom among coal ty pes. Itadioactive elements of concern co.d cleaning and storage are similar to but of jewer in coal include 2"U SU mTh. and awociated magnitude than those awoeiated with coal mining. daughter products. Concentrations of radionuclides Concentrations of trace contaminants in atmo-in coal are generally less variable than those of trace spherie emissions from coaldiicd power f lants do elements, values of I ppm for U and 2 ppm for Th not appear to be a significant ccological hazmd. being reasonable national aserages. Trace elenient concentrations in soils fail rapidly Trace and radioactis c elements can enter the envi- with distance from power plants and tend to be at ronment prior to coal combustion thiough runoff background lesels at di tances > 1 km from the from mining, cleaning, and stotage operations: dur- phmt. With installation of efficient c!cetrostatie pre-ing combustion in atmospheric emiwions of respira- cinitators, atmospheric emissions of trace elements ble particulates and volatile elements: and follow ing should not be acutely harmful to vegetation and combustion through nmoff and leachate innltration other biota, especially beyond a 3 km radius. Only into ground water from bottom ash. By ash, and Cuorine appears to desene special watching. scrubber sludge deposited in settling ponds and 1.ikewise, the potential for chronic toxicity to landfills. Trace contaminants released to the envi- ecosystems is relatisely low. except in local areas ronment from the coal fuel cycle may result in ex- already enriched with a particular element. liow-posure of organisms at considerable distances duc to eser, sublethal, chronic or synergistie effects of atmospheric transport of particulate and gaseous trace elements on ecosystems base receisetl little fomis, or contaminants from solid wastes Iash) may attention. reach drinking water supplies through hydrologic About 92G of particulate materials produced in transport in ground and surface waters. . utility boilers i, remosed by electrostatic pre-At 'neaily eveiy point along physical transport cipitators. Fly ash, bottom ash and scrubber sludge Emironmental llcalth I crspeclim 228 L b,. a
all contain trace and radioactive elements. These aie 'Ihere are sesetal areas of unces tainty w hich generally released to ground water at low concen- should be pointed out. ~1 hese m ea . m e liste i behm , trations, with attenuation occurring veis close Jo the recommendations foi needed iese.uch ate listed at disposal site. Very little information is avaihible on the conclusion of thi ieport. the chemical form, bioavailability and toxicity of (1) The chemie.d foim of tiace elements is sery these contaminants. Ily 1985,60 to l(0 million tons important as a deteiminant of transport thiough the of11y ash with elevated les els of trace elements will ensironment and of toxic ef fects on health and be annually discharged into settling basins or land- ecosy stem s. Most studies of coal emissions and filh situated in close prosimity to coal-lived power teachates focus on simple elemental an.dysis.1.ack ' plants. Islements such as As. Cd, Co. Hg. Ni, Pb, Se, of knowIcJpe of chemical species of tiace elements U. and Zn all exhibit mobilization rates from the e precludes making a confident :md aJequate assess-tieposits that are larger than 10'; of the naimal ment of the potential health and ecological clTects of weathening rates. Cadmium. Hg, and U appear to be trace elements from co.d utili/ation. mobili/cd through coal combustion at rates com- (2) l'otenG.d cont.uniuation of diinking u ater sup-parable to their natural wcathering rates. These ele- phes by seseral tosie or radioactise elements in ments base a definite potential foi runo!f to surface teac'ates from waste disposal riesents a seal publie waters and teachate intrusion into giound water and health problem. The chemical foim of each element their concentrations should be monitmed closely . may be significanth altered by mietooiganisms in There is reasonable concurience that some trace the phy sical transport process. and these chemical contamin.mts in coal may constitute human heahh fonns will determine the rate of ens uonmental problems from either dir ect toxicity or risk of cancer. transport, the bioaccumulation and tosicity of these Among those most toxic to man are Cd. lig. and Pb, elements. Too littie is know n about the .e pr ocesses. intake levels of which me already neai tolciable W Gisen that sesenal traec elements in leachates healthlimits.Three elements- As(111),Cr(Yl), and exhibit mobilization rates that me laiger than 10'; of Ni (embonyl) - me accepted as hasing high car- natural weathering rates. do these elements ef fee-cinogenic importance to man. Of the e. As (111) and tisely remain in settling basins or are they injected Cr (VI) probably occur in fly ash teachate. but at into waterways and into food chains? Unquestion-enknow n concentrations, w hile Ni (caibans h does ab!). the mosement of trace elements from coal not occur. These is little oi no teratogenic potential combustion disposal sites should be iegarded as a from Cd, lig, or Se compounA at concentiations potentially significant heahh piobkm and beats in-found in atmospheric emissions or th a .h leachate. tensise monitoring in some sites. The potential for contamination of drinking v.atcr (4)Wlute the ambient atmosphetic loading of trace supplies by trace elements in leachates fmm settimg elements does not appear to be as pical a potential pondi or landfills is very real and needs to be pmblem as int r usion into wnterways fmm leachates. evaluated. As previously noted ash disposal sites there is a need to monitor atmospheric concen-willincrease in both site and number, amounting to trations at selected sites. Few data esist on trace 60 to 100 million tons of wastes annually by IW5. element ambiem concentrations. fallout and re. Estimated annual release rates for radionuclides entrainment fiom disposal sites. Atmospherie and from a 1000 MW(el coal. fired power plant amount to ensimnmental lesels of cadmium, Iluorine. mer-t 0.(M to 035 mrem'> r w hole body Jose, as a maximal cury. lead. arsenie (111). and pooibly Ci tVli should l annual dose commitment per indis idual. To compare be particularly monitored at these selected sites. l the magnitude of radiation from coal combustion emissions,it is useful to use dose equis alent rates for natural background and coal emissions. The dose CUflOhl Status j equivalent rate for the w hole boJ3 fmm all natural Sources of liarardous Eleinents in the Coal radiation somees is 80140 mremTi. ,The corie-f,"d N, CE
~
I spending coal combustion radiation rate is 0.007 mremlyr. On this basis, atmospheric releases of Estraction. cleaning. transportation. storace. l radionuclides from increased coal combustion do not combustion or conveision, and ash disposal are the represent a significant public health problem unless sources of trace elements and radioauclides in the coal containing > 5 ppm U come into gencial use. coalfuelcyclem).The e contaminants may enterthe Radionuclide releases from ash disposal sites have atmosphere. landscape, and hy dmsphere and. de-not been evaluated, and depending upon ash leach- pending upon physical. chemical. and biological l ing rates, could become a signilicant human health factors, enter food chains leading to man. Contami-con, sider ation. nantsintmduced into the atmospheie may reach man Deccinher 1979 229 4 l - l l b.
, labl I. ber.u:e trace dement concentr.nion in coat by stav Trace element conen. ppm Northern Pow Ai A ppat iebi.m Southern Apr.dachian l'astetn intenor
. Rnci Repon i out Omnm I auern Ws stein New W. V.i . Penn. K). Ala. Va. Tenn. Ill. K). Ind Mont . W> o. steuco Am As 9 16 6 11 10 9 6 7 7 (6 1 2 2 .
IL: 77 70 79 I10 99 120 49 44 31 180 170 270 39 lic 1.2 0.b 1.5 034 1.1 0.54 1.3 14 I .7 1.5 24 0.94 0V
, 11 20 15 19 10 11 24 bl 70 M 60 16 41 49 Cd - --
2.9 - -
< 0.1 0.46 2.6 ( 0.54
- Cr 19 24 19 19 20 19 29 18 19 3 5.b II 9.7 Co 17 1h 15 th 14 11 is 16 24 7.7 5.2 15 -
Cu 11 11 ll 14 11 11 83 8.b 9.7 1.2 44 5.9 49 F 70 90 10 90 50 120 59 - 50 70 160 160 70 l'b 4.9 5.2 4 3.7 61 49 31 64 7.2 4.X 0.61 4? 3.9
- lj 44 64 78 75 14 16 4% 16 24 27 19 16 19 Mn 21 21 26 19 42 2.4 74 19 26 57 14 19 9.7 fly 0.12 0.20 - - - -
0.IN - 0.0s 0.07 0 05 0.08 0 05 Mo 62 9.N 52 II F.1 7N 88 7.4 5.2 4k 2.2 2.0 09' NI 15 20 lb 17 22 16 25 16 33 31 41 >l 49 Sc 1.4 1.7 3.1 5.1 4.4 4.9 2 31 4 3 0h 2.0 2. ! Tc - - - - - - - - - - 0.025 0.01 ( 0 02 11 - - - - - - - - - - 04 0.24 <02 Sn 1.5 1.1 4.6 22 2.1 18 2.6 2.5 0 74 1.I I4 1.9 0 97 Y 30 U 29 31 31 34 33 32 35 12 15 25 9.7 Zn 17 22 15 22 23 23 140 48 73 42 37 19 9.7 2r 61 (44 60 56 44 4% 88 77 100 77 19 I10 39 U oange, < 10 30 2019a 10 -
- 10 -
.c 10 80 -
10 10 140 10 f ooa 10 6200 - not ap.)
- Source: thot ak M and other animals thiough inhalation and plants promotes transport to surface and ground waters, through fumigation w hile those entering the aquatic Trace elements of concer n include A;. As, Cd. Cr, and teriestrial enviionments reach pl.mts and ani. Co. Cu, l'e. Ph. Mn. Ni. Se, and Zn 1/2). In w estein mais through root uptake and ingestion. Trace ele- coal prosinces aciJ formation is almost nonesistent.
ments and radionuclide in U.S. coals base been but transport of all. aline drainage containing soluble widely studied (.J. 7. Al. Concentrations of trace ele- salts from mine spoils to receising waters is one of ments in coal me sometimes dif ficult to determine the most significant wates quality problems in those accurately and tend lo vary considerably among dir- regions (/h ferent coal ty pes (Table 1 ). Thus. it is not appiopriate Coal processing or cleaning produces coal fines to compute a national average for each trace element and rock material. The refuse is sep.oated into gob in coal (9). Radioactis c elements in coal. 2"U.
- U. (coutse-boulder to pebble-site rock) anJ slm ry Wlh, and associated daughter products. are also (clay-sized paiticles of coal finest Piol lems as-variable (Table 2h but saines of I ppm U and 2 ppm sociated with coal cleaning refuse are generally liu-l Th have been assumed to be reasonable national ited to the coaliegions of centralinte ior and eastern I
averages (7. /hL prosinces (6 h Acid drainage or runoff of refuse piles Coal estraction. both surface and subsurface, are sources of trace elements to terrestrial and produces solid wastes and acid or alkaline mine aquatic ensironments. drainage which contain trace elements and I.arge coal-fired electricity-generating stations radionuclides that me transported to aquatie envi- [21000 MW(c)} require coal storage in order to ronments (6). Acid mine drainage from inactis e un- maintain a continuous supply between shipments. derground mines i, difficult to control and is the Permanent coal stockpiles for a typical 1000 MW te) greatest single source of drainage in the eastern plant may vary from 500 to 900 thousand short tons United States (II). The acidic nature of acid mine and require from I to 2.5 hectares (6). Suspension of i drainage tends to hold metal ions in solution and coal dusts and infiltration and runoff waters are l B0 Emironmental IIcalth Perspectises l 5 I t 5
Tah'le 2. Range of uranium and thorium concentrations and gemnetric n. cans ecy.cotd saturo fur coat ump!n taken from s arions regionut the 1 micd .st.:tr%* L'ranium concentration 1hormm wnecnnanon (ppno" # ppn o* Number of Gwmeine Geometne Region Coal samples Range meat. i< ante me.m Penn9 1vania Anthracne 53 0.L25.2 1.2 2 F I41 4.' Appalachia lhtuminous 131 s 0 2 10.5 t .0 2.2.17.8 2x Intenoi lhtuminous 143 0.2-41 1.4 <3N I v. Nodhern Great ILins Subt,ituminous brnde 93 <0 2 2.9 0.7 -2 0-8 n 2.4 Dulf Iagmte 34 0.5 10.7 2.4 < 10 2x 4 1o Rocky Mount:un [htummous, 134 < 0.2- 21. 8 ok <3 0 34 8 2.0 subbitununous Alaska sum'itummons 18 0 4 5. .' t.0 < 10 18 3.1
- Source Melinde. 4i
. "T he arithmetic aurage wncennations of thorium and m .nium for a!! co. ! vmpics aral s arious e ani.s ol' coat hu the v.holc l'mtcJ States are pnen in lable 1 latite 3. Arithmenc auraged coactatr.tions of uranium and Trace elements in coal tend to utition or con-thorium in cual for the w hole l'.N. centM' in cd hin NN dmiq'.Codmtiom Klein l honum. L ' ram.um et al. (16) catecoii/ed traec elements into thice Coat iank Samples Opm ppm classes: t !) c!cments that ne not s ohttih./ed .m the combustion zone, but instead form a me!! that be-AI! coat 7W 4.7 1.8 comes both Oy ash and slag ( Al.11a. Ca, Ce, Co Eu, Anthracite $1 5.4 1.5 };e, IIf, K, I,a Mg, M n, lib Sc. Sm. Sr. Ta,'l h. Tit t tuEou, Q eleinents that are volatili/ed on combustion, and t.igmie 54 6. 3 15 condense or adsorb on the ny ash as the One pas cooh, leading to dep!ction fioin slag and concentra-
. tion in the fly ash ( As, Cd Cu, Ga. I b Sb. Se, Znt major tiace element and radionuclide somees to the and On elements that remain almost completely in environment. Terrestrial ettects are generally neg- the gas phase tIig, Se, Cl, litt 'I he elements Cr Cs, ligible except on areas immediately below and adja- Na, Ni, U, and \' w cre intermediate in behasior anJ cent to the piles. Cnound sealing prior to establishing w et e placed betw een classe s one and Iwo. Follow ing the coal pile can reduce in0lt rat ion into gi ound water combustion, Irace elements released 1o the atmo-(/4). Contamination of aquatic environments fiom spheie in awoeiation w i1h particulates may be selec-mnoff from coal piles is similar to but of fewer mag- tisely adsorbed in different p utiele size ranges (17) nitude than that from acid mine drainage. and may be emiched on ny ash pmticle suifaces Coal combustion produces Oy ash and slag of relatise to the interior of the partiJe flM.
bottom ash as solid waste products. Slag is that por- Coal pasification appears to be the only coal con-tion of total ash w hich melts to a viscous Guid at sersion technology that will be on-line by the year combustion temperatures, and bottom ash is the re- 2000 (10). Trace elements and radionuelides may be mainder that does not melt and is too heavy to be released to the ensitonment trom pasification pii-entrained in Oue gas. The amount of slag and bottoin marily from noncombustible solid wastes t hat will be ash produced in combustion is a function of coal type dispo' sed ofin land 0lls or slurry ponds. Atmospheric and boiler design. Bottom ash is generally mixed releases of solatile or hydride-forming species is a with Oy ash and pumped in a slurry to settling ponds potential but unJeOned source of trace elements or dewatered and transported to landO!Is. Settling from gasification. ponds are sometimes lined with clay to reduce leachate mosement into ground water (14). In the Ens ironmental Transport absence of liners, trace elements and radionuclides in Icachates can move into underlying soil and Before the effects of coal-derived trace contami-ground water t/5) and are subject to a variety of nants on man and ecoq stems can be es aluated, it is chemical, physical, and biological factors that gov- necessary to estimate the transport, tr ansformation ern.their mobility and availability in the environ- and bioaccumulation of these contaminants as they ment., inos e from the power plant to the icteptor. In addi-December 1979 231 I E.,
tion to determining routes of transport and transfor- particles to ieal surfaces (e.g., giass shiubs, tiees. nution. rates for these procewes also must be de- lakes, etc.)is an unknow n. Best avadab!e "guenti-tennined before we can piedict ensiionmental fate m.'tes" suggest using a dry deposition s elocit y for all - and levels of esposure. Information the phric.d p.uticles to all real surfaces: v4 = 1 cm'see. Ilow-and chemical characteristics (e.g., p.u ticle si/e. sol- evei, ddlerent values are obtained for ddlerent at. ' ubility.and valence state) of materials ieleased to t he mospheric conditions and surface toughnesses. environment is a vital prerequisite to study of tr.ms- Resuspension of particles has only recently be-port processes. The following discussions of en- come of interest in the atmospherie scienas. al-vironmental transport are , ned in part on an ' though much useful infoimation is avaihible in the
' analysis by Crawford et al. 00). soil and apiicidtural science literatme. liowes er. in A tinosplurric Trunninore naul I)i,penion. Sea- these fields. the emphnis has been more on wind sonal and annual pollutant concentration fields in the crosion than on the iesuspension of submicion parti-atmosphere can be calculated with reasonab!e accu- cles which is of dominant interest foi evaluation of racy (within a factor of 2 to 4 at distances of up to 10 inhalation health effech in this icpaid, attention km from the effluent source if attention is restricted must be paid to bounce off during the depositian to simple terrain types and ty pic.d daytime atmo- process 07), resuspension by rain splashing C0, spheric stability categories C/. 22). Probabdity dis and h ecing of submicion partic!es fiom super micr on tributions of hourly concentrations from seasonal particles during dissohition in water CW and by and annual data can also be calculated with simil.a bombaidment of Imper pmticles Uth.
accuracy. At longer distances, models can be for. Water und Nintes 7)nn pos t in hih. l'or sites mulated to account for transport and, to a lesser downwind from a coabbmning power plant wheie extent, dispeision. The data iequiied foi distances trace elements or their ccm;,1 eses v.ach the soil sur-
> 10 km ate not readdy as ailable howes er, and the face by wet or dry deposition fiom the atmosphere, models base not been thoroughly validated, the most impoilant deteiminants of their ensiron-liit Depo ition. Precipitation scavenging of mental fate are likely to be smption and desorption particles and gases has been measmed in the neigh- on soit paiticles at the soil smface and the sub-boihood of coal-fired power plants, and the es- sequent mobility of these trace elements as a result of perimental results are faiily well modelled theoieti- soit erosion caused by both wind and watei.
cally, at least for estimates of total mass scavenged. The transport of coal-de'ised trace elements and Details of the remova! as a function of par ticle si/e, radionuclides uithin the soit depends on ' vater however, remain in a piimitive state. movement and chemical reactions within the soil To estimate precipitation seasenping on a total- piofile. The use of as ailable techniques fo: p: edict-mass basis, two appioaches me available. In one, a ing and monito:ing mosements of soil water in the scavenging rate coefficient uhich accounts for the vicinity of a coal-burning power plant depends upon pa 1icle si/c of the trace contaminant is used 03). accurate field determinations of the hori/ontal gra-Estimates of the removal rate for snow seasenging diems in the water table head and h> diaulic conduc-are also available 04 ). In the second arpioach. a w et tivily at the site in question. deposition velocity is deriveJ using washout ratio When the mosement of nater through the soil has data C3,25). These washout ratios show relatively been ch.uaeterized. information about chemical and j little variation for the trace contaminants and using physical reactions uhich occur simultaneously with I them, one can define a convenient uet deposition the soil w ater behas ior i required in order Io predict l vehicity for typical annual rainfall amounts in the the retention and transpoit of trace elements in the northeastern United States (~ 100 ent'yr) as ap- soil. Piocesses of sor ption and desorption betu een proximately I cm'see for t race metals ofinterest. It is the organic and inorganic solid phases ef the soil are appropriate to use the washout ratio for long-term- usually strong and can piesent rapid leaching of a'verage estimates; the seasenging rate approach these elements into surface and ground waters. On should be used for short-term estimates. Met hods for the other hand, some chemical forms of trace sub-including precipitation seasenging in diffusion cal- stances are repelled from the solid phases and may culations are available C6). leach icadily with the water. Many reactions in the Dry Depo >ition nint Rc3nspension. D1y deposi- soil are Eh- and pH-dependent. Some contaminants tion of particles to smooth surfaces as a function of present in coal waste material ma> interact with the particle si/c and imbulence intensity is fairly well soil exchange comples and may be far more soluble known from wind tunnel studies. and theoretical than one would espect from a simple water estract: analyses demonstrate a fair understandmg of the others, although hichly soluble in water extracts, l processes invohed. Dry deposition of submicron may precipitate with materials present in the soil. 232 Ensironmental IIcalth Perspectises l t L.
Procewes of erosion and sedimentation iepresent water sticams may h;n e different properties and be-large. portions of the mass flow and should be in- hase ditterently when ingested by consumers 62L cluded in conceptual models and measurements of Elements may return to the phy sic.d ensironment hydrologic transpoit 01). through death and leaching. or they may enter food When the kinds of information described abou chains through ingestion by coasumer 1 ollowing are available, estimates of the migiation of tiace ingestion, elements may pass stiaight through the elements fiom land disposal sites that teceis e slag, digestise tract or they may be awimilated. Assimila-sembben effluent, fly ash. and bottom ash can be tion rates mas sary from - l'; per d.:y for certain ' made. Vertical and horizontal mosements in both elements up to IW i per day for othas depending the water-saturated and unsaturated /ones of the soil upon both anim.d and element specie in question can be estimated from the dispowd site to the ie- Oh. Folitming assimdation, elements are distrib-ceiving waters. uted in vaiious tissues at various rates in the con-somei s body. Cadmium for esample tends to ac-Transport in A,pinric Enrironinents. Trace con taminants that enter the aquatic enviromnent aic cumulate in renal tissues and methylmacury in the usually rapidly taken up thiough adsorption by com- central nen ons system. Othei elements. p.o ticul.n ly
. ponents has ing the highest sm face-to-s olume ratios. heau metals and transmanics tend to be bone seek.
primarily the small suspenJed solids and sediments. ers. Elimination of elements fiom various tissues and absorption by similar sized miciobiota. The proceeds at various rates and iesults in release of the largest iesersoit of trace contaminants is the bottom chemical into the digestise tract to bc eliminated sediment. liere a comples awociation of inmganic fiom the consumei thiough egestion. Consumcis and oiganic components similar to Ihose found in soil may die or they may be consumed by subsequent foim a system w hich goseins the availability of con- steps in a food chain. Compounding this simplilled taminants to the rest of the ecosystem. ~1 he phy sic.d pictme of a food chain are the Fiotran formations factors pil. Eh. pore space, and chemical transfoi- that may oecu r. changing the so uctur e.md biological mations influence the retention' mobility of contami- actisits of chemicals, and the question of direct up-nants in aquatic systems. Simil.nly, biological take from sm rounding air tinhalation) and w ater (gill transformations play a key role in aquatic transport and epidermal absorption). and distiibution. In sticams. contamin.mts may be Soils tend to be the sink for most chemical con-transpotted dow nsticam in diwolsed for m or in as- taminants seleased to terrestiial enviionments in sociation w ith suspended sediments. ultimately to be addition to watei relations and soil sorption-deposited into lake sediments or taken up in food desorption phenomena, microbial inteiactions and chains and e>cled among various biological compo- root uptake play major rola in transport anJ dis-nents. tiibution of chemicals in tenesnial sy stems. M i-ciobes can operate in both aaobic and anaerobie environments and ha e piofound ef fects on element liiolog.ical ,I,ransport Imd 'I,ranstbrmat.mn mobihn . liom the soil-soil-w ater continuum plants At nearly esery point along the physical transport may accumulate elements through root uptake, a pathway s in both aquatie and tenestrial ensiron- piocess of both actise and passise natme. Plant ments, opportunities esist foi interactious uith the tootuhow piefeiential uptake of particular elements biotic components. Organisms can ab-oib hazard- and can eselnde others at nembiane boundaries. ous elements from their physical ensitonment and Heavy metals entering p' ant roos me believed to be dilute. concent rate. t ran sfor m. and immobili/e t hese chelated prior to their movement in ylem anJ materials w hich may or may not affect ultimate con- phloem streams tu). taminant toxicity. liiological transport play s a major Typically, aquatie food weas me more compics role in determining exposme of organisms to con- than those found in seriestrial s> stems. Adsorption-taniinants, but only a minor s ole in material transport desor ption of elements on suspended sediments and through the ensironment with littie or no effect on direct abserption by organisms from u ater are added contaminant ins entory. parameters in aquatic systems. Chemical contami-Foo,I Chains. Primary pioducers generally serve nants generally s cach aquatic em ironn'ents by direct as the base of food chains and may accumulate ele. deposition tdisposah. runoff 6 om land surfaccs, and ments through ioots (plant uptake), leases trohar leac hate s in ground wates. Chemical and phrical absorption), absorption through cell walls in aquatic reactions among sediments, inteistitial water. the plants, and adsorption on esternal surfaces. Ele- water column. and decomposers can affect the ments physiologicalls thed in plant tissues as op- routes and rates of transfer as well as the chemical posed,to those on plant surfaces or in intracellular and biological properties of contaminants. Aquatie December 1979 233
. .w
p'lants obtain elements from the water column panisms are ser) scisatile in their ability to chemi-through absorption although surface adsorption is cally interact u nh natural and 9nthetic chemicals
'in'iportant because of high suiface-to4 olume ratios N/, J? L found in algae and other phy toplankton. Decompos-ers may act upon organic matter in anaerobic sedi- The biochemical process of meth>lation of heay ments resulting in release of heas y metals to intenti- metals and metalloids has ieceis ed uoriderable at-tention in recent > cars allhough Ihe s caction w as first tial waters and their subsequent diffusion into the ove:1)ing water mass. Ilecause of the chemical and obsened with aisenie in the late 193W t4h Meths -
biological actisity present, sediments may act as lation is beliesed to be a detosilication mechanidn forcont e ling toue ions to a more s olatile foi m Ihat sources and sinks of chensical contaminants in the will be released to the atmosphere W4L Seseial mi-
, aquatie environments crobial species me capabic of reiforming this trans-liiologire,l Concentrusiore. The ability of animals and plants to accumulate chemical contaminants to Ibnnation in soils and sediments undei both aerobic ami anaerol-ie conJitions Meth> !ated for ms ofin.cc levels above those of their food source or subst rate is metals aie frequently more tosie and are more re uf-a common biological phenomenon. I race elements, ily abso bed by higher organisms than are inorganie
, including heavy metals and radionuclides, are ae- fonn% Methylation of mercurs by miciobes in cumulated to varying degrees US-37L in aquatie systems, water is typically the :eference point, w hile marine and freshwater sediment s is the best documented ease of Ihis t> pe of biological tiansfor-soil senes a similar sole in terrestrial > stemt mation 65L Arsenic selenium, lead and tin ate Iliological concentration of elements is pos er ned by examples of other tosie elements that undeigo the amount of element piesent in the diet or sur- methylation 45L rounding ensironment, the chemical and phy sical fomis of the element which deteimine its biological Hieher orcanism% includine m.m. me capable of availability, the quantity of food consumed contain- affeciine bibuansfoimations of ha/mdous chemi-ing the element, the degree of assimilation of the cals. Reactions of Cd anJ metallothionene in scien-element through cellular bar riers (i.e., cuticle, long, tion of this element in senal tissues aie well digestive tract, gills etc.h and the estent ofietention documented bs 1 iibere et al. W^ L in the mganism's tissues liiological concenuation itiotransforniations df ha/.odous chemicals in ihe ensironment me p.u ticulml> impor tant in detei-occurs with natural elements for cellular main'e- minine c!fects on man and other organisms because nance and grow th. It can also occur u ith ha/ar don' clements u hen there is a strong chemical on phy sical the mbleeutar form and biochemistn of these tmns-formed chemicals determine theii Evailabilitv. per-resemblance to a common element or molceule sistence, bioaceumulation. and toxicit s . which is necessary for es erplay hfe processes UA).
,% y,,,y;,,y, una g y,yyyn f.,y, The combined ae-Due to the variations that exist in the factors pos -
erning biological concentration among different en- tion of two diffeient chemicals mav be creates th.in or less than the som of the independent actions of vironments and species as well as within one species in a pmticular environment, it is not true that be- each mateiial. If chemical effects me simpl> addi-tis e. the inercasc is a simple algebraic adthtion. lf the cause biomagnification ocem s at one step in a food chain, it will also occur in subsequent step % effect is greate than a simple algebraie addition. Iliological concentration factois for ha/mdous then unercism or potentiation has occuried. If the elements (Table 4) may vary oser many ordeis of effect is less antaronism esists. In the case of additise effects. fl-e'tw o compeonJs hn e the same magnitude (10 ' to 10') in aquatic and tenestrial ensiionments 66. 37,39L T 3pical!), biomagnifica- points of anack. In potemiation one compound usu-tion is greatest in aquatic ensironments w here ally acts on the metabolism of the second compound. surface-to volume ratios are greatest and u here ad- The concept of sy nergism or potentiation cosers sorption may overshadow absorption in relatis e im- both ineieases in uso.d effects of toxic compounds portance.13ioconcentration factors for trace ele- and production oflesions not obsened by the action ofeither losie compotmd alone W7). S) nergisms and ments in terrestrial environments me generally less than unity with some exception' antagonisms are important in sy stems receising muhiple inputs of trace contaminants ti.e.. aquatic flintoulent Tinn forinations. Tiace elements and ecos3 stems and giound u ater L radionuclides introduced into the ensironment me subject to biochemical interactions ty pically with microorganisms in soils and sediments ahhough 1,cological Eff.ects there are some biochemical transformation of Ecological effeers of hazardous elements h.n e ie-hanir lous chemicah in higher organisms. Microoi- - ceived inci easing auention in recent y e.u s to. 48,49 h 2M Ensironmental llcalth Perspectises t k.-
t Table 4. Hinlogical concentration f..cton for scircini trace climents in a.pi.aic and terre trial ensironimnts." Iholope.il con;enitatian f.s toi As Cd lig I'b /n Agiutic Water I I i l 1 Planis 170 lHin 100() 200 lini invertebrates 330 2(m c 100.t u n too 10.000 , Fish 330 2ai !000 3U) Um Tei .est n.il
- Soil i I I t 1 Pl. inh 0 01 0.1 04 0 07 OA Ins ertebrates 0 Ol 17 0.02 N Marnmals 0 001 0Um 5 0 001 06 thrds 0 00I $0 0.00 t
. %tuce: Van liook I.hn 6 Ratio of conecniranon in organism to concer'ti.dion in subsnaic although most of this attention is focused on atmo- u ateis in w estein coal icgions a; pe.u s to be due to spheric teleases of particulates and associated trace soluble s.dt in mine spoils 6.4L M face co.d e xtrac-elements. Only recently hase the pioblems as- tion can also .dtect ; iomsd u.ner iesom ees. Gr ound sociated uith ground water contamination from ash waier aquircis are commoul> intercepted duiing dia. pond come to light Li. l.9) although theic has been oscibmden iemosal with sub% quent eff ects on considerable woil with acid mine drainaye and the ground walei ihm and quaht). Ha/ udous elements hazardous elements contained theiein t/> L Simi'.aly , may enter these distm bed aquifeis .md be mobili/ed coal-derived iadionuelide impacts base been and leached into surface w ateis addressed fiom the human he.dth point of sicw W. l'cological elleeb of coal cleaning and stor age m e 50). but insufficient data esist to es aluate the poten- .imilar in natme but lewei in magnitude to those tial impact in natmal ecos) stems. 'I he f ollow iag awoeiated u it h acid mine di.uuare h om co..! estiac-discussions are based prim.u il) on the u oi L of.iones lion Acid drainage oi innoit hem refuse piles may ct al. 49) with supplemental information added alfeet tenestiial and aquatic sy stems bs lowering where appropriate. plI. Soils soirou.-ding the refuse pdes may accumn-Coul Ca rruction, Cicensinc. unni S#m uge. Effect s late potenti.d!) toxic les cis of trace elements or of ha/aidous elements hom extraction on aquatic radionnehdes leached from the a fuse by acid water. ecosystems will iesult primarily nom acid mine Aquatic ens i:onment s adjacent to retuse piles ean be drai nage and erosion-induced siltation 6/). IIistoii- seseiely impa ted through sedimentation of fines cally, these effects base been sesere throughout anJ associated elements t/d 't he maior long-tea m eastein coal regions. The recently passed Smface impact to tenesn ial u stems w ill riobably be that t he Mining and iteclamation Act of 1977 shoulJ defi- dispos.d area can only be ietmned to limited land nitely improse this situation. Effects include de- uses (i.e.. w ildlife cos er. recreation L creas.eJ productisity and disersity . temporally and Coal pile runoff anJ Icachates contain coal Ones. spatially alteied .pecies composition, atteied ha/.u doos elements, and laimie acids and may be species composition. and, in heas ily polluted sys- aciJie. Teirestual ef fects are limited to land under tems, absence of life.17 actors which influence the and immediately adjacent to coal piles w hile aquatie effect , of acid mine drainage and associated hazard- ef fect s including eles ated element concentrations ous clements include degiee of eftluent dilution in anJ suspended solids u dl be moie widespread. In receising water.s. the presence of othei pollutants arid ensironments. oi during di) pells in other including sewage and industiial wastes, rhemical areas. fugitis e dusts Dom coal and refuse piles may states of metals in natmal w ateis, pH. temperatme. be suspended in the atmosphere and me subject to organic mattei content. and sy nergisms dh West- deposition on s egelation surfaces and inhalation by crn coals generally lack acid-formmg substances animals. (i.e.. pyrites t w hich. along w it h the alkaline nat m e of Coul Cmulmstion - Soli,I tru3ics. Combustion western soils and osetburden, suggests that acid of coal results in solid wastes including piccipitated mine drainage should be minimal in westein coal fly ash, bouom a h. slag. .md SO, sciubber sludges regions. Incicased salinity of surface and piound which require onsite disposal, and gaseous and par-December 1979 2.U
.mm ,
\
ticulite emissions that pass through emission control standards for these elements Resuhs liom Ihis study
. Qcvices and are released through stacks to the atmo- varied f rom simple to sample and c.ne must I e es-sphere. Currently, about 929 of the particulate ercised in generah/ing to new situations.
material produced in utility boilers is removed with To undes st.md the eff ects of coal-fired ste. w electrostatic piccipitators (54). Fl> ash. bottom ash. plant-dern ed elements on the aquatic sy stem. it is and slag all contain trace and radioactise elements. necewa 3 to quantify discharue of these elemeins. but the exact composition can vary wi fely depend. Calculations reported by Vaughan et id. MM .md ing on coal geology and boiler operating conditions. Ihoiak et .d. W indicate that the atmosphesie dep# . Elements tend to partition themsches into dif feient sition of elements deiis ed nom coa! sombustion ash components as has been discusJed emlier. should exert a minimal influence on the chemi,al
- Studies of migration of trace elements f rom ash pond composition of la!.es .m I ih eis. 'I he only elemems leichates through soih have produced buiable re- that conhl be uesated were lig. Co. Sn. and Mo.
su!!s depending on coal t3 pe. operating conditions. 'i his conchnion was reached despite the use of and ash disposal sites. One study suggests no migir maximum tr.mstei ones of fly m.h deposited on sod tion into ground water 135) whereas other inves- and its migiation to the drainage sticams in the , tigators (15) indicate that trace metah ate released to h)pothetical watershed. An import.mt additional ground water at generally low concentrations, with consiJeiation. howes ci i the impact of sL :and fl 3 attenuation occurring s cry close to the disposal site, ash disclunges into the aqueous ensitonment. The While this may tend to minimi/e ground water con- I asis for this concein is that approsimately 32 - lir tamination, it does not prevent uptake by plants tons of11) ash with eles ated les ch of tosic element-whose roots penetrate the new wates table created is annually dhchm ped into settling he. ins situated in by the presence of the ash pond. Water and solutes cio'e riosimity to many t oal-bred steam plants (57. will mose upwaid and laterally through the soil fiom llecause it is known that m.my elements ate leached the new water table when soil sulface evapor.ition hum the 11 3 ash r/5 L it k impm tant to deteimine the and plant tlansp[ralIon esCeed rainia!I infiltlation. Inobili/ation [solenti. l of losie metals f rom ll) ash Accumulated ha/ardous elements may be tosic to setti.ng basins to the n.nion's sm face and subsuif ace the vegetation, or they ma) simply be stored and w aters. then become toxic to animah which consume the To obtain a bettei understanding of thh mobili/a-vegetation. tion potential. Klein et al.158: calculated the quan-Aquatic ensironments ieceis e trace elements and tity of elements that wcre annually dischaiyed pitor radionuclides from ash disposal tinough ground to 1975 in slag and 11) ash to settling ponds and water (minimal) and direct runoff frem setthng ba. compaled these vahres with J.ita on natmal weath-sint Direct iunoff may contain dhsohed and sus- ering. Results of these somp.uisons indicate that pended materials u hiCh may of ma) no! be available esCep! fol III. w hiCh is almost esChhis JI) emitted as chemically to the biota. EPA guidelines call for ap- a sapor. the discharp into ash setthny beins ae-plication of IIAC'l (best asailable control technol- counts for more than IG of the elements mobili/ed ogy) to waste water effluents by 1983. Cunently, by weathesing Elemems such as As. Cd. Co. Cu. best practicable control technology is applied at Fe. Mo. Ni. Pb. Se. Se. U and Zn all exhibit mobili-varying leveh of success. At least 30 trace elements /ation lates that are larger than 10': of the weather-have been identined in measuiabie quantities in coal ing rate. w hile rates for Mo. Sc. and C are compara-ash and a number of these are tosie to aquatie or. b!c to naimal rates Appheation of thh anal) sis to ganisms at either the initial concentration or foi!ow- more reeem informatiso m. /W on coal combus-ing biological transformation and oi con.entration tion 16.X 10' t s r)and on Cd and lig concemrations (56). Concentrations of radium, thorium. and in coal (0.5 and 0.2 pg'g. iespecti el> ), in soil (0.2 uranium have been reported in fly ash (50). but Ihere and 0.03 pg g. respecih elyL and in water (0.1 and are insufficient data to awew the effects of these 0.07 g'I. s especth el)). indicates that these ele-radionuclidexor their daughter products on aquatie ments are currently mobilized in coal combustion at or terrestrial ecosystems from ash disposal sites. rates eqaivalent to their natural ueathering rates. These data are particularly impor. ant consideting Cadmium releases are predon inantly associated that about 92r; of the ash produced in coal combus with precipitated fly ch in settling ponds and land-tion is placed in settling ponds ard landfilh. There Glk w heieas the ma.iorit) of the llg eshts in the rlant are few data on the effects of trace elements on stack with only about 10"; poing into solid waste surface waters, but a study by Holland et al. (55) disposal sites. Due to these considerations. it would demonstrated concentrations of 11. lla. Cr. lig. and be appropriate to investigate the regional effects of Se in ash leachates exceeding federal surfiice water these fly ash derned elements that is, do the ele-236 Emironmental llealth Perspecti es t L.
~ _ - - . _ . _ _ _
menh effectisely iemain in the settling basins of are remosed by existing high etticiency piecipitators. they injected into the n.itionN w atern a) s. Until such Cannon and Suanson U,n) tound th.it concen-evidyations base been m.ide, it will be impossibje to teations of Iraec elements in soih (i.e. lip. As. Se. predict. in a quantitative m.mnet , w hethei coal-fu ed 'Ic. CJ. lie, and Phi diopped rapidly with distance steam plants will exert any modification on tiie from the Four Coineis limes I'lant. and concen- j chemical composition of the nationN waterway s. trations were kmei than those for average soils at
'ihe sery high pli encountered in ash settling ba- distances beyond 3 km. Vegetation within i km o!
sins may influence the behasior of trace elements if the pl.mt had not, within the time span of their study . this pilinfluence estends be)ond the confines of the accumula'ed signi!icant quantities of 1bese poten-ash settling basin (i.e.. into subsm face and surface tial!) toue tiace cientents. 'I he autho:s concluded wateis). 'l his high pil iesulh from the h idio!> sis of that uith the installation of more elYicient pie-adkali and alkaline earths auJ may often eseced i 1. In cipitato s. the atmospheric tiace element enussions most ash settling basins it appears that atnuwpheiic f om tFis pl.mt wou!J not be consideied harmful to ! CW diffusion into the water is not apid enough to the biota. llorton et al. t6/ i measmed the concen-lower the pfl. One would piedict that many metals trations of 29 trace e!ements in soils am! s egetation would piecipitate eithei as hy drosides or by co- withia apriosimately 11 km of a coal.fned i nmer precipitation (e.g., calcitun can bonate). If setIlin;: is pl ant in South C.nohna that had been ope ating since not complete, howeser, p.u ticulate matter contain- 1952. With the possible exception of Se tin soihland ing elevated les ch of metal eathonates, h> di oxides. Mn tin mound water), none of the traec elenu nts or sulfates cooli ieach the discharge waters. Upon releaseJ to the atmosphere f rom the plint connib-reaching limer pli dischaig: w atei , these p.u ticu- uted signiheantly to the conecutrations of the cle-lates might redissohe. thas producin; an incicase in ments in the immedi.de ens iionme nt. No em ichment asailable metah to aquatie phmis and oiganisms. or depletion of trace elements u..s detected ia oih in Alternatisel) high pil effluent watet s might pm the sicinity of Alien Steam PLmt near ' RmpFis, duee a beneticial eff ect. in teims of metal iemos al. 'lennewee. but the soi! was under the intluence of on tales and is ers with loa buf ferin : capacity. The agiieultural practices m2). 1;lein and Ruwell (6.71 change in pl!. honesci. might aho atfeet the p! ants howes ei. iep.u ted that sandy soils on the castein and oiganisms in the receising w aten. These impli- shoie of '. ale Michigan nea: a pow e t plant weie cations should be consideied befoie the impact of founJ to be enriched in Ae, Cd, Cs. Cr. Co. Fe. lig. coal.fiicd steam plants on the aquatie eces) stem can Ni. Ti. and Zn. Vegetation w as emiehed in Cd. Fe. be evaluated. Ni.and Xn. (lmtf ( ,mdmstion .ltmosplerric 1.tnissiour.. Coal Vaughan et al Al modeled the cumulatise im-combustion emiwions iciemed thr ough stacks to the patts of Mace element emiuions oves a 40-y ear atmosphere can be transported m er considerable period tium a h> pothetical NoAMWie) pner plant distances bec Fnsiionmental 'liansport scetion). in the westein United States bmning icpiesentative The ecological effect of ha/ardous elements a s- western coal. Their n;odel predicted that four trace sociated with these emissions u di sm) as a 1onetion elements. Cd. Mo. Co. and W. might accumulate iby of chemical and ph) sical form of the element. Ihe site at least a f..etor of tu op in growing plants. Ilowes er. of deposition. and the amoant of material deposited. they did not has e suflicient data to make istedictions As pointed out emlier, s olati!c elements in coal in- foi a numbei of nace elements sceh as Ga. Ce. Ra. clude As. lle. Cd. F. llg. Sc. Sb. lu . Cl. Cu. Ga. i. Ir. Te Th. T1. and V. In a similar analy sis on a j Mo. Pb. and Zn U6 M. 50). All ;we some degiee of h> pothetical 1000-MWie) pov.ei plant. Ih m ak et al (6i concluJed th.a es en when the atmovherie p.u-potential ha/md to man and might whersely impact the ensisonment at some thieshold concentration. ikulate emiwion late is at the maximmn a!! awed by NSPS (0. l lb'10' P,TU ). t he impacts to s egetation m e The amounts and forms of these elements that esit the stack of a coal-fired powei plant me Lu pely un- espected to be minimal. These authors point out Cd know n and probably s m y betw een plant s. depenJing anJ Se as having the greatest potential for adschely on the coal sonree and pollution conttof technology . affecting animals. The effect of electrostatic precipitators in ieducing A number of the nace elements (i.e. Fe Cl. H. l these emissions is likewise unclear. although some Mn. 7n. Co. Mo. Co Se.1. Cr. Sn. V. F. Si. and Nil l ! consider a high percentage of these elements shou!J are ewential at low concentrations foi either plant or be found in the paiticulaie of the piccipitators. animal hfe but are tosie at higher concentrations Natusch et al. U 7)iepoiled that As. Sb. Cd. Pb, Se. (Mi. Sqme of the nonessential nace elements such and Ti preferentially concentrated en par ticulates in as Cd and lig and essential Zn and Cu in matine the sespitable sange a large part of which is not ensironments, are toxic to sensitive species in con-l 2.17 1)cccmher 1979 W
, Table S. Polential tositity of trace elemer.ts in co.d.*
Tenestnal
- Element Plant Animal Aquatic Comment s As Iow low low 11 ihgh Medmm I ow" Know enough on tosien) for terie-toat eco > stem . m some instances may be bercticut Be McJmm lhph fliph Speci.dion unportant .
Ili Med.um Iou l e w CJ lhgh liigh thsh Co t hr.h Medm n ihph
- Cr thgh Medmm McJmm Cr'* sen toue - necJ to know speci.ition Cu lhph Medmm liiph Compt:sion in soi! reduces toxicity.
F lbgh High I ow Ilg McJium lhph lbgh linnehtd in plants. tosicity in fs od ( > cle Mn Iow Iow low Potenti.:1 for net ben,Iieu! etlects Mo Iow McJmm Iow t hyh emiehment m pt nt - Fenelleiat or adm se eMeet-Ni ihgh thph McJmm Ver) n.oN!c in p!.nns Pb low Medmm McJmm Sb McJmm thch* low
- Se McJmm lhph imw* Interasts with othet trase metals. e p., Ni. lig Sn Iow Iow low li tow lew' Methum*
11 ihgh thph M cJ m m* V lhph I ow " McJmm* W Methum Medmm* Iow" Ver) mobile m r.l.mt-7n tow McJunn Mt Jmm Poter.tvl tm net beneSeiat effect
*Somee lones et af. m Sl'nceit.on.
centrations only slightly above those ocemiing metals on important soil microbial piocesses and the natm ally (65). Iliotic dose-i esponse t elationships for rolc of soil microoiganisms in influencing the long-traec elements me at best pooily defined.and almost tenn availaNiity of trace metals to plants are largely nonesistent for those species comprising natural unknown. Inhibition of microbial processes may ecosy stems. 'I he effect of high concentrations of base impo: tant secondai) effects on the ecosytem. trace elements is ultimately a function of the to!er- l'orthermoie, microorganisms esist predominately ante of individual plants or animals. in the imniediate sicinity of the soil pmticle w here Jones et al. bN) has e classified the potential tos- traec metal concennations are highest. Mic r oor-ieity of various trace element s in coal into t ht ce main ganisms thus hase the potential for aheration of the categories- high. mediu m. and low - for ten esu ial form of the metal throuch interaction with normal and aquatic life Crable 5). The authors consider this metabolites or by direct cons en. ion processes. infonnation to be a "best estimate' based on their Trace elements have long been know n to affect collectise esperience. Isnowledge. and intuition. It plants. In the case of the essential trace nutrients should be pointed out that the impact on the oserall (Fe Cl. IL Mn, /n. Cu. and Mo). a broad range of soil-water-plant sy stem is also a function of the possible responses exists,ianging from deliciency to chemical state of the tiace element u hich impacted toxicity. In the case of the nonessential trace ele-the system and its interaction with the local ensi- ments. only the no-effect (tolerant) and tosie por-
'ronment. This interaction will determine the trace tions of the dose-response cune are espressed I element availabilit3 and, therefoie. the fraction of Under natural conditions, there are examples of the total trace element concentration that can atteet plants growing under both delicient and tosie condi-grow t h. tions. Whether the trace element emissions from Soils represent the piincipal repository of nace coal-fired power plants can enhance or inhibit plant contaminants from fossil-fuel combustion over growth depends on w het her thesc elements w ill has e geologie time. Theiefoie, the soil is the principal a signilleant effect on naturally occurring concen-medium for long-term esposure of coal efiluents to trations. Thete is no reason to espect acute effects tenestrial plants and animals. The effects of trace on plants from atmosphesic trace element emissions ni Ensironmental IIcalth Perspectises i .
( h. l
fro'm coal combustion sy*tems and little season to lation. The major health effects of conecrn relaris e to expect acute effects to aquatic systems. T he poten- coal combustion p:oducts include phy siological in tihl*for chronic toxicity is relatively low except for ritation. direct toxicit y. carcinogenesis. and phy sical particulaily toxic elements such as F (66) or in local syneigisms. The fol!ov.mg discuwions center pri-areas already enriched with a particular element. marily around atmospherie eminions from coal Some trace elements combine the properties of combustion uith n,uch lew emphasis on solid w etes high toxicity. a potential for bioaccumulation in food (ash and slag). ~1his is due to a viitmd absence of webs, and per istence in the enviiooment. Many of information about the contribution of coal-ash-these substances are toxie in sen itive animal species deiis ed ha/mdous elements to the ambient lesch in at concentrations that aie only slightly above natur- man's ensironment or their subsequent contamma-
. ally occurring lesels tM. 65). liigher tiophic lesels. tion of food or drinting water.
as a result of bioaccumulation, may be affseted at Elcetro,tatic piccipitators aie 1) pically more citi-
" ambient" concentrations that would not be ex- cient for lar ger diamelei p.u tieles in flue cas. P.u -
pected to affect plants. Even with these resena- ticulates existing the rower pl.mt siacL aie generally tions,it is probable that trace elements in emiwions in the respirable si/e class. 'l he toxic eff e ct pioduced hm e littic or no discei nible effect on aninnd s. l:lfec ts by respirable paitieles depends on the chemical would seem possible only if the emiwinns that aie species they contain. Smatici p.u ticles tend to be currently accepted are in error by an order of mag- more tosic than lar,ter ones dae to si/c and selectis e nitude. Sublethal, chionie, or sy nergistic effects of adsorption of heavy metals U7L Submieron fly ash trace contaminants that may be of significance in particles seriesent a double llueat to human he.dth natural tenestrial animal populations base seceised (6); they teach the pulmonaiy tecion and remain there for estended tim; petiods. and they can dchs er little attention (6L liowever because some of the trace elements have been icpoiled ta adscisel) af- a given concentration oiha/aidous element to a s cry feet soil / litter communities (67) and powibly altet localized aiea theieby magni!>ing the cilect. primary productivity (67. 6N). and, in turn, secon- Conl lh f rarthm. Clenning. uiol Ntor age. Iluman dary productivity. potential long-teim impacts on healib elrects of ha/aidous e:cments awociated with ecosystems could occur if trate elements emitted coal estraction, cleaning and stomre indude inha-from coal combustion persist or accumulate in lation of coal dusts u hich may conuibute to de-ecosystems to toxic lesels. selopment of black long (coal workeri pneumo-coniosis) (72). and ingestion of tuce elements and radionuclides riom diinking water con:aminat. d by IIcalth Effects acid mine drainare. Acid mine drain.qe impat.s are Any awewment el powib!c health effects from coal. combustion contaminants requises, inter alia, genei.d!y more widespicad, and in communities without alternate souices of water, or undes ch, ped definition and quantitation of source and tianspoit water sources, these impact can rep e sent a ses cre terms. Given information on "what" and "how problem (6 L Runolf from co d piles anJ co.d-cleaning much" can be breathed and ingested, an evaluation wastes contiibute to watei qua!ity degradation but of the human exposuie and intale c'timations can on a much smaller scale than acid nunc drainage. proceed utili/ing background. dict ary. oecupational, Atmospheiie loading of coal paiticulates arises experimental, and ensiionmental information, pro-vided these data exist. A number of ieports hase through resuspension of coal fines nom storage piles and from accidental ignition of both coal piles and been published on health aspect < of trace contami-coal-eleaning waste piles. nants from coalcombustion U.4.6.JN 69-7/ h These Coal Cornhedm. The radiofodcal impact of reports have been utilized in deseloping the foliaw-coal.lired powei plants appeais to be adequately ing discussion. evaluated for atmospheiie teleases U. 73 L Melhide Physiological and pathological responses of a population to radionuclides and trace elements from et al. (4) estimated annual ielease rates for a 1000-coal will ieflect the individual's ability to respond MW(e) power plant bmning coal at a rate of ap-an I the dur'ation of exposure. Short term adserse proximately 100 tons <hr. containing i ppm of uranium and 2 ppm of thorium (both awomed to be in effects will be manifest in those subgroups more secular equilibiium). and iele.ning lG ofits ily ash to sensitive to the pollutant (i.e.. children. aged. infirm) as an increased incidence of tespiutoiy diseases, the atmospheie tthe as erage ash rdease for 1972 was aggravation of preexisting chronic cardiopulmana y F7 h Under these conditions. ' ! h. 2Th. "'Ra. an.12"Pb cach contribute approximately 5 x 10 ' diseases,and premature death. Chronic exposure on the other hand may iesult in an incicased meidence Ci'y r; 2" U. '" U. ""Th. 2 "Th. "'t. 2 '"Pb. 2 '" Po. 2"'Hi cach contribute appioximately 8 > 10-
- Ci'yr; of respiratory dise[nes and cancer in the total popu-239 Ikcember 1979 t
jind ""Rn anJ *Rn together account for a;,prosi- and :"Ra combined actisity to 5 rC I.. gross n ae-mately 1.2 Ci'yr. These release rates u eie then tisity to 15 pCi I.. and any comNn ition of j50 v. Ini-applied io a population of- 3.5 million perops hving concent r ation s pioduce a dose equis. dent of :
'sithin a 90-Lm radius of the power plaro 'I he dose mrem'p to the whoje bod3 . Whethei any of th.s cafeulitions took into account doses f om immer- regulations might be esceeded in the inenedi.:te en-sion, contaminated pionnd surface, inhalation. anJ siions o! a coal-fued pow er plant is uncaiain. 'I hk ingestion, wherein all doses from food and water unce:taimy is due to a lack of info:mation conecon weie derived from within the 90-km radius of the ing the release of radionnehdes hom so!id w.m i plant (74. 75 h disposal si'es u hieh acceive in iddition to Ivuom . .h l The following population dose commitments w et e and s!ap. the e i o! the 03 ash fmm comhmi. n IL.i determined: 10 to 25 man-rem'y w hole body dme is remos ed from flue pas by elect:estatic ric- , and approxinnitely 10010 240 m.m-s em ') r bone d.ne. cipitators The corresponding asetage indisidual dose com- Monou et al. (6W have maJe cstimates of chemi-mitments were 0.003 to 0.007 nuem'> r and 0.03 :o cal toxici:, of nomaJioactis e trace eleo.cnts u ang 0.07 mrent'> r. r espectis ci) . w heie t he r anges pei tain maxim.d espeett d ai;boine les els I m ahne the to emission pat!crns fmm different stack heights ground associated u ith o to l5m m diamete p.u t is ie s (300-50 m) 'lhe nritimum indisidual dose commit- witlun a 2tLLm :alies of a 140VJ Wic i coal-th ed ment at 503 m fiom the stack was 1.9 miem'3: atal pner phmt with a plume hught of 90 m Fee TaNe l was indepenJent of stack height The dose emomit- 23 of Ynghan et alim]. 'I he pieJict J air conec: I ment is based largely on "Ra inrestion and coen- trations icsulung from theii calculatiom :mJ pa .
tiall 3doubles if the U content of the co.d is dooHed. sumaN) goed to a lactor el 3. were compared ta lf bituminous coals are us.ed. the U concentiation is ambient ai. concennations, atmospbeti: stanJ.o is often as high as 20 paits pcr mil! ion so this tuuld foi population espanes ic!H en.e iaan dat., loi ineicase both the reica.e and dose commitment fic- inh:dation intakt s. and occupation d 'I hie sho'd ures by an order of magnitude, assumine a!! other I.imit Va t ues ff! VL IQ this appmach. gene:alis factors remain constant. accepted. safe range of atmosphaic co:a entratie; . Orieles ance me the data of Martin et al. (3m. ".ho weie establi .hed. measuicd dow nwind les els of U fmm a l40MMel Results of their analy sis screated ses cial coaI4 red power plant and found ICi in' concen- uneenaintis t llu ce elemer.t s l.b fillt Cr t \ l trations. imp!)ing daily intakes by Mmans a vi U be idoh. anJ Ni c.e baa)ll m e e nera!!3 accepted as of the ordei of a few femtocuriet Ambient aii !cs els h,n ing potential caic;neeni. impoum c. m ths of approximately 400 aCi m' of U Lase be o re- pencrat are:o..ch u "J in this taMiation ma , , e in-pos ted, inJic.. ting a concentration of about 2 pCi g appropr iate l 'o: Ni. As. .oul Ci . a criticai questhin for atmospheric dust or appmsimately 2 ppa' by concerns :he mmience and nw;mitu& of the car-weight, which is not yteatly different from the U cinogenie tonas of these eltman:s namely As(IllL concentration in Oy ash from an as ciage antia acitic Cr (VI in oh, and niel el cm!vn)L oxide s uifid e. coal an:1 c.obonAc in co.d combm Fon c!Duents On the To compare the magnhnde of the iadiation dose b. mis of ths currently asailaNs infoi m..:.on. Cr ( V l i from coal combustion emissions to that fmm natural p:obaN 3occurs:the na:me of the n ckel somp mnJs background 66h it is useful to use dose-equivalent is unknae n. but !L highh s oLtile caikny' is as nites. On this basis NCRP CM indicates that the suicdl 3 a!went from 03 ash. l'or As. the espectation dose equivalent rate for "Ra from naturW back- is poad ior both th. !!! .mJ V ovdawn oaks. bm no gromid is about 7 miem!): for bone and less than ! qu.onitalis e hudini s exist - only the i.6.. tion t h: t mrent'> r for the w hole body. The da e equiva'ent H3 ash kasiutes watain both fo:ms. rate for the whole body from all natural radiation The reponed temiogenie pmpeities of certain Cd. sources is 80 2 40 mrem'yr; the cor responding coal Se and Up compeands, the mutagenic rotential of combustion figure would be 7 x lo " mrem'yr. Radi- certain pb and Ilg compounds and the emcinogenic ation protection limits for w hole bod 3 irradiation of propeities of He anJ Se C7) aie, in pencral. only individuals within a population are set at 500 demonstraNe at high dose . or unJer uncommon cii-mrem!yr with an aserage genetic dose hmited to 170 cumstaneet Consequently they u.n rant no species mrem!yr (5 tem in 30 3 earsh A proposed guideline concern at this time. wou!J limit the whole body Jose to members oi the infonoation on the met.dlo oiganic forms of Up is critical population to 5 miem'yr from atmosphesic lacking. as it i . for other elements but thcie is little releases. like!ihood that they ocem in the emissions fmm coal The new EPA Primary Drinking Water Regulation combustion as ociated with p.u ticulate nunct. Es en for Radioactivity (40 CFR 141,1975)iimits the ' "Ra if alkyl meteury weie the singular form of lig emii-240 Emironmental !!calth Perspectises
ted,its acceptable aii concentration inJicate that it limits for heas y metals by adahs. the M;n tet Itastet probably would be unimportant toxicologically . Sun ey estimates for total lig. Pb. and Cd intake me I}egause of the uncertainties in the awumptions about 7.14. and 759. re .pectisely. of the WilO: and modeh used, the variability in the trace element FAO hmits. Cadmium has an unusually wide dis-composition of coal and in the naturally occurring tribution in foodstuffs so that soil lesch will be ic-levels at specific power phmt *ites. lie and 12 may tketed genet.dly in wates, truit. seget..bles, meats. constitute potential health problems in she immedi- and dah y piodnets. In addition.curient moNi/ation ate entitonment of cmd power pLints. Otherwise, of Cd and lip thiough co.d combustion is ne;u the > the n ajmity of the elemental concentrations calen- natmal weatherine rates for these elemenS muf can lated by Mot row et al. (6W appear to be one or more be espected to in: case with increased co.d u e. orders of magnitude below the "acceptab!e air con- Tiace element . and radionuclides do not esist in isolation m the enciiorunent: they .ne teleased in cent rations.' llerry and Wallace C) samp!ed the plants and soil awociation with majoi coal combustion contami-around a coal-fired electiic plant at Moapa. Nevada. nants ii.e.. SO,. N( L . p.u tico!. des hmd may ur. dei go buming appiosimately 100 tons of high ash coal per chemical anJ ph> sical transfm mations folk m ing hour, and concluded that forage and mill fiom the discharge f rom famer plant stacks. It is probably area could become seiiously contaminated if high that such econd.u) chemical ;md phy sical interac-arsenic coals P 503 ppm) were u.ed for several tions of the major and tracc emissions.together with decades. Fsccwise Cd contamination of forage and their phy siologie int eiaetions w it h tiene s of e sposed daily products aho ceuhl be ensisioned and some penons. may seriesent a most inipo: tant a n et of concern was expreswd regmding F contamination. the toxicology auociated with combustion of coal. In other studies of coal powei plants, some enrich- 'lhe two folkming esmoples ilkstiate the potential ment of trace elemems (e.g. !lg. Sc. and Pb)in soil impoilance of such inten etions and plant hfe has been icported Mo. 6/ h in the Four Ga .cous pa'let.mts, inch;d:ng M t. NO,. anJ 0, Corne.s study M. pb was found enriched in soih. that increase the rate o! cell prohfeiation of the but no toxic trace inetah weie found in excew of tische.d-bronchi.d epithelium aie highly suspect as aserage soil values at a khm di t.mse trom the plant . impm t.mt promoters or cofactm s in the patho-Comparisons of dat.. f rom Vaughan et al. (JM. gene is oflung ianeet. In a son c) ef smelter wm k-Pinleilon el al. (7N :md llottor, et al m2) indicate ers esposed to As.Oi the picatest eseew of lung that the .oi! bui!J up ortrace metalcont:mdnants will cancer was found in instance w here there w eie ac-be slow, and allowir order-of-magnitude pet turba- cempanying exposm es to high to moder ate les ek of lions in depasitions and soi! conditions, one would SO2 , not espect excewive bioacc umulation to ocem in OxMation of SO: to Mb doe not alua)s ocem at plants unless the bioavailabihty of esortuous frac- peretf:ible sates in the atmo .pheir. Such osidation tions is order s of n.agnitude gicater than that of appem to depend on the simultaneous piesence of typical soih There is evidet.ee that exogenous ele- other factors -- powib!3 h3 dioembons from auto-ments are more watei sohiHe. imp!ying gieater mothe exhaust or liaee metah which may act bioavailability on the one hand end shoner soil ie. cataly tically . Adserse health effects in sensitis e tention 1;n.es on the other. A potentially more im. memben of the population nov appear to bc b tier portant source of watei and biotic contamination related to concentrations of sulfate acrosch than to relates to slag and fly ash disposah Pom!ing, ground SO; Acidie ulfate acio'ois base. thcotetical!> the burial and other dhrosal techni.;ue will lead to potential to combine with heas y metal cations with cem.equen.es of greath difterem magn:tude. and as unknown consequences Thus a arie:> of 9 neigh-pointed ont eailier. very fev data me ava;!aNe in this tie actions fiom polluvnt mistmes can be antici-area. Thus, one of the greatest uncertainties in this pated w hieh w ill cause and or exacerbate palmonary health effects evaluation relates to the potential in- dysfunction and chionic cardiopulmonary discases.
- uke of heavy metal contaminants from water and food esposed to ash disposal eftluents.
The firs.1 Food and Drug Administration Market COGCluGIOnG llasket Sunev (7W indicated that for some metah
~ C,urrent Situal.mn (e.g. Cd) the dictary intale fevels are aheady ap-pioaching toleiable limits. The initial soney esti- Ultimate!, . tiacc elements fiom coal retm n to the mated the daily intake of the selected metals in soil or sediment system . w hence they originally g/ day for a U.S. adolescent male as follows: As. came. The traec elements and radionuelides m coal
- 10. l; Cd. 51.2: lig. 2.9: Pb 60.4: and Se 149. On the naturally occur in soils. Consequently an-basis of the provisional WilO/1 AO tolerated intake thropogenic conuibutions of these clemenh in soih 2 11 December 1979 t
h .,
are hard to distinguish from the laige natural vmia- to I.mJ6!!v Some co.d ash is used for commeicial
' bility at distances of more than a few hilamerei .fr om pmpo es te p., cement additivet I cachate infdtra-a paiticuhir power phmt The chemical f orms of trace tion intu ground uate s immediatety behm ;md adj+
contamin.mts me important determinants of tnme cent to ash drpo .al sites is not w cil tudied. Ibla are port and effects. >ct most studies hase foensed on laching on themical species present; chemie.d torm total elemental amounts os concentrations poseins mobility, availabilit > . and Iosicit) . Ihtsic concepts and modeh esist to desenbe the 1.ihewise. these are Icw d.ita m adaHe on the con-various pathways of emitomaental and biologieal tiiNtion of settling psvid outfalls to the hanudous . transport. 'i he rates of lianspoit. how esyr. are not element bmden of surface waters. Diiect inrot of
' well know n, not are input data on climatology . dissok eJ and suspended trace elements and hydro!ogy, and environmental chemisu > avail d'!c radionuclides into the e water s can E.c.e a diicet formost sites. it is impart.mt to obtain impros cJ data efTect on watei quality and aquatie ide depenJing on on tninspost and transformation rates.paitiendail in u.ote watei treatment. An undeist:mdine of the televant chemical and biotopical aica These data problem. associated with coal w:nte leachate and will be ewentiat in deter mining organism e srosm e to runoff cos,t.hing ha/mdeus elements is ewenti.d coabderised ha/a:dous elements when we con ider that curienilv 92'i of the ash in Cont Ltructiem. CIre,nint,. omI Ntanaw. Acid coal is inipped by preci, itators and di p ned of on mine diainage paiticulate leading ofIL atn,ospheie the phnit site. l'ielimm.u) estinuies o! tu:ce element from coal and refuse piles. anJ groural water con- relercs from coal t ombustion to ash disposal sites f amination continue to be major problems awoeiated indicate thit 12 tiace elemenh. ineludiny &, . Cd .
with mining. proces .ing, and storing coal. ~l he'e !!r Ni, Pb. . :.d l' aie icleased at rate th it :ne problems aie espected to impiose as the new Sur- '. Irl of natmal weathedng taie . meaning that face Minmg and Reclamation Act is imriemented. coal esuaetion end use is sho:t-circuiting the Acid mine drainap fiom both suiface and deep geochemical t > cit toi trace elemenh. mines is piewdent in the liastein and h.tnim Coal root coral,,o rion .1,,a,3ptic,ir Cminio n s. f liosinees of the linited St..tes whi!c alk:Jine mint livaluatian of tk ecological eflech ot uace clemenh drainage pre cnts pioblew in the m stan pios- and radionulides fron. coal wmbastion icquires inces. Abandoned inines repic ent the nnjar sous e info:stion abaut the hinds and amoanh emitted of acid mine drainage in the eastein Uni'ed States. deiing the coad neion p;ocem lhen trans; oit anJ Particulate loading of the atmmpF ;c f rom the derodtion in the em i orment.an !! heir aw R iht), estiaction.piocewing end of the co .i f nel ey e!c ce- accumut.; tion, and tositit) in ceoq stems. it .eJ on cin:s from snspension of coal fines a".d coal mh da sh an incomplete data set conce,ning the ittms de-from stable and burning coal end waste ash pk. scribed abos e. it appe.o that atmosphclie icteres ElleCh fiof n these dusts aPd coal titles V dl plesnina of liaCe and radioaCllie e!cmenh ale not hhel) to bly be conGned to the immedi..te surroundingt Coal base snineant, detectab:c effects on the chemical and refuse piles also serve as sources of ha/ardous com;wition et soil. vepciation. and w at er in t he neai elements in runoff and teachates w hich may ente: the term. Thee aic howes cr. ces tain : 'eas of the coun-soil system and in some cases contamin ,te giounJ tryw here detectsNe enecis nny occur (e.g. mens of water. Gencially, pround w ate; contamination Gom s. ndy soils anJ low fertility on aieas with si/able these sources is minimal becau.e of utienuation in a,nbient concentrations of trace contaminantst in soils. Effects of treee elements and iaJionuchde the e area several trace e!cmenh Nar wahlung. from ceal estraction, ele. ming. and storm me t en 'l rese inchide: l'. Cd. Ni. TI Co. V. 7n Co. Mo. W. erally subtle when compmed to the acid natute of and lig in terrestrial ecoq stemst and As. Cd. Co. drainage and runoff. Acute elTech will be scry dif- lig. Cu. Pb. and Sn in aquatic ensironments
.ficult to soit out. Chronie effech nuy occur as a Fluoride may w airant special attentioa because ofits function of biological eoneentiation and transfor ma- icactivity and high toxicity in tenestrial systems.
tions that may render elements more ha/atdous be- In dealing with soil.pl.mt ielationships. emphasis cause of amount, form, or location of accumulation. should be placed on ha/aidons elemenh that enter C<ml ComImstion - SoII,I tt aste.s. SoliJ wastes soil in the highest concentration (e.g.. lir. W. Cd. from coal combastion consist of slag, bottom ash, and Vn me soluble and thus more as ailable to plants precipitated Gy ash, and scrubbei sludge (if SQ (e.g.. Cu. lig, and Nin are mobile in the plant and scrubbers are used). These wastes nie typically transported to edible tiwues (e.g.. Ni. TI. and Wu stored wet in setthng ponJs or are dewatered and and are most toxic to riant and'or animals and man depenited in landGils Settling ponds may also be (e.g.. Cd. Ni, F, Ti V. U. and ligt I mihermore, mined following tiying with the dry ash then moved ircognition should be gisen to the potential beneG-242 Emironmental llealth Perspectises t t . .
s cial effects of Mo. Zn Cu. and (
- in tenestrial Tmec element and radionuclide effect s on health and systems and to the stimulaimg effec' ,,.articul.u l) in the ensiionment must be loohed at hom the point of respect to cutrophication of some of the traec ele- siew of the impact of the NiiP on the co.d fuel cycle ments in aquatie s> stems. The major pollut.mts in and the nelatis e contribution cf ha/aidous c!cments stack emiwions f rom etul-fined pmser pl.mts PsOf fiom coal contrasted with other seinees o: tegional No;, and their tr.msformation piodnets) aie of im- and local ensiionmental burdens.
poilance in terms of their interactions h> nergisins' Coal Ca tturtion. CIco,,ing. nr..I .stor,o:v. The antagonisms 1 with trace elements an.! r.alionneliJe NEP wi:1 h.n e a dheet impact on co.d estraction. as well as in teams of their direct etYeets. cleaning. and stime s 1)oubbng and triphny coal There is an inadegnate dat;i base for determining ptodiretion iii the next 25 ye.as uill iesult in in-1he heahh effects. piesent or potential. of the tiace cicases in acid trine drainage. The amount of the elements from coal combustion of con s ei sion increase will depend upon enloiecment of curient plants. There is, howeser. hiehly suprestise esi. icpulations and tlwe piomulgated under the Smface denee that some contamin.mts le.g.. Ni, Cd.Cr WI). Mining and lh etamation Act. With IIACT being As (111), and il may constitute potential be.dth appUed, westein coal s are leu attractise in the e.rt
- proNems from either direct tosicity or earcino- Imuse of high ti.mspoitation cost and hm lirU genesis. Meremy. Pb. and Cd shou!d be followed content es en thouyh they are loc sulha coals. East-closely because current intahe lesels are neat the ein etut thigh sultm ) wi!! be used in plams equipped toleiaNe intake limits. Iblioactive emiwions fiom with SO, sciul beis. This leads to a consideraNe coal combustion currently contiibute tr < to l ath- incicase in eastein coal minine with attendant acid ground radiation dose from all natural somees. mine draina . pioNems. !!a/anhus elements in flowever. they could become a heahh tonsiJeiation mine diainage may icaeh peuma and s.n fact water s if bituminousco.d4 with hich U content n 5 ppmhut with subseinient ir.: ntion by m m and ether ani o.ds.
utilized. Important syncipistic effects between cer- Westein co.d production will .dso incie.ne with at-tain co.d-derived metals an.1 other inorganic and terd.mt aP aline mine thainage pioNems. Coal organic substances in the envit onment can be antici- cleanmp, ty pi ally restricted to the east and cential pated, and these may prove impollant in heahh el- tes:ons, wip in rease with leach..!c and t unof f con-feet awewments, in the domain of food and watei taining haudou elements raos ing into gionnd intake, particuhuly as affected by ash ettiini r.mds u ster. Stor . e rites wiH be more uide pread with and landfills, no toxicologica! asseument of 1: ace mot e orp.u t. mines foi ionott to icach surface w ater s elements or wJionnelides is leasiNe at this tone. and peilup. pound waters. AJhtional mining and lioneser this should be tep.uded as a potenu d!) cleamng of etul w di lead to incicased spods and significant health proNem area w hich jusiifies cleaning w.rtes Ceut Ones hom these wastes along monitoring of these sues. with dusts h um t tul stor ag .o eas wil! sen e as fugi-tise somees of p..rtientate s cortaining ha/.odons Natiotial Eftergy Plati ImplicaGo3% element s to th. at m+pher e. Ileperahng on local en-Implementation of the N Ep will tesult in a dou- si:enmeual conditians. these p.a tico ates ina) con-Ning of eoal estraction and use by IT s and a ttiphng stitute a beahh ha wl. Rom the point of view of by 2NO. Indust rial boileis em ienti) using gas and oil tuce elements anJ udionuclhks. the greatest im-will switch to coal, and electiie utilities ui!! adJ pact of ina cased coal mining. ek. ming, and storage consideraNy to their geneiating capacity thmugh is the adJ. tion.d landen of these c'ements to aii . soil, coal combustion. Gasification may become a signifi- and u ar u m em iiome.ents th:.t a ahead > stressed cant coal consumer before 2000. The NEP calls for by amNent lesels of these and othe i pol:utants The application of the flest AvailaNe Contro!'lechnol- degree of sy neigisms ocem ring among these con-ogy (ll ACT) to new boileis. It is awumed that this tamin.mts is not w ell hnow n. Potential ha/ aids from a'pplication will result in a 19 release of ash from elements teleased in mining aaJ cleaning will be combustion to the atmospher e. Assuming U.S. coals testricted to particular iegions, wheicas potential averagc 5'; ash. ll ACT application in 19S5 w ill result ha/ards from coal storage may exist nationwide. in 0.6 million tons of fly ash released to the atmo- Co,J Condm, time -Solid U mtc. Application of sphere and 59.4 miUion tons of sotid w.istes t e(p: iring il ACT coupleJ wjth a proposed t.ipling of coal utili-disposal in settling ponds or landtills. Cons ei sion of 7ation by 200d wiu iesuh annaally in some 95 million industrial boilets to coal will sene to disperse tons of ash requiring disposal. Scrubber sludges for [ I sources of particulates to aii and will require SO, control will aJd to this soliJ waste disposal l additional ash disposal aicas. Regional air and water pmNem. Unlew new engineciing designs are de-4 quality may change under this dispeised concept. teloped for settling ponds and landhlb.. du cet iunoff I ecember 1979 243
to soiface waters and leachate intrusion into gtound waref will certainly occur on a larcer seale thin at switching to coah containine higher concennations present. Trace elements and radionuclides enteiing of these elements or their pments. Hecause of the surface waters willadd to e sisting burdens and result ubiquitous naime of Cd and lly n.nd peilups Pbhmd in degradation of water quality and potential toxic the fact thA their daily mtake aheady appuuches effects on aquatic species. Contamination of drink- tolerable lesels these elements m.i> become seal ing water supplies presents a real human ha/ aid for heahh ha/mds from coal utilization. elements yuch ayC 1 and lig which are aheady near - tolerable mtale hm$ its and causes an economic bui- RecommendcNns den in the form of aJumced water treatment plants Although prese"t studies indicate minimal grounJ T he abi'ity to awew the be.d:h and ens ironmental impacts of trace elements and iadionne.lides desis ed water contamination from coal ash lanJ611s because of attenuation in soils the national impact of an fiom emient and fumre coal utili/arion deren is on a additional 60 million ton . of ash by 2mKI will add basic imdeistanding of cat the chemistry and phy sies significanti) to the trace element and radionuclide of elements in co.d and ash in the natmal craison-ment (mininct in settliny ponds and landh!!s Isolid borden in soih and in some cases exceed their baf-fesing capacities, which will lead to aceclerated wastes). and in fly ash tatmospheiic emissionst thi ground water contamination. Fm ther. this additional the physie;d and biological trans;wl through aii. co.d-ash waste wi!! be much more widely dotiibuted soil, water. and oipmisias ic) the interactions aclow the Country as a residt of indusMial bollets amony en. ss;ons and :onHent poMo! ants. w..tes and switching to coaladded to the new coal-fired boileis other natnial cnsironntental chJHNs:ds; and ld) the put into ser vice. Mobili/ation of eleiaents thiough ecolo,ae.d and human heahh effects of coal deiis ed emiwions both singly and in the p:e ence of other coal combustion ahead) exceeds 1(G of natond weathering for seseral trace totie elements and can ensitonmental sucots. ()nec !!s information is only be es pected to incicase w it h incr easeJ coal use. available. it uill be pooiNe to detconine ie.ronable Coed Comi,u rina .tsmor;dweir Emiai era. P.u- trace and saJmactise cleraent rele.ne rates as lune- , ticulaie emioions from coal emnbustion and com er-tions of both ensiiomnental tolerance and costs av sion by 20.10 are estimated to seach one mi!! ion tous sociated with effinent contiois. lintil ibi infmma-annually. 'l hese emissions will be predaminantly in tion is on hand. certein actis ities should be pursued. the respitable range and will coutubute both tiaee (1) Characteri/ation of concentrations and element and radionnelide insohs te plants and ani. ph3 sicochenceal states of specific nace elements anj iadionnelides in both atmospbcii emi sivas mJ mals. Volatile forms of ha/ardous elements will ac aqueous eflinent s fiom coal combustion and com er-company stack gas emissions it is difiicuh to awcw sion should be peitormei 'I hese n onitoiing ae-the direct health and ensironmental elfeets of coal- tisities should be canied out even : hough ha/aidaus combustion. derived ha/ardous elements Their ac- elements are not considered esiteria pol!utants and celerated release from increased coal use wi!I add, perhaps signiGeantly. to the ambient atmospheiic theh telease rates me not regufated. Special a' ten-loading flom all other sources. Sy nergistic actions tion should be gn en to characterization of elemen:s with coal-derised and other organic and inoiganic inchiding As. Cd. Cu. lig. Ni. Ph. and Zn. in chemicals in the atmosphere will become moie im- leach,tes from ash disposal systems to the o sidation pottant in deteimining mganism response to in- states and chemie.d foims of Ni. -\s and Cr. to the cicased ambient les els. ~1 hus, a major detei minant io nature and ocemience of organameta!He com-potential coa!-der ived ha/ardous element eueets will pounds, anJ to the les els of Cd. I!e. and Ouoiides in be the ambient air quality of the region (i.e.. indus. tenestrial ensiiomnents within 40 km of coabfired power phmts. trial vs. rurah receising the additional burden. The general pubbe heahh of the ti.S. population will be a (2) An awewment of the contiibution of trace and factor in deter mining ha/aidous clement effects from radioactis e element s fr om t he co.d fuel cy cle relatis e the point of s iew ofin itants co-factors and physical to all other somees s,hould be made to put coal-s) nergists derised ha/mdous elements in proper reispectise, 11 is unliiely that atmospheric emissions of O)ltap;d. s eliable methoJ . should be des cloped to ha/ardous ch inents will have a measurable effectsicinity aseestain on the mosement of water and solutes in the of coal a h disposal sites. concentraliens in soil, secetation, and water. In local situations, how es er. ces tain trace elements ( F1 (4) Watershed-scale maw now budgets for trace and radionuclides (Rnl may reach levels causing elements from coal mining and procewing opera-concern because of both incicasing co.d use and tions are needed and shonii be based on both mea-surement and model simulations. ' 244 Emironmental llcalth Perspectists t k
6 Nt kl G +2'? t'.s N ncie - Rc; niaioi s ( o anu on. (5) M,ot,lels shotijd be developed that accurately " " *'"> i o n D C C 22t rr track anti predict atmosphetic transport and diffu ' ' Sw.mson. V. l .. McJhn. J 11. It.as t . l . li . ( n'cc m. S I ston of co.il-derl\cd emissions oser tilpged tellain. M ood. ( e il . W omlielt. S IL and I!JJem.md. R I ( of ditring \ cry st;nble conditions. and o\et long dis. imtn,n. on.,u s s ,,na es j,m a ,gn ,q eo, s .m,.res m pc t. s Geom; md w .es open tw Rerm t > As. t' s hcr o tment lances. Special emphasis should be at,phed to dr3 of the In'co"' Geoh'e J Sonet in deposition on natural surfaces. * * ' "c"" " i P ' " " " 3 ""J ' "b'"' 8 H N P* (6) Infoimation about chemical and physical be- . trashenim at An ae.w'so'l
. l ul Ash loi l t aic E! ra nts t t N.
havior of specib.e lu/ardous elements in sotis and Pouu of uca Rt x e su 9 u,s. E M iian,11 )..mJ V ora.(. M.f- P.ccid u t Water is needed. llita requiicments include sates.of h"' soltibili/.ttion ;tthi tillnsfoi nLitton, ph,ise disti-ibu- h'utann in i o-if I oci- t s 1 ns honmen J tion tions, chemical form. and availabiht) . 'I he iate and . . W P" 2 "'"" '"""" 2 3 " k '"" "'" * ' " 5 "
- Npt mytgid \ a . 19M estent of sollibi!i/ation olt ;t lepion:ll l%nts is ;tlso M ( dJem N P . M K . l! . ; M f m 's s j l . H N u m-nCCdCd-it) in fly .nh tium a un ' hur rn. pmi l f n!. I r. In La Nmi soc ta o i Pel, (7) The tote of the coal. derived ha/anlous ele- ll.I M R. D heJun h e ':nen' st.dt of M and s e-ments As, Cd. Ci'. Cu. Hg. Ni athI Pb in drinkity "" "" b f "' P # " * # "' I"""'U"'"'""'-
Water should be es.iltlated in testns of to\ico!(gie[il Omo.19u e 3,.p a g n .n m ,., a cr.,, n n, w a u m.c n , y e m and eaieinogenic potential. (S) Compli.itice lesting of envitonmental contIof App.lacia W cfung n. li ( ,19 a 1( M % honci. II it . skoy i .1; };..o.J % d--a .G W techtioloaies for atmosphkiie entiuions sliould be " "t " C"' " c"'""I '" ""' ' r" N t r n ( i N ' d I:n ci siporotis 3 pursued with einphasis on impio\ine
.' ie- ll c m t s I ns Pos mentd Pn a s teva \; ncs . W .4 i one.
Inoval efh. .elencies fot ]Xtrticulates in the resptmble pg ;9s 14 Der o tmer.: i ! tia .b om I ma' I r", u i "ic ' t o . .t s' oc si/e r;m pe. me nt . stubm m Coen (u'4 .n " P:ot. * +u04 (9) Methods of temo\ino ha/ardotis elements. in- Coima . M n moo: ii sIun.caIt-st.st.BJ. h cltiden" As. Cd, Ct . Cu. lib. Ph. atul /n. from waste r pr4 sticams (i.e., acid mine di.tinape, co.il pile tuneO.. ,,, y, , L, g, ,g g. , ,g,g , y , yy
- u. N n pmd .- '
h em In SCltling pond oulfalb*l IICed to bC dC\CIoICd 10 'C' 1 i !J na c N w s o' O . , a h Jnrod i %.m h - t*
- Ied ?" W'I*
duce the environmental contiibution from coal utili- Ik h 3'"" Il II \"di'" \
- C " 'I \ ' I ") ' L I mtion. I eldnun. ('. . I uiker un. % .1 um W % . f le'i I % . I ato
*' ' " ' "' ' " ' ' b + " "
l t wish tothank member of the ORNI. Endroanental hcu orce "" O " ", C* 'Pe[ s' ' " ^ ' " I I # " f "' I " ' ' "" D Center who piodded ms aluable mtonn..non scmt e Jwr ' the luhnd ' desetopment of thn rarer. I aho wish to thaak the foh. mun DI. .ani...,,mj n . renew ei s w bose mmments anJ cut;eisms u cre mcor pot a i d i"to I. , '# "'s H t Ni I m \o.' ' "pua
' ' " " " I " ",'
this pger. C. W. Gehn. D. E. Reisbie. C. R. IN hmenJ. W It ' ' ' N *" " # ' Shnhs. the Nation J Coal Aw cistion. and the \mcrican Mine 19 I r.cin Rt w a S ..rJ It s doyne i \.huon ! #" ^ nnt .! . I nsP i end Sri ds sis K-. il t . \ L d i' d . I..leti f i,6 .I 4 6 m. Conriew m u ) . W 'MM on.11 ( . . I F K.R., klT~ I~ RIM'T' 5 20 Cras.bml l V.. Con m..I I .. Cu d ni . C. L t i ' on Dan.(, IL ( .av. D ! ..( n t! ace . R A. .Geet ' l~.lloskte.
- 1. Comar. C. l.. and Nelson. N. licAth effet ts of tow! tatl R P.. Na hen. D R . P..nenon. M . H. . Shen. W (.
N . . ml combustion proJocte icport of a Wer kshop.1 ndron licahh Slut nu. Y l'ns nonwraal li e p , i rp 21 - lei l fi tsts Peopcct. 12.119 ( 19M b of Ira.e Conta m. o'h t uan ( ~n .! ( o , N s: ,P i V .o i
- 2. lien). W. l.. ond W.JI tec. A. liace clements m tb en.e 11ool. an : W ttstab 1.c- F l:'i i M s o o.. tit.h ronment - their ro'c and rotenti. l touc.t> e irlated to io ut meal fr'o nunon st snt. N- e ' cd
. 4C " ;3 fuels A prthqunary stuJ) . L:Cl A 12 946 t nu u s:t . of 19ns
- 21. Slade. D 11. l .I W cui i;) . J \tonos Iu' Cahfor nia at 1.os Angeles. 19 7
- 3. l hen.T. I..The potentuf tr.ne metat eontannnation ot w ater llD 241W Nanonal ic t:nical Infotinaoon her ne.
icsources through the Jnposal of th ch. Parcr presentcJ at Spure tie:J. Va .19m 445 pp
- 22. ANI M l ek l'o;ce Res ommci:Jed GmJc f or the l'it.hthon 2cd National Conference on Comrfete Water Reuse oft N D npcruon et \n bon:e i ti'uenS. 2nd cJ . \meirean i AIChlil PAh Chicago, llhnois. May 19'3.
Society of Wsh .% J I-n/ r.cce i s New Yor k.197
- 4. Mcitude. J . P., Mooie. R 11 Wither spoon. L P and 21 Gau. D. l . %wenyneiano meem cments m Mi i Rf1M1 L 111anco. R. E. Ra&ological impact of Aibor ne etllucnts et pp 'l41 In hear,1.noa N,.m r m:: il- R h i % mrosunn coal tired anJ nnelear rower rlanh. Naence 202 Um t l9's Senes .I l i . H G semoran a .J K % Itcame s co.u J t i.
- 5. Van llook. R. I., and Shnhs W. D 1 Js i f fcch of tiace '
iut w.J 1: Iosm..o.u w rs u . contammann from coal combushon*1.Rlr \ N Natrona! C()N1 7 W Na o Tcebnical lnfennation Ser s ice. SpungticlJ. Va. 19" ~9pr SpurcticlJ. Va .19'6. M6 pp.
- 24. S!rnn. W 0 N Sorne arproumahans foi the wet ..n3 63
- 6. Ihorak. A J. lirow n. C. D . Denman.11 t{ . l{mchx..m. temoud of panies and reca. trom the atrno'rhef e Walef R. A. Jetrow . J. D.. Kot nera) . l . C.. I a i vance. C. R..
1.ew h.11. G. I und). R. l . Ohen. R. D.. Parket. J. l.. An Soil PoMot.. m Prew 2i junyc. C. I: Anno pl- 6 Chemis :) anJ P.A ' m ay. Pentecost, l.. D.. Saqumsm. L 1. . and \ inaom . W . S i ne endsomfiental ettcets of usine coal for generating elecniaty . Acaderme ISew New 1 ork. !WA b2 rr. 24" December 1979
.e. a f
k
s
- 26. Engelmann, R. J. The calculation of precipitation wasenging 45 Ridley . W. P.. Dmkes. I . Cheh. A .. and Wood. ! E Recent 6p. 208 221. IN: Melemlog) and Atomie 1.nerg) - 19ns. i.tudies on b!omethylation and demeths tation of toue cle-D. ll. Skale. ed.. 'l lD-24190. Nanon.d l echn; cal lnfor manon inents. I:nuron litalth Penpect.19 J i i lC's Senice. Sprmpfield. Va.. I% 445 pp 46 l bberg. l ..et .d Cadnoum in the l ns uonment CR( hew
- 27. Chamber Lun. A C. Pollution in pl. int canopes, in: fleat and Cle s cland. Ohio.19'4 M.ns l r.msfer in ~l he lhospheie. Part 1, D. A. deVoes. and 47. M.c os.1. Piobtems of umiJiancons espame to twoor morc N. A. Afgan. I'dt. Wdes. New Yoik. IC5. pp 56132 forcyn con'emnds IN: Preecedmp. I \1 \ Ss c tenim on 2h. Shnn. W. G, N. Ih > deposinon and reunrendon of an osol Co npar.dn c %rudies of I othi and LiaisonmenLI Cont.anL partiefes - a r.ew look .d some old poihh ms in A t mo r atnu l \l. A ' '.I 175. Inteirational \ tom I aerp ige ncy ,
sphere-Suit.se lach.mpe of Paith ol.de .md t rcous hidu. Vienna.194. 0p. 50'
- l 4 lant41 RD \ Sy mpmmm henes ht ( ONiom:1. Nan , al E \au/lon.It i. Abd. k .11. Cat dd.. D. \. II As. _t M,
. le chnic.d Infor mation Sei s k e. .s pringric!J. V.i. 19%. pp ll*c. ( ' l. R. cGclh. I \ . . Roubon. R (' . WJJ.mg 1 40. R.l. and E :t.I G Res icw of po'ennal enn hi on Incalth 2'A Rosmsks. J.. l. anger. G.. Nasamoto. C. l .. .mJ itopard. J S :mJ en 6 p omecm.d ya ',b t e m enetal ciaz ir e ik c.n o on.
Generation of secondary p.uth les f rom sinc!e land p.a thles ment as a se+h of t oal .d. anor it.t4 Uc 1 nci . s hogram upon nopxt In .\lmosphere.Sm face lat hanye of P.o ns o Rep ut. Itat tel'c Memon u! losninte, R s i.l.md. W .n h . IC5. late and (ineous IWlutant s il RDA S mposnan 3 Nern <. AM 75 pp CONii74W21. N.. tion il 'l et hnical Informanen Scisice 49 Jones. ll (' . \i d'en. \ M Im Hington.J. D .Itcin . % .I. Sriinfield. Ya.. ICri, pp. 64 617 f.aton. J C . I a.ml hn. R. I. . Hes L. % % .. I hr ton. I ll.,
\0. Gillctie. D. A. hoduction of fin; dust by win.f eie, ion ef mil _ 1 c c. n. R. \ 4Ylode i .I . % faci . D S.. .md % i'Jung.
effect of wmd and sod testmt in Atmo'rh.cre sm fat e I' d R l-. I'so!ock al citai - rp H % In I ties t- of l os e Co. ch.mpe ef Pa:ticul.dc and G.neous Po:h.tanh a l RI) \ %> m- ' im.n.mh hom Uml Co > % non. R I \ an llook a , I W D. posium Senes IM. Ct )NI 4W21. N.dron.il 'lechnwal Infoi 's hn h s. I'J . I Pll \ ~ r : N mon d leshmcal te m inon mation Senise. Sri mrtield. V.. , ICts, pp. $91.t.24 Sei s es e. %rO/tk hl. V.. N rp-
- 31. Field s, il li CalNNI.D. Simn! anon of w.bn ent and trace
$d M.ctm.J.! .lluw.ed.111) . and hal le) . D 1. ( o..;parisen contaminant tran pos t a dh sediment contamm mt inicim . . f r.uhtw in i:> tona to d t uci .o.d m.t br pon ei 3 : ms tion. ORNI.'NNI"l:A I C- 19. ( Lk Ridee Nat.on.d I abor.. I in nonmci i t' l 'tect s et h oducme 1.!caic lh r -. Pm t 1.
tor) . Oak kider l enn.. Irvi. 204 pp. \prendn 14 Conumu u h n.t. J.iu roia:.uth e on Ato me
- 32. Iluomi. J % . I t o:ogical aspects of ninc:a behm ior m the 1.nory 91 a ('o, erew ot !b C.N. Ist uso in. % nlancton, ensironment. Nasl Saf.12 126 19'! 1) C. 19u, 3.L Under v ooJ. I'. J. liace l'lemenk m lion. i i an 1 Amm d 51.1;enderrh. S. C.1:colm > w ith Sp. cut Pt .ciencc Io \mm.ds Nunrtion. Ac.nlemic Prew % u York. ICl. and Mm l'ientic-Il ill. V w io l.,174.4 N pp 34 !.ager w ein, J V. I cad. merm) . and cad. mum .a enut on. 52 lierocks. f. l . nd Canim J.. Jr . IM. J 5 inon e: sneams mental eontamm mt . In. Miaoantoc nh in \p k uhme. J. I ics ch mr .ul nnne d'am ee. Itu!I f- \ ormu W aci Re.
Mortsedt. P. M. (heiJano. and W. l.. Imalsa . FJs . W somces Cento. Blackau m V i I" 2^4 rp Science Swict) of Amenca. Ma.l.wn. % nc . IC2. pp % $l Ma tin. J. l . Quala) .o J < Macra ben t. al i e n s ri:c s In 616. ho.cedoft1e-tN)m >m m on M me an.! h cp u, non P!..nt
- 35. D'lui.1. M. The I rn nonmeni.d Meicm> h ub!em CR(' Rcrose 1)%#.d %Do - d ( oal twou dian WAo ton, h ess. Clo cland. 0;no.1972. D C. IC4. m 26 P
- 36. 'l bompwn. S. E., lim ton. C. A., Qumn. D J . and Ng. Y. C. 54 I cJer.d Pou cr ( emmu o sit am ci cs n,c rl 0 .a and Conc entration !.Ntom ot chemwal elenient s m obble .quane watti sonnoi datifoithe 3eo enda : lAu J a 11. IC2.
organkms CCPI .505td. I awitnce lacin.o e I abor. dor) . I edt ul Pow er Comonmon l'eport 1 ix N2,6. W.ntan ton. l .h er moa . C;Jd . 19'2. D C. ICS
- 37. Van ook. R. l. C.ufnuum, lead. and /mc datobunens N 55 Hoi .ma . % . l .. WJJr. k L Pan . I i . I ou t l!. P. % . .md tween earthworm and sods potenn..ls hu bio!on.d ., Pohici. R. I . I m u o:veraat sitet h er o.s c s k a na fiom cumulation liuil I.nsiron Contam. 'lowo! 12 SoWIC4L pon Rd .nh .m l sinbi cr s iu've i let n t Pows: Rs s .ch 3K Nanon.d Academy of Saent es h mari s for ladu.itmg Instdute Ro roit W 202. P.do \ho.(~Jn .IC' Oncmwals m the Ern nonment. W.nhmeton. D C.. IC5. 56. Cushman, R M., liddel rand. N. G . Sn anJ. R. II , and
- 39. I imicite. N., Hohwor t h. W. N . kedh. J T , Peart e. P. L AnJmen. R. M 'l bc lo n a s o! " n.se c'emt i.h m to.d to and Giuch). I M Meient> m Oh and li h c.om; b rds cear iteshv ater biola a s' o b. n vdh mom.Jed refoa al sites of industnal tentammanon in Canada Can I iciJ N.it. o p A hnes tWNI f M 5' A (U RiJge %non.d I at ou-85:211119711. tor y . Oak Ridp l enn.. IC. 45 pp.
- 40. Van flook. R. I 1 ransport and transfornution pathw a s of 5 ' fira,Lett. C. l . hedunon anJ enb/ anon of ash m the i mtcJ ha/ardous chemie.ds f rom sohJ w aste dnpoul. Ens uon. States C N Hm eau ef Mmes infor manoa Cixul.n 8M C.S.
lie.dth Pcrspeci.in press. Derrtment of the traenor. Washm7 ton. D C.. IC2.
- 41. Alesander. M. lin3 hemical ecolop> of nuaoorgannms in 58 klein. D.11. \nJicn. L W. atJ liohon. N I.. J iace ele.
Annual Reuew of Mwrobiolo;> . C. l.. Chtten S. Ratle!. ..nd ment dnchatres tium co.d combustion fm powci produs non M. P. Stai r. Fds. Annual Reuew,. Inc. P.do Alto Cahf . % ater An Sod Po!!ut. 5- 71 ilC5i 1978, pp.161 192. 59. Ilfot k. C. and Dann R ' study of tb ash enuwion dunne 42 Ehrhch.11. l. lhochemhtr> of the nunor cicmen:s m wit. In somhusnan of co.d I ns noo Su I ca no! .10 lbl I i ICro Soil liiochen,hn 3. A. D. M61..a cn and J. Skogans. l.dt. Vol tu C.mnon,11 !. and Su mson. V.11. Contobunoin of major
- 2. Marcel Dekker. New Ym k.1971. and mmw slaat nb to wih and scretanon by the coal Ib cd
- 43. Ridle). W. P., Dirikes. l.. J . and Wood. J. M. lhomethsl+ i our Corners Pew er Pl.mt. San Ju:m Pueblo. New Mewo.
tion of fosic elemenh m the ensironment Saence 197 329 U.S. Geologwal Sun cy Open inte Repor t No ?$- 170. U.S. 119771 Geviosal Sm s e) . Dens er. Colo. IV et 4 pp
- 44. Wood, J. M. Iholopcal cycles for toue elements m the ensi. 61. Ilorton. J. H.. Ibrsett. R N.. anJ Coopei. R.11 'liace ele-ronmerft. Science 181.1049 ( 1974 L ments m the terrestruf enuronment of a coal.thed pow-28 Emironmental llcalth Perspeclises t
L
s erhouse. Dbl 475. Saunnah Rnce I dwatery. Aikcn. S.C., ?O Coen6d on I.nsnonmental Quabb KTQ) Rep 0it of the In-1977. teragenc) MoiLin; Gioup on thahh and I nmennwnial I f
- 62. Iloiron, N. I'. 1.> on. W. S. Van llook. It I., Andren. A. W. feeb of linerp lhe. Wadmgtoa. D C .19'4 1:ulkerson W.. Carter.). A..and I.mery.J. F.Traec c!cment 71. llanuhon.1. D.. .md Morin. N C. Ileahh cihets of to a d me.nurements at the coal-fiieJ Alle n Ste.cn Plant - Progrew fuci powei planb in Piecce,%p Eth Midse.u loncal Repin 1. June 1971 - Januar) 1973. OPNIJNSF EP 4L Oak S> mnumm on Popa: .non I s posuies ilcalth Phwes sm Ri#e National I.aboratory, Oak Ri@c. lenn 19n. M rp. et> , Knou die. ~l ennecce. Octof ei 1974. pp kit t17 M Klein. D.11., and kuoell. P. lleas y metah: fEout arounJ a 72. Moipn. W. R. C. Coat woiket s pneumoconto is. Va. McJ.
power pl.mt. Ein non. Ssi leshnol 7. U711974 Monogr. % 712 % M Schwart. K. Recent thetary trace c!cment rese. neb. es- 73. 11011. -\. P. Radut, m m reispectn e: some temp.ohonsof 16 cmplified 14 lin. tiourine, and uheon. I'cJ. Pros . 13: 174A ensitonniental risks h em nus h ..: and lowl f ueled pow ei (1974h pla.it t NocL Saf. f 2 M :19711
- 65. Iloose of Rcricsentalis es, Committee on Neience anJ Tesh- 74.1urrier. W D . Kay e. s V. and Hohu er. P. S INKl M .mJ nolog3.The costs und efin b ot chromc e s nwuie to low Jes el INRI M ton,putei u Jcs fot est nuatmp rad..: hon Jo-e s to pollutants m the ensnonment. Document 49. 94 h Concic" poputanons from ccest acnon or a v i resel canat we m of the Uruted States. W.nhmyton. D.C., 1975.14P pp. t ie.n e s plo sn e s K ! ?$2. Dal Red.*e G.3cous thflusion m McCuen. D. C. On estabh hment of ait quatii) criten.i. with Plant. Oak IOJge, f emi.. (9t.s teference lo the ellects ot ain.o phene Puo me on s egetanon. 75. Iloot h. k N . and lia> t , S. V \ p:c!.n.ir.aq 9 0cno,malris Air Quaht3 Monograph (n t. Amentan Petroleum 'nstitute, modet of tadioas tu n> tiansf ci to m n fiom Jgosinen m a New York, luf x. tenestri .! cns nonsnt ORNl i M ll R O.ii h@s N.
tion J l .A rators . ( bk Rid. e. Teim .19't . 21 t p.
- 67. Tyler. G. I' fin b of he.n 3 met.J polletbm on Je.om; wit on and nunershianon rates m foiest M in initin.noaal 70 Nanonat coon. d on R id:. non heto hon .cd M.asmements Conferen,:e on licas ) Metals in the I nsironracnt. Teinnto. (NCRPr Natut al IN pound R nhano" in Ihe 1 en J Canada. O,1.193. Vol 11. P.u t 1. p. 217. States Repoit No.15. I'cr t:a mon 1% ss. New i ori. (C5 68 l >ler, G. licas) metah p s! lute natre. in.i> icJuce ruoJue- 77. W alJ Y .(i l lic .hh IJtec et i 'n oowet.! d Po!Is .mt-Ibi1>. AmN 1 5211972)
C V. M osbs. St i om . Mo 197 4. 'It m
- 69. Mon ow . P. I' , limyh u.i 1. . Iloig. D C ., Cothn. I I 7N hnteit.. e C., ( reas en J P. . fl.enmei . D I, and C.h t.
I owici,11 A . I rench. .) . Headh.1. C . Itemr!n'!. D D . A. V. M.dumcJu ind ses of en.wnmt et .I tia e.mrt.d c e llopps, il C.. Whallo . k R . M uo- D.1.. Ncn;4cua. poso:e m lumunt to I s ace I len nt *.fethm m An m A P. , Nonis. W. P.,Pli'/ci.1 A.. and W nschi.11. R Heahh Unnets.a P.ok h os ltdtnuo.c. MJ , re 7 "V Wic 3. K ft. Ow nehusw n. P. l ., Jehos-i . C.1. ,u ul cifceb In: 1.tlecb el I i,a c Cont.. .t e lio.aCi.ICom boshon. R.1. Van lloot and W. D Shult i J- I.RD \ l im ma J. \. lle.a 3 inet.d etrosure lion. h.1s. 1. n s i, o: t 77-61. %tional 'l echm al Inf o:nunon %cisicc. S,siin::li, h!. lleahh Per pectn es 12 M ( 197.s) Va ,1977, pp' t t 76 s 247 December 1979 b.
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CATHERINE ARANY ,* FREDERICK J. MILLER,i SANDRA ANDRES* D ' RICH ARD EHRI.lClf,* JAMES FENTERs,* b - DONALD E. GARDNER.i AND MICHAEL D. WATERst f k
- Life Sciences Research Divisinn. lIT Restorch Institute.10 West ."rts Serret. Ch; caro. h~
lll nois 60616 mid 'Leurun.nental fro:rctwa Aunc.s. sisa;u: f.;in ts t?esearcn g
., Laboratory. Research Triangle l'arl, North Carolina H711
( Received December 27.1973
- 1 Fly ash fractionated into <2. 2- to 5. and 5 to 8-gm size ranges and coated on the ).
., sarface with PbO. Nio.or Mno, was used to exarnine the :ytotoxic etTectsin sitro of particle i
concentration and size to alveolar macrophages (AM). For the various fly-ash sampics,
.. statistically significant decreases were demonstratec m viability. totz) protein. and tactste 1
dehydrogenase activity with increas;ng concentration and decreasmF panide size. The toxic (5 b effect was not due to solubilization of the test metals in the media since no toxicity could be
, .- demonstrated using particle.frec teaches. The percentage of metal adsorted on the fly ash C W @},.q ;N.--
varied within a narrow range and therefc,re at a given concentration the AM were exposed to fairly constant amounts of the test elements irrespective of particle size. Thus cytotoncity is particle size as well as dose ocpendent and the greater toxicity of the smaller p. articles
.'J E t .
c ' '*f;M appears to be due to their larger surface area.
,,s, ,.g ,
I 3 INTRODUCTION 54Q'
. ,jc, .- y Alveolar macrophages (AM) play an important role in the detoxification and y'fN'y., % .
, protection of the lungs from inhaled particles and infectious agents. There is b,
evidence that certain trace-metal-containir:g paniculates released into the envi- %[('tj '
- j ronment as stationary or mobile source emission byproducts can adversely affect the phagocytic, bacteriolytic, and metabolic fun:tions of AM Since the health g
hazards associated with potentia'!y tcxic metals or m:tal ccmpounds entering the t body as respirable-size particulates have been recognizec, their effects on the
.j , , , pulmonary cellular defense system has been increasingly _ investigated. (Bingham ci al.,1968, and 1972; Graham et al.,1975a,b and 1978; Graham and Gardner,
;} l, 1977; Gardner et al.,1976; Adkins and Gardner,1976). These cells have also been 7 1 used for the in vitro screening and toxicologic ranking of various pure compounds j
that may represent inhalation hazards (Waters er al.,1974 and 1975. Aranyi et al., ll 1977). .
!' The objective of these studies was to evaluate whether physical characteristics
{ d such as size and surface area of fly-ash particles alone as w eli as those coated with 3 various trace metals are contributing facters to their cytotoxicity to AM. Fly-ash P particles are formed during burning of coal in power plants, when at temperatures r exceeding i100'C the mineral residues fuse and are cairied into the efDuent stream 4
, by the gases and the volatile coal fractions. it is known that in the fugitive emissions L l
' This paper was presented in part at the Sixteenth Annual Har. ford Biology Symposium on " Pulmo-l 3
l p nary Macrophage and Epithebal Cells" held in Richland Wash. September 27-29.1976. 2': v l 14 0013-9351/79'050014-10$02.00c0 1" *. Copynght C W9 by Andems heu. loc.
',
- Ai' ngNs of reptud set,on se any form reserved.
y 1
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.. . . -%.W.M.y.< < s.
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.g;~'L
' :9 ;. .v .- ". p." ~f 7. --5.? ; .C.V;.'.-
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, . .; . = H. m '.;~.L y . ' M qmc %x ..
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m + ~ %* ~C ' " * '
- . p g.a. w ,u.- m .c u. .
=W
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, %4 .-
16 ARANYI El AL. 1 e,
~- ! The test suspensions were incubated for 21 hr at 37'C in a humidified 4Tc CO: ;
} atmosphere in wells of disposable plastic cluster dishes that were placed on a
$ j rocker platform for agitation. Atter incubation the suspensions were transf.:rred 2 4 into siliconized centrifuge tubes and the AM attached to the cluster dishes were j i removed with rubber policemen and combined wi th the corresponding suspen-Q sions in the centrifuge tubes.
Viability was determined by microscopic counting of 400 to 500 AM. The per-centage of AM that had phagocytized the test particles was determined from the same slides. For monitoring celllysis via loss of cellular protein, the test suspen-1 (J sious were subsequemly w.ahed and een:1.iuged ta::e tinas in LESS and :!.: j
; i pellets were resuspended in 2.0 ml of HBSS to remove serum and other interfering media supplements before determination of total protein levels.
l For determination of enzyme activity the washed cell pellet was resuspended in i distilied water for osmotic shock, the volume adjusted to 2.0 ml, and the suspen-i l sion placed in ice was sonicated with the microtip of an ultrasonic generator. The 7 cell suspension was divided into two portions: one portion was used for enzyme i ' assays after centrifugation at 63g to remove the fly ash particles and the other
,j portion was treated with 1% sodium deoxycholate (Schwarz!Mann, Orangeburg,
' N.Y.), the resulting lysate centrifuged at 10,000g, and the supernatant used for protein assay.
f g ' Enzyme activity was determined using commercial assay kits (acid phos-c.< phatase, lactate dehydrogenase (LDH): Boehringer-Mannheim Corp.; #-
.j glucuronidase: Sigma Chemical Co.). Acid phosphatase activity was determined by using the enzyme to hydrolyze p-nitrophenylphosphate at 37'C and measuring
'} q ,
the liberated p-nitrophenol colorimetrically at 405 nm. LDH activity was analyzed by measuring the rate of oxidation of NADH at 366 nm. This oxidation is propor-
] tional to the conversion by the enzyme of pyruvate to lactate. Total protein
; y content was analyzed by the Lowry method (Lowry et al.,1951) with the use of bovine serum albumin standard (ICN Inc. Irvine, Calif.).
Erperimental Design and Data Analysis
}; Three to six replicate experiments were conducted for each test sainple using i AM obtained from one to three rabbits. Within one experiment a minimum of five
! exposure coni:entrations selected to produce a viability response over a wide I s range was tested in triplicate cultures using three wells of a cluster dish and three replicate assay determinations within each well for every parameter examined.
1 Specific enzyme activities were calculated as mU/mg cellular protein. Except l where stated, changes in enzyme activity and of total cellular protein content were expressed as percentages of the corresponding controls. Since viability of the I control AM was not affected by the 21 hr incubation, the viability values were
! reported directly as percentages of total AM in each culture.
I For statistical analysis, linear regression and inverse prediction were used to i determine the EC3 valu:s, i.e., the concentrations of ily-ash partic!cs which reduced the responses nf the various parameters studied to 50% of the control levels. Williams' test (Williams,1971 and 1972) was used to determine the lowest p
; effective concentration (LEC) among the dose levels tested, for which at this and j
] a!! higher doses there is evidence of an effect on a given parameter. The error 1 a
l I e Y n i
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~ {:.. ., y 7LY-ASH TOXICITY FORROPHAGES ALVEOLAR NfAC 17 ance wherein the control responses were include the variability in overall response from ea ned from analyses of vari-t...
separate determinations and via a blocking factor. Duncan's multiple range t - elucidate significant differences particle types. est (Duncan,1955) in was theusedphagocytic to s,- I-" rexpe sponse of AM for the various [l. Choracteri:ation of Fly-Ash ParticlesRESULTS The percentage of adsorbed lead, nickel or ma same treatment groups.erent The overall change b[. rang size fractions of the untreated fly ash sample containing less than 0 03% from 2.63d to 3.85 - In order to demonstrate that no cytotoxicity . o the testfrom v (Table 1). metals [ of the test elements orother compounds the fl'as contributed (," by so , fly-ash particles per se were preincubated y ash, the metal in th oxide-treated i . 37C at the highest concentration used for exposue maintenance medium
~
{. with-AM, the viability-of the cells did not differthfculture ncubated for 21 hr at 37'C Cytotoxicity of Fly-Ash Particles rom the unexposed control AM. C I Ql
;d AM viability. When cells were tions of PbO , NiO , or MnOrtrea e incubated in thThe tox y measuring their effect on t
to 5, and 5- to 8 dose-response regm size ranges, ted, or untreated fly-ash )k partic i k,.; . c i 1 AM were found lationships for all treatment between groupsparticle and f viabilityconce(ntration andhighly (kp ;j of the least-squares lines resulting from or all thesize linear ranges. Figure I shows the kl- ]4. ,.; mean of the viability observed for each concentrati p ". ;y, The results indicate that for oneach tested. particle si2 regression I analyse
-kf..'M toxic, NiO- and MnOrtreateda particles hdi
.e, PbO-treated fly ash was most h, EW than the treated particles. The data alfly ash was7,&least at markedly higher concentrations :
p
~ ]H-to 7 reduce viabdity to the same level. group, as particle size !f'. incrensg l
. O Mt ti retained in the alveolar region (<2 and ose size ranges that can be 2p[1 to 5The V;)
?.S M gm) were subsequently used in "y 1 TABl.EI It AulYSIS OF METAL Tt5t ELtute,ts Aosonst I o ox fly-ASH PAniscLas* k .)j e Test $
Weight percer. tare cf r teJ NM or p rt: clernent --
<2pm cles sitet ..
2-5pm 4 Pb Ni 3.85 5-8 pm [4. . j 3.84 /a Mn 2.63 3.15
!F ,;5 2.91 3.22 -9' 3.67 2.77 $
W
- IJacoated dy ash contained <0.03fc Pb and Ni and <0.0lG Ma. 2.98 M
g . g3 4 g % ,
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, I PbO-Trooted FlyAsh , Mio.Treeted fly Aah " !
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200 400 e.Jo f 800 1000
-j; FLY ASH CONCENTRATION , pg/mt FLY ASH CONCENTRATION,pg/ml
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l \ 6 FLY-ASH TOXICITY FOR ALVLOLAR MACROPHAGES 19 O
*0 . . 50 i i . ,
so- - PDo Treated Dy Am - Pbo Treemd Dy Am '. p 90 - 9 eo - o - J eo- - r a mo- N a
,_ x.
b
- a
- - a o
- F g g {
geo- g - geo- 0 - j g 8N g so-
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so-I go . o LDH --- % - 4c o LDH , a TololProtem - a TomiPromin , o g 6
"o obo e$o eco o ao 4Eo e$o soo FLY AsM Co'ecENTRaT10M. g/mi FLY AsM coNCENTRaTBom,pg/ml Flo. 2. Effect of particle concentration and size of PbO-treated fly ash on total protein content and y l LDH specific activity in macrophages. Results are expressed as percentages of the control responses. L
( Each point represents the mean from three replicate experiments with tnplicate assay determinations for each parameter. All regressions were significant at the 0.03 level. f. { e Mc l*C i . . [N
, i ,
-~
N!o Ttseted ny Am Nro Trected ny Ash g eapa -spm e me- - tro o - o sioo- - a ce
\ -
E g
.<, E g
o o p:'. f Oc.g:;; Seo-t* 880- t-i i MOM 0 1-h g eo- - b g eo- - i f$tf.5 t.i.' 9 a '
.7.
.I u s
.s. 4'c4 i,' *0
~ o LCH
~
** ~ oLDH -> I h[? gt'M.i a Tomi Protein a Tomi Protem y 4
. , , . ,c , , , , , ,
s et; o zoo eco eco soo sooo soo soo cx;o coo Hoo seco moo axo . 4 (.* FLY AsM CCroCENTRaTION pg/mi Fly ash CCNCENTRAT1oN.pg/r
,li t$ - j.,
f n. Fic. 3. Effect of particle concentration and size of NiO-treated fly ash on total protein content and l LDH specific activity in macrophag s. Results are expressed as percentages of the control responses. , [i : 7 - i Each point represents the mean from three replicate expenments with triplicate assay determinations )N , .... . Z: ., for each parameter. All regressions were significant at the 0.03 level. l l$ W studies conducted to determine if similar dose-responses for total cellular protein g levels and specific activity of LDH acid phosphatase, and #-glucuronidase could . be established.The MnOrtreated samples were omitted, since their effect on viability was somewhat similar to that of the NiO-treated particles. y'e When AM were assayed atter incubation witn tne test particles at concentra- a tions chosen to produce cell viabilities rangir; from 30 to 80Tc, total cellular !.1 protein Icvels and LDH speciEc activity for the PbO-treated fly ash (Fig. 2) and h Fic.1. Effect of concentration and size of fly ash on viability of macrophages. The mean viability obsersed at each concentration is plotted, although the regressions were calculated using the indi- St
. vidual data pomts. Each r g:ession for the 5-8 gm particles mas based upon 50 data points, while the sample size for the other regression lines varied between 56 and 81 points. The "zero dose" data points h
,-e in = 2Shhown as a sohd circle were used in each regression and all regrenions were significant at the 1 0.0001 tesel.
l ,
.r
- I
/d*-
h ( a v
* [ e- - *
- O ' - '
I -. d g
.:- =. ;= - . - - - - - - c~'a- $..,,14___ .,
_ wmumQ
--- ~~=
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- 1 '
d !
, 6
. ,' 20 ARANYI ET AL. l a
e '
! TABLE 2
. ! CosctwinArios ut FLv Asn P4miscs as REQt;It&D To Rt om MacaoPH4C.F VIAhfLlfY, 4
- Tovas PaarLIN Cosits t. Aso 1.DH Sru IHc At rmt) s o 50", (t'.CJ r
~.
- . EC., fug m'6 1 F
'3* ' '
Viability Total protein LDH activity
? Panicle treatmentisize (pm) <2 2-5 <2 2-5 <2 2-5 l
1 I'bO 470 584 681 488 586 707 h g Nr0 670 1250 749 1007 2779' 1325* g itwv g:rvwe [ y Q
- Extrapolated above the tested concentration range. Y 1
- Highest concemration tested. l 4l . I i
t.i. J NiO-treated fly ash (Fig. 3) generally followed the decreases observed for viabil- [ ity. However, this was not the case for the two lysosomalenzymes examined. The [ $'M 3 ., specific activity of acid phosphatase showed a moderately decreasing trend that ! was not entirely consistent and no change in the specific activity of #- L y.,g$g glucuronidase was observed. I 4 Regression analyses demonstrated significant (P < 0.03) negative linear re- 1
'# ffi < lationships with particle concentration for LDH specific activity and total cellular s protein levels. The estimated concentrations of particles that reduced these pa- [
7 '-[.,9;,Qr.;~;';,% ' ramet'ers and viabilit" to 507< (ECw) are summarized in Table 2. For LDH specific g g activity of NiO-treated AM, the ECw values had to be extrapolated beyond the y W. / tested exposure range. i
;,$;p[h. Based on the ECw values a toxic ranking can be established for the particles y with respect to treatment as well as to particle size. As noted earlier, the results
}[.c'g' b'- for viability indicate that PbO. treated fly ash was more toxic than NiO-treated fly T ash and within the same treatment group higher concentrations were required to reduce viability with increasing particle size. The estimated ECu concentrations i . j of the particles for total protein content, representing celllysis, and LDH specific l ' i.1 . activity generally confirmed the toxic ranking determined in the viability-dose- - l 3: response experiments, with the exception of total protein values found for the
$ PbO-treated fly-ash particles in the 2. to 5- m size. {g Although it is ofinterest to establish the relative toxicity between these parti- !
cles, more meaningful information to the environmental toxicologist is repre- 6 l sented by the lowest concentration of the particles that re:ults in deleterious i effects. Thus Williams' test was used to estimate the lowest etTective concentra-tions (LEC) required to reduce a given experimental parameter significantly, rela- ! l tive to the corresponding controllevel. The results summarized in Table 3 demon- 6 strate that from the LEC values the same general observations as noted earlier can g 1 be made, namely. toxicity is more pronounced in PbO- than NiO-treated fly ash v l and smaller particles cause greater damage. It can also be seen from the data that y l ;j . in contrast to the estimated ECw values there is no inconsistency in the toxic j t ranking based on total protein determinations. As expected. the LEC levels are g ifj substantially lower than the ECw concentrations for all of the metal treat- {' ment-particle size categories. In addi: ion, whereas 'no ECw estimates could be ., g obtained for acid phosphatase and g-glucuronidase by linear regression analysis, LECs for acid phosphatase could be determined for PbO-treated fly-ash particles 8
- n. 4
'l using Williams' test.
i Se
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FLY-ash T ICfrY FOR ALVEOLAR MACROPHAGES 21 \ ,
. TABLE 3 ,
Lowest ErrecTavE CONCENTaATION (LEC) Or FLV-ASH PAaTicLes Rzoutaro To Pitoouct A f" Saoe.ortcANT Eartc7 RELATIVE To CONTROL ReseoNses' l h, ,. ,c ' .
> ! c' N
* .- LEC (ps/ml) w
$ J
. Acid I Viability Total protein LDH phosphatase '.
g Particle { g treatmenusize ( m) <2 2-5 <2 2-5 <2 2-3 <2 2-3 s
}
- PbO 50 200 100 200 100 200 400 400 NiO ' 200 250 200 750 1000 6 6 6
)
- Determined by Williams' test. I J .
- Among the concentrations tested. none was found significantly (P < 0.05) dirierent frosicontrol J The effects of fly-ash treatment, particle size, and exposure concentration on ,
I phagocytic activity were determined using analysis of variance. The analysis of , jl . the significant interaction between particle size and concentration is given in ,
. Table 4. In the presence of <2-gm particles, approximately 93% of,the- AM '
j phagocytized at the lowest concentration (250 pg/ml), while almost all of the cells - had engulfed particlesvthe next-highest concentration (500 g/ml). This repre- 1 M, . sented a significant difference between the percentage of AM that had - 3 1jj phagocytized at 250 ggimi relative to all other exposure concentrations. In the presence of the 2- to 5-pm particles, only 82% of the AM phagocytized at 250 lf h. P*; pg/ml, the process was more concentration dependent, and more of the differ-ences between increasing concentration levels were significant. g.hhi jr ma c.%gyi w .d.n I. j DISCUSSION Comparisoii of the toxicity of test substances on the basis o'f ECa concentra-W. arg.w ...t.3 i gf.$r tions is often advocated. Unless the slopes of the dose-response curves are 'I k J.fg I parallel, the toxic ranking may be different if comparisons are made at lower dose %A.tgu
!I ranges. The environmental toxicologist is greatly interested in determining the NM jf lowest dose at which there is evidence of a response. However, there are seldom y@y d
i enough dose levels studied such that there are sufficient data for determining the .S 1 true regression model and often there is disagreement about what magnitude of bj *c
- 4. . ;i r.
.s' r " *
, i i j TABLE 4 cG ErncT OF ParTict.E Sizm ANo ConcENTRATrom on Ph. m-I3..y.pW n.
; 4
; 1 1
%,;].f.'
{ Particle Percentage of macrophages that had * ! Da2
. < concentranos phagocytized sized particles * , gj (pg.ml) <2 pm a 2-5 pm ; .I 25o 92.9 8I.7 )
50o 96 6 91.7 'f 750 %.7 93.0 t'. i 1000 97.7 95.I jk i [. ..--
- Means connected by vertreal line do not differ significar tly (P < 0.05) from each other, as deter- ; g ];
i 1 1 mined by Duncani multiple ranse test. G .d Q .A :. . i %e 6 !rs:, ' - r ' . b5(b c t 2. F u ( =-
bN$?NE$!$ Y - $3i Yb ?'*. *~ b'h_-5 Q%;n,gg,Q yh 3bt.~f S' _ JQ
,i
, 22 ARANYI ET AL.
# difference between the fitted regression and the backgrour.d response level is
) . biologically significant. '
h.$ ' Williams' test provides an alternative in that the analisi.s is based only on the assumption that the responses to the toxicant are monotonically ordered. Thus,
*8"
/1 [
, j; the experimenter assumes a priori that if there is a response it will be in a known
. f.? direction and will. if anything, increase in magnitude with increasing dose. There f is also a nonparametric equivalent of Williams' test which can be used if the j requirement of normally distributed data with equal group variances is not satis- 4 y fled (Shirley,1977). While in the current study the ranking between PbO- and l {
NiO-treated fi>-as poriisics si not dufer using vvimams' rest irom ine ranking
+q
, obtained on the basis of ECa values (except for the total protein values of the -
r 1 PbO ticated samples) such would likely be the case if another EC level would be (q
- chosen for comparison. Funhermore, the LEC is of considerably more interest 4 fih .1 My' from an environmental perspective than is the dose causing a 509c decrement .h sjyd fj relative to the control response. 3
. ph,3:q The effects of the various fly ash prticle preparations on viability, total protein content, representing celllysis, and LDH specific activity in AM showed sicnifi-j
,l
,, t
@i.5:G.$y ~-
cant dose responses with particle exposure concentration. The results demon- .e
;4p3 J.1 strated that for a given treatment and a given concentration of fly ash, toxic effects 4 37?/W N increased with decreasing particle size. The percentage of adsorbed metal varied :d.
dE$i " within a limited range for all test particles, and within a given metal treatment il y f-[
. category the variability was even smaller. Therefore. since the AM were exposed #
hpd .! to the panic!cs on a weight concentration per cell number basis and, the percent-Mbl4 age of metal was approximately the same for the various size ranges within a given
~
3@U .I treatment group. the AM were exposed to fairly constant concentrations of the 4 Mp'f test metals irrespective of particle size. 4 k g$ WA? t It also has been established that cytotoxicity was not due to any solubilized compounds released from the particles into the incubation medium. Thus, the 4l j increase in toxicity observed with decreasing particle size sug;ests that the tcxic j effect is due to surface interaction between particles and AM as well as to particle h j concentration. This is in agreeme'nt with the observation that for a given concen- ;
- tration, the percentage of phagocytizing AM increases with-decreasing particle-- - --
l size. Moreover, since the smaller particles can be phagocytized in larger numbers. i they provide more surface area for interaction with the intracellular millieu. Large ( , particles do not affect AM as readily, because they canr.ot be engulfed in similar numbers, and, after engulfment, a smaller surface area is exposed in the
~
phagolysosomes. 3
, Thus, these studies provide experimental evidence that the size of the carrier '
particles affects the cytotoxicity to AM of a substance adsorbed on their surface and thereby demonstrate that for evaluation ofinhalation hazards the size of the ,, j particle delivered to the AM as well as the size range that permits penetration into j the alveolar region is extremely relevant. ]
- I ;
i ACKNOWLEDGMENTS ' this investigation was conducted with support from the Environmental Protection Agency under a i l EPA Contract 68 02-0761. { e a ( , w
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e d.v:m.c.m t- v yi m,
-{f sq V ,
h , ht M,e . . . ,".O FLY-ASH TOXICITY FOR ALVEOLAR MACROPHAGES 23 7 s .1 c. i x ' REFERENCES I Adkins. B.. and Gardner. D. E. (1976h Effect of niciel on the enhancement ofinduced streptococcal { infections. Proc. Amer. Soc. Microbiol. B-45. Is. .
- t Aranyi. C.. Andres. S., Ehrbch R., Fenrers. J. D., Gardner. D. E., and Waters. M. D. (1977). !
; Cytotoxicity to alveolar macrophages of metal oxides absorbed on fly ash. In " Pulmonary y
; E. rochages and Epithelial Cells." Proceedings of the Sixteenth Annual Hanford Biology Sym. ~
posi ir, at Richland. Wash.. pp. S't-65. , Bingham L. Pfitzer. E. A.. Baridev. W., and Radford. E. P. (19%. Alv eolar macrophages: Reduced t b number in rats after prolonged inhalation of lead sesquioxide. Science 162. 1297 - 1299. d Bingham. E. Barrev. W. 7e-was. '.t . 5 r" er, K., :nd Tavtor. P. (197'). Rees of afveolar macrophages to metals.1. Inhalation of lead and mckel. Arch. Enmon. flrolth 25, 400 - 414. Coffin. D. L. Gardner, D. E. Holzman R. S., and Wolock, F.J. (1968). InDuence of ozone on f I pulmonary ce!!s. Arch, f.n iron. Iltalth 16, 633 - 636. Duncan. D. B. (1955). Muhiple range and multiple F tests. B4vnerries 11(1) 1-42. I Gardner, D. E., Miller. F. J., I!!ing. J. W., and Kirtz. M. (1976h Alterations in bacterial defense mechardsms of the lung induced by inhalation of cadmium. Environ. Physiopathol. Resp.13, [ 157 - 174. , . j(, Graham. J. A., Gardner, D. E., Waters, M. D., and Coffin. D. L (1975ah Effect of trace metals on phagoe)tosis by alveolar macrophases. Infect. Imm.,=M. I1,1278-1233. i-Graham. J. A., Gardner, D. E.. Mdler. F. J., Daniels. M. J., and Coffin. D. L (1975bt Effect of l I nickel chloride on primary antibody production in the spleen. Envima. #rulih Fersp. 12.100 - 113. Graham, J. A., and Gardner. D. E. (1977h Effects of metals on pulmonary defense mechanisms i against infectious disease. In " Proceedings of the Seventh Annual Conference on Environmental Toxicology." AMRL.TR.76125 Aerospace Medical Research Laboratory. Wright-Patterson Air . .. Force Base, Ohio, pp 171- 187.
. , S,*.
Graham. J. A.. Miller,' F. J., Daniels. M. J., Payne. E. A., and Gardner. D. E. (1978h Inf'uence of k .- y' 3 F cadmium, nickel and chrumium on primary immunity in rnice. Envirun. Res. 16, 77-87. w .(;(.:; ' ' I Lee, R. E., Jr., and von Leheden. D. J. (1973h Trace tr.etal pollution in the environroent. APCA J. .i i 23. s33-s57.
- a-4.tYi lI i Lowev. O. H.. Rosebrough. N. J., Farr. A. L. and Randall. R. J. (1951). Proteta measurement with ~ k.E,I.'t i foito pnenol reagent. J. Biol. Chem. 193. 265 - 275. Ogg i {; Myrvik, O. N.. Leake. E. S., and Farris, B. (1%ih Studies on pulmonary alveolar macrophages y,.p c. f-
' from the normal rabbt: A technique to procure them in a high state of purity. J. Imv.uwl. 86 ,
h s 128 - 132. ; Natusch. D. F. S., Wallace. J. R., and Evans. C. N.. Jr. (1973h Toxic trace c!cments: Preferential ,, , _ concentration in respitable particles. Science 183, 202-204. JIE.,;-k@.' Shirley. E. (1977). A non-parametric equivalent of Williams test for contrasting increasing dose levels of a treatment. Biemetries 33(2), 386-389. Q' .'i,'t
$#, #is, I Waters. M. D.. Gardner. D. E., and Coffin. D. L (1974h Cytotoxic effects of vanadium on rabbit alveolar macrc phages in ritro. Toxicol. Appl. Pharmacol. 28, 2, 253 - 253. ; /, t* 3f
-,6) . #
- Waters, M. D.. Gardner. D. E.. Aranyi C., and Coffin, D. L (1975). Metal toxicity for rabbit alveolar . .
h macrophages is inro. Em*rm. Res. 9. 32-47. -- F 7-t Weissbeckcr. L. Carpeater. R. D.. Luchsinger. P. C., and Osdene. T.S. I1969L In Virro Alveolar b[-! [ macrophage viability. Arch. Earrrna. Heat:418,756 ;759. . ~.WOV "Y,~r2[; Wittinens. D. A. (!971L A test for dttferences between treatment means when '~several dose levels
'E*
1
! .are comperm! with a zero dose control. Biomerrirv 27(th 103-177.
Williams. D. A. (1972L The cnrnpanson of several dose levels with a zero dose control. Biometries [
] 23(2) 519 -531.
a h g 1, j .
.e- .
- e. L yp
( L. i .
, P r
U M ' .?. ~t c t I it 4 1I
,,_..,3' .
f. MM. v>. g)., t ,n.
. n .n Y"C. -.' ?***"5..:.9p '.W,%.-. c.'.7. ..C 39 C. w.n. E.E_".dT [.9N - T 9. . . .e
[*
-c y .,:.a.n .,..=... . . = i
- . . . + , . . - . , .
m-t i., - h bN D e
.} ,
2 peup of asthmatics rep 'rted daily symptoms f or over se' en
. / r <- '[
- cs whit: air po:lut;on and weather parameters C /' #'* CN,(I,ED
; ett nvutored. S:gndicant correlations were found l 'mo 4
- We L(^g I
63 { ':.-:cninlarge ria:kcities rate and poFution levels com nety & -
! '84 JE -3 NO :@ .
(tl tw - Ast1ma anc Air 3 0 luti'ontfrom ; w, a l. Coa -Fue ed Power 3 ant latroduction l Earlier studies of the relationship betw een air po!!ution 1 a,J acute asthmatic episodes have generally been of three Atlan A. Cohen, M.D.; Steve B.romberg, M.S.; j tyret in the Grst type. specific allergenic pollutants (e.g., Robert W.Buechley,Ph.D.;LeoT.Heiderscheit,
. ca tor bean dust or prain dust) were clearly established as M.A.; and Carl M. Shy, M.D. .
j ethmatogenic on the basis of patientC history, skin tests.
. a tJ re.esposure to the pollutant under control conditions.
j in the second. awoeiations were found betw een air poHution , 51ost subjects had been told by their physician that
} .euncrol and asth ma sy mptom* recor ded in dianes. m emer- they had " c asthma,.. or :. asthmatic .
. ;cncy room. elinic or physicians' records, or during inter- bronchihs.jisthma .. "allergem.
Each subj,ect was asked if he knew of neighbors +
, s tw# In the third type, the clustering of asthma episodes unh respiratory symptoms this enabled us to find sescral
( c.J their association with low wind speed indicated that an
'"d ' C " " * "E O# b* I"C"' famil es without telephones.
) aiiborne substance was invohed but standard poHution Forty.three suitable subj.ects wereidenafied.Of these.
. .ea uremenu showed no correlation with attack rates. 'a "
In none of the studies invoking the usual ubiquitous M w ne 1 si to the study, because oMusal to N intuden ed l (ll.pr tracted ?.osp,tahration i or travel t2).or repeated failure
- rollutants coulJ researchers specifv the harmful auent or the remaining M suNects.
~
to return aary fums O lh
} agents.or find those les els of pollution at w hich health'efTects 9 reported no attacks or one attack during the tudy. All I f.at become marked. Nor could thev generally disentangle analyses presented are for the data of the 20 subjects who i the etTects of air pollution and weath'er. ;
f reported more than one attack. The present study was designed to obtain such infor- ,
^ 9" "" " " " * * #
j rnation. For 7 months daily symptom reports were kept by . N"# 4##'"##'.#Y"#" "' " "' I" "'" " '1' a ranel of asthmatics who were intermittently esposed to
" '""N " """' "'# #'"# "'"" #"' *I ""
hmh levels of pollution because their homes were within , l 'I mile of a coal-fueted power plant. At the time of the " E "" "##"."""# "" M # "E"" i
"""Eh """" * " "# ' " ""*"E #
cuJ). the plant had low stacks. no abatement desices, and ".*. " " "' used high. ash, high-sulfur coal as fuel, and therefore emitted """} I"" " " "' " " ' " E " #"" 8 of the fm.'al participants. The group of subjects escluded -l I obstantial quantities of particulates, sulfur dioside and becauu the,n anach une too inhequent was younger, had
! cudes of nitrogen. Our purpose was to quantitute the relation-I# " " '"* "#' # " '"' # " I" E i ship between short term relatively high. dose pollution ' ' " " ' E inore rent than the final study group.
. esre.ure and frequency of asthma episodes.
I t nHoring i Pollution and Weather ,: Vtthods Three poHution monitming stations were established , Population Selection I { at sites picked 1o give a representative sampling of populatmn l l New Cumberland. West Virginia was chosen for the esposure. At each station. continuous measurements made l Present study because air quality measurements shoa cd uide meluded total suspended particulates d ligh Volume Sampler i dapto-day Doctuation of poHution lesch, and because its -24 hour samples)." sulfur dioside (Coulomenis ma!! area il mile by % mile) made intenshe monitoring method)." smimp indes AISI tape sampler-2 hour tape sam-
? of pollution lesch relatisely simple. Subjects were located ples)." suspinded sulfates (24. hour sample #1'and suu ;
by lelephone survey of all households in the small town pended nitrates (24. hour samples:"). t;vpulation 2.100). AII residents claiming respiratory symp. At one weather station in the center of town, and tonw were screened b3 a stalT phy sician : W I. Csiteria one on a ncaiby ridge. meteorotocists took eontinuous hourt) b r melusion in the stuJy were two: measurements of tempe ature, wind speed and ducetion.
- l. Ilistory ofinter mittent episodes of respiratory dis- humidity and huometsie psewure.
new. generally unacco tramed by fes es or inese.ne i sputum l i paslachon. in which wheeting u.n tne predominant sy mp- D% &porb to.n.
- 2. Esperience ef three or more such episoJes in the Each subject secched a diary form (Fipme h and f receding 12 months. tur envelope weekly. I he diary form asked da3 of week ASTHMA AND AIR POLLUTION 1181 6
t s, time of day, duration, severit), and place of onset for each . crisode. Three to the day s after the end of each week'Y Association of Attack' Rates with Poffurrr;,i or Weafht' reporting period. nontespondents w ere phoned and reminded Parameters: Two-Variable Analysos to submit the missing report. Each week approsimately 15 per cent of the study population had to be telephoned. A vrages--Correlation coefficients weic calculate!
- between daily averages of each measured pol weather parameter and reponed dml> att.ick rate, and thes i Physician Visits between pollution and weather p.ir.imeters. As the Grst tok ,
umn of TaNe 2 res cals ull pollu: ants as well as temperate:t
- A staff physician made several week. tong visits to New Cumberland. During these sisits, subjects were asked correlated significantly with attack rate, although te to contact the physician each time they had an attack. TFe correlations. Figure I shows scattergr doctor an asthmathen visited episode. each one to conGrm the occurrence sus each s of ariable that wanigniGeanth awociated with arracf rate. "Best fit" hnear regrewien bnh are superimposedceI the scattergrams. We attempted to fit threshold functions.
Analysis of Data i.e.. S shaped curves to the data. I or each sasiable. the best Gt S shaped curve did not explam more attack ra variation than the best.Gt linear.regrewion hne.
'4 Methods of analysis included a stepwise mul:iple Lars.-The data wcre re.anat3 /ed assuming 6,12,15 l regression procedure with an analpis of the correlation coef- or 24 hour lags between pofbtion or temperature Icvcis and ?
Gcients, for.!og transformed as wcll as for untransformed occurrence of asthma episodes. Temperature and soilirg data. The association between attack rate and each pollutant wn examined within three temperature ranges, as was the indes remained signincantly corre!ated with attack r anociation of temperature with attack rate within three pollu. 4 tion ranges. Regressions were aho cateurated for each pollu. Figure 1A-Scattergrams With Best Fit Lines for Attack ' i tant on the temperature-adjusted attack rate. Ilest fit lines Rate versus Significant Variatics w ere plotted for each pollutant agsinst attack rate and against ,o ' ' ' ' ' i temperature adjusted attack rate. y ' ' ' ' n , )_}
*n a
Results g se - lw :
. I The Population - . :. .
5" ~ l Tabic 1 gis es the popul.iiion's age. ses. duration and
- x - ,
~
E x - '
. t severity of asthma. allergy and smoking history . and educa-tionallevel. The Gnal study group cont.dned primarily adults el-n - . '!
i r ' ,. I tSO per cent), with at le.nt a high school education About no i r i i _I half the group w ere male, half were smokers, half had a e n m a *
.a in m a i
ma A history of allergy. and all were Caucasian. ret u u*rs:r o
- e c...r e -oe si. .. 2
'",o -
i i i i 1 - i i i { g a2 - , R re - ' p Table 1-Characteristics of the Study Population ~ jdw -
~
Va riabte .; , .#- Category 5 X -
; o 1_
Age ~ f 16 or less Over 16 { 4 16 h _[';., Sex Male ,o _ Female ' 9 p i i i i i ' ' 11 ' ' Duration of 10 years c 03 c o* 8" c' '" : " c at Asthma More than o. . c7 o or less 10 years '" s..'.4O M t ..- i i i , L 9 11 i
+ 6
" e i
-l
~
Frequency of 12/ year Episoces More than H - or less , 0 12.'y e a r ,; - 20 ,. - (Non-asthmatic) Positive Negative j '0 - ~~ . l Allergic History - 50 - T-, O 10 ! Smokmg Smoker 10 Non smoker 5*
; r
~
History 11
- s. ,.-
9 M - ' - j Educationat Did not Level HS or more to - graduate HS , c i ' ' ' e- t 7 g 0 0. 5 10 ** t$ 23 3C _a 3.S 40 eg
@.*Cis0Es.c.s 1182 AJPH SEPTEMBER 1972. Vol 62. No. 9 =4 m . =ee a
l W. f.,,x J -
> z u.~~~<~ w ,~. e =.
m L . .;
-_L x- www n.pmmy.._,.. ,,
sy : l~ s.: f 1
' i. i, t ? g e
- e. t. r 6
any of these lat:s. The correlation between attack rate ar'd !I i
; Tguo 1B--Scattergrams With Best-Fit Lines for Attack '.
sulfur dioside Ib el decreased wiih increasing !.g. becou,iup
< s tea versus Significant variables insignifkant at hgs of 18 hours or more.
;, a (i f u . iiiiii i i i i6 i , ,
l'roh-Analyses w ere repeated for all s ariables 'j :( g ab. characteriting Nhour temperature rather than by 21 hour 8.
; d _
as erages. Cors etations were sirtually identical with those {j yl l , { , ,,1I found for daily aserages. ll ,
'. . ~
Too few dan occmred with a low 24-hour pollution e; lh
; j :n , ~
as erage but a high Ghour peak, or with a high 24-hour as er.ge }l N [.. I ** '. .- f;j]*(~ -- .j ; '
~
temperature but a low 4 hour minimum for us to make a meaningful analysis. The present study therefore could not jf
,i
{[t.
*8 -
l! g a - thstinguish the effects of short term (4 hour) high polhition b hf.' D- esposure from those of longes teim C4.houi t lower dose j! 7 { i i i i i e i i e i i i i i i i i i i e s posu re. to ao x .: w a n es *o m 1.o::5-Analysis of averages, lags and peaks of foc- f I y' e p suse r et o sa r am ,. -) transformed data produced results no dif'ferent from tho e '
' ' ' ' ' ' ' ' ' described abose.
,l .o
{ [ , _
//ich-low Annlysit-Table 3 gives attack rates for -
J l
~
high- and for low-pollution days ar.d for days of high and l
~
low temperature, humidity, barometric pressure and , 'U
)"
~
windspeed. Cut off points demarcating "high" from '1ow' r,! g )
~
sariab'e dan were arbitiarils chosen so as to roughly h !j j - equahre the number of days in each category and because [ ' " j 3*,
- these w erc pomis at w hich rehitis ely large increa es of attack '[ f
{
~* ~ .;
rate occur red In addition the table shows telatis e iisks of ; j] 5 -7 ' ; ,
'8 - E- high po!!ution.highbumidity,andlow u mdspeed. low tem; er- '
' ' ' ' ature and low b u ometiic pressme. Relatis e risk of high l
, [j {f e
pollution vaiied from 1.03 for suspended sulfates and sus- ,
; ft s
sa tet o wneirn ,, 2 pended nitrates to 1.24 for soiling indes. The relatis e risk
" oilow temperalm e w as 1.29. Signifie.m! High-low dalfer ences , {f j
'J 3 ' ' ' ' ' ' '
i" """e' '"'e " ere ro""" r r '"'re"ded r"""'"'e '" ' ' ' " ; 4 ii J indes. sulfur dioside, temper.itur e, humidity and windspeed. , .,
- Ciencrat Temporal l'attenn-Temperature, sulfur .
t ' q [. 10 dioxide and soilir;i-des, the three variables showing highest t' ..r'
.- correlations with attack rate. were tabulated with attack rate lx .:::
- ,- by quarter of day. day of week, and momh of 3ear. 9: .h y .o - Pollution les els and aitack rate both peaked during ti '.
'; x -
- - the second quarter of the day; oser half of all attacks were ' ii {- '
! (i 7
- 7. -
reported to hase begun duiing this interval. Temperature il n _ was lowest between midniglit and 6 a.m.
, , , i i , , , ,
Figures 2 and 3 show aserage salues of temperature. , , ,
;S
'o e i. 2. n .: .s u . 22 is sulfur dioside, soiling inJes and attack rate as functions of I
tr resarv e r.**
,
- I; *, l f, Table 2-Correlation Coefficients for Pollution and Weather Parameters, and Attack Rate
'l 4 I
I g (ljh Attack Suuur Soiling Total Suspended Suspended Suspended , i. particulates nitr ates sutfates ; j l [ rate dioxide inder Temperature j
! Attack rate !{
j+ r
.320t I
i Suitur dioside Soiting index + 387t - 5251 i!i d, _.205t _.466*
, ei ; Ternperature .427t -ll d' Total suspended I -
particulates + 537t m419t .021
+ 241t
- Suspended
.. " p. .
, .543t
. . t;*
nitrates - 169* - 316t .438? 084 1 i t Suspended
- 197*
- 5671 .361t ,
.480t i sulfates .199t .3497 .
Barometric + 165,
- 107 ,,
- 043 - 156- .
- 055 .122 l' pressure Windspeed
- 038
.050 - 072 _.290; .124 .033 _.023
- 2671
,j i J 168' _ .186* - 089 '
Humidity .112 _.112 - 223 _ .162* i . 6 f . 'l ^ 4 p. OS * - fP ~~
* .l
__Ci -- _ ASTHP.tA AND AIR POLLUTION 1183 3
~~
day of week and mon:h of year. Figure shows a "midd:e 4 of the week" trend for at:ack rate and pollution. but no Figure 3-Attack Rate, Temperature, Sulfur Dioxide trend for temperature. Figure .khoa s as erage monthly attack Concentration, and Soiling index as Functions , rates sarying directly with .acrage rnon:hly pollution lesch of Year ' and inversely with temperature; thew relationships obtained i in cuch season studied. Identical t. bulations of the other pollution variables, though not presented here, showcJ - I i i I Cuf! . similar characterhtics. e.or - / As these Ggures and TaNe 2 show. ca:h sariaNe signi' [ 's - uI ficantly correlated with attack rate was correlated with un 'N
--u, sescral other variab!cs as well. These simple analyses thus failed to distinguish betw een primary and secondary5iassocia-
-[I f
\ ~ U"h i.
tions. "' T \ suvue onono:
\
u; j m , g ,,, , s u{
; c.e4 -
8' f. U N, 4 Figure 2-Attack Rate, Temperature, Sulfur Dioxide = et {: tl
, c c3 -
Concentration, and Soiling index as Functions of Day - "I 2 j of Week l 1 I us - [ y le - g5 I ~ 01 fg 0.01 p' \ ATTACK #if f
= f.3 f
r s - ,
- g3 ;
40 - f
\
g o 1 i i r i -ll l
# ci t. Jm. i ,3 r t e. hae. apa.
j j war y ' \ jv.,g _ \ MONTH of vfas
#,s ---- m
?, %_ ,/
y Tf**t'aTJ't # 9
~ ~ % .e f ~
I g 3 ^ Q g i l 1 m
- m
- pg - g 5 I 3# -
l I 0 88 -
~ N
- x
. - , , , -N
._/ a t l a c e: tatt \ ;
io - - x s s 4
)
lI 'e g 43 - s. e ==%
%,* ,5, }
0 ' .$ % E e 1 svM. WCN. Tu t s.
- t o. 1% # s **t sa f.
0 3c I{
- Cav C8 ot te flmpleatung
,f ,
8 -
~
3 I , t i i i 1 i '
- o ,, _
t s.es -
- to
- I i
- o I
,: i f 1 1 !
- s.s 1 1 es c. s au. ,
r e e. u n a. e % sutrue - u a r e. may wt j o.es
-r %
s C'0 * *' .ouin er vs e u I i s e / m ,,, . N u i m:t n
!. I g s o. -
\ ug Separation of the Effects of Weather anct Pollulicn j 3 g Parame cts: 1.fuitivariate Analysis .
b un ts i j j;' - Since temperature e.howed by far the strongest .
~
oa tasociation with attael rate, each sariabic was examined i
"' ~ {
separately after the effects dioside, soih werej- re of temperature e.s
- e. a in a multiple repreuion analysis. Sulfur 4 s ui - indes, total suspended particulates suspended sulfates iar.d
- c. :
e.: suspended nitrates were each found to esplain a signifkc: ; f*
.. I l ! I
- e. i amount of iesidual sariation in attack rate (lane 41. Afie
- su . mow, I )
o temperature and any eme of these fhe variaNes had I.cer. ~1 furt e r o. t r. e s. *=i. air. taken into account. none of the other four s ariaNes esp!ihed . car or weer a signineant amount of attaet sate saiiation. These sewh- q are conGrmed in Figuie 4. ubich shows b, st.Gt hnes fo: 1184 j AJPH SEPTEMBER 1972. Vo! 02. P.o 9 , l r I
g_ --
.ti; -
a i, c
' ' i t],! '
i : ';'-
)- ..
Table 3-Asthma Attack Rate and Po!!ution and Weather Variables: High-Low Analysis t.'8 '
- a s
Relative risk of Significance of }j
'! yr Attack rate on Point d em a rc a tin g Attack rate on "high" variable differences in
. " low" variable "high" a nd " low" high" scriable days (BJA) or low mean attack ', i j (
8 ( days (A) days days (B) Te mperature ( afb) rates , Varia ble ?
.(
So,nng index 0 342 10 Co% 0422 1 24 Pc01 ,, q; Su"ur dio6de 0364 .07 ppm 0448 1.23 P < .01 ;j G. [ Tcta! suspended . particulate 0.349 150 pgWm2 0 412 1.19 P< .01 i,' (. t Suscended
- l! f a
0.374 2 pgm'm 2 0.383 1 03 NS *d }
.i nitrates . , ** Suspended e ...
I. sulfates 0378 23 pgm'm2 0 382 1.03 NS ; [ 0441 32 F 0346 1.29 Pc01 ;. Teraperatu re } l}
*r Barometric
>i I
0.380 29 4 inches Hg 0374 0 98 NS . I, l
! pressure 0391 1.06 P< .05 ,;l f; windspeed 0367 4 rr.ph
{ 0.362 80*. 0.393 1.09 P < .05 ;!i J Humid,ty I
*i.l l rbj i e
-d t:
1 i ;l '; I i l "ternrerature ad.iusted attack rate" acainst each poHution tion on attack rate. but could not specify which pollutants :.. p
; vari.ible. On these graphs the dif ference betw een ebsers ed were most important. ;(('!
t , p;
; a:t.ck rate anJ attack rate predicted from temper..ture data Figure 5 shows best fit lines for attack rate versus j each pollution variable as a function of temperature range. ,- l j
{ n plotted against po!iution lesel. l he best-fit lines are all 'ti ;
', d graficant slope and esp?ain a significant prorottien of These graphs show that air pollution's effect on asthma is e I
' resida.d attack rate sariation. This series of ana!yses thus greater at moderate temperatures than at temperatures below i! i j hed independent effects of temperature and of air poliu- 307. but that asthma attack rate is greatest at low tempera- .! {
! tures. (*l l.
/ Figure 6 shows best-fit lines for temperature versus attack rate for three pollution levels and tu o indicator pollo.
![
t [ 't
!' ngure 4-.-Temperature. Adjusted Attack Rate versus tants, su! fur dioside and soiling indes. These res eal that j
Pc lution Levels: Best Fit Lines temperature variation has a greater effect on attack rate at g\ 'j. q I w p llution lev:ls ;han at high pollution lesels. ,; ;; [l'gnn. a
> 2 o i,,,,..... ,
me ee
~
i i i i 4 .
~
Physician Vissis .s t 5 t d' ~ t, j !
; e, 3" - -
is -
~
The attack rate reported during the several physician b ' ' r - i'. j 'i sisits was not significantly low er than that reported for other *, h[ [
~
[ l l1* n':, ,f, ,,,,,., ,i- 2u . weeks matched for season and general pollution les el ', ! 'j
- ! . e n c s. e s. e 6. s .c c i: % g-l y
; , mu ce t .ic ..- g ,, _
;,. ,}
n se
,,i.... ii
_. _ 4.i 1g
.i
; e .
Rate
~
Table 4-R e sidu al Variation in Attack 't (( . '
! k ". ;ij yJ g
n -
- Explained by Each Variable After Effects of l- 4{ ,n 5
n - -se
. i i r r i Temperature are Removed j ti :
1
" ,'j i
I j, .u , ,,i,,,,>- ' Degrees Sum of % of sum d ?
' ' d*g '[ .:',*. 'd ' ' Factor freedom squares of squares f-value P ; gtr j '
Totat 2 53G3 100 i j T emp (alone) 1 0.5151 20 31 38 7395 .00005 ' ({
. ,,, n _
j e se- -
@ ,, . _ Temperature with: ] 'l Vy AtSi 1 0 0990 3 92 7.8268 .00585 . !
, bn- _
fi",, [ M ,, _ _ 502 1 0.1002 0 0979 3 95 3 8G 7.8772 .00570 7.6875 .00630 {n. TSP , .
' 1 n re- - {p ,, ,,,, ,
Nitrates 1 0 0601 2 3G 4.6265 .03315 , Suttates 0.1391 5 43 11.1641 00106 !
- i. 0. . "-
- 6. ,,,. 1 Barometric .iq
[ [ , 0 00003 0 00 0 0022 .9627 .' k[ ,,y n _
, i i e i ,
-"." i i e i i
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Pressure Windspeed 1 1 0 0044 0 17 0.3271 .5685 g l},:
.n e ex rx r c .e4 we ex no e . : e s . Humidity 1 0 0047 0 10 0 3544 .5526 .i-i . ..,f 'l:,W.',W.. . " " ' " " " ' ' " ' ' =
S ASTHMA AND AIR POLLUTION 1165 ..
) .
6
m - - - , _ _ - _ - _ . , _ - -.-MG.2g m y 7 - ,, n .4 -y. - _ - yy; y-
' r-i.
Figure 5--Attack Rate versus Po!!ution Levels Within Figure G-Temperature versus Attack Rate for Each cf Three Ternperature Ranges: Best-Fit Lines Figui Three Pollutant Concentration Ranges: 'lest. Fit Lines
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e M r. Discussion ! I I l 1 Y c to 20 30 a so u _ We had feared that New Cumberland residents. in T E P t a4 Tun e, +r their discontent with the local power compan), weafd os er-report illness on days when pollution levels were sisibly g elevated. Howeser, since attack rates reported during the were remoseJ. Thn finJing may reflect only the unusa! 3 weeks ia which a doctor confirmed the presence of each temp powirc orrelation of suspended sulfates and temperate:e l asthma episode were not lower than those reported for pre- envir L!! other po!!utant sariaNes show negatis e or insignificant ceding or following control weeks. it is unkkely that tha cerrelationsl. or may selleet the irritatis e properties of sul. was a significant bias. mm furic acid mist. Presious studies bas e shown that sulfuri: c;;;cs We attempted to judge seserity of attack by inquiry acid mist is capable of incre.ning pulmonary resistance h . g ., . . into duration of attack. restriction of actisities, dose of healthy adults? and hase shown awociations of morta!q , f;[ medicine taken and whetheror not a doctor siut was made. with suspended sulfate les els.- l These pros ed to be oflittle value for this popuf ation, becau se A single po'luiant cannot on the basis of this data. i little within-person, between-attack variation. occurred. than be singled out as the prime cause of asthma episodes, it Most subjects rarelv saw a doctor. rarely sta>cd home from for C is clear. how es er. that although temperature is strondy ;9g work or school because of an attack, took one dose of awociated with a' tack rate. air pollution concentrations a e medicine, and had sy mptoms for less than 2 hours. Furth sign:ficantly aucciated with attack rate.100 es en after 19 Several aspects of the data desers e further comment. sion i i effects of temperature has e been remos ed. First. po!!ution tevels and attack rates were associated sinhin of nc inercases in air po!Iution concentrations w ere fourd emp! each season. The months of peak attack rate were Jana.yr) to base a greater effect on asthmatics when temperatures j i;g; i and February. These months also had the highest po'lution were moder.ite than w hen they were below freezing (Figure 1 levels and lowest temperature levels, and are characterist-ieally the time w hen acute respiratory infections are most .4.a!though the reported attack rate on dan oflow tempera' l have t0re was usually high reg.adiess of air pollution concentr:e i yp frequent. tions. Similarly, decre.neun temperature had a greater eflec . Second. the diurnal pattern for reported attack rate tion l on attack iate on low pollution dan than on high pollutiet { oI in this study showed the peak rate ef sy mptom onset occur- day s. On high po!!ntion d.i> s attack rates were unusua!b t ring between 6 a.m. and noon, rather than belu een nudnight ,, h ph, and wete not sigmtie. int!) affected by temperature sar. l ., y I and 6 a m., as reported c!sewhere.* The reason for this is sation. ~1 hese data scent to imply that these is an upper tirrft { u nclea r. poHu to the aNht) of ensironmental facio;s to being'on asthm.i ,1 sme Third, suspended sulfate levels showed the stror' gest awociation with attack rate after the etreets of temperature episodes. at least in the tempeiature and pollution r.mp j 7,3,,; nadied Once this hmit has been reached. by sirtue of 10 1186 AJPH SEPTEMBER 1972. Vol. 62. No 9
WWWWW.W77WS%._v;L:&- m- M L ;i& W ^^ * ._ .O . -~~M~~~ 1 m. i i i . ach es 4te 7-New Cumberland Asthma Diary D'n$'en o' Health Effects 8tesea en 4 hational Air Poliv: son Contro' Aim.n.stration llf4%
- PwDrac Health Seruce. DMEn s NER CUMBERL AND ASTHu A DI ARY t oato No. Your Name i-Sancay Moncay T uescar neccescar Thuascay F esca r Salv< cay 4
e No C4 you have an asthma O' """" { ~m2 etiack today? Yes 1 alia:a u.cnighi lo 6 A M 6 01 AM to Nooa . af e%st t*** did the {, e s o.pnt Noon to 6 PV 6 01 PM to micmant 4 . d ese 9pu en New Cumberland No e%a the sueca began?
- e N@e
' co" te e
~r .,o,es
.c,re e youorm., 2 eos.s
~ more than 2 ccses
; e.s m. eneck t.d .nwh to make you see a doctor?
No .. g o
..s i.e an.a se.eee h eaovsg to see; you from E s:hool ce *orm. cr frn No
{ your uswas a:tivmes1 O l esat co you tMak ;
- % awoqM on the susch?
D i Less than 1/2 %f
I Ho= long did the atta3 1/2 to 2 bovs
"I 2 to a hovs wore inan a ness L '
I ' "'""! tem,acrature or high pollution tevels. further variation in other sively and continuously monitored, a fairly sensitive device ,
"' " cmironmental factors has no effect. was used to measure attack rate, checks on biases were O Cd "'
The temperature-independent pollution effects made and a clear, generally acceptaNe definition of asthma
) was used. With these precautions, significant efrects of pollu-I '"I' i murred at pollution levels commonly found in our major II""' ancs. In New York City, for esample, for the months June tion have been found independent of, or in addition to, those i
- ' I" through November 1969,14 of 38 representatise monitoring of weather. In this study, too, ceria'n desirable information
'"II'I could not be obtained. The effects of the several pollutants ;
g otions reported sulfur dioside averages greater than .07 could not be separated, since they came from the same source i Trin, and 33 of 38 reported aserage soihng indices greater *
"3"- '
tbn 1.0 Coh.22 The city-wide userage sulfur dioside level and accumulatet! under the same inversion conditions. For "* I' fer Chicago esceeded .065 ppm in 1966 and 0.07 ppm in both pollution and temperature, it was not possiNe to tell i, IM.with corresponsingly high particulate concentra' ions.:' whether 6-hour as erages or 2thour averages were of greater l [""b ^" brthermore, as the need for electric pow er inc reases, espan- predictive value for asthmatics.The effects of sharply falling ! r the barometric pressure could not be evaluated, since no such g s.onoresisting coal-fueled power plants and the construction
. cf riew plants appear inevitable. The present data should drops occurred. Finally, since there were no nearby com-aund emphasize the desirabihty orespanding facilities in sites tela- munities without significant pollution esposure, there were
) :nely distant from population centers, no area controls.The conclusions of the piesent study would T"' ' Pievious attempts to relate air pollution to asthma be strengthened b3 linding t'iat a group of asthmatics in a nera- hn e been blocked by several problems Pollution monitoring nearby but minimally polluted .u ea did not alw a3 whow q mp-uira' Im been inadequate because of unsophisticated instrumenta- toms increases on the same . fays as the New Cumbciland tion or the impossibility of continuous monitoring ' asthmatics.
""
- Procedures for quantify ing morbidit) has e been inaceu- 11 is clear that similar i tudier, in other areas and with
""b ! " rate or insensitive. '"' " Terminoloey has been unclear, more subjects wouhl be desir bic.
[,'T"y II rollution " It has notofIemperature, from those been possible to separate season. barometric pres- the effects of air Summary l wre or windspeed. or to reasonably estimate dose response '
"F#' l relationships between air pollution and health effects.'" Twenty asthmatics gave daily symptom repor1s for I""
In the pr esent study . w eather and ro!!ution w ere inten- oser 7 months, while local air pollution and weathet param-l ASTHMA AND AtR POLLUTION 1187
. . a s
* ' escu were intensisel) monitoled. Synific.mt torielat .1. 'I *
- d8 " M. " 'A de' S ' ' "
u o a ...<. i r .'. ,"t. . . . s c. nac..'" ns win ** "l . . n i.h*d* i,u iUe
. " " *b.i. i.-
weie found between reporicJ attack rate and tempera:ure im.a and between a: tack rate and pelhttion leveh after the effects '* "
- of temperature had Iseen rcraosed from the analysis. These
" 'u.h. *" '.'.. ": s." 'a".."n
. 'w.".a. c".'",d ".a.".ic t 'ms e,s,. is .lM""'*"*'"*""
l . o i .on u I e r .4--d..n .* s<- < h k n I r.sem- ww . s'PH. 9 v7*. temper.iture independent air pollution etTect occurrcJ at o '".ai, s H I lesels of pollution commonly found in larce cities, and s . i .u . i . . %:J< c.gr. s . p : a u ..<. u i. t eia.n..s a e r -. u . . b. P.dha-m .m ihe in.-ses u .~ i r . - - se uJh. .a u,..
- b. : iir.. s .
appeared greater at moderate than at low temperatures. ""'"' '"' " ' * *- '#" in ( c. n. n w" ."na.'rH'.aJ k et.a..n h.r .4 4a Poka. .* 'o \He.s.c h a f nas R. rs-i u=A e kr.cs.h (.,,ne u i eae. nn. .a .4 he t*.c.en.n ocp ime,
..I fle tth. I do. : e nJ % cif4ee. L' h. PoMar ficans. %. .m e. %,sbepon. D C.
I tai pp l*9 , Refererices II Jy,,,,p
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un 1717. Ima 3 i gles . A D .4 LiivJ. R. H. EnJem.e Awhm. Due to C stot iteen Dust. J Ol %. 18. liesk m n Inurus.awi R. 4les Nis 1616. Die.km n lastrumenh leiecepiv icJ. I der.en g
* "9 P!.1928 Cold..sm \pra I~.C
- 2. MenJet f eJ rerer. 4 18. V Co.!c. hie 4uhm. kmulahng e rp Jemic Pros.skrJ 19 Hsnicen. H . C. C. Bl.unct (. r., Jr ; .nd lJe. H M Descenunatum cf it.n cd l
ks C shir he e Dast. J. Micrg 24 2* t-249. t944 sm.4e ( cucentre e >= 0 .her P pc. V.mrl< A 8 MrP.=' ) !! 25. l'il. l
.t Co..n D w . w.mr n. H J. P elus. H J . .W MiciLe. P. H1 ImmcN.J Aunn.a 2n %IcucJ Mdb=i..t..e the Mr.n reniems of 4.s PolksureisT s Dcpanmen..dHe JA
%sm.% teJ e.B A %.r Poilu..ats from the C.ca.n InJuurg J 4.r Po't conic 4wItta
!' . l' d t Jut i.cn nd % cit.ve. N.isiwi41 4.r 1%illui.on Ci.nirol Admeeu.te in.n. s Puhigas.e {
\tt 9W AP.j l. M s .1W4%
4 (.e. .a s.. sn% > . D.ct. C .u w.a n.,. . s 4 sia, .= the op,Jem .o : s m. v. u ..a P, a,. a 5 . I nu .., P ,s.Ne s,i,, i,, .n,s n nu.,.,, m, f - sif 4 .tm. .n (ht J:en en PhJ.Jefph.4 A 481stg .1914*.lj7.1%*. J Ol 4 If.4 im%.tH( ISf ** 4 \ bent H H . Hs.a an. H . ( l.n een t. D . t atafer. % M ; snJ %esler. Il 22 slauer.P n \tmo.pl.cs.s so.t te enJ ibe %p..tp s.s.4.Ihe h.ust...e.4 Age 4rs One nt 4er Puhuhen .a Den.v.. Pennstf. n.4 I r.demnilogy as lhe L'ausval Smoy Lpnt%fe %ecofi.: u.=taht3 Raies u .sces . insert hon. Repen,1 (,ence Dep ri,nene. t . cf Octcher. IW8 pun.c He.hh flullehn No tun.1949 e4 Penn 1970.
- 6. %barittin. C. E. .nJ LanJau. E. A.a Polluten and Asthm.he Att.ckt en the 1et II M.*this so.nm.p.e.of %. P.ohnneD t . Nc ) crLC iy Departmem of Aw Itria rtes '
Angles Area pun.c lie.hh Rep Th 44* 448. Iml INre.e.. of T schm..J Ares %rt June Pn.9 Nusember I.e 's . I /c.J* erg. L. O ; Pr.nJic. R. 4 : anJ 1 nJau. E. the Nashsdie A.r Pollut.on study 24 C eno . n Mein.J..h.p I.g bsc.s.ng she Nei,.inie.shp e4 4 w P.illutants in Mrirt.'., a suif . D.o..se and aronch.I A,ihm, s P,er.m.n,.ry Report. Amer Res. Resp Pfe.cated at she gan .J \fsc..ng cf the \me. c n ruMec lie.hh %.% mn. Hewu.n. D.o h4 JF9 901. I%I. Tes.t Ossubcr 24.19M a ) osbJ . M Osh m.. H . anJ imai. M. br P.siluhen anJ Asthma en i ELL..che \rsh f1 Faseron H;th 1836t?Nr. 3%J. , Ihe auth n of th.s r .re msw 4. Hic h+< of suNmsw* .n 'he ( o**unH et w.a o*b l.. I4 h hk*lJ. H : enJ Im.a. M. be Po.bt.on m she 1 4 Lak, be4och sees ! me,.,J to ire P,osem er -).LtAb As hm. inJusi, Hiih. : 5.94. iv,. Mr re.h Da n..n .4 i f's.l, k. s esh b. PoDoh.as ( . masc 4 011 %'c. } n. ..n.e.eniM l'.Wr. j e h.m sun.s in ( . w ih .' si.J.< J orr.se. .. nr. . .e .J. n .n me.i.s.nc .i rr;- ( in i e..s. m : C,aesen. u. u.: .w u;cwe . R o 4., Ponu t.on .a se. one n, nenin,.w.m n.-c.u n....m i ne -ih., ueh. s c mien-c ..ii. i r s hat. .er.. 4.shm.. PuM e He.hh ker 77.947.9% 19*J ttg..ests to ( .ul M shs . MH Ocpuis Dar.cor. Da n .n el 6tc.Jih I f7csis k r rw.8 i A ll % c.11. H . Ink.aJ. I M . D skerson. R-; and Dernet sJ E p.Jem.c Asthm. m %)hC iP \ N . .c o. '. l ..aewk P.u k. No.th ( ,uchn,. ?*?ll. I hs p per m e . 6ewwd bem Orfe.ns J OIA. iv ha f 814. tve a. s. r poN.eaien m u .s t< t ,. 6
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e-11BS AJPH SEPTEMB'ER,1972. Vol. 62. No. 9 .h .,---,--m-- - - - - - . ,---.m-... _._m m _a _g-%~_ ,, s
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M= Pl% ' - (A @ Mutap*enicity of Filtrates from Respirable Coal Fly Ash v w c. Q.. - ants in either the saline oracrum filtrate
~
p$ , ,, (Table 1). Abstract. incubation ofhistidine-requiring auntrophs ofthe bacterium Salmonel. Further work was designed to evaluate S la typhimurium with cyclohexane , saline , andserum soluble surface components of the chemical nature of the active t1y ash respircolepy ash particles produced an increased number ofrevertants in twoframe. componentsQl?1y at>h was extraqed.di-shift tester strains. The results are consistent with the hypothesis that both organic re,ctiy
^^P with cyclohexane'. a rion@ar.
and inorganic mutagens are present in coalfly ash. nonmutagensc.organjc. solvent. The ex. tr,ajt w.y evaporated to dryness 'and re-I
# Coal combustion for electric power carcinogenic heavy metals (5), Fly ash constituted'with tiijnelhylptfoiide,~and generation is predicted to increase
~
- samples were incubated separately with this mixture was test_~_ed fortnatagenic,it'y.
matically throughout the- deror each orthese tnedia for 2 weeks at 37*c. A_bou140 percent of_the mutagenic acJix. l this century It can be estimated that in Afts bation, the fly ash mixtures i_ty of the serum filtrate was present, and s 1974 a total of 2,4 C10Laosric- were centrifuged at 35.000s._atullhs.sc. metabolic _acuvauon mereased th~e~num-fly ash was released to the atmosphere permtrarits were passed thraneh = 015. ber of revertants 2.2-fold (Table 1). At from all coal-burning facilities in the ;rnrih' embrace fther_to_ remove =rticu- least a portion of the activwy thus en " U;ited States (1). As part of our studies laEmatter. Media controls of serum or probably be attributed to mutageruc non.
~
of the potential health impacts of electri- saline were t'reated in the same fashion p5IWrganic compounds. In contrast, cal energy-producing coal combustion as the fly ash mixtures. Filtrates were after extraction of the usin, strnte with ~ j t:chnologies, we evaluated the muta- addedJtpflgr paper _ disks in.1he standard cyclohevana m u t u-Me activity was i gInicity of soluble components of respi- s22t_testand also added to_softJop agar found oniv in the aaucous fraction. TDs - 0 rable coal fly ash. R.e_c.ent studiat h=ye pour plater. No mutagenic activity was c,onprm-d 'h _oolar nato _r- art :tivity { shown_ a high positive _correla.tiort he- found with the spot tEbut revertants of the saline-soluble fractian w m-tween carcinogenicity of substances for were seen with th'e piate l techni_que. This gested the presence _of at least rwn mufn.
, animals or man and mutagenic.actisitsp w yavidence_that_ the mutagen or muta- genic compo_unds. ~
a bacterial test system Q). gegn_ot., diffuse into the medin from To_ further assess the ehe' mari-j Kilogram quantities of size-fraction- the paper disks. Of the five strains test- ation of _the mutaranic utivitv in 4he l ated fly ash were collected downstream ed IA98 and TA1538 showed his* re- serum filtrate. 2 mM disodium ethyl-of the electrostatic precipitator from the .4ertan_ts, whereas TA1535. TA1537. and enedianimeteiraacenc acid (EDTA). a smuAes:ack breeching of a large modern (TA100 did not. Because strain TA1538 metal chelator. was ;tdded to scrum fil-pow er plant burning pulverized low sul. showed two to three times the number of tra EThMer of his revertants was far. high ash coal U). Of_the_four sized revertants as TA9_8, T_A_1138 wa's m.tdjn ingm*hy aboulf0 percent compared j frne' ions obtained,_ the finest fraction, subsequent tests with varvIng concentra. to the untreated filtrate (Table 2). In or-I u,.@_a.:n_ ass median d'=meler (MMDlof tions of f!v ash. Serum filtrate had ap- der to teiinne nypotnesis that EDTA had 2.2 pm and_ geometric standard deviation proximately tenfold greater activity thiin
~ ~ chelated mutacenic metals complexed , b.d.kf .1;f isih'e[m7st biolggi,cally irn- tfie salinifiltrate (Fig.1)..foftiSilit%f w%rurn nroteins EDTA-treated and pungtgnce particles _of this size have su'5 stances responsible for mutagenic ac-untreated serum _ filtrates were fraction-l the lorptatm_ospheric residence time, tivity in salme. a noTr~ solvens3 _ _
ated on a Sephadex FD-10 colarnn with a
; are_ most e$cien'ly dede_d_ia. deep rested the pre [sence of,po.lar organic or, cutt)ff at 25M?aTrons. EDTA (2 m.if)
'~
'; lopp. and_are least_ efficiently removed i{rcahutagens. Although these Cndaed to one portion of serum fil-Cl. Fise grains of hisudtne requiring tesis_ confirmed the_p_resence of dire _ct - -
trate and stirred overnight at PC before (his-) auwtrophs of the bacterium SaI- mutagens, many mutagens requite meta-' clution on the column. A second portion morch tyridmurium (supplied by B. N. boificonversioTrty ceITular microsomal was prepared in the same manner with. Ames) were used. Th testing methods en_z1rnes to active mutageni(2). In fur-
~
~-
out prior treatment with EDTA. Each of ar.) mu:ations involved have been de- ther experiments. additi6ri of optimal these two filtrates was eluted with three semei : B ze:iy."stRiiins TA100 and concentrations of rat liver homogenates
~ void volumes of double-distilied water.
TA!5M have been used ~to detect base- ffom rats treated with polychtonnated Thyfirst fraction contained more thu 95 p it sutNitution mutagens; TA1537, biphernUArochlor 1254) C) d.d not sit percent nf the 'am' "r protein. The ~
'I.M-$. and.lA98 are, strains that are nificantly increase the number of reve'rt. second had the remaining protein and a su w able to frameshift mutagens.
5:'.c" T A95 and TA100 have an arnpi. cW-resicant R facIoinoTpTei en' t Ethe oth7r 7:..G33. S_umcient hiUIdirle was Table 1. Number of TAI 538 His* revenants per plate with and without metabolic ac:ivation. 4 t-
," .;3- -y.:t Plates to_u]{ow the h. . The concentrauon of fly ash incubated with serum and saline before filtration was 7F mg'ml.the isti-c)cloheune extract was evaporated under nitrogen and reconstituted wnh dimethyl su!foside tu":
Un"r b neteria to replicate sev- to the equivalent of 78 mg*m!. All controls were treated in a manner analogous to the test vt wr ir Se presence of the test sub. materi.als. Spot tests were positive with 4-nitro-quinoline-N-otide without 5-9 (the wrernatant
' i Alh trcubation, the histidine- fraction of rat liver homogenate, centrifuged at 9000g) and with 2.aminofLiorere an. 5 9 added 9 ^' "*MP revertant) bacteria Mean values : the standard error of the rnean (S.E.M.) were for three replicate determin. tien s.
3,.m , , The number of spontaneous revertants per plate was 7 : 1. The nurnber uf resertants with addition of S-9 alone was 20 I-1 e e r .4.s were selected for muta-P' ' 'Jiei bnh Ey ash. Dulbecco's Test S-9 not added S 9 adaed rnedia r i' -' v . P .:9ered saline was u'sif e Ue'. Fly ash Control Fly ash Co'it ro?
' ]! }
~" --
f."H and tonicity of ph'si. y and horse serum was Saline futrate-Serum fil: rate
- 154 32 10 = 2 20: : 19 I: : 5 N ' 17 : 3 4: 1 40 : 9 le. :
' 'c e rum ha a chemica con- C)cloheune estract 6: :
t:r:.x: 0 n-- : . p wu w -- 52 151 : 6 27 : 5 &
small amount.of low-molecular-wiight Table 2. Effect of EDTA treatment and serum sul6tc, which m y be present on the su l
- cothpounds, whiln the third fraction con. fractionataan on the number of TA1538 His* face of fly ash QO), Las alsopeen shown
*
- toined*only low-molecular-weight com- '",
Ponents. Eacli,of the three fractions was Table 1). The mean values : S.E.M. were for [ .fg
',"g f,,8Y to be mutagrnic Cl).
Although we have not analyzed for lyophilized and reconstitudwith dou- Sve determinations. The number of spontane- organic compounds, they (particularly . Ble. distilled water before testing. Re. aus revertants per plate was 5 e 1. Contmis polynuclear aromatic hydrocarbons) gardless or prior treatment wrth EDTA. wm se,mm sarnpies with EDTA added and have been reported to be present on the the total r!iu.tagenic activity in th'eTra~c- _ [ M "th j *
,"* surface of fly ash (22). Studies of sus-tions was Inner shartshat_in the aripnal pended particulates in urban aerosols siirare fT-* 2). Of the total net activity 8'"" Fly have also resulted in the identihcation of Fly Con-aEr subtraction ofLe-a r=wert- (,";, , ash EDT IF03 Polynuclear aromatic hydrocarbons, as
- l. ants (5.0 21.0 percent), 79, lj, and 1. well as oxidized species, including poly-gercent were present in theb,,second, UF 162 m 13 261 2 25 g=2 cyclic quinones Q3). Although most l =Ethird untrusted ". c ess. respective- f*" f 2 i j i Ij polynuclear aromatic hydrocarbons re-IYsOf , the *~-8 ==r - Arity =3;e sub- Fractson) 7z 2 22 a 3 4mI quire metabolic activation, some of the o traction of 4.e control _ values oxides do not Q4). It has been postulated 3 (Table 2)s30 j _,.and 17 percent were Q3) that, in addition to polyeuclear aro-
[
- ' found in the'three EDTA tr6ated frac- matic hydived,vos, urbes aerosols con- J tions, respectively. The signiAr==* in- stile metals and_their oxides on the_s__ur- tain other extractable orgense com- U crease (P < .001) in the activity of the rnce or fly ash partscies (16). 'Dierefore, ponents that are mutagenic in the Ames '(
ic: n'=-i-weighf'1ksttion- nf the aHhough average concentrations of po- test system. Since our fly ash samples t' EUTA-td ===__nitate_lcads.cre- tentially toxic materials on the surface of were collected at 100T from the power deuce to Ehyiisthesis that EDTA act- these aluminosilicate spheres (17) may plant smokestack, concentraisons of or-ed 'by chelatine inari ; metals rrom be on the order of tens or hundreds of ganic compounds were probably lower b s6tn_ proteins. The mutagenic activity rriuerosrams ner era'mTsiirface concen- than would be present if the fly ash were 9 was swdea.i=nriv_ ==.arke.d with the trations may be as high as I to 5 percent cooled rapidly to ambient temperatures ! fraction of higher molecular weight, with (13). Of~ the metals found in fly ash. a as occurs in the smokestack plume; how-or without_ EDTA treatment. This activi- number have been demonstrated to be ever, the organic compounds may be al-i ty may be due to organic compounds mu@ic in the bl=mwilo reversion tered by interaction with refuent gases jiiistulated, as a result or the cyclo- assay (8). These include compounds of _ or light and other environmental constit-heia'ni extraction studies, to be present ' chromium (ib,11), iron (12), manganese uents (22). on fly asti surfaces. Mutagenic nrganic 13), and selenium (10). Sirover an in summary, evidence has been pre-ccmpounds--Tor exam 61e. colynucle- Loeb have suggested that the mechanism . sented that filtrates from a respirable rfaromatic hydrocarbons-have been of damage by many mutagenic and car. fraction of coal __ fly ash collected from a shown to bmd to protems (o). Additign_al [cinogenic metals is due to decreased fi. power plant over a 30-dav tieriod cont.ain explanaggns fnr the ref= Live _ enhance qd elity of DNA synthesis (19). Sodium bi- substances._th A Lsause frameshift muta-mehue= mea N : serum tions in a haetarh1 <rrniQckitt normal l filtrates cogm.she saline altzates . excision rer; air. These substances appar-ano inctude the possib_le_nr==> ace of (i) en, . ently include both organic and inorpnic zymes in serum capable of convertid ., comp 6unds. InstsisedTthiisageni$ty of promutagens to mutagens or (ii).prgtgin- a e the serum filtrate compared to the other - i mutasen compjexts e that_are. mare mvnil-b ' cop sor / c filtrate,s m'ai_Idicate that extraction with tble to the bacterial cells u I$ / . serum. meresses the sensitivity of. the We have studied the trace element
- I c, Amesfechnique for detecting routagenic-composition of the fractionated fly ash. 3 co - -
ity of complex misturps. It may be ex-The respirable fly ash fraction, relative }83; picted th'at substances on the surface of 16~the other sized tractions, has the high- ] ,, fly ash depesited in the (eep long should esTTorrceHtMTf6H brmIhy elements (7) ac. se N be similarly soluble in alveolar fluid.The
~~
that in some enemical forms have been o prospect of a large increase, irl, the 8 reported to be mutageme M-ifj~or car- ,, ,,,,,,,,[ ,,, ,, ti, ,, . ,,, g j aritount of c~oal burned _for, energy.ffo-cinogenic (11). In _ order of decreasing Fig.1. Dose response curves for mutagenicity d,uction nrant< sfe_cik._ identification _ concentration enhancement, rciadic to of 8) ash filtrates with strain TAI 538. The of these _mutmeaa'- m6'=ces and a the coarsest fraction (MMD = 20 pm; number olhis* re.vertants yr plate is the ,. - _ eprnt m,um,nr nr the.cossibIe carcin-og -t:9T the following elemental _cpr1- mean of 5 to 20 replicate d_eterminanongrny- ogenic properties of respirableWy~ ash. centrations (micronrams per gram) _for hMhW,
- ne) he d
~ E ""'5" sorne murneenic or earcinonenic metals reversionvas-define 3 'as thrTroup mean of G. L. FISHER. J. E. LAsisirsi analyzed bv instrumental neuttunactlyp- the-spontaneous revertants and the appropri-
~ ~
Radiobiology Lahorutory, ti n analysis or stamic shsnm'Ma mac. ate media control after it was deterrnined that University of California, Dads 936/6 trohtometry (/$) in the finest fraction's themumber of his}revertants in all negative
< Nontrola was not sigmficantly different from g,g_
' hive been determined: Cd(4.6). Se(198). that of spontaneous revertants. The means (: j A5(132), Sb(20.6), Mo(50). Pb(278), S E.M.) of the background revFrtants were I. The esumaic is based on the ERDA balancj '
,r Co(21). Cu(137), Be(10.3), Ni(40),,/3.8 ( 20.4). 6.9 (20.91. 4.0 (:0.6) for the Spon-41n(309). and Fe(32,000). The inverse tane us revertants, serum controls,and salme M" al .aboratory. METArgonne,it!.. $ NE[".7YUioa.
Imp volJ. Pr I and 161.
- Nch indicated iha: U.S. pa cf rldat' controls, respectively. Fihrate (100 g!) was dependence of concentration on particle added to 2 mi of soft top agar before plating. bumed a iotal oniou se im ar..u%*))
, size has been explained, for the most Plates were incubated for 2 da)s at 37'C. The iY r 7 a E $ c Dap7roY m'f [ E cent n ,
! part, as being due to condensation of Vol- vertical bars are ! S.E.M. teleased to the atmosphefe.
.s N sc!ENCE. VOL W /
p
, _ _ - _ . . _ . , .. . , . . - - _ _ - . . , _ _ _ __ _ _ _ _ - _ _ _ _ . _ _ . . . , . _ _ _ _ . . ~ . _ _ _ _ . _ . _ _ _ _ - . . _ . _ - _ _ _ _ _ - - -
N g :/
,,. 2. 8.16 Arme' J. McCaen. E. Yamasald. Maser.
Perne..H. L54. CaarerInss. Falk. 1165 H.(1975); N. MacFarland.J. T. J. Lm. R. LNatt Cles; in later isolations' inoculum was ob-Am. JI. 3481975).
- 3. A. It McFartend. G. L Fraher. B. A. Prenuce. Hackett. F. W. sunderman. Jr.. Caarer Res. 32 tained by expressing sap from pc!ioles W Bench. Emowon. 3d. Tethael. II. 788 225 1972) A. Fu lauder. D. P. ses-y .
With forceps. The inoculum was blotted
! 4. T. T. Mercer. Aero,or T,chaoter, da Na-a,ir ts. J. M. cndow. R. L Rasaini. R. E. Heft. G. L directly from the petioles onto the me-
) Eret-erasa tAcadernac Press. New York.1973). Fisher. D. Saberman. B. A. Prentice. Pro.
, pp. 21-62; H. C. Yeh. R. F. Phaien. O. G. credags ofrAt Eig* A M8:enals ReseereA Sym- gsa. Colonies on the JD.I medium ap-
. Raabe. Eeveroa #calth Perspect. 15. 147 possam. Methods sad $sa.edards for Er veron- peared after 2 to 3 weeks of acrobic in-8 (1976). mearst Measuremeer (Nauonal Bureau of Stan.
I @3. C. Heath. M. Webb. M. Cafrey. Br. /. Can. dards. Gasthersburs. Md.,in press). cubation at 28*C. Progressive refme. I c" 23.153 (1969). I 6. C. Heidelberser. Asam. Ace. Aische=u. 44,79 16. R. L Danson. D. F. S. Narusch, J. R. WaBace, ments in the culture medium shortened o C. A. Evans Jr..Eeviron. Sci. Technod. 3.1107 . (1975). (1974). the necessary .meubation period. On the
! 7. G. L Fisher er al. Second Joiat Chein. 17. G. L Fisher. D. P. Y. Chans. M. Breenmer. Sci.
ical la uiste of < = WAamncan Chemicai eace 192. 533 (ir76). JD-3 medium (Table 1). small but distinct society Conferesse. Montreal. 29 May to 2 June 18. R. W. Linton. A. Loh. D. F. s. Narusch. C. A. colom.es are visible without magnifica-lyn. Evana. Jr.. P. Willansas. lbid l91. 852 (1976). . -
- 8. C. P. Meneet, in leerrenic and NarrWisaaf As. 19. M. A. Sirover and L A. Loeb,iend 194, led lion Within 6 days. Colonies are Circular
]. af Cancer. G. N. schrammer. Ed. (Phmust. (1976). With entire margins, white, sanooth' and York,in L 20. L D. Hansas. D. J.
j4 f.T.Raamame.t Meys.w.Tras.uarar. Aes, as.157(IF75P. H. Nu aa Jbid. 31. Is3 (1975); aanholomew. C. L L WImens. C. H.
. R. M. Izan J. J. convex, and reach a diameter up to 1.0 Chnstenman, in Castferener on Trece 3 6 I
M. Grose. W. Muriel. B. Sndsms. deal. 3s. 33 samaces he E-- * #sekA. Procerdags, mm within 2 weeks. (79% L L Weed./. aererrusi. al. IGl3 (1963L D. D. Heraphis. Ed. (tJniv. of Mmaouri Presa. We have consistently e.<<4=a.et the PD
- lo. G. Law sh and a. N. Amen,im A6areers Eavi- th== 1974). vol s. p. 393.
1 e em s.ciet 21. F. Makai.1. Ha.rynut. R. shop.re. a che beCterium ff0m dI5*ms*rl grapevines. le - eassa Muesse uw.,Cderado$y sociary. (Enviro prings. Cdo., aFeb. tal ys. Aes. Comaram. 39. 953 (1970L one isolation experiment, single petioles
- 11. K. d.D.$ R. Warren. P. D. skast, in """'" "' fmm 195 moted cuttings of eight Euro-
, de=t. p 23. E Pierce and M. Katz Eeveron. 3d. Tech.
pean grapevine vadeties (Pinot Noir *
- 12. D. E,ru. 49.eick. F. Glecen. D. Jara===rh. tJ. mal. !s. 45 (1976L . .
Weeks. wasas. Res. as. 3s6 (1976). 24. J. 54cCann and B. N. Ames. Proc. Nart. Acad. Mission, Ruby Cabernet Flora, Caber-l 13. C. P. Flesret, personal - M- : W. 3d. U.SA. 72. 5833 (1975). net Sauvignon, White Riesling. Barbera Prazmo. E. BaRan. H. Baranowska. A. Ejchart. 23. J. N. Prns. Jr.. D. Grosjena. T. M. Maschke. -
'l A. Putrament. Gener. Aes. 36, 21 (1975). Toxicot. Istr., in press; R. Talcott and E. Wei, and Thompson Seedless) were used.'
'I 14. A. Foru. Proceedings ofrAstarernationatAsso. J. Natt. Cancer tast. 53, 449 (19n). 4 cission of A4eenorgssic Scientists, in press; le. 26. supported by the U.S. Emergy Research and Pierce's disease had been transmitted ( ternational Agency for Ressarch on Cancer Developrnent Administratson. we thank 1.loyd with leafhopper vectDrs to Il6 plants. Of Davies and Dend s,1bermaa for technscal esust. [, M Enniuerson a( tAs Carcisorcur Assa of CArm cars to u.= (1972). vol I. and the 79 remaining plants categortzed as ance. Dr. Marvm Goldman for advice and en-c Jame Jaariramic and Oryanomeretlic Com. couragement. Dr. teon Rosenblatt for matatical healthy,52 had been subjected to feeding support. and Drs. s. Book. O. Raabe. M. Shrf-poseds (1973).a vol. Ree.2;(1963). J. C. Heath. Sr.3s9; Emd. by leafhoppers but did not develop PD, {' Cancer Cs=pai siert 2. p. . rene, and F. Wilson and Mr. J. Azevedo for ent. D. stoner. M. d. shunken. M. c. Troxen. T. L ical readens e uw manusenyt. 3 I, Thorripson. L S. Terry. Cancer Res. 36.1744 and 27 were noninoculated controls. (1776s; A. D. Ortoienshi. J. K. Haseman, w. W. 17 June 1977; revised 15 August 1977 Positive isolations on the JD-2 medium fg f (Table 1) of the PD bacterium deter-i [j , ~ mined on the basis of colony character-istics were obtained from 97.4 percent Pierce's Disease of Grapevines: (" " O r the diseased plants. only l
' one plant m each group of healthy plants.
Ii Isolation of the Causal Bacterium j or a total or 2.5 percent (2n91. yielded j g bacteria with colonies resembling those 1 Abstruct. A Gram-negative, rod. shaped bacterium has been consistently isolated of 1he PD bacterium. Other bacteria from grapevines with Pierce's disease. Grapevines inoculated with the bacterium were rarely isolated from diseased or developed Pierce's disease, and the bacterium was reisolatedfrom the plants. The healthy plants. ,) bacterium was serologically and tr1trastructurally indistinguishablefrom tne one in The pathogenicity of the PD bactenum s naturally infected plants, and also indistinguishablefrom a bacterium isolatedfrom was tested by inoculating green stem cut.
, almonds with almondleafscorch disease. tings of the grapevine varieties Pinot Noir, Mission, and Ruby Cabernet.The The etiologica! agent of Pierce's dis- constitute a new group of plant patho- upper end of each two- or three-node case (PD), an important and often devas- genic bactena (8). cutting with leaves intact was attached to tating disease of grapevines (Fitis vinif- Recently, a Gram-positive, catalase- a vacuum pump, and 0.1 to 0.2 ml of a era L.) (1), is also considered to cause negative bacterium that could be isolated turbid suspension of the PD bacterium alfalfa dwarf Q) and almond leaf scorch from infectious leafhopper vectors but (approximately 5 x 10' bacteria per mil-diseases O). Prior to 1971. PD was con- not from diseased plants was reported to liliter) in sterile tap water was drawn into sidtred to be a viral disease (4), but be the etiological agent of PD (7). How- each cutting. Controls consisted of non-chtmotherapy. thermotherapy. and elec- ever, this bacterium did not infect inoculated cuttings and cuttings in.
tron microscopy subsequently impli- healthy plants following direct inocu- ocu!ated with sterile tap water alone, or cated the "tickettsia like" organism lation, and contradictory evidence as with suspensions of Erwinia amylorom seen in the xylem vessels of diseased to its causal role has been reported (9). (8 x 10' bacteria per miliiliter). After in-grapevines as the etiological agent G,5, We now report the consistent culture oculation, the cuttings were rooted on a 6). Many investigators have reported of a Gram. negative, catalase-positive heated bench under intermittent mist for l friture to isolate the PD pathogen from bacterium from grapevines with PD, and 14 days and transplanted. Typical PD diseased plants using artificial media C, evidence that this bacterium causes PD. symptoms (1) developed in 86 percent
- 6. 7). Similar insect vectored bacteria A rod-shaped, Gram-negative bacte- (43150) of the cuttings inoculated with the have recently been associated with a rium was first isolated on our 3D-l medi- PD bacterium within 2 to 4 months, and number of other plant diseases. and al- um (Table 1) from grapevines experimen- :nany of these plants died within 5 though determination of their pathoge- tally inoculated by the leafhopper vec- months. All 47 of the control plants re nacity and taxonomic position has been tor. #ordnia circellam (Baker). Initially, mained healthy throughout the stud cefayed by the inability of investigators the inocu!um was collected by centrifu- Colonies characteristic of the PD bact
- I to culture these bacteria, they apparently gation of sap from surface-sterilized peti- rium were reisolated from 35 of 36
)
- k. .riz Jiow that the mean absoiote re. mea r - -- s. J. S. deoi.-s. A* >ea. 2.t. s.
'4"ig
- 3 ivm.
}s fractory periods of CMA neurons were 1. !!. P. Michael. Dr. Ated. Smit. 21 (No.13. s7 E m ' g hr and K n. p signincantly shorter in castrated rats af- N.D*sw t pZ h'M.J ,ed '*[khy *""p*,,N j.,I u y A
- ter treatment with TP (U = 5.P < .002, jgaadgggNQgg r .
, g. E Egned s. D. sessis.pn,,,w. s,4 .'
two. tailed). Compensons of refractory tw2 . voa. 5. pp. 2os-2'I. no. u. van Dis asd K. t.arsso.. rays 4.t a,4. . s. oeriods between the Arst and second ex- 2. R. D. Usk. Ana Endanad. 48. IM (1%2h G. C w. Mainteury. sA,d. 7. 7M ti971).. . - . w. Hems and R. P. Michmei.J. Physiot. (Lan. 35 4, (IMih,g y,,, ,.,g g, c,,,,,, g, ens Ass st. W penments show no signi5 cant difference deas in.275 (1964h J. M. Davideos. Eadwa- (test. between the IDeaft refractory period of # mtact (experiment I) and testosterone.
- 3. R. . Dyer. in The Nyporksta-mi.s. L Marties. M. Morta. F. Frankens. Eds.
g j. g $,, [ j Y g enre 1:2. 2:3 (IW3). [ a treated (expenment 2) animals (U = 7L I$.de=c Prus. New M. IMil. m iS 12. gw,,, gsaa g,miy .: oc.m n. N = 12 and 13. not signi6 cant). His ex- 4 D
- Pfar*ad C. PtWrmas. Semen Res. IS. m
# 13. (J. F. R. Kongand it. A. Klippel. The stat Danma periment shows, therefore, that testos-terone reverses the effect of castration
- 5. 'a R. Ko-isaruk. N. T. Adler, J. Huscluses.
*re 17s.12M 3"ost. Neur JIM 2f;L M. Kow 14.F T'
- 13. Suppt ned r a " ' ~bt).
once Research Councd p P .- y 12 299and D. w. (1973/4h 7000492. we thmak D. Harper for has help with observed in the Orst experittent. R. F. Drewert et al.,-hasms.cience 2.1933 du histology Sosne iaidal esperiments on thss
, in a third experiment we mcasured re- **"
fractory periods c# CMA neurons stimu-
- 6. Sa'r and W. E. Stumpf. Eadscrinoloey 92 23t oM3).
rs $ y' h lated antidroeucally not from the MPH 7 EM"d$,,I',,""aJ,#*M,8'g$," . j'
- o97m.
Ra'""' 'e9"** s should be m se R.F.D. but froa the VMC. Refractory periodst so owns. 2d Jety ins; revised 20 November IMs were det:.rmined for 57 net rons from 13 intact rats and 59 neurons from 13 cas. trated rats. The results show no segmS- -
*'"* d#""** I" ***" "'"**"'Y Period between the two groups. Means and Physical Factors Affecting the Mutagenicity of ranses are 1.23 and 0.s4 to 2.11 msec for Fly Ash from a Coal-Fired Power Plant intact rats and 1.21 and 0.97 to 1.79 msec for castrated _ rats .(U = 8l, not sngm& ____ Abstract. The ssofnnest, most respirable coalfly ashfractions collectedfrom the cant). Q __ ; '
. smokestack ofa powerplant were more mutagenic than two coarserfractions. Muta.
AE the neurons for which results are genicity was evaluated in the histidine-requiring bacterial strains TA !$38, TA 96, gives were located in the cortical and and TA 100 of Salmonella typhimurium. Ash samples collectedfrom the hoppers of medsal nuclei of the amygdala as dehned an electrostatic precipitator in the plant were not mutagenic. The mutagens in coal in (13). In acconlance with anatomical yy ash were resistant to1. ray or ultraviolet irradiation, possibly as a result ofstabili-svidence38), the-anurons driven-front zation bypy ask surfaces. All mutagenic activity is lost with heating to 350*C.
~ the MPH and VMC were encountered in the same caudal region of the CMA. The in 1977, fly ash produced and collected fecting the mutagenicity of(i) four size-refractory penod is altered, therefore, in by coal-Ared power plants was consid- ~ c lassined, stack-collected Sy ash sam-amygdala neurons projecting via the dor- ered to be the sixth most abundant min- ples;(ii) one size-classified. ESP-collect-sal stria to the MPH, but not in a4pa:ent eral in the United States (1). Of the 50 ed sample; and (iii) one unsized, ESP-amygdais neurons projectmg via the dor- million metric tons of fly ash produced, collected sample.
sal stria to the VMC.So the effect of cas , 13 percent was reused commercially, .The stack sampling,was performed at trataan is restricted to the pathway predominantly as a partial replacement 95'C: two measurements of the stack gas known on other grounds'to be involved for cement or as All material in construe- temperature during the 30. day sampling in the control of sexual behavior. The ef- tion; of the remainder, most was depos. period varied.from 107* to ll5*C 0). The fact of castratson must be due to the re. ited in landfius. Electrostatic precipita- volume median diameters (VMD's) of moval of testosterone, since it is re- tors (ESP's) are used in most coni. fired these four size-classified samples, frac-versed by testosterone injections. Tes- power plants for in-plant couection of tions I through 4, art 20,6.3,3.2, and 2.2 tossenene must be affecting.these neu- acrosolized particulate matter. The total m, respectively. AU have geometric rve directly, since it is the refracto- mass collection efficiencies of the ESP's standard deviations (cr.) of approximate-ry penod that is altered, and a change in vary from 95 to 99.5 percent, with the ly 1.8. tefractory pened imphes a membrane lowest relative efficiency for collecting We also couected fly ash from the , change. respimble, submicron-sized particles (2). Power plant's ESP hoppers (6). Three l The change in refractory period that Because vast quantities of fly ash are measurements of the temperature of the . we have demonstrated would al t er the produced in the gercration of electric. ESP's during 2 days of collection varied ! output of the pathway to high-frequency ity, detailed studies are required of from 104* to 107'C. Because the ESP fly inputs. Presurnably these inputs would the potential public and occupational ash is predominantly composed of rela-be olfactory. This interpretation receives health hazards of fly ash released from tively large particles, it was aerodynami-cspport from a previous study (4). which smokestacks and collected in power cally size. classified to obtain a fraction shows that testosterone does altcr pre. plants, with a VM D of 2.3 gm and <r. = 1.4. The , optic neuron responses both to electrical We have demonstrated that extracts physical and chemical properties of the sumulatien of the olfac:ory bulb and to from a stack-collected. respirable fly ash stack-collected samples and of similarly natural sexual odors. sample were mutagenic in the Ames bac- collected unsized ESP ash have been re. K. M. K n narcx terni assay U); moreover because of the ported (7). R. F. DnEw sTT* correlation between mutagenicity and We evaluated the relative mutage-(>partment offsp hology. carcinogenicity Of). our study in<!icated nicity of serum filtrutes from the four U,vhersit,5 ofl>urham, that fly ash is rotentially carcinogenie, stack-collected fructions usmg TA-1538 Durham. England We describe bere physical factors af- because our presious studies indicated it WWNCE. VOL 208. 23 %4AY Im 00440*WOMS-0079stw SDe Copynshe e im AAAS 879
l
* , . , , j.
, yere observed t.t temperatures above ash could be collected at lower temper- Estimating Fotness 200*C and 300*C, respectively. For the atures thin normally pressnt in ESP's.
'f three bacterial strains studied,2 S-9. no However, if such an approach were Part of the controversy between l, mutagenic activity was observed for fd- used, the industry would be confronted Frisch and Trussell (1) 1inges on the trates from ny ash heated to 350*C. in 1980 with a predicted 100 million tons manner in which Frisch has estimated l Our studies of physical factors af- (1) of weakly mutagenic solid waste. A fatness as a linear function of height and fecting the mutagenic activity of coal Ay reasonable strategy, therefore, would weight rather than measuring it physio-ash extracts provide msight into the consist of high-temperature, high-effi- logically. It appears that the random var-
~ chemical properties of Ry ash mutagens. ciency collection of particulate matter imbility of the estimarer has an impact on i The Andmg that the greatest activity is from the Rue stream, followed by sub- the arguments which has not been fully e associated with the finest fractions of sequent condensation and in. plant col- appieciated heretofore. Rather than ac-j stack-collected ash is consistent with the lection of volatilized organic matter: tual measurements of fatness Frisch observanons of Natusch (13) tb *^t' G. L. FtsHEa uses the Mellits and Check equation (1): i '" I are adse.h na omrticle a '- _ C. E. CHalsP N = -10.313 + 0.252WT(kg) + cooling of the effluent stream. The obser- O. G. RAAaE 0.lM (cm) vation that ESP-collected Gy ash was not Jtadiobiology laboratory, University of mutagenic (whether size classified or Ca4fornia. Davis 95616 to predict a girl's total body water (TW) not) suggests that c '-_7 = ' - " (assumed proportional to fatness) from
,,,,,,3,,,,
ggns on ny ash particles occurred after her height (NT) and weight (WT) at men-passage through the ESP but hafar* [ #* gE ".*y*,,Ng$D.E'd arche. Since this regression line has a or'wumn the stack samgiling system. g g g Yp,8 g8(1yk , j multip;e r8= .97, one might be tempted Nitusch aMeiuna d4) have predict- enre m. 73 (inst to suppose that the random variability is t Casa. E. Yamseh. Wasar. negligible, but this is not the case. Exam-ed that a temperature near 100'C is criti- d p,,N.3 w cal for the adsorption of PAH onto fly S. A. a. McFartend. G. L Fisher. B. A. Pnatace, ination of the Meilits and Check data Q) 8 """' ' ' " "' shows that one needs to provide a band ash. Our observations of_the enraal-'e ,"i,rri "
.a metsiew with-eggggs.- 6, we coescted 30ss ks et By ash ham the dry dis- of 3.03 liters to either side of the line to loss *" r chere.a,et mental " ta t'a - ~ -:-'-t -
ca - oginn anssp can=r*.a-umsensi. hoppers. tened meThe er nas cover 90 percent of the individuals in the with the hypothesis _tha_t the_ bulk of the *a
,,,,, =,,de
, g Q g f uoa Mellits and Check study. With this error - -
I mutagenic activity of the Ay ash samples assemeepehe. naims.A y Med 75 ks etre%, band one has: is associated.,with70ssiiiiiE~@ ,, RDaher,5. A. Pwetice. D. Silbumes. J. N = -10.313 + 0.252WT + This loss of activity ~f a== -W ' Mad M. Oedow. A. H. Ibernamn. St. C. Ragnimi. A. R. hicFartmed. Environ. Sci. Techaed.12. 447 0.154HT := 3.03 ~ Sy ash appears to' begin at tem _peratures towsn J. M. ondev. m. C. nasas'si, m. E. Heft, and thus' - G. L Fihr. D. sdhenamn. S. A. Prentise, im J greater than the operating temperatures -10.313 + 0.154HT ~+ 3.03 of the ESP. The temperaturediffesence pmcevears syn ,. . .. ue/mand,abr Eie.hs4 Mmmelsformeseerr*
.d sam.d.,d, E. WT=
probably renects
'"" "' Me=='"" (SP'=8 P'"-i fW/WT - 0.252 .n
-- the fact. rkar ne-nic "as4 N"aziones awamm et scandards. Gmihere.
------ - 4 are chemisorbed to Sy- ash Md.,GL
. 3ss-572: w. G. Jemmass.
inn.Ii'h'r O. G. Ranke, anda,. Now, according to Frisch, thena- nu. -- - ~' L . susNes --d e- = '= ; r : - h:-k.e
**aber La6=ro*=r7 daamat Arpeer uCo c2- mum required weight for the onset of ~
;,- = r a, '
_w This by- su (Neiieens Tscheces insanmanien servsm, menarche is given by the 10th percentile -
~
synesseM. vs., isin. p. 24. Pothesis .is snapported by our observa* s. D. F. 5. Nansech. 2. R. waltese. C. A. Evene, fatness line, where N/WT = 0.598.., tions that the aiutagens m fly ash are re- Jr.,seware ass.2st(tw4A , , , ~ . and thus we have, . I
*ie=t to photochemical decomposition 9. M.
t,rr.Jacobs.,T.
- 2. si tiern.s. Masmey. A. C. Gnam.
t w. wamenters. Camrer Ade. f.as y., x. - upon UV- or x-ray irradiation. Similarly, , Q'geas i,wNL L seish.umm. Minimum required weight = ~T x :r-- - Natusch and his co-workers (8,15) have ses. 49 is3 wsA d "*"****'** -10.313 + 0.154HT z 3.03 r obsesved that PAH adsorbed from the 81 ** *"r'".*vep*o*r mercu y i *mmy(V-i""d'l Genera Elecmc Gi3 Tot 'O ( vapor phase on Sy ash surfaces may be wo mens-red tbe radia i thin wet a remosainee 0.5918 - 0.252 stabih, zed against photochemical decom- asemesseer ,is,. G,,. calvee and J. ,N. Puts.From
,,g,,,,,,,,,,, Pho-,this it can
,, se,, bei ee.
, ,,g, seenpp.t' 7s)-
hat about 9 kg y ll pmioon at solar radiation wavelengths; .===
,p ,, id.T,s ,Y of uncertainty is ;.kled to or saibtracted photodecomposition occurred with irrr.- du:ened ches as pareent er ins ama m is* from the predicted minimum required The penes e dietion of PAH as dry powders, in solu- g g g ies cc , , d w re weight by the error bands. Clearly, this tion, or adsorbed onto silica, alumina, or sy days .ad tour clew days. An emmased cu- 9-kg Variability in estimated minimum massieve near.uv (295 se 3ss ami espo.no or .
glass. 22so J == coac ansed two concem.: menswe. weight occurs for all he.ights and weights These studies demonstrate that (i) the ments as a nearby need umason tdana impphed by involved. rendering this procedure for l most respirable stack. collected Hy ash 82. bi 'r isidies di, we have demon- determining fainess rather questionable 8 samples are the most mutagenic, (ii) the y am e e'Uh "" b[ee pasi'd and undermining any support these data ESP-collected fly ash from the same nismuse .au.e, ,.un. TA los. might be thought to give to a critical fat-emmh.Ennma. #euse rmpres. 22. power plant is not mutagenic, (iii) the 13. D F, ness hypothesis. surface-ansociated mutagens are resis- 34. and e. A.Tenhias.Carraaaveaesis J. P. JAxx REEVES W. Jones and A. I. Freudensamt. Eds, iRaves.
; tant to photodecomposition with UV- or w,w yors. insi, pp. i45-15). .
Statistics Deparrarent, finiversity of N est Ic n" " l x-ray irradiation, and (iv) the mutagenic- ig (F h es sup. Californin. BerAr/ry 9r720
' ity of fly ash is completely removed by p,, or 3. g. t e t. o. saberman. and s. A.
heating to 350*C. The observation that r="uc* *ad " (" *8"*"d""**""- secre===== senpa by S. A." Deck.'"C. P. Sadi. and L S. R.*- mutagens were associated with di ash wnw.is Thiire,eurch wes ==pported b time or. i. J. Tnown. 3dem e 2es. iM6 (197st R. E. see er Emuruemental Rew.rsh of the U.S. De- Fnsch. s A.I. . p 99 particles when co!!ecied at tempersiures partment or Emersy under contract EY.4-C 04- 2. E. D Mett.h and D B. Cheet. Waerr. Soc. below 100-C suggests a possible im- s472 ..th
- Unnerway or Caidorma. Dem. ar O dJ un. 35.i2licot 2, sammary ivve. revoed 1 March 1979 14 screemewe ie'ai. revi.ed in January 1979 provefr ent its control technology. Fl>
N newest $'7903254: Wit $ss.500 Copynsha t 19N A AAS Ist SCIENCE. VOL 2s4. 25 MAY if"9 3 -
r *. . i.' ' ~ ^ , ~
.1 i<. -
O, . CqTm ; {1 l Envimnmenbal Health Perspectives Vol. 22, pp. 70-90,1978
-+
, ? 'M JZ' -3 A0 M3 !
, t F
4, m. Potentially Carcinogenic Species " - l j
! Emitted to the Atmosphere by Wf t > .
l lj Fossil-Fueled Power Plants ,6 y - a
]j by D. F. S. Natusch* &- 1 y pe , c c, x ,
9 o The ideontles and phy '-- ' W characteristia of patentiaBy carcinogen species einitted to the
)
o at===rken by fossil feeted power plaats are presessed and discussed.11 is pointed out that many i so cased cercinogens are preferentiaDy cancentrated on the surface of respirable ny ash particles thus ; entbling them to coene late latimate contact wkb lung tinues when tahaled. Relatively little taformation is avaDahle about the Idristitles of particulate polycyclic orgamle compounds whose emission from coal fired power plaats may weg be substantiauy greater than httherto supposed. The importance of chemical
.f.
changes, which severns species may undergo fetowlog enession (but prior to inhalation) la determining bimpact,is stressed
}{ simirpotestinia
!g) 1 lntrOductlOn Fossil-fueled power plants are considered to be
; those utilizing gases, liquids, or solids as primas,/
j l'roduction of electric power from the combus- fuels derived, respectively, from natural gas, oil, or a tion and conversion of fossil fuels represents a coal. Some difficulty is encountered in specifying ubiquitoe and increasing means of obtaining individual pollutant species since defimitive data on
" energy in most countries throughout the world. It is carcinogenicity are sparse. For the purpose of this now well established that such power plants emit paper, therefore, compounds are classified as
;1 substantial quantities of many carcinogenic and po- known carcinogens, suspected carcinogens, and ,
tentially carcinogenic chemical species to the at- reactants. Compounds classified as reactants are {: mosphere. Consequently, it is of considerable im- those which are considered likely to be involved in :~ I portance to establish whether these materials are chemical reactions which may result in the produc-
, 7 active in promoting the occurrence oflung cancer in tion or removal of carcinogenic species or which l' s[ populations resident in the vicinity of fossil-fueled may interact synergistically with known car-power plants. cinogens. In Table I are given examples of concen-i
,{ In order to make any assessment of risk it is trations of known and suspected caicinogens in
}
necessary to have knowledge of the nature, con- urban and rural atmospheres. a centrations, and physicochemical characteristics of g potentially carcinogenic materia; emitted from the Gaseous Emissions o various types of fossil fueled power plants. This 4 paper, therefore, presents a brief survey of the in- Gaseous emissions from fossil-ft:eled power
- fom1ation currently available. Special emphasis is plants generally contribute more material to the at- :
f placed on what is known about the physical and mospt'ere than do particulate emissions (except in r chemical characteristics and behavior of each the now rare case of uncoritrolled coal combustion). ;
- species since these properties may have a profound The major emissions,in terms of mass, involve car-
- influence on the inhalation toxicology of individual bon monoxide (CO), hydrocarbons (HC), nitrogen species (1,2). oxides (NO,), sulfur oxides (SO,), and oxygeriated a species often classified as formaldehyde iHCOH).
Representative contributions are indicated in Table [: 0 2 (13). In addition, minor emissions of mercury
- Department of Chemistry. Cobrado State Ur.iversity. For; ?
Collins. Ca .,:o som. occur, and it has been suggested that bromine (Brs ), o g February 1978 79 e o
~.
_ _ _ _ _ _ _ _ _ _ _ __M. ^Y EY ("
'5
. . .i l ,
E
! )
[. g . . Table 1 (cont'd.) l Pol3eyclic nitrogen compounds, ng/m* (2.12) i f Acridine Suspected 0.1-0.5 - - p Fluorene carbonitrile Suspected 0.02 4).1 - - 1 o L. cad tetraalkyls, ng/ms I (6)
,, Tetraethyllead Suspected 50-2000 75 -
) Benzene. soluble organics, ng/ru8 Recognized 1000-20.000 7000 200-1000 1P (2. 4. A >
y 'The substances listed include both known and suspected carcinogens for which reasonably reliable atmosphenc con.
- centration data are available. Also listed are several compounds which are considered to be capable of promoting car.
ciouscuk activity in noncarcinogenic compounds or modifying that of carcinogens as a result of chemical reaction. y *Most values represent 24-hr averages established over periods ranging from several days to one or more years. -
' Approximate averages values have been estimated for urban air noting that individual areas may exhibit atmospheric f concentrations which differ considerably from the average. Due to paucity of data it is considered inappropriate to estimate
, similar averages for rural atmospheres.
- Fluorine is present in the atmosphere as bcch fluorine gas and particulate fluorides. The values IIsted refer to the sum of T both forms.
o ,
' Values listed for lead refer to concentrations measured in countries utilizing lead alkyl gasoline additives. Significantly o lower values are encountered in counmes which do not use leaded gasoline, p
, ' Selenium is present in the atmosphere in both gaseous and particulate form The values listed refer to the sum of both (
I forms. Also, selenium has not been implicated as a causative agent of bronchial care: noma but only of liver sad kidney J
.f" cancers.
'The two sets of values listed for vanadium refer, respectively, to urban areas where considerable use is made of fuel oil e for power generation and domestic heating, and to urban areas where oil burning is minimal.
p *A very large number of organic compounds have been implicated as causative agents for bronchin! carcinoma. Only a l
- h few of these are listed here, however, since reliable atmospheric concentration data are unavailable. In general, com-y pounds are listed by ciass with specific examples being given where data are available.
L 'These hydrocarbons are not in themselves considered to be caremogenic. They may, however, promote formauon of photochemical smog which contains several carcinogsnic components. i 'The data for nitrosamines are very tenuous; they are, however, included because of the considerable current interest in 4 { these compounds.
*Several noncarcinogenic polycyclic compounds are listed, since some of these are known to react photochefrm;aily to produce oxygenated derivatives (such as quinones, phthalates, and endoperoxides) which are suspected carcinesens. It !
U will be noted that some sery wide concentration ranges are listed for the polyaro natic hydrocarbons. The upper ends of [ these ranges correspond to values measured in European cities where estensive coal burning is practiced. { Y L s i i Table 2. Anrnge air penetlos emivslees frase powee plaats sence of controls the amounts of sulfur oxides emit- , 4 acmeng ** fbi type.' ted from a fossil fueled power plant are directly re-Emissions. Ib/1000 lb fael lated to the sulfur content of the fuel burned (Table ; Fuel Particles
- CO HC N O. SO, HCOH 2). In this case, typical SO, emissions lie in the range 500-3000 ppm with 1000-2000 ppm being _
Coal 85 (1 - EP 0.25 0.1 10 19 S' O.002 most commonly encountered (15). Nowadays, [ . tural gas 2 - E) n s. I however, most major installations utilize control , 7' " ' equipment which typically achieves 85-90 percent E :colle tioneft ency the control equipment. removal of SO,. Generally, about 1-2% of the emit- i t 'As the percent sulfur content of the fuel by weight. ted sulfur oxides are in the form of sos, which - f reacts Iapidly with water vapor to produce sulfuric - acid mist. A small amount of the sos is also f chemisorbed by fly ash particles to form metallic -
?
hydrochloric acid (hcl), selenium dioxide (SeOs), sulfates (primarily calcium sulfate and alkali iron g
^
arsenic trioxide (As.O.). and organometallics such trisulfates)(16). = as nickel carbonyl (Ni[ COL) may be emitted as The rate and extent of sulfur dioxide conversion j i vapors (6.14). to sulfuric acid mist and solid particulate sulfate in a
- power plant piume are unknown; however, current thinking is that these processes occur fairly exten-Sulfur Oxides sively, s that a significant proportion of the gase-f$ ous sulft:r oxides produced actually occur m urban
. Sulfur oxides are not. in themselves, thought to atmospheres as sulfuric acid mists or as particulate r- be carcinogenic. They are. however, quite reactive sulfate (4). This is an important consideration, since lI and are known to react with, for example, polycy. it means that the health hazard presented by gase-ous sulfur oxides may be partly manifest through le clic aromatic species t2) and to prornote lung damage . when associated with airborne particles. In the ab- inhalation of sulfuric acid and sulfate paiticles, s o , February 1978 81 4 '
s U y sqsy W yr N uusimuc ~ N "uut M l'E N W W l . , . asamEfit
t j.. , ~ . ' <- - - einey. m - r * '
. 1 .
many countries the proportion is even higher. As addition, the size of a particle determines the ( indicated by the data in Table 2, particulate emis- specific surface area which can come into intimate [ sions from coal-fired power plants are much greater contact with body fluids and tissues. The size dis-g than those derived from oil or natural gas combus- tributions of particles produced by diDerent power h tion. Some idea of particle mass emission factors plants exhibit considerable variation; however, a T can be obtained by noting that modern electrostatic typical size distribution of fly ash emitted frum a I precipitation equipment usually operates with mass coal fired power plant equipped with an electrostatic I removal efficiencies in excess of 98c/c. precipitator is presented in Figure 1 (21). It is ap-
? Assessment of the carcinogenic hazard as- parent from this figure that much of the enitted ny
{i sociated with airborne particulate material such as ash falls in the respirable size range. fly ash is very much more difficult than is the case I for a gaseous pollutant. This is because particles iao r I contain a large number of potentially carcinogenic -
? chemical species including both organic and inor-ganic compounds. The reladve amounts of these
~
$ g j species, and thus their net carcinogenicity, can vary ;
4 significantly with the type and origin of the fuel 2 3 burned and even with the operating characteristics 3 r4 of individual power plants. Furthermore, the way in i 80 r f which a given chemical species is distributed among 5 4 different particles and even within a single particle a can strongly influence its potential health impact. i l f,? Finally,it must be recognized that, although many f I potentially carcinogenic compounds may be as-
]y sociated with solid fly ash particles these com- ,, .i..i i i , i i i i .i i
; pounds are unlikely to constitute a hazard to health 0 01 10 1 5O So 90 95 99 999 9999 unless they can be mobilized into solution, e.g., weish' % Lasi Thon s'ated sir.
. body fluids.
The extent to which information is available Ficuas 1. Representative aerodynamic panicle size distnhtion I about each of the above factors is discussed in the following sections. For convenience, different class-of fly ash emitted frorn a coal fired power plant equipped with an erecmatic precipitai r(21). o es of chemical compounds are considered sepa-1 rately even though all may be present together. In Relatively few measurements have been made of o this regard it is useful to note that a single particle
, particle size distributions in power plant plumes. As
. effectively concentrates many chemical species m a a rough indication, however, particulate material .
o localized microregion so that its influence is likely collected at a distance of 5 miles downwind from a
. to be exerted over a very localized area of lung coal-fired power plant plume under stable plume o tissue when inhaled. This is in contrast to the more conditions has an aerodynamic mass median diamp a genera!ized influence ofinhaled gases. ter in the range 0.08-0.25 m. Such samples usually exhibit a bimodal distribution, with the two modes Particle Morphology, Size Distribution, and being centered around 0.(M m and 0.3 m. The Matrix Composition sm Her modal panicles are thought to represent a
{ secondary se osol consistmg primanly of sulfate ,7 l
- articles emitted to the atmosphere from fossil particles. Comparable information is not, to our I ,,
fueled power pLints are more or less spherical. In knowledge. available for oil or natural gu-fired
. the case of coal combustion both solid and hollow power plants, although similar general behavior . spheres occur and some of the latter have small would be expected. . respirable spheres encapsulated inside them (IS, The reator rn M :!r em ;ren:n S cr! $ 12 . 19). Particles derived from oil and natural gas com- are Al, Si.and Fm vith minne mm d C , ";. . bustion have a highly porous structure rather like , P.*:r Ti nnd @me typical composition ranges, o that of a sponge (20), e sed as weight percent as the oxides, are pre-The aerodynamic size of a particle is a major fac- sented in Table 4 (22). The matrix elements in oil Oy o tor in determining the efficiency with which it can ash are C, Ca, Fe, S, Si, Ti, and V (23), whose a be collected by control equipment. its atmospheric relative proporticns vary considembly in individual transport characteri ties and lifetime, and its depo- particles. Coal Oy ash consists primarily of a semi-la* sition and cleara ee behavior when inhaled (1). In transparent aluminosilicate glass with small amounts lO February 1978 83
{ a g i 4 e
i
- t. .
Tatde 5. SpeaAe concentr=*t and vehune concentr= i of d. ants la coal and on of ashes . t Coal fly ash Specific conen. oilfly ash Element Volume conen, Specific conen. us/s us/m' Volume conen, At 70,00 % I 000 ~ as/s us/m2 10,000 As -50n 100-5000 l I E 300 Au 0. 30
- 4-7 B 10 400 -
Ba 504 7000 - Be 30-110 50 4 10,000 I-10 - 1600
' Br 0.3-20 -
Ca 1-5 - 6000-180,000 -
/ Cd 300-1000 IA1000
- 0.1-50 - 500-700 Ce 1 C1 100-300 -
( Co 10-500 hig 1-2 1-5
.P Cr _50-300 90 16 8-20 66 6 Cs 20 ' - :2 ? Cu 54650 -
0.1 Fe 25 50-2000 - 10,000 10,000-100,000 700-1000 HT 5-10 -
- Hg 0 02-0.4 -
t I 0.5-7 in 15-40 - 0.1-0.3 - K - I l_a
~~1500-35,000 -
1000 - - 35-100 2-10
) Lu 0.5-2 2.5 s Mg
!D 11,000-60.000 300-I000
' Mn 5M-5000 -
I g 50-500. - M 5-do I-100 8 74200 Na '1200-18.000 Ni 2000-50,000 N000 h!M- 10-25 - Pb p 10-20 Rb 200-2000 - 40-300 - f Sb I-13 0.5-3.0 sc 5 g 10-40 2-4 l w - I-20 5-15 3 ! Sm i 10-20 - - Sn 30-30 5 5, 50-4000 Ta 0.5-1.5 - - Th 15-70 0.5-3.0 - Ti 0'13 i 3500-8500 300-700 - TI 2-30 U 5-20
- - ]
7v ~ d200,000
"$ hi -
1000 200 2470 2E3500 W concentations are employed. This is because vo!- have been measured in coal fly ash (25-28): how-ume concentrations depend upon the way in which ever, only *Pb and "U are enriched with respect the bulk particulate mass is distributed with respect to the levels found in soil. Measurements of Ra , to aerodynamic particle size. Some typical elemen- 8'*Th, and "U in the plume 6 km downwind from a tal size distributions determined in the stack gas of a coal fired power plant show that these elements are coal fired power plant are presented in terms of enriched over normal background levels by factors volume cencentation (ng/m 3)in Figure 2 (23). of 9, 4, and 28, respectively (29). These authors - As mentioned previously, coal ccrnbustion re. have assessed the lung doses from a 1000 MW coal stdts in the emission of several carcinogenic fired power p! ant to be approximately 10 man rad radionuclides in paruculate form. Specific concen- peryear. trations of ""Pb, SRa. "Ra, "Th,22'Th, and "U February 1978 85 l
~
p - . ) - t J ready availability. (2) Conventional bulk analyses the dependence of concentration on radial depth ) of particulates provide a poor measure of the actual into coal fly ash particles before and after leaching ] concentrations of toxic trace elements to which the with water (16). ) external environment is exposed. This fact must be The factors controlling the rate and extent of sol- ) considered in designing toxicity studies using ubility of individual elements associated with fly 2 synthetic particulates. (3) Since the surface layer ash are complex (32); however,it is apparent that a a contains an increasing fraction of the total particle substantial fraction (probably-50%) of most poten-J mass with decreasing size, small, lung depositing tially caremogenic elements is extractablefrom re-a particles will have a greater proportion of their as- spirable particles. 2 sociated toxic species in immediate contact with It is appropriate here to draw attention to the s lung tissues than will large particles, i.e., as indi- distinction between the concentration and amount l cated earlier, long-depositing particles definitely of a species extracted from a particle. Thus, the 7 constitute the most potentially casemogenic frac- total amount of a given species may be quite small i tion of allfly ash particles. and unlikely to constitute a hazard. On the other , hand, the localized concentration of that species a Solubility may be,very high (due to its surface predominance) and quite capable of causmg damage m a micro-3 y Probably one of the most important properties of region surrounding each particle. The question is g particulate matter emitted by fossil fueled power whether or not such local effects are important. If ) plants is its solubility. Indeed, unless the associated not, then the surface predominance of carcinogenic g toxic chemical species can be extracted by lung trace elements may be oflittle consequence. g fluids their ability to act as chemical carcinogens is p probably negligible. Surprisingly, this point is fre- Particulate Organic Compounds quently overlooked. It is now well established that only about 2-3% of Particulate associated organic material emitted i the mass of both coal and oil fly ash is soluble in from fossil fueled power plants is known to contain i water. Very little more is soluble in most ddute both aliphatic and aromatic compounds. To date acids or bases. However, while the fly ash matrix is essentially all studies have been directed towards effectively insoluble, the so-called surface layer, in the latter class of compounds with special emphasis which many potentially carcinogenic elements are being given to polycyclic aromatic species which - highly concentrated, is quite soluble. This is illus. include many well established carcinogens (2). trated for the case of Pb in Figure 3, which shows Even within this group, primary emphasis has been App *onmate Ocpth(d) O 16 0 320 480 640 800 960 i . - i i 4 y tosp g 3 J D 240 - E { h - 40000
'6 $ -
3
.' f160 -
30000f E - Y
', 20000 h - .. 80 - - B l } ,
t - 0000 .Eg i i
~
<- *- WW -
. g 4
l o ' ' ' O , O 40 80 120 16 0 200 240 ' Time (secs) j Facune 3. Depth profiles of Pb moeiated with coal fly ash recorded (a) before, and th) aner teaching the fly ash with water and i dimethyl wifotide (lu. February 1978 87 ;
N YNbM 9.. s {D ~ i i Chemical Conversion of POM rudimentary knowledge is available about the {, - A number of studies have shown that particulate changes that these species undergo prior to inhala-tion. Consequently, contemporary estimates of T polycyclic organic, species can be modified in the human hazards must, of necessity, be based on atmosphere as a result of photochemical decompo- what is known about emitted species plus what can h sition or reaction with sulfur or nitrogen oxides (2). be inferred or guessed about the ways in which their This is of considerable importance, since such reac- { , tions may significantly alter the carcinogenic poten-carcinogenicity may be modified prior to inhalation. tial of POM. Indeed, the chemical compounds ac-tually inhaled may be quite different from those Part of the research described herein was supported by grants originally emitted to the atmosphere. ERT-74-24276 MPS.74-05745, and DMR.73-o30206 from the
}* Recent studies (34) of the photochemical decom- N,d$*i' La N nal unit i es njr "
tIP g position of several polycych,e aromatic compounds Agency. j adsorbed onto the surface of coal fly ash indicate j that some compounds, e.g., phenanthrene and y pyrene, do not decompose appreciably under the REERDCES influence of solar radiation. A second group, e.g., I. Narusch..D. F. S., and Wallace, J. R. Urban aerosol ton-1 ar.thracene and benzo [a] pyrene, decompose with icity: the influence (particle size. Science ls6: 695 (1974). halflives of several hours, giving the corresponding 2. National Academy of Sciences (U.S.L Particulate Poly. cyclic orzanic Matter. Committee on Biological Effects of qumone as the mdor product. lateresting behavior Atmospheric Pollutar.ts, Division of Medical Sciences, Na-is observed in the case of fluorene, which decom- tional Research Council, National Academy of Sciences, poses to fluorenone in the absence oflight. Washington, D. C.,1972. Data such as these illustrate the point that .esti- 3. National Acaderny of Sciences M S.)., Vapor Pbw Or-mates of the carcinogenic potential of POM emitted sanic Pollutants. Coir.mittee or. Biological ENects of At-mospheric Pollutants. Division of Medical sciences. Na. from fossil fueled power plants must necessarily be tional Research Council, National Academy of Sciences, based on analyses of particulate material collected Washinston D.C.1976.
) from the plant plume at some distance from its
- 4. American Chemical Society. Cleanins our Environment:
ongm. Until the results of such analyses are avail- The Chemacal Basis for Action. American Chemical Soci.
} egy,w ,s;ngton, o c., ggg, y able, very little can be inferred about the nature and 5. Rhan, K. A. The chemical composition of the attrmpheric ) amounts of potentially carcinogenic organic species aerosol. Technical report, Graduate School of Oceanos-likely to be present. raph/, University of Rhode Island, Kingston, R. I.,1976.
- 6. Schroeder H. A. Trace metals in the air. Environment 13:
18(1971).
- 7. Sax, N. I. Toaicolog' cal effects of non-nuclear pollutants.
COnCIUSIOnS Im Atm sphene Schnce and Pown Productia D. Ram derson, Ed., US.ERDA. WashinFton, D. C., in press.
- 8. Lee, R. E., Jr., et al. National air surveillance e=We im-It i.s aEparent from the foregoing remarks that the
. . pactor network 11. Sat.e distribution measurements of trace P identities and amounts of most air pollutants emit
- metal components. Environ. Sca. Technol. 6: 1025 (1972).
> ted by fossil fueled power plants are reasonably 9. Naconal Couacil on Radiation Protection and Measure-p weli established. The major gap in knowledge of ments. Natural Background Radiation in the United States. P this type concerns the, emission of particulate 10. ha$. D. Nitrosamines Scientists on the trail of prime P polycyclic orgame matter (POM) whic,h probably suspect in urt an caecer . Science 191: 268 (19761 includes the most potentially caremogenic species. 11. ge,tssz-S& rinser, M.. .md Morfin. Z. On the occurrence af it b aho apparent that simple knowledge of the polycyclic acomeric bi drocarbons in the urttan area of E ider.tity of a toxic substance is scarcely adequate to Budapest, Atmos. E nviron. 9:831 (1975).
- 12. Lao R et A cati n o g "
{ enable assessment of its significance, as a health ,p e na sI
! hazard. This is of primary importance m the case of the polycyclic aromatic hydrocarton content of airborne g particulate matter for which such factors as po:lutants. Anal. Chem 45:908(1973).
aerodynamic size distribution and surface predc.mi- 13. Goldstein, R. F., and Waddams, A. L. The Petroleum ( nance may play a major role in determining toxicity. Q*,micals Industry. 3rd ed. E. and F. Spon 1.td.. London, f !n this regard, the information which would be of ' 34, o,,; son, R. L.. et al. Trace riements in ny ash: dependence I most value is a quantitative measure of the ava,ila- of concentration on particle size. Environ. Sci. Technol. 8: I bility of carcinogenic species associated with parti- 1107(1974). l Cg"S*
- 15. Natasch. D. F. 5.Cha:acterization of atmosphenje2ailu-While there .is considerable m. formation about po- TiinIs Tr6rri-~ power plants. In: PrdLFei!HigT5Fthe Second I Federal c onierence on the Great Lakes. Great Lakes Basin tentially carcinogenic speaes which are actually Commission.1976.
emitted from fossil fueled power plants only 16. Linton, R. W., et al. Determination of the surface predomi-I February 1978 89 l
. ly
& rudimentary knowledge is available abput the N
Chemical Conversion of POM changes that these species undergo prior to inhala-A number of studies have shown that particulate tien. Consequently, contemporary estimates of h*' polycyclic organic species can be modified in the human hazards must, of necessity, be based on h atmosphere as a result of photochemical decompo- what is known about emitted species plus what can
- sition or reaction with sulfur or nitrogen oxides (2). be inferred or guessed about the ways in which their This is of considerable importance, since such reac- carcinogenicity may be modified prior to inhalation.
b/ tions may significantly alter the carcinogenic poten-tial of POM. Indeed, the chemical compounds ac-f tually inhaled may be quite different from those Part of the research desenbed herein was supported by grsnts [ ERT.74-24276. MPS-74 05745, and DMR-73.o302% from the originally emitted to the atmosphere.
. United States National Science Foundation and by grant Recent studies (34) of the photochenu. cal decom- R.803950 01 from the United States Environmental Protection position of several polycyclic aromatic compounds Agency.
adsorbed onto the surface of coal fly ash indicate that some compounds, e.g., phenanthrene and - REFERENCES f pyrene, do not decompose apprectably under the influence of solar radiation. A second group, e.g., I. Natusch. D. F. S., and Wallace, J. R. Urban aerosol tos-d
" ici'Y:'h'i" fluence f article P size. Science 186: 695 (1974).
anthr.acene and benzo [a] pyre.ne, decompose with
. 2. National Academy of Sciences (U.S.). Paru,culate Poly.
m halfitves of several hours, gleng the correspondm.g cyclic Organic Matter. Committee on Biological Effects of quinone as the major product Interesting behavior Atmospheric Pollutants Division of Med cal Sciences Na-is observed in the case of fluorene, which decom. tional Researth Cour_il. Nauonal Academy of Scinmces, W"5
! poses to fluorenone in the absence oflight. 3. Nau.hington, onal Academy D. C.,1972.
of Sciences (U. S.). Vapor Ptuse Or-Data such as these illustrate the point that esti-
't mates of the carcinogenic potential of POM em.itted garuc Pollutants. Committee on Biological Effects of At-mospheric Pollutants Division of Medical Sciences, Na-
] tional Research Council. National Academy of Sciences.
V from fossil fueled power plants must necessarily be
' based on analyses of particulate material collected Washington. D. C.,1976.
- 4. Americar. Chemical Society. Cleaniris our Environment:
fro.m the plant plume at some distance from its The Chemical Basis for Acuon. American Chemicat Soci-
, origm. Until the results of such analyses are avail ~ ety, Washington D.C.1969.
? able, very little can be inferred about the nature and 5. Rhan, K. A. The chemical composition of the atmospheric i amounts of potentially carcinogenic organic species aerosol Technical report Graduate School of Oceanos-
' raphy, University f Rhode Island, Kingston, R. I.,1976.
likely to be present. 6. Schroeder, H. A. Trace metals m the air. Envirorment 13: t p 18(1971). g
- 7. Sax, N. I. Toxicologica! effects of non. nuclear poDutants.
In: Atm spheric Science and Power Production. D. Ran-
- CONCLUSIONS derson, Ed., US-ERDA. Washington, D. C., in press.
It is apparent from the foregoing remarks that the 8. Lee, R. E, Jr, et al. National ai,r surveinance cascade im-k . pactor network II. Size distribution measurements of trace identities and amounts of most air pollutants emit-
-1 metal components. Environ. Sci. Technol. 6: 1025 (1972).
6 ted by fossil fueled power plants are reasonably 9. National Council on Radiation Protection and Measure-3 well established. The major gap in knowledge of ments. Natural Background Radiation in she United States. NCRP. P this type concerns the emission of particulate IO I E **'****i"* 8*itists 3n the trad of prime
. f. polycyclic organic matter (POM) which probably
. . . . **P suspect'Y'n i urbar. cancer. Science 191:
268(1976). Includes the most potentially carcinogeme species. ii gert4sz.S4 rinser. M., and Mortin z. on the occurnace of it is also apparent that simple knowledge of the polycyclic aromatic hydrocarbons in the urban area of identity of a toxic substance is scarcely adequate to Budapest. Atmos. Environ. 9:831 (193). T 12. Lao, R. C., et s'. Applicatien of gas chro natography-mass li e enable assess. ment of its significance as a health spectrometry-data processor combination to the analysis of hazard. This is of primary importance in the case of the pd> cyclic aromatic hydrocarbon content of airborne
.; particulate matter for which such factors as ponutants. Anal. Chem. 45: uos (1973).
- 13. Goldstein. R. F., ar.d Wajdams A. L The Petroleum aerodynamic size distribution and surface predomi-I Chemicals Industry. 3rd ed. E. and F. Spon Ltd., London, nance may play a major role in determining toxicity.
In this regard, the information which would be of ( $7-; son, R. L et al. Trace elements in Oy ash: dependence { e, most Value is a quantitative measure of the availa- of concer.tration on particle size. Enviroc. Sci. Tect'nol. 8: bility of carcinogenic species associated with parti- 1107 (1974).
- 15. Natusch, D. F. S. Characterization of atmospheric pollu-m cles.
J While their is considerable information about po- /tants from power plants. In: Proceedings of the Second Federal Conference on the Great takes. Great lakes Basin o tentially carcinogenic species which are actually Commissien,1976. err.itted from fossil fueled power plants only 16. Linton, R. W., et al. Determination of the surface predomi. February 1978 89 l i-o M :!! M W 5'P2P
0 j- [O-@,9 Q o
- UCD 472-502
/. DOE Research and Development Report l']_ UC-48, Blomedical and Environmental Research 84 J.'J: -3 K0 :48 z ; '1 '
- f. F r a. _,,_
9-Z L C C ". . ^ lt '; & .t ds - b5AhCh e:, } E1 .
- r;y
'1 SIZE DEPENDENCE OF 3;; THE PHYSICAL AND CHEMICAL PROPERTIES OF FLY ASH g
1 4 p.s p ..~r' i;q vr f.~e f ~.v,4 ,
,.!2
.\ G.L. Fisher - < .. .. s., a i
, c r.d
' " " ' # " ~
4d D.F.S. Natusch 7
- u. o u, s.
E bc?i?k u 01 /
.q.,
aj Radiobiology n 1 1 -
~'
Laboratory
.- . ' ' . < tu w; r ,. .
.,.i ,._, ;, 5,:.. !!-
I te - , r? ,
*{ ? v Y .
e . ,- >a_
UCD 472 - 502 f
..a..
fj yy SIZE DEPENDENCE OF THE PHYSICAL AND CHEMICAL PROPERTIES OF COAL FLY ASH
,.e E. 4 M G. L. FISHER 0?
,,/ Radiobiology Laboratory University of California Davis, California 95616 p<1 ,
.K '
g D. F. S. NATUSCH Department of Chemistry
$;hj Colorado State University
'T1h Fort Collins, Colorado 80523
^4 .:V ,si
- N
.e .'..(::, .
k.1 ..
,./ /s # )
l ?$.i Q.a ci [ # Spring, 1979 > g.1 C MN.') Md r- w. -
- .; .- This report reproduces a chapter 2-;J in
- Analytical Methods for Coal
( f. . ,
- l. ~ and Coal Products, Vol~ume III (C. Karr, Jr., editor), Academic l ' Press, pp. 489 - 541, 1979.
l . . . , l ') l b' .~, :
',' Q .
\: c,e This research was supported by the US Department of Energy. i llL {.1
!. INTRODUCTION In order to assess the envircrvnental significance and potential health hazards b4 associated with exposure to envirorynental pollutants, detailed studies cf physical and
/ chemical properties are required. It is these properties that determine the route and biological consequences of exposure. The aerodynamic behavior of aerosols released during coal combustion will determine the potential for atmospheric transport and subsequent human exposure. Large particles (>10 um) escaping the power plant's control technology will fall out near the plant, which may ultimately result in general population expcsure V by ingestien of agricultural products or water. Thus, exposure of agricultural products e
by soil or foliar deposition or contamination of water sources in the environs of the power plant will reflect, for the most part, the chemical composition of the larger
.9 perticles. Long-range transport and general population exposure will be associated with
- g. j the more stable aerosols. These f.ine particles (<10 um) are of _special interest becay
;r; theyre less efficiently collectd by existino control tentnolooiet ha v e a r*1' 4 v al v -
.$ .lon) atmospheric
.< __ - --resi.dence time, and upon inhalation, are effic iently danm4*ad 2nd %--
,,,,,m
.e. .' ly resoved
.- s from the pulmonary region of the respiratory tract.
~- -
.t In a review of particulatIa5 agent tecnnologies, vandegriftTt'al. (1973) des:ribed
,f collection efficiency as a function of particl.e size for a variety of control technologies 4 including electrostatic precipitators, fabric filters, wet scrubbers, and cyclones. j{, Average collection efficiencies for a medium-efficiency elegirostatic precipitator imi
,9 were"90, 70 m4Dd_351 fnr 1 c 0.1. and 0.01_pm_Rar.tici" "";W i M s . Inkusun9177 the Venturi wet scrubber (WS) was more efficient (99.5%) for 1.0 um particles and less
%] d.' efficient (<1%) for 0.01 w particles. A crossover in the ESP- and WS-efficiency curves was observed at 0.35 um. s' Respiratory tract deposition of inhaled particles is determired by the physicr. and j chernstry of aerosals, the anztomy of the respiratory tract, and the airficw patterns in 74; the lung airways (Yeh et al.,1976). The most important physical factors affecting lung
.[./] , deposition of inhaled particles are the aerodynamic properties uf the aerosol and the 3 .l chemicai reactivity in the airways. Lung deposition is generally described in terms of
~
3*( ; fractional particulate deposition by mass or number in the three major regions of the [k'~1 respiratory tract: the nasopharyngeal, tracheobronchial, and pulmonary regiens (Task Group
,p
^)$.
- on Lung Dynamics,1966). The nasopharyngeal region is composed of the nose and throat, at extending to the larynx; the tracheobronchial region consists of the trachea t.nd bronchial *M .
tree, including the terminal bronchioles; and the pulmonary region censists of the respiratory bronchioles and the alveolar structures. Farticles gretter than 10 um are 9 effectively collected in the nasopharyngeal region; tracheobronchial and pulmonary depo-1 1 sition generally increase with decreasing particle size. Fractionai deposition in the .g.; pulmonary region ranges from 30 to 60% of the inhaled aerosol fcr pt.rticles rangir.g in m'6 size from 1.0 to 0.01 um (Task Group on Lung Dynamics,1966). ilmilarly, tracheo-vt
i , bronchial deposition ranges from 5 to 30% for inhaled aerosols f rom 1.0 to 0.01 um, ,~ respectively. Respiratory tract deposition profiles have been calculated for f ron, lead, and t.enzo(a) pyrene in urban aerosols (Natusch and Waliate,1974). The hygroscopicity or I
3
.. ___ _ ____. - *i
' 1
=$ - h. s s C
] j
'% +
. reactivity of an aerosol in the airways may dramatically alter the particle size and d'
") the regional deposition. Parks et al. (1977) have shown that, upon inhalation, amont E 1 sulfate aerosols with initial aerodynamic diameters of 0.8 um and 8% relative humidity
.$ may rapidly grow to 2.3 um in the water vapor saturated atmosphere of the respiratory MJ tract. The rapid growth of the aerosols resulted in deposition predominantly in the nasopharyngeal region and lower than expected deposition in the tracheobronchial and pulmonary regions.
] g The rate of clearance of deposited particulate matter from the respiratory tract
.i will be determined, in part, by the chemical behavior in the lung's unique micreenviron-4
,1 ment in the vicinity of the particle. Hygroscopic particles deposited in the respiratory
, tract will be rapidly cleared by dissolution and subsequent passage into the bloodstream
' .' ] for ultimate exposure of internal organs. Less soluble particles deposited on the M
pucocilliary escalator of the tracheobronchial region and on the ciliated epithelium of '
-1 the nasopharyngeal region will be rapidly cleared with half-times on the order of one k day and a few minutes, respectively (Task Group on Lung Dynamics,1966). Relatively in-soluble particles deposited in the pulmonary region will be phagocytized by the ]**- 1 pulmonary alveolar macrophages (PAM). These particles will be slowly removed by either o
dissolution within PAM or transport within PAM to the mucocilliary escalator. The biological half-time of material in the pulmonary region is very much a function of particulate chemical composition; haif-times of hundreds of days have been reported for j,*] insoluble particles.
-y y It should be emphasized, however, that dissolution of surface-associated chemical components need not be a requisite for their interaction with the biological system.
~*
For example, inhaled particles may be phagccytized by macrophages where direct particle surface-cell interaction will take place. A reasonable compalison of " insoluble" E particle interaction may be made with asbestos. M,. ' In this chapter, the size dependence of physical and chemical properties of coal L-fly ash is reviewed. Because the size dependence of many of the chemical properties
. results from surface-associated chemical phenomena, a detailed description of surface analysis is provided. An understanding of the bioenvironmental significance of ambient
(,< fly ash requires a detailed understanding of its chemical reactivity and biological l' interactions with fly ash surfaces. This chapter reproduces the material found in a d DOE report published through NTIS (Fisher and Natusch,1979).
- g I
II. MORPHOLOGY AND FORMATION OF COAL FLY ASH I f A. Morphological Analysis a Morphological studies by light and electron microscopy have described the hetero-h geneity and structural complexity of coal fly ash. Based on morphological appearance, much can be inferred concerning origin, formation, and chemical composition. McCrone
- t. f and Delly (1973) indicate that particulate matter derived from combustion products is 1 e-
[ fj) readily identified under the light microscope. The fused glassy spheres in coal fly ash [.y are the result of exposure to boiler temperatures >1200 0C. Aside from the water-white sh glassy spheres, McCrcne and Delly (1973) also describe the presence of opaque " magnetite" spheres and spheres containing trapped gas bubbles.
2:r Light cicroscopy has be:n used to define 11 major morphol::gical classes of c:a c 5S9 ash particles (Fig.1) in stack-collected, size-fractionated material (Fisher et al., l 1978). The characteristics employed in morphological characterization were particle a The 11 classes include (a) amorphous, nonopaque particles, d shape and degree of opacity. I (b) amorptous, opaque particles, (c) amorphous, mixed opaque and nonopaque par (d) rounded, vesicular, nonopaque particles, (e) rounded, vesicular, mixed ) opaaue i nonopaque particles, (*) angular, lacy, opaque particles, (g) cenospheres (hollow sphe 3
~j (h) plerospheres (sphere filled with other spheres), (1) nonopaque, solid spheres, A morphogenesis opaque sheres, and (k) spheres 1,ith either surface or internal crystals.
scheme (Fig. 2) has been developed relating the 11 morphological classes to extent and duration of exposure to combustion zone temperatures and probable matrix comaosition. ' l Opaque amorphous particles and angular, lacy, opaque particles were tentatively Stbsequent
' as unoxidized carbor.aceous material or iron oxides (Fisher et al .,1978).
SEM-x-ray analysis (Fisher et al.,1979a) indicated that these opaque particles were com- [, Furthermore, calculation of the effective atomic
'y posed of low aton:ic number matrices.
number of class t particles based upon Bremstrahlung producticn indicated that this fi The opaque class is predominantly composed of elemental carbon (Fisher et al.,1979b). spheres (class j) appear to be predominantly magnetite and may be identified by (1 ig netic separation or passing a r.agnet near a liquid mount of the sample under a micro-
.u- The amorphous and scope and (2) by observation of small clusters of these particles.
rounded-vesicular, nonopaque particles (classes a and d) appear to be aluminosilicate i particles. Rounding end vcr.ichity reflect increased exposure to boiler conditions. Further heating of these particles will give rise to nonopaque spheres tnat are either s :. .{ Similarly, the mixed opaque, nonopaque,
. . ,Z solid, hollow, or pacxed with other particles.
amorphous, or rounded classes will give rise to spherical particles upon increased ex-
,q,,V The nonopaque, solid spheres ranged in posure to combustion conditions in the boiler.
- l'g ; color from water white to .)ellow to orange and deep red. Analysis,of single particles
- .gg} in this class by SEM-x-ray technicues indicated that the varittion in color was associ
' N . . . Cenorphere and plerosphere formation will be
,( . I with iron content (Fisher et al.,1979b).
discussed in detail in the following sections. Crystals within glassy spheres (as
,..j detemined by light microscopy) are probably formed by heterogeneous nucleation at the h
~ ' ~
In this regard,
/
*d O
j surface of the molten silicate droplet (Fisher et al.,1979a). h
't a Gibbon (1978) has demonstrated the presence of mullite crystals within and on the sur- '
face of fly ash particles (Fig. 3). Crystal fomation within glassy spheres was derncn-
'.* M strated by transmissien electron mi roscopy (TEN) of hydrofluoric acid-etched replicas W ..j l
In this process the original glassy material is dissolved, but tre insoluble mullite
- afW by electron-diffraction analysis.
, , ; ;. remains. Maliite str4cture w::
%g
- x. N
/ '. s ;.W
~'
f '.,:y..M. . , .e 9 3 f'
....__.p.- .
.a r 1
d _g 20pm B 20pm , N,
-l
. . .s
?ll
... .g
.f # ,4 l
- g0 -
l l -'- O 3 W
'O
. c, w. -
.e .4 w a p[$ % ..n 5 s
.8
' ),e.g*- <
;lM 4, _
p a c..
'9 I '
h *'., I ' A . D '{Yg N' l - !
.~. ;-
e Q. s -
. .;-: 20pm 30pm
;)
~. N..k. ---
~
w ':. ~ :Q,
.e .
.' ?
[ [ -
. .g i
- 4
~ ~~Q y *> -
. - 'c s 4%.' . k /'4 l, .
% V '-
i '.; }. ' 5pm-M0pm e,gP ~ 20 pm o w @ MM - b-c '(q n. . . g) " d , ' '* i %9 L :. ;.;l~ j>,; . - . . . ji n;
- 4. i.p:i e,y
.'# 1 4
+
, - m
/ 'V.G '
f H f
/ .
*g.
%p s WI L. '
l' .AT{ b,j ,
. to pm , :,
A'a , ~ ,
.,>cn L bJ.M
.% s C
,n' / + *,f y
.h
,, y:
. .i / .
, 4 'Y j '
- .1 )
s'.-
'a s
m # 5pm ' t4 ' r=1 o,0 p n w __ hi h _ ._ . .
,f *4. * . - . . . . - --
l Y
'{' i,
.; ,T*
-(m . .
30pm
- jr.3 .-
Ji9 m -
~ ~ ' '
M 9.,$)
,7
'4 *
* (
.x
. =
ag i ,
\ \
20pm 15pm J s Fig. 1. Light photomicrograph demonstrating
..q
(", et0 g'e vha pd the eleven major morphological classes of coal fly ash: (A) amor-
. s.
*o
, phous, non-opaque particles,
, (B) amorprous, opaque particles,
,.; (C) ano*phous, mixed opaque anc 4' , g/ , e non-oraque particles, (D) rounced,
.. vesicular, non-opaque particles.
.- '" #'1 (E) rounded, vesicular, mixed
* * "a'-
8 opaque and non-opaque particles,
< * " f 'F) ar gult r,1scy, opaoue particles, 1 ./ {G.1 cencspheres, (H) pleroscheres,
- t. I )' non-opaque. Solid soneres,
, 'g 'J) opaqu? scheres, and (K) spheres with eitner surface or internal 3 hj crystals. (Reprinted with permis-C,
-. 15 pm .'.
sion from G. L. Fisher, B. A. Prentice, D. Silberman, J. M. Ondov, t A. H. Biemann, R. C. Ragaini, and
.c1 A. R. McFariand, Envircnmental J-Q '
Science and Technolocy 12, T4T(1978). CcpyrigCT!78 by tne AErican
, Cremical Society '
f, t
. 5
l' u U; OP.CiTT sat t e svat l .......... t ..... ...... 4 '~~~ i i .".f.* .', ,
~
'"tl 'dtt; *, nw " . ..... .
Fig. 2. Fly ash morphogenesis a
scheme illustrating
] probable relationship of ! '"ov ' ' " =os
'" oi . T -
'* *I'l"
. opacity to particle Ii composition, and ,,,,,,
relationship of particle l ,,6.c, _j , R ne t 9 permission from G. L. 4 P"'*" " " ' 2 " ' *-' "4 ---- Fisher, B. A. Prentice, d D. Silberman, J. M. **'"*'*,I d Ondov, A. G. Biermann, R. C. Ragaini, and A. R. McFarland, Er.vironmental Science and Technology 12, 4S0 ~ (1978). Copyright 1978 by the American Chemical Society.")-- 1
'l i
\- 'f.~ /
..l ./j-
! (e,
. -lj '. y . Fig. 3. Transmission electron micrograph of a 1
D' '
- g. ' ! replica of a fly ash sphere showing j
y, abundant mullite needles. The
~i.,.y*I
' ' association of crystals-within-sphere j .
is retained by the replica; the
.: 'jd.'.' - - -
L ,, 0<~
%- \ -
/
f original glassy material is dissolved 1 during the replication process, but i . k' W /s -[ mullite is insoluble in HF. (Photos c ~.: + s e y o f G . a . W e i t ! , D. S. McKay,
.2N.
- and D. L. Gibbon, Lyndon B. Johnson Space Center, Houston, Texas.)
i
.- 7
' .?
.d-1 b
I 1 6
i
/
#+ Fish;r et al. (1978) have quantified the relativo abundances of the 11 light-
/ +, microscopically defined morphological classes in four size-classified, stack-collected fly ash fractions (McFarland et al.,1977). The four fractions had volume median ,
f diameters (VMD's) of 2.2, 3.2, 6.3, and 20 pm with associated geometric standard devia-j j tions (og) of approximately 1.8 for all fractions. The data in Table I demonstrate that the relative abundances of all particle classes are size dependent. In particular, only
,J the nonopaque solid spheres increased in abundance with decreasing particle size; all Sj other morphological classes appeared to increase in frequency with increasing particle size. Amorphous and vesicular particles (classes a, b, c, d, e, and g) predominated in
]
the coarsest fraction (66% by ninber), while solid, nonopaque spheres predominated in the finest fraction (871 by ntzaber). 4
/* Tabl e ! . Relative Abundance (%) of Morphologic Particle Classes in Four Fly Ash Fractionsa a
el Fraction y ~
, M a VMD a VMQ m y@ a
.'. 1
, Particle class 20 um 6.3 um 3.2 um 2.2 ta x
s .. . (A) Amorphous, nonopaque 7.25 2.13 0.79 0.33
'.4 0.18
- '{ (B) Amcrphous, opaque 0.42 -- --
(C) Amorphous, mixed opaque 0.77 0.09 -- -- N'{
,; and nonopaque y (D) Rounded, vesicular, nonopaque (E) Rounded, vesicular, mixed 12.39 2.27 6.67 0.24 2.91 2.99 0.03 F! --
. opaque and nonopaque 1 (F) Angelar, itcy, opaque 1.34 0.57 0.17 0.33
. :: (G) Nonopaque, cenosphere 41.11 25.22 13.20 7.91 J (H) Nenopaque, plerosphere 0.S1 0.21 -- --
- 2. 5 (I) Nonopaque, solid sphere 25.5E 56.01 0.90 79.16 0.33 86.99 0.24
( (J) Opaque sphere 1.56 [ . k?-ii (K) Ncnopaque sphere with 6.80 6.79 3.18 0.95 [ crystals V.'. ' " From Fisher et al. (1978c). b
-] Volume median diameter.
s 1 I . i 1
w l
, s Cp
. hg
#t4, g 100.0 i Pulvertred j
%, ' ^ f -
Cool-Fired l . by/ -
~
s
/2 4/ f 10.0 -
Stoker Cyclone Cool-Fired
, c4 _ Cool-Fired k b
- Fig. 8. Size distributions for boiler a: -
/ particulate emissions from coal W combustion in a chain grate stoker, f f W / / a pulverized coal fed unit and a E i.0 -
// / cyclona fired unit. (:ce-educed 5 by pennission of Southern Research E
~
/f/
I/ Institute, 1975, and Electric Power y /// Research Institute.) c - lf/ e f /
*1 .
o.1
,1 0.01 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' '
'u
~
00 0.1 1 , 10 50 90 99 99.99 WEIGHT % LESS THEN STATED SIZE
)f
.u 1
[ i From a practical standpoint, one is primarily interested in the aerodynamic size l l distribution of the fly ash that is actually emitted from a coal-fired power plant. lhis
*! is, of course, largely determined by the collection efficiency of the particle control
-}
equipment. Specifically, the size distribution of the emitted fly ash is determined by
'l the product of the functions descr:bing the site dependence of fly ash mass entering i a control device and describing the dependence of collection efficiency of this device j on particle size. Examples of the aerodynamic size distribution of fly ash mass emitted from a coal-fired power plant equipped eith different control devices are pre-
] sented in Fig. 9.
1 1 4 l 3 l 1 17 4 _I
p t j 8 5
^' 10 -
10 SCRUBBER '
-kG 'd 4 ESP 4 -
m 10 - m 10
. a w w N- ;MJ m m ' 't.9 a 3 m 3
- r. 3z 10
- o l0 z
f mA NM w 2 2 w 2 2
% r4 10 -
s 10 - 4
. 1;. J a w w a:;
m 10 . m 10 -
- N
- .4 Mk 1 l0.01 0.1 I I i 12 10 I 1 l 0.02 I i 0.10.20.5I i It j-[ ,
...y DIAMETER (pm) DIAMETER (pm) f; Fig. 9. Size distributions for particulate emissions from similar production units
, 7:f,] with either electrostatic precipitator (ESP) or a Venturi wet scrubber at w the same power plant (Modified with permission from Ondov, et al.1976).
"'E .
3.- ll&
.'dkd Density and Magnetic Distributions
$- ';I:'i B. Detennination of the density of coal fly ash as a function of particle size is
?.%.'.
y 3t largely of interest in obtaining an understanding of aerodynamic behavior and of the f_.y factors responsible for the intrinsic heterogeneity of coal fly ash. Thus, determination
,A EN: of the densities of different fly ashes, and subfractions thereof, provides a means of I;. h interconverting aerodynamic and physical sizes according to Eq. (8). In addition, some differentiation between distinct morphological and compositional characteristics can be r4r
.;j,g+ achieved. For example, cenospheres can readily be distinguished from solid particles on
-U I-j the basis of density as can predominantly carbonaceous particles from aluminosilicates.
. YR t Determination of fly ash particle density is most simply achieved by means of the
,:stg traditional " float-sink" method that employs a series of liquids of different densities
.)
' .7/jj to separate particles of greater and lesser density than the liquid (Ruch et al .,1974; Olsen and Skogerice, 1975). Altern:thcly, sc-:-:tb can be achieved by placing the
.g
_ ;j - particles in a liquid in which a density gradient has been established.
, y'c While determination of particle density is of considerable interest in its own E71 right, more definitive insights are obtained if density separations are carried out in . r::tv conjunction with sequential size separations and with differentiation between ferro-
- p magnetic and nonferromagnetic particles. Such a three-dimensional fractionation scheme
.<Qd, ,.
OSh has been presented by Natusch et al. (1975), and resulting mass distributions are pre-gs sented in Tables II and III for fly ashes derived from typical midwestern United States i, tl s.. . ?y W s .
- i.'5 18
.*,.1 .
*? Lu L - $!! -.
St5
-n %
N N - Table II. Mass distribution of size-classified, magnetic and nonnegnetic fractions of a midwastern bitwinous coal fly ash (%) a Density (g/cm ) Size Nonmagnetic Magnetic (um) <1.6 1.6-2.0 2.0-2.3 2.3-2.7 2.7-3.0 >3.0 ,
<2.1 2.1-2.5 2.5-2.9 2.9-3.4 3.4-3.6 >3.6 <20 b b 0.2 28.0 b b b 0.6 0.4 1.3 14.9 0.5 20-60 1.4 1.3 12.1 12.9 0.1 b 0.2 0.6 1.8 11.5 3.1 0.1 60-90 0.7 1.0 0.6 1.1 0.6 0.1 0.5 0.8 1.0 0.2 b b >90 0.1 0.1 0.1 0.6 0.5 0.2 0.1 0.2 0.3 0.2 0.1 b a
From Natusch (1978c), unpublished results. Less than 0.05%. G Table III. Mass distribution of size-classified, magnetic and nonmagnetic fractions of a western sub-bituminous coal fly ash (%)a Density (g/cm ) Nonrugnetic Magnetic Size (um) <1.6 1.6-2.0 2.0-2.3 2.3-2.7 2.7-3.0 >3.0 <1.6 1.6-2.0 2.0-2.3 2.3-2.7 2.7-3.0 >3.0
<20 b b b 0.7 b b b b b b b b 20-44 0.2 0.4 0.5 21.3 0.3 0.2 b b b 1.0 b b 44-74 0.5 0.8 1.0 45.6 0.6 0.5 0.1 0.1 0.2 6.8 0.1 0.1 >74 0.2 0.3 0.4 16.1 0.2 0.2 b b b 1.5 b b a
from Natusch (1978c), unpublished results, b l_ess than 0.051.
. . ., x
-j bituminous and western sub-bituminous coals.
- 3. M. .,, ;e
- g ,q;1, 1
bulk fly ash into several physical size fractions by sieving.These
.i .,$ t h '
then subdivided into a number of density fractions that wereEach size fraction wa s
, in turn, separated into 3 .[s 5 y magnetic and nonmagnetic fractions according to whether the particles net or not. mag-
,.0 nature. The designation of magnetic and nonmagnetic is entirely opera
. Y, 13*M, 5 ,11 A number of characteristics of coal fly ash can be distinguished a pre-from sented in Tables II and III.
E.L w, 3 It is anparent that both fly ashes are compositionally W. ,y extremely heterogeneous, although there are very considerable diffe
~ nass distributions for these two fly ashes.
As discussed in the previous section, much l
- y of the variation in densities observed is attributable to morphologica compositional characteristics.
g i .A
. This is rather well illustrated by the data in Fig.10,
~
, ?y where density distributions have been determined as a function of p before and after crushing the fly ash.
- -%-2.d
; c..: 3 , g.. indicates the presence of vesicular particles and cenosphere rger size fractions, as discussed previously. ~
E: 2.g Interestingly, determination of the x-ray powder diffraction patterns the subfractions presented in Tables
.! II and III reveals no convincing differences in *. l'M_$
e I T y hs.M matrix composition that depend upon either size or density (Natusch This finding further supports the contention that the density distributions i
.,1975). et al n fly ash are largely determined by morphology rather than by composition.
4 There are, however,
. ,, 9 very distinct differences between the amount of magnetite 0 (Fe3 4) present in e mag-5,'
netic and nonmagnetic fractions (Fig.11). jM. ,.. ~A
" responsible for the ferromagnetic susceptibility of coal fly ash.Th C.
14 Electrical Resistivity Distribution [%;&4 d
-k3% The electrical the standpoint resistivity of coal fly ash is an important physical of control. y from prope .$[;; E.) Thus, it has been established (Bickelhaupt, 1974,1975) that
-h{ the resistivity. ash collection efficiency of electrostatic precipitaters increases with dec reasing fly !9 Bickelhaupt (1974,1975) has further shown that both the surface an , _p , volume resistivities of fly ash, at precipitator operating temperatures
, are inversely
! '.Of,@ proportional as to charge carriers. the specific concentrations of alkali metals, which are thou C.,N.: v t These studies have shown that considerable differences in g ",<, electrical resistivity occur between different fly ashes, and correlations { ', ; ' between fly asn resistivity and alkali metal content, but no measurements ha relating resistivity directly to particle size. ve been made k.
., Some insight into the dependence o' rchtb ity on particle size cany be ob considerir.g the data presented in Table IV.
X }[ This table lists concentrations of
-%g potassium measured in fly ash that has been fractionated sequentially ac density, and ferromagnetism as described previously.
N.;bI a., It can be seen that in the non-(Q magnetic fractions (that account for 64% of this fly ash) there is a pronounc ae QJ.[ in the concentration of potassium (and also of sodium), both with decre size and with decreasing density. 8 i." -. '.Q. This suggests that, for this fly ash sample, L*4
.d
'. ";le Li \ . !' z ,G%\
'C tg4 ,
# ,b # # IO i i i . i i .
4y . A. Portide Diometer .. B. Parh Demeter. 20-44 p m O
$p~
b/ - 01 *
<20pm ,
m g as ei o s 5 - z:s 0.5 - t i, e i . Fig. 10. The effect of crushing on the mass distrBution of size-classified (Iy ri c:i - i e
/' E . .
ash fractior... The shift to h'gher [4 $ 0 densities indicates the presence of E n helic. or .Z i:.'lar ar"ic'es (figure Y ID O' P2 Diomew~*' PwhOsmetw~ - by courtesy of D. F. S. Natusch).
> 74pai
..j l 44-74 pm -
' J,. . ..
-75
. . ,< . g . ..
c O
'g
~
$ O.5 < s ,5
.n >-
s i %
%N. 2 .
g %
.s .'3 e ,0 .jg Ei - i '. - a \ .
- c. *
./
n , l = .
- .' o 2.1 2.52.93.3 2.12.'52.93.3 J';
- j DdNSITY (g/cm3 )
. .s v :'ll .
~ .;
..w..
O
. ,d.l
[ mi ) NONMAGNETIC pu H-hemofite c Q-quortz j' ;[j Mu-muliite n
.. ..m -
y
- H Mu
- 4. I', y t .-
'5* ' ' ' ' ' ' i I[.'. .; '[1 Fig. 11. X. ray powder diffrac- u
' tion patterns .5 demonstrating the .3
.L s .2':
'*; cor. positional MAGNETIC l' j differences betwten E H-hematite I magnetic and non- {e magnetic fly ash Q-quartz fractions (#1gure M-mognefite c, by cour tery of M g D. E. 5. Natusch).
HHM g H
,)Q I t t t t t t
; f I .e 1 l 60* 50' 40' 30' 20 26 Angle 1
4 1 21
..:-),
'1.
b .
%;. Od "
h- .$ '$ ,h ,
+.. .
^i Table IV. Concentration (1) of Potassium in Fly Ash Separated Sequentially
-J by Size Density, and Ferromagnetisma
>q
? Density (g/cm )
f Particle size - p s Particle type (um) <2.1 2.1-2.5 2.5-2.9 >2.9 . M Nonmagnetic
<20 2.69 2.34 2.22 1.73 20-44 2.63 2.28 1.33 1.09
' ))
-j 44-74 1.89 1.63 1.05 0.45
.~]. >74 1.79 1.48 1.06 0.13 I" b Magnetic <20 -- -- 0.76 0.70 h .-
20-44 -- 1.92 1.48 0.73
% 44-74 1.78 1.60 1.27 0.85 h
3 >74 1.37 1.62 1.49 0.83
.T
,';
- From Natusch et al. (1975).
b
. c. No meaningful data.
l i resistivity decreases with particle size and with density. Similar, though less pro-j nounced, density dependencies are obsarved in the magnetic fractions, but size depend-U.] encies, if any, are obscure. Since both decreasing density and decreasing physical size contribute to decreasing aerodynamic size, it is apparent that the efficiency of
- . y M
electrostatic precipitation per unit mass of these size-classified fly ashes increases 8..-p
'i/
..m with decreasing aerodynamic particle size. This is an extremely desirable characteris-f,i.4 tic. It shosld be pointed out, however, that these studies require extension to
- respirable particle sizes.
%1@ L. s -( D. Surface Area Distribution The specific surface area of fly ash particles is an important parameter in de-
, termining a number of the behavioral characteristics of coal fly ash. It is the sur-F.@j face area of a particle that determines the number of electrostatic charges that can be
.' -1l placed on that particle in an electrostatic precipitator (White,1963; Bickelhaupt,1974, c 41 1975); it is the surface area of a particle that determines the extent of condensation
! cr adsorption of species frem the gas phare (W::t et al . ,1974; Natasch and Tonkins,
...) ,
1977); and it is the surface area of fly ash that detemines the rate and extent of its
,h aqueous leaching (Natusch et al.,1975; Matusiewicz and Natusch,1979).
To a reasonable approximation, one would expect the specific surface area (square fl, y meters per gram) of fly ash to increase linea-ly with decreasing particle diameter k since the particles are predominantly spherical. Similar trends would also be expected for nonspherical particles having similar shape factors (Butcher and Charlson,1972). Ne x h ,. .M,
- .w l
y 'e
-f 22 1
Ng
, /y . In fact, the expected trend is cbserved; however, two important points are noted. t First, the surface areas that. are measured for spherical fly ash particles are con-siderably greater than those calculated from measured particle diameters. Even taking i into account the assumptions inherent in surface area measurements, it appears that coal
@.s ' fly ash has a significant " internal" surface area. This is probably in the form of pores \ or cracks or a porous surface layer, although, as previously described, surface crystal formation may contribute significantly to the measured surface area. However, several fly ashes show no significant dependence of surface area on particle diameter (Table V), especially for small particles. These data indicate the existence of substantial internal surface area that is effectively proportional to particle volume rather than j external surface area. In this regard, it has recently been suggested (Natusch,197Ea) that collisionally efficient condensation processes may result in deposition of material l from the gas phase predominantly onto the external particle surface, whereas much less efficient adsorption processes (Natusch and Tomkins,1977) can deposit gases and vapors on both the internal and external surfaces of a particle.
- 9. .
.- Table V. Comparison of Measured and Calculated Specific Surface ,a Areas of Size-Classified Fly Ash Fractionsa 1*- Physical size Measured Calculated s.- .
y (cm2 /g) [ (um) (m /g) yQj <45 2.02 >267 y; 45- 63 3.55 191-267 63- 90 2.55 133-191 90-125 2.43 96-133
.j 125-180 1.20 67- 96 E >l80 3.11 <67 s '. N Q
$L es
- From Kim a'nd Natusch (1978). Unpublishec results.
Y.' ?J4 ' h; , S ,M
~;
e
'l
^
~
a. mby d 1 23 1
- , .3 -- - - - r:-. -, . _; ,y .- . - u., - -:,r ~~- ~ ~ .. --
~__;- ~7-333
. . th '
y a n;. i. -. IV. ELEMENTAL COMPOSITION OF COAL FLY ASH: PARTICLE SIZE DEPENDENC ?, f. Studies of the size dependence of the elemental concentration of fly ash can be
!b
,~ ... *h.,3 classified into two categories. The first category consists of those studies that re-
~
- -t late the elemental concentration to the particle size of size-classified material. For these studies, sufficient mass of size-classified material is collected to allow
'e 4.... (g.y. g gravimetric determination prior to elemental analysis. The second category are the many g
Q~j,rg studies that have employed inertial cascade impactor systems for aerodynamic size classification. Aerosol sampling is performed isokinetically to avoid anomalous alter-
.%f ation of the particle size distribution. Because impactor stages are often coated with
[ sticky adhesive to prevent particle bounce off and reentrainment effects and because o r,(
' small masses of material may be collected on the stages, accurate gravimetric determin-ation of sample mass is difficult. To obviate this complication, specific elemental
{: masses of deposited particles on each stage are often ratioed to the mass of an element j. that does not demonstrate a marked concentration dependence with particle size. In F this regard, Ondov et al. (1977a) have analyzed four size-classified, stack-collected fly { ash samples ranging in particle size (VMD) from 2.2 to 20 pm (McFarland et al.,1977). Mj The elements Al, St. Ca. K. Ce, La, Rb, Nd, Hf, Sm, and Cs varied in concentration by
- i. A less than 20% among all fractions and should therefore be suitable for mass estimation.
. .%r .. A second approach that has been used in the analysis of impactor data, reports the size distribution for the mass of each element analyzed, thus avoiding the compounded errors
] in data derived from elemental ratios. Impactor studies also report elemental con-centrations in terms of mass per unit volume of aerosol sampled. Thus, because of the
- ._.;D.w; limitation of gravimetric determination, results from impactor studies are often re-J.*V,-Q ported as ratios of elemental masses or mass-to-volume ratios rather than specific con-centrations. l y .h . Many studies employ the enrichment factor (EF) of Gordon.and Zoller (1973). lied EF is defined as the ratio of an elemental concentration in the fly ash sample to the The Uc.$ elemental concentration in the coal. To provide normalization relative to total mineral j%.1 content. EF's are often calculated frem the ratios of specific elemental contents in the
*?
fly ash samples and coal, respectively, to those of mineral matrix elements in the fly ash samples and coal, respectively. Thus, the EF may be calculated from: y% l *^: - EF = (IX}s/INls )/IIIIc /INlc )' ('}
} where [X}s and [X]c represent the mass of element X in the sample and coal, respectively
[g. d and [M]3 and IM} represent the content of the matrix element in the sample and coal, YW, respectively. A number of " matrix elements have tean used in the EF calculation: Al
* ' (Gordon et al.,1974), Fe (Ragaint and Ondov,1977), Sc (Ondov et al.,1977c), Ce (Coles et al .,1979), and 40 K (Coles et al.,1978). In the following section, studies of fly ash analyses using gravimetrically determined masses will be discussed separately from studies enploying smaller masses.
,A 0. lf' ~ .h 1..
- s. .
%i 24 L-g -l r ! m_ _
A number of analytical techniques.have bIcn employed in the determination of the 34 , '# fs 4, elemental composition of coal fly ash. For complete analysis of the major, minor, and
# e,, # trace elements, a combination of analytical techniques is usually employed. The physical to, 4 and chemical heterogeneity in terms of particle size, chemical distribution within and among individual particles, and the fused aluminosilicate matrix provide a unique com-t4 %, f binstion of difficulties for the analyst. The techniques employed for elemental analysis may be divided into two categories: (1) single Clement techniques that generally require a matrix dissolution and (2) multielement techniques that generally are performed on the undissolved ash. A detailed and extensive review of the elemental analysis of particulate
[ matter has recently been published by Natusch et al. (1978). See also Chapters 11 through 6h 14 in Volume I, and Chapter 45 in th: . c h:: . f, A. Studies of Specific Concentrations Davison et al. (1974) published the first detailed elemental analysis of coal fly ash as a function of particle size. The ash was collected from a power plant using southern Indiana coal. Two types of fly ash samples were analyzed: (1) fly ash collected i by the plant's cyclonic precipitator and (2) stack-collected material. The precipitator
~ I .9 ash was size separated by sieving the larger particles and aerodynamically separating the remaining mass. The stack-collected fly ash was aerodynamically classified using
,-1 an Anderson impactor. These authors presented the elemental concentrations in three ..
categories based or? the degree of concentration dependence on particle size. The // ,- elenents showing " pronounced" concentration trends of increased concentration with de- k
-l.$ creasing particle size were Pb, T1, Sb, Cd, Se, As, Ni, Cr, In, and S. Elements .
N classified as showing limited concritration trends were Fe, Mn, V, Si, Mg, C, Bc, and A1. Iron concentrations decreased with particle size for the precipitator ash, while no
.7 trend was observed ir. the stack-callected samples. The elements dest ~ibed as showing no concentration trends were Bf , Sn, Cu, Co, Ti, Ca, and K. The mechanism of concentration enhancement has been postulated to be volatilization of the element (or compound) at combustion temperatures (14000-1600 0 C) followed by condensation on particle surfaces
.7 t
l -l , (Natusch et al.,1974; Davison et al.,1974). Thus, fine particles with their large ratio of surface area to mass will preferentially concentrate volatilo inorganic species. In particular, those elements displaying the greatest concentration dependence with f particle size generally are associated with elemental form! that boil or sublime at 1 coal combustion temperatures. l Fisher et al. (1977) and Fisher and Chrisp (1978) !iave described the size dependence
.j of the elemental concentrations in coal fly ash collected from the stack of a power j plant burning low-sulfur, high-ash, western United States coal . lhe fly ash was size classified in situ, downstream from the ESP, using a specially designed instrument em-
{ ploying two cyclone separators in series followed by a 25 jet centripeter (McFarland et. i
}
l,$ al . , 1977 ) . Elements were classified into two categories: elemental concentrations (1) dependent on particle size and (2) independent of particle size. Concentration de-pendence with particle size was determined qualitatively with the criterion that constant concentration trends beyond experimental uncertair.ty were observed for each of the four J l 1
y 'l J'tW. s
.4 ,
u -; vim , fractions analyzed. In ordir of decreasiry dependtnce on particle size, the eleming [h.1 - Zn, As, Sb, W, Mo, Ga, Pb, V. U, Cr, Ba, Cu, Be, and Hn displayed increased concentrat
' a.h with decreasing particle size. Silicon was the only element to decrease in concentrath with decreasing particle size.
- '.'. j The elements not displaying clear-cut concentration dependence on particle size M for all fractions analyzed were A1, Fe, Ca. Na, K. Ti, Mg, Sr, Ce, La, Rb, Nd, Th, Ni, Sc, Hf, Co, Sm. Dy, Yb, Cs. Ta , Eu, and Tb. Of these elements, Na, Sr Ni, and Co
' $6.h.~ ..
%p displayed marked enhancement in the finest fraction relative to the coarsest fraction.
~ _h. 2 Coles et al. (1979) have described the elecental behavior in the four size-classified i ? '!j fractions in terms of elemental enrichment factors relative to the parent coal.
. . . . , The elements were grouped into three classes: group I elements displayed little or j no enrictur.ent in fine particles and were lithophilic; group II elements displayed marked
, , 5 ?:1 enrichment and were chalcophilic (sulfur associated); and group III consisted of elements "h'h
- w. . .
with behaviors intermediate to groups I and II. Group I elements included Al, Ca, Cs, W.a4 'f Fe, Hf, K Mg, Mn, Na, Rb, Sc, Ta, Th. Ti, Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb; group II i elements were As, Cd. Ga, Mo, Pb, Sb, Se, W, and Zn; and group III consisted of Ba, Be,
. 7. ..f 'll m
,rjjy : Co Cr, Cu, Ni, Sr. U, and V.
;['W In a separate report, Coles et al. (1978) described enrichment factors for 228Th, 7% .y 228R a, 210Pb, 226Ra, 238U , and 235U , relative to 40 K in the four size-classified fractions of stack fly ash. Although the EF's fcr all radionuclides appeared to increase with j decreasing particle size, 210Fb, the most volatile radionuclide, showed the greatest size y dependence. The authors proposed tMr U is present as either a carbonate [Na2UO 2 (C0 3 )2 or j I,f] Na4 UO 2 (C03 )3) that upon heating in an oxidative atmosphere may give rise to either g'g volatile UO 3 from oxidation of uranite (UO 2 ) or the silicate-soluble, nonvoiatile
,;} mineral, coffinite (U(SiO )1-x(OH)4x}.
4 Thus, U behavior would be expected to display m; 4 an ir.ternediate behavior depending on the relative concentrations of uranite and coffinite. The behavior of Th was rationalized to be due to coexistence in submicron
)(.%(
'f
. zircon grains in the coal. The authors suggested that 226R a enrichment may have been due to 2380 , while no explanation of 228R a enrichment was presented.
K?[ V,9 Campbell et al. (1978) have studied the elemental distribution of size-classified Mj' ESP-coll ected coal fly ash from a western United States power plant. Reaerosolized
.5[IQ ESP fly ash was separated into nine size fractions ranging in size (VMD) from 0.5 to o
t. Y 50 um. The authcrs describe fine particle enhancement for elements " volatilized during
.,M combustion," i.e., As, Co Cr, Ga, Pb, Se, and Zn. Their data also demonstrate that K,
$~5D A1, Mn, Mg, Na, Ba, S Ni, V, Cu, Cs, Rb, Sb, Br, Mo, and Sn display an inverse con-
.s l
centration dependence on particle size. Silicon rad rossibly Zr were repcrted to in-
.i l crease in concentration with increasing particle size. lhe concentrations of Ca and Sr Q,. . demonstrated a maximum at approximately 5 um. A similar concentration pattern was re-MM
- mS.?4 ported for Ce, Eu, and Yb.
l
;; .}J ,
These studies are in basic agreement with the hypothesis of Natusch et al. (1974)
~3) in that.the most volatile elements (or their oxides). Cd. Zn, Se, As, Sb, W, Mo, Ga, Pb, -Y k and V, displayed the greatest size dependence. Furthermore, the least volatile elements
- 7. Ah C: 4,
- D 'k 9 26
- - s; T 21 1 _
r b
- len ', Cl
) c *Cg
* %e:4 did not display a strong particle size dependence. With regard to enhanccm:nt of Ba and "Cen U, Coles et al. (1979) postulated that Ba may form the volatile species Ba(OH)2 and U may ,
be volatilized in part as UO3 . Fisher et al. (le77) have proposed that the presence of I
%/ ' Cr in the organic fraction of coal, Mn and Sr as carbonate minerals, and Cu as sulfides.
may explain the behavior of these relatively refractory elements. Campbell et al . (1978) 4
- speculated that the concentration profiles exhibiting maximum particle sizes of approxi-c, mately 5 um for Ca, Sr. and the rare earth elements we're because of the presence of these elements in apatite.
.i B. Studies of Relative Concentrations I.
,. Most studies of the chemical properties of size-classified fly ash have employed
[. cascade impactors for stack or plume sampling. Zolier et al. (1974) reported enrich-ment factors relative to Al for stack-collected fly ash. The ash studied was collected
)
7 'i downstream from the ESP at a power plant burning puls erized coal containing 10% ash and 1% S. In agreement with the previously described studies, enhancement of the volatiie
- elements, Sb, Se, As, Pb, In, Ni, and I, was observed in the stack fly ash relhtive to their concentrations in the coal. Bromine was depleted in the stack ash relative to tne
. .: coal. The authors point out that the EF's for Se,1, and Br are underestimates because i
portions of these elements were probably in the vapor phase. Elements not displaying A enrichments inclLded Ti, Sc Th, Ta, Na, K, Rb, Mg, Sr Ca, Ba, V, Cr, Mn, Fe, Co, and
.; six rare earth eleinents. It should be pointed out that although the stack sample was not size classified, a relatively fine particle distribution (i.e., MMD 5-10 um) may be presumed for this post-ESP material. In a subsequent repJrt (Gladney et al.,1976), the 7 research team described the size dependency of the EF's in the stack fly ash.
Three patterns of eleneqtal behavior were described. The elernents Na, K. Rb, Ng, i Ca, Sr. Ba, Sc, Ti, V. Mn, Co, Zr, To, Hf, Ta, ano all rare earths except Ce dispityed an EF distribution that was not size dependent. Interestingly, the authors also report that the relatively volatile elements, Cr, In, Ni, and Ga, also exhibited little size , dependence. A definite increase in EF of fine particles was observed for Pb, As, and .(
%y Sb. The velatile elements, Se, Br,1, and, to a lesser extent Hg, displayed bimodal activity. An enrichment minimum was observed from 0.7 to 5.0 um. Iron anc Ce displayed
.d EF's that decreased with dect easing particle size.
' .i Klein et al. (1975) described the pathways of 37 trace elements through a cyclone-fed power plant burning ccal of 3 S and 111 ash. Consentration ratios for ESP out' et
! versus inlet ash indicateo enhancemerit of As, Cd, Cr, Pb, Sb, Se, V, and Zn in the finer fly ash fraction. The authors point out that the ESF efficiency was 96.5% during their first sampling trip, as compared to 99.E% during their second sampling trip. Interest-ingly, the rencval of the major elements was more complete during the second trip, al-
';j( though no change in capture efficiency was observed for Cd Pd, and Zn because of association with fine particles. The authors estimate that 60-90% of the Hg was re-j leased from the stack as a vapor. In a subsequent study Andren and Klein (1975) pre-sented ex' tensive data on the mass balance and chemical foam of selenium emissions from I the same power plant. The auth3rs concluded that 68% of the Se was incorporated into fly ash. Based on an ESP efficiency of 99.6%, the authors also concluded that 93% of tne l
27 _d a
4
*g .
,1.+ >
.j Se released to th2 environment is in the vapor phase. The oxidation state of Se was og
.j termined to be Se0 based upon inefficient extraction in hcl and complete elemental ex-
.f traction in Br/Br~-redox buffer,16M MNO 3, IBM H 2504, or 1:1 HNO 3:HC104 . K, Mercury emissions from coal-fired power plants have been described in detail.
. Billings and Matson (1972) and Billings et al. (1973) studied mercury emission from a
, ($[ power plant burning low sulfur (<1%), high ash (21%) pulverized coal. The authors con-
., . . M cluded that 90% of the Hg was released from the stack as a vapor and that fly ash parti-f.'f s les c represented less than 1% of the Hg emissions. The annual release of Hg from all
}h '
' coal-fired United States power plants was estimated to be 103 metric tons in 1971.
-, Similarly, Diehl et al. (1972) studied Hg emissions from a 100-g/hr pulverized coal com-bustor and a 500-lb/hr pulverized coal combustor. Although these authors experienced
^ *
- difficulties in their collection of Hg from the flue gas, 35 and 60% of the total Hg was
.- ) found in the fly ashes generated from combustion of cnals having ash contents of 21.6 and Q ', #;
6.9%, respectively, and sulfur contents of 5.2 and 1.2%, respectively. Subsequent studies in the larger combustor using coal with 10.1% ash and 2.1% 5. resulted in fly ash contain-Ef,[ ing 12% of the total Hg. The authors present calculations for twn Illinois power plants,
~0
+
indicating that the Hg content of ash contair.ed within the plants accounted for 7 and 19% of the total Hg in the coal. Thus, in agreement with B'illings' work, most of the Hg in coal is volatilized and released as a vapor to the atmosphere. Similarly, Kalb (1975) q has reported that the major portion of Hg in coal is volatilized during combustion and 3 released to the atmosphere. Approximately 10% of the volatilized Hg was found to be ad-
,, ,, sorbed onto fly ash; organomercury compounds were not observed. The author points out
. peg that Hg emissions could be reduced by coal cleaning, which results in renoval of higher density minerals, including pyrite that is relatively high in Hg contents.
.y In a review of trace element studies related to low sulfur, high esh coal combustion
.i in Four Corners, New Mexico, Wangen and Wienki (1976) described enrichment factors for
,j '[ electrostatic precipitator ash relative to bottom ash. Enhancement in the precipitator
~' )]
.,. ash was observed for the following elements in order of decreasing magnitude: Se, As, F, l4 Sb, In, T1, Hg, Mo, Ga, B, pb, V, and Cr. Enrichment factors near unity were observed for the other 22 elements studied.
Kaakinen et al. (1975) studied the behavior of 17 elements in the inlets and outlets of a power plant burning pulverized coal containing 0.6% S and 6% ash. Although particle
'[
l~ r size was not reported, the author described the specific surface area of his samples. The p g' surface areas reasured by nitrogen adsorption for the bottom ash, mechanical collector F a ".M- hopper ash, electrostatic-precipitator hopper ash, and electrostatic-precipitator-outlet h fly ash were 0.38, 1.27, 3.05, and 4.76 72 .';, renc:tively. Enhance.nent in trace
< s element concentration relative to Al was observed for Pb, Mo, As, Zn, Sb, and Cu.
g,g,j The magnitude of the EF's correlated with relative distance of each outlet downstream
#y.).l from the boiler and the specific surface area of the ashes. The authors point out that s'[ As enrichment de;: ends on the Ca content of the coal; As2 0 3 is associated with low Ca coals
(.[' while As20 5 is associated with high Ca. Zirconium was the only element displaying a de-
,i.I.d. .2 crease was thought to be because of the occurrence of Zr as zircon, a relatively high den-
%+ sith mineral that may be more efficiently captured by the mechanical collector. Contrary to this observation, little or no enrichment was reported for Nb, Sr. Fe, Rb, and Y.
,9 28 q.?
pj
cr
</
4 b y Ondsv et al. (1977b,c) have performtd extensive analyses of element enrichments in
/ fly ash as a function of particle size. In the study of two large trestern power plants
'tefj burning high ash, low sulfur, pulverized coal, Ondov et al. (1977c) reported considerable enrichrr.ent of W, U Ba, In, V, In, Ga, Br As, Se, Sb, and Mo in fine particles for the e plant with an ESP rated at 99.5% efficiency. In the second plant, with a 97% efficient c4 ESP, EF distribution tended to be bimodal for these elements, with a broad maximum of ty 2-10 um. The authors also point out that Br, Se, Cr, Mn, Ta, Co. and Zn displayed en-I richment in both the fine and the large particles, i.e., an EF minimum was cbserved from approximately 1 to 8 um. The authors indicate that the biphasic distributions may be the hj result of artifacts in collectior because the larger particles will be collacted on the f first impactor stages, through which vapor containina volatile elements is initially drawn.
/lI Fisher et al. (1979d) also reported data supporting bimodal elemental distributions.
Filtration studies with neutron-activated, stack-collected fly ash (VMD = 2.2 um; " 1.8) were performed by dispersing ash samples in buffer at pH 7.4 and filtering thrcugh 8 a membrane with pore size of 5, 2, 0.8, 0.4, 0.2, 0.1, 3.05, or 0.03 um. The elements were classified into four groups based on their behavior: (1 ) Na , Ca , Co , Se, Mo , and Ba
, were partially soluble and did not display filtrate concentrations that were pore-size j dependent; (2) Sb, As, Zn, W. Cr, and U displayed a pattern of filtrate concentrations W that appeared to be bimodal; (3) K. Si, Fe, Ce, Sm Eu, and Th were only detected in filtrater; fre* membranes >2 um in pore size; and (4) Zr, Cs, Nd, Rb, Tb, Yb, Hf, and Ta a were not detected in the filtrates. For those elements displaying bimcdal behavior, a
,2 relatively large increase in concentration was observed in filtrates derived from the
. 0.4 um menbrane. The concentration profile remained constant thereafter. These data
, fj suggest a concentration maximum for Sb, As, In, W. Cr, and U in fine particles less than i 0.4 um in diameter.
Ondov et al . (1977c) have compared evicleent factors for the two power plants to J those published by Klein et al. (1975), Kaakinen et al . (1975), and Gladney et al . (1976).
? The comparison (Table VI) for EF's for elements in stacir-collected fly ash inoicates
- N relatively good agreement between studies of different power plants with ESP conzrol systems employing a wide variety of coals. In light of the uncertair. ties, only Mo, Se',
and Mn showed significant differences between plants. The volatile elements $b, As, and t s Pb were clearly enhanced in samples from 411 power plants; In, Se, Cr, and V were en- ' j hanced in stack ash from those plants with tha most efficient ESP's, i.e., those plants
- presumably releasing the finest ash. Bromine was the only element displaying a sig-nificant fractional EF. Ondov et al. (1977c) point out that the EF's for stack ash ccliected from a crit with a venturi wet scrubtier (VWS) art ganerally truch higher than
; those for plants with ESP's. The authors attribute these findings, in part, to the
,.{ high efficiency (>S9%) of removal of particles >2 um and the low efficiency (40%) of f removal of particles <2 um by the VWE. In another study, Ondov et al. (1979b) indicated d that the ratio of VWS-tc-ESP fracticral emissions of submicron, suptrmicron, and total
, surpended particles were 1:6,11:1, and 10:1, respectively. They also proposed that i
1 , 3 29 I 1 t ----, -. - -- - -om -e .,- - -- - - n : .---.--,-.,------.vc.- ------e.---- -. we
/ .
N.U s s.; c o [ n
' Y,] Table VI. Enrichment Factors for Elements in Stack Fly Ash from Coal-Fired Power Plag
; A.i
. .r1 ^
- . v. -l Western Western
.; Western U.S.bplant U.S. plant 8 Allen Steam
. '..%yp.J U.S. plant t A (ESP)C plantd Chalk point' Valmont (VWS)9
.- 1 ~, -
St, 7.0 5.3 6.7 4.0 Ql;h,.tj
.h~ Cd --
6.0 -- -- 120 py'jj W -- 4.9 .- -- -- 70
*' As 6.6 7.9 6 6.3 -- 100
~*
In 5.5 3.7 -- -- 20
'r g, Zn 4.3 4.3 7.8 1.5 2.5 19
'"{
Pb -- 3.8 8.1 3.7 3.1 -- J.),Y Ga 4.3 3.0 1.2 -- --
.W.r,:
U 3.3 2.5 -- -- -- 13.5 F.. w; Se 3.0 5.3 5.5 5.7 1.7
.- 400 i.,j.4 8a 2.5 2.7 0.7 0.92 13
.. Cr 2.5 2.6 3.0 1.1
. -- 100
'/:-j Co 2.3 1.7 1.4 1.0 4.3 V- 2.0 2.5 2.5 0.75 --
21 Ma 1.8 3.5 -- -- 3.0 43
, ;[.' '
Hg 1.1 0.8 0.54 -- -- 2.7
' ;i f.;- Fe 1.1 0.90 0.84 0.83 1.0
,i;
.9 2.0
- g. - Na 1.0 1.1 0.99
~ '
3.2 Sc 1.0 1.0 1.0 1.0 , 1.0 P. . - K 1.0 0.7 0.95 0.83 -- 0,86
'$ .t' , Th 0.95 0.90 0.76 D
0.89 A1 0.86 0.75 0.44 0.83 0.94 1.3 Ca 0.76 0.89 -- 0.92 -- 7.6 [, h.1i! Mn 0.68 1.1 0.78 -- -- 21 P . . - 5;
, se --
0.6
~ 1:. .
0.64 -- -- / ;,- ' Br 0.2 0.1 -- 0.17 -- 57 Qq,..s s .. .; [* *.f. i ,. - *y Modified from Ondov et al. (1977c).
.:5 iW c Plant A employea an ESP with removal efficiency of 99.6% (Ondov et al.,1977c).
' ,90 Plant B employed an ESP with efficiency of 97% on one unit and a venturi wet scrubber (VWS) on a second unit (Ondov et al.,1979). d ,. c ,... r . Employed an ESP witn 99.5% efficiency (Klein et al.,1975). ' ' ..W5 h' ' ' ' '-
- #. 4,i.*';
.
- Employed an ESP with 75% efficiercy (Gladney et al.,1976).
kh.'N W. Employed a mechanical collector and an ESP with 91% efficiency (Kcakinen et al., 1975).
- v. , i:
~ % ..
- s. $*
'. ~
e< hh .
- E Thus, although the VMS may
+% p , ' corrosion may enhanca VUS emissions of Cr, Co Cu, and Zn. have a higher removal cfficiency of total suspended particulate matter, the ESP may more efficiently remove respirable particles. Ondov et al. (1977b) have reported enrichment factors for plume samples collected r, #t,3 frore a power plar.t with five generating units, of which two units were equipped with Elemental enrichment factors were relatively con-ESP's and the other three with VWS's. 7 stant as a function of distance from the stack for Sc, Na, K, Cu, and the lanthanides. Enrichments for Mo, V Ba, U, Ga, In, As, W, and Se increased from the stack to the plume. Subsequent plume samples indicated decreased EF's with distance from the point of fl release. The only elements displaying increased enrichments with increased distance The increased Er for Br was postulated to be from the stack were Br, Sb, Zn, and Co. because of mixing of plume aerosols with high background concentrattor.s of Br, possibly f1 because of autcmotive sources (Ondov et al .,1977b). In a further comparison of the stack fly ash from an ESP unit with that from a VWS unit Ondov et al. (1979b) reported that the mass median aerodynamic diameters (MMAD's) j for the elements As, Ba, Sb, Se, U, V, and W in the ESP ash were approximately tenfold The authors concluded j higher than in the VWS ash, which ranged from 0.47 to 0.59 .an. that despite an eleven-fold higher total particulate emission, the ESP unit is far more q Thus, the scrubber unit
? efficient at removing submicron particles than is the VWS unit.
u tested appeared to be less effective at reducing potential inhalation hazards than the i precipitator unit. . A 4 C. Surface Deoosition Models A number of investigators have presented mathematical models relating the concen-trations of relatively volatile elements to geometric parameters associated with fly ash y particl es . Assuming a volatilization-condensation mechanism, Davison et al. (1974) proposeo a simple mathematical model for elemental concentration as a func.cion of particle size. Their modei predicts that the elemental concentratior of a volatile Kaakinen et al . (1975) presented a species will be inversely dependent on particle size. u sinilar mathematical dependence based on the specific surface area (square meters per
" gram) of fly ash. If the specific surface area is proportional to the surface area:vol-
' tsne ratio and if particle sphericity is assumed, then elemental concentration is inverse-ly proportional to particle size. Based on mass transfer argt;ments, Flagan and l '
and Friedlander (1976) indicated that concentration should be invcrsely dependent on particle size for Knudsen r. umbers >l (i.e., for ccndensation when the particle size is greater than the mean free path of the depositing gas) and inversely dependent on the square of the particle size for Knudsen numbers <l . koplication cf this model fits Smith et al . (1978) existing data equally as well as the model of Davison et al . (1974).
*' extended the Flagan and Friedlander (1976) and the Davison et al. (1974) models to in-clude fire p1rticles in which the thickness cf the deposited surface layer approached the
] diameter of the total particle. This modification resulted in concentrations that 1
i asymptotically approached m&xima at particle size <1 um. The models were demonstrated to fit the concentretion dependence cn particle size of reacrosolized, ESP-collected 1 2 31
,y ..
. . . _ _ _ . . _ _ , _ , . _ . g,._
fly ash. J Bisrnann and Ondov (1978) have proposed a model with an inverse sq ' 4 ence and an asymptotic maximum for concentration as a function of surface thick f' Their results indicated that the thickness of surface-deposited chemic propertional 2 to particle size and that total elemental composition is proportional to f 1/d , where 1 is the thickness of the surface layer and d the diameter of th . Analysis of 12-stage impactor data with increased resolution in the submi supported the mathematical model. Further studies are required, however, to extend the
- presently available data on concentration as a function of particle size th 4 evaluation of the validity of the existing mathematical models.
D. Suma ry In sumary, most studies of the size dependence of elemental concentratio
. fly ash support the hypothesis of Natusch et al. (1974); the more volatile elem
! (or chemical forms) are preferentially associated with fine particles. The fine
; particle mode (<l.0 um) in the bimodal elemental distributions is generally con j
to be because of coagulation of primary particles (Whitby,1977). Bimodal size distri-
" butions may also result from the presence of multiple mineral forms, some y o
decompose or may be associated with a fine mineral grain size.
} It should be noted, how-ever, that the bimodal distribution of the very volatile elements (Se, Br, and I) observed in impactor samples my be artifacts due to vapor condensation particles collected on the first impsetor stages. Also, the biwdal distribution of j metallurgical flue gases. elements may be associated with entrairunent of corrosion prod Similarly, small particle enhancement of relatively nonvolatile elements f
}
may be because of a combination of decomposition, chemical reaction, miner size, or elemental association in the organic phase of coal. V. MATRIX AND SURFACE COMPOSITION OF COAL FLY ASH ' A. . Matrix Composition 3 Elemental analyses of coal fly ash show that the major matrix elements , Si, are Al and Fe together with a few percent of Ca K Ma, and Ti. Fly ashes derived from western United States sub-bituminous coals generally contain higher levels of calci than do bituminous coals and lignites. ! The actual compounds that constitute the fly ash matrix have been iden for a comparatively small fraction of the mass. The techniques that have proved most useful for this purpose are x-ray powder diffraction and infrared spectroscopy (Natusch et al.,1975). In addition, selicted area electron diffraction has been em-
- ployed in the icentification of small crystals often found associated with the su of fly ash.
X-Ray powder diffraction studies have demonstrated the presence 2* of a-qu mullite 23 (3Al O 2SiO2), hematite (Fe2 3), magnetite 0 (Fe30 ), lime (Ca0), and g 4 4 2 (CaSO 2H O) in aged fly ash (Natusch et al .,1975; Miguel,1976). However, there is evidence to suggest that crystalline species, associated with aged fly ash may from those in the freshly collected material (Fisher et al., 1976, 1978) because of I i
.32
'9ug ,
4, either the presence or lack of moisture in storage atmospheres. In addition to these
*/ crystalline spIctes, x-ray powder diffraction patterns indicate the presence of a sub- %'O stantial amount of material that is amorphous to x-rays (Fig.11). The composition of "4e/
%t f this material has not been established with certainty; however, it is widely accepted Y/ - that it consists of an impure aluminosilicate glass and constitutes the bulk of the fly ; Sv ash matrix (Natusch et al.,1975; Walt and Thorne,1965; Simons and Jeffery,1960). ) ta 1,,
~
4 Infrared spectroscopic identification of inorganic compounds present in coal fly ash has largely been restricted to the tentative identification of residues of evaporated aqueous 'leachates (Jakobsen et al .,1978). Several sulfate species have been identified; however, it is not clear whether these represent the actual compounds that existed prior to removal from the fiv ash. In addition, studies have been made of glass melts derived from oxides of alurrinw2, iron, and silicon (Henry et al .,1978). These have provided information that suppo-ts the contertic'. that the strix of coal fly ash is predominantly an aluminosilicate glass. B. Trace Elemental Distributicn 3 Further insights into the factors that detemine the distribution cf elements in a
. bulk fly ash sampie have been obtained from multielemental analyses of the 32 subsamples G presented in Table IV. Specific concentrations of the elements Al, As, Ba, Ca, Co Cr.
,] Cs , Dy, Eu , Fe , Ga , Hf, K. La , Mg , Mn , Na , S , S b , Sc . Si , Sm , Sr , Ta , Ti , Th , Y , a nd Zn
( were determined. In addition, x-ray powder diffraction patterns and BET strface areas
.h (by nitrogen adsorp'tior.) were obtained (Natusch et al .,1975).
As. an aid to the interpretation of the extensive data sets obtained, multivariate
.h statistical analyses, in the form of both common-factor analysis and hierarchical aggre-
.h gative cluster analysis (Harmon,1967; Blackith and Reyment,1971) were employed. Comon factor analysis makes it possible to detemine tre way in which each mcasured variable in the system is related to a set of n factors cor:acn to the system as a whole. The i important causalities that give rise to the observed data can thus be inferred. By 5 comparison, cluster analysis pemits an objective assessment of the similarity between y individual subsamples.
The results obtained indicated that the distributional pattern of trace elements in fly ash is controlled by five rajor factors. These factors have been interoreted to in-
; clude particle size, particle composition, ar.d the geochemical behavior of the elements.
l Thus, specific distributional patterns are otserved for the chalcophile, lithophile, I and siderophile elemer.ts as classified by Goldschmidt's Geochemical Series (Bertine and Goldberg,1971; Coles et el .,1979b). It would appear, therefore, that Lte size factor arises as a result of the volatilization and condensation of certain t*ta metals as described earlier (Davison et al.,1974). The dependence on particle ccmposition possibly reflects the association of some element (e.g., As and Ma) with certain types a of mineral inclusions. The dependence on geochemical class of the elements, in all { probability, reflectt the different enemical characteristics of each of these classes under high temperature combustion conditions. 1 a 33
...-..--- sc=3 m m = y - _- .. - -- -- ._ -
. 7 '
4
- SEM-x-ray analysis has provided further insight into the complexity of the matn, composition of coal fly ash. Elemental analysis of morphologically similar fly ash
[,, f particles from the NBS fly ash reference material indicated extreme matrix heterogened
'} .
(Pawley and Fisher,1977). Particles rich in K, Ti, Fe, S, or Ca were observed. In
' nearly all of the Ti in a field of 100 particles could be accounted for by a single
-j Ti-rich particle.
It is interesting to note the extreme matrix heterogeneity of indi- \ e, viduci particles in the NBS fly ash, a material that is well documented as being homo-
., g geneous by macroscopic analytical techniques.
C. Surface Composition
- ~
As pointed out in previous sections, the inverse dependence of trace elemental con-
,' [ cent' ration on fly ash particle size is generally held to be due to condentation of metallic species onto particle surfaces from the vapor phase (Davison et al.,1974). One
- g would expect, therefore, to find certain volatilizable elements preferentially concen-
.N trated on particle surfaces. This has been observed (Linton et al., 1976, 1977; Keyser
. et al .,1978).
The techniques that have been employed, to date, in analyzing the surface regions of I.. D..p coa 1 fly ash are electron spectrometry for chemical analysis (ESCA), Auger electron
};j
'j spectrometry (AES), and secondary ion mass spectronetry (SIMS). In addition, some surface analytical information is available using electron microprobe x-ray spectrometry. The operational characteristics of these techniques are sumarized briefly as follcws I (Czanderna,1975; Kane and Larrabee,1974; Keyser et al.,1978).
yd
,m.: The electron microscope (EM) and microprobe (EP) bombard the sample with a focused y]
, ; .. c beam of electrons to stimulate emission of x-rays characteristic of the elements present.
-[ g The technique is useful for analyses of individual micrometer-size particles and has a lateral and depth resolution of about I um, detemined by the, x-ray emission volume.
[_) The electron probe microanalyzer is described in Chapter 48. I - ).1 Surface analysis capabilities of EM and EP are poor since the depth resolution is
-[ very much greater than the thickness of the surface layer normally of interest. Indeed. #*N P infomation about elemental surface predominance can be obtained only by varying the
, Mr'; energy of the electron beam (depth penetration) or by ion etening of the outer surface
-; and by comparing elemental ratios for inner and outer surfaces.
Q The ESCA technique employs an x-ray source to eject core-level electrons from the p1y sample. Energy analysis of the resulting photoelectrons provides chemical bonding in-formation since the bonding energies of the core electron are sympathetic to changes in %. f,-@, p f the electronic structure of the valence level. Elements present at levels greater than 1 at. 1 in tne uppermest 2C k are detected. Depth profiling is achieved by etching the surface with an ion beam between analyset. For details on ESCA (or XPS) see Volume I, jh Chapter 11. T. ..'.M+ The utility of ESCA for individual particle analysis is limited because of the if/.- difficulty of focusing x-rays to a beam diameter smaller than 1 m, although recent ad-
- }h.
vances indicate that lateral resolutions of 10 pm are feasible. Normally, the sensitivity g of ESCA is insufficient to enable observation of trace constituents unless considerable "] surface enrichtrent is encountered. hn.q .2
-, 34 I
.b
h 9, / - (p In AES the emission of Auger electrons is' stimulated by bombarding th2 fample with a k beam of electrons. The energy of the secondary Auger electrons is characteristic of the k, emitting element. Spectra are recorded in the first derivative mode to discriminate I against a background of inelastically scattered electrons. Elemental detection limits lie in the range 0.1-1.0 at.1 within the analytical volume (cepth -20 A). Depth pro-filing is achieved by etching the sample surface with an ion team (normally Ar+) as in ESCA. Most AES spectrometers possess microprobe capabilities with incident beam diameters of 1-5 um. 4 In SIMS the sample is bombarded with a strecm of ions (most corvnonly, negative oxygen ions) and surface material is physically removed. About 1-107, of the sputtered material is in the fom of se ondary ions (nat are mars analyzed by a conventiorial mass spectrometer, f The ion microprobe represents a special configuration of SIMS in which the primary ion beam can be focused to a diameter of about 3-5 um. Both irdiv' *ual particle analysis 3 and elemental-mapping capabilities are thus available. Depth prcfiling constitutes an integral part of the process of secondary ion generation. A major advantage of SIMS is its er.tremely high sensivitiy, with elemental detection
.; limits ranging from 10 10-6 at. %, depending on the element and the primary ion used.
Typically, it is possible to observe as little as 1 ug/g in the analytical volume,
,: thereby enabling studies of species present at trace levels. Secondary ion mass spectro-metry is, however,' subject to several types of interferences and artifacts. In parti-cular, spectral interferences from molecular- and multiple-charged ions make the high resolving power of a double-focusing mass spectrometer cestrable. Also, volatilization losses and migration of sample ions under the influence of the primary ion beam can give rise to spurious depth profiles. Such effects are eften difficult to identify in SIMS since removal of sur' ace material is an integral part of the detectior process. . Of the above techniques. AES and SIM! are generally most useful for surface analysis ; and the depth-profiling studies, owing to their sensitivity and good lateral and depth resolution. Electron spectrometry for chamical analysis, however, has the important ad- ., vantage of providing information about the identity of molecular species present. With all the techniques, difficulties are encountered in establishing even semiquantitative depth scales, which are nomally attempted by calibratir.g the rate of removal of surface material against that obtained for a standard having a surface layer of known thickness.
J The main problem, however, lies in matching the matrix composition of the standard to that of the material being studied, which, in the case of coal fly ash, is not well definea. Seface analysis and cepth prufiling studies of both indivfudal coal fly ash particles and groups of carticles have established that a number of trace elements, in-
. cluding C, Cr K. Mn, Na, Pb, S T1, V, and In, are substantially surfcce enriched,
, whereas the matria and minor elements A1, Ca Fe, Mg, Si, and Ti, are not (Linton et al .,
1977). lhis observation clearly supports the hypothesis that the more volatile elements, or their compounds, are vaporized during combustion and then condense on the surfaces of coentrained fly ash particles at lower ten;perature. 35
4e .
,m 8 Depth profiling stadies of fly ash have also demonstrated the utility of using in.
. , . [ strumental techniqv% in conjunction with solvent leaching to remove soluble surface
[j material. An exaeple of this approach is presented in Fig.12 for the element 2 Pb and 1-i This study demcnstrated that extraction of fly ash with water or dimethyl sulfoxide re.
; moves the surface layer of both elements. Determination of the amounts of Pb and Tl in gy solution then enables estimation of the amounts present in the surface layer. Assuming Tifd . . . .6 a surface layer thickness of 300 k, one obtains average concentrations of 2700 ug/g for J.? M*
e- .. Pb ar.d 920 ug/g for Tl in the surface layer as compared to bulk particulate concentra- ,V,,.-Q tions of 620 ug/g and 30 ug/g for these elements. Similar estimates for several other .y ' trace elements are presented in Table VII (Natusch,1978a). I c.' 4
-a, Solvent leaching can also provide some insight into the chemical forms of elements
( f.) . present. For example, although AES and SIMS indicate little surface enrichment of iron, Q '.1 aqueous leaching rapidly removes this element from the surface region, thereby indicating _$y. g.y its presence in a readily soluble form. Similarly, comparison of the leaching and depth profiles of K. Fe, Na, and S suggests that these elements may be associated with
] each other in the surface layer, possi'J1y as alkali-iron sulfates. Further support of ~[.M the existence of simple and/or complex sulfates is provided by ESCA studies that show I,*f.
that the oxidation states of Fe and S in the surface region are +3 and +6, respectively W[.9 (Wallace,1974) . Surface analytical results, such as those presented in Fig.12 and Table VII a] demonstrate the considerable differences in composition that exist between the interior of fly ash particles and their external surface. Since it is the particle surface that is in contact with the external environment, determination of surface composition is of
- ~
hn tec considerable importance, as previously discussed. Finally, it should be remarked that there are no coherent data that relate surface composition to particle size for fly ash. Q' ' q,4 However, if the volatilization-condensation process is primarily responsible for surface
$8h .a, enrichment of trace elements, then one would not expect surface concentrations to vary y ';
greatly with particle size. This is because the amount of vapor deposited is propor-Q tional to surface area, thereby resulting in a constant elemental concentration per unit
.M surface area. Of course, if other mechanisms are responsible for or contribute to Ik surface enrichment (e.g., agglomeration of accumulation mode particles with coarse NTO particles or thermal diffusion of trace species to the surface of molten particles),
'. then some dependence on particle size would be anticipated. pjN " A?) :- D. Solubility and Leachability A number of workers (Shannon ar.d Fine,1974; Theis and Wirth,1977; James et al.,
' N 'a 1977; Dreesen et al.,1977) have reprted thn the balk sciubility of coal fly ash in
' 6.' f water is very low and rarely exceeds 2-3% by weight. The bulk solubility is clearly a ky..;c r property of both the glassy and crystalline matrix materials identified earlier, and one
- 3 . ij would expect elements that are either chemically or physically trapped within this matrix to exhibit low solubility. On the other hand, at least some of the material present in
', [
the surface skin is readily soluble in water (Fig.12). Indeed, it is now quite well es-u.% tablished (Linton et al.,1977; Natusch,1978a; Fisher et al.,1978e) that most of the Q soluble fraction of fly ash is derived from this surface layer and is thus very rich in 2/ trace elements. I{'.N
.q 36 1
- a. --
hy0 9
#c h ' F19 12. lon microproba Awo am oeom&
depth profiles for o e 320 480 so 800 9e
#4
# a/ Pb and Tl for un-
- 4. ' i
/,,, e 4v extracted and ex- g
( 7/ /
-P
" tracted fly ash samples (reprinted ;
240 - _ f} (,op with pennission g } from R. W. Linton, E h 30000}s
# P. Williams, C. A.
Evans, Jr. and D. F. I'60 .I j S. Matusch, Anal, Chem. 49,15C j \ - 2oooo j J Tl917)7 Copyright eo-N,\_ - toooo = I
'/ 1977 by the American Chemical Society). cP N' '-
o k r aosTi* ' E 36 - g
; E E -
4000 .fl F s-e
.1 E. 3
- 1 3 -
2000 y
,1.. 12 -
g 7.
>$4 - - - - _ ~;-
O do So ~ 120 @ 20o 240
' Tene(tacs)
* = =Wstracted **DMSo Entroceed ..H ao Estracted
.j biC;
,y q
- Table VII. Estimated Surface Concentrations of Elements in
! Coal Fly Asha
' ',!, " Estimated surface 9
Bulk concentratinn in
, o Elemnt concentration 300 A layer y
(99/9) (u9/9)
}
600 1500 As
"..; /,l Cd 24 700 Co 65 440 l
l Cr 400 1400 Pb 620 27C0 5 7100 252,000
~
. V 380 760
- From Natusch (1978a).
1 I 37 D Ma ** M E # # 8&"#g*,g
# * * " * * *g* 9 'M9 6M*yg ,89. (W g]* Qg
- ggggQ ,
. . ,1 #.
t, ' g t; :1; At the present time, th;re is consid:rable confusion involv:.d in int::rpreting anc
.} .,'
understanding results obtained from different studies of fly ash solubility. Specificai ,
,, Ad quite different results are obtained by workers using apparently similar laboratory leaching techniques and none are readily transferrable to field studies. It is appropri.
l ate, therefore, to consider the factors that control leachate composition under both
- t. r[.'.k laboratory and field conditions and to standardize one or more laboratory leaching g techniques whose results bear some relationship to real field conditions.
.yM ,5 Some insight into leaching behavior can be obtained by recognizing that soluble in-y3k organic species M g A, associated with fly ash particles can dissociate into their compon-ent cations Mj and anions Aj in aqueous solution, and that both dissolution and de-
['. ] position (e.g., precipitation) processes can occur. Furthermore, cations and anions Y,3 present in solution can interact so as to set up multiple equilibria that may involve
.n ., ltj ion pairing, complexation, precipitation, or acid-base behavior (Mg Aj or MjAj). The
- .
- ::, ,%/h result can be expressed, simplistically by the equations F.M
,,h ' n P4' n kt n P IM A + P + IM + IA e- .:,,h. jii ji ji k 1,y -l .M . m m 9j I"j 1 J j (10) s 1;j kquk2 k
-3H k3
-f.-/ @
.Ly M; an mn
.F I M,A I M)A,
._:b ij ' d fj (4 Here P represents the parent particles and kn , k -n are the rate constants for forward and "I f,j reverse reactions, respectively. It is apparent from Eq. (10) that, when leaching
. .1
;-; .A
-~y studies are conducted under batch conditions, such that the amount of fly ash and solvent
~
are maintained constant, an equilibriurr. will be established between particulate and D.'.)g
**b solution species. Consequently, only a fraction of the potentially soluble material will ,3, e enter solution. On the other hand, if conditions are such that solubie material is
..% T ..i coritinuously renoved by provision of fresh solvent or by providing a large solution sink n:.d f n the fom of complexing ligands or acids, then all potentially soluble material wil 1 lf; . ultimately enter solution. Matusiesicz and Natusen (1979) have conductea very extensive studies to demonstrate d - the validity of Eq. (10). They have established that the rate and extent of leaching de-g
--n . , pend upon the leaching method, the fly ash: solution ratio, temperature, pH, complexing
/C agents, particle size, and fly ash origin exactly as predicted from Eq. (10) for both
~~
' equilibrium and nonequilibrium conditions When equilibrium is established between i particulate and solution species, as in batch leaching, little dependence on particle 1:p
..a YY - cg j " 38
,p - o
r
' \
*P u!
e4 4 size is observed since the amount of a givzn element is detennined by its solution con-
#s
'6o,, #4/ centration (solubility) that is only weakly related to the amount of solid phase present.
### Exhaustive (nonequilibrium) leaching, however, removes all soluble material, the amount
/,
de #r, 4o of wnich is directly related to particle size because of its presence in fly ash surface 4 th " layer. p It is apparent from the foregoing remarks that any leaching process that establishes i the solid-solution equilibrium given in Eq. (10) will result in changes in solution Io, composition with equilibrium position. It is hardly surprising, therefore, that widely l
- 4. differing results are obtained by workers who use different leaching conditions. Lever-theless, some significant generalizations can be made. First, it is readily apparent I that much higher proportions cf most trace elements are soluble than is the ctse for 1 matrix elements (Table VIII). This is due, in part, to the predominance of trace
/ elements in the particle surface layers in quite soluble forms (probably sulfetes, oxides, and carbonates). Second, it is clear that, under batch leaching conditions, such as are l<
sost likely to occur in the field, the amount of each element entering solution is
? /' . 3 l
strongly dependent on the dilution (fly ash: water ratio) and the initial pH (Matusiewicz and Natusch,1979; Dreesen et al.,1977; Theis and k'irth,1977).
. $ Table VIII. Percentage of Elements Leached from a Typical Coal Fly Asha 1 .
-1 .
Element 1 Leached ij A1 0.2 8 5 h 4 j Ca 35
.' - ; Cr 30 K 40
- Ag 0.2 Mn 0.4
~
Mo 85 b ha 10 O' e 6 f, P I < Pb 100 l Si 0.1 1 Sr 6 _ Zn 6
" From Matusiewicz and Natusch (1979).
74 1 39 l i
*==---___e.. _,w,,m ,,g,.pg, _,
u
'M
.. E. Organic Constiturnts
- d[ To date, no exhaustive determination of organic species associated with coal fly ash h has been reported. Rather, emphasis has been placed primarily on the determination of p>1ycglic organic matter (PCM) in fly ash, due to the potential carcinogenicity of several compounds of this type (Comittee of Biological Effects of Atmospheric Pollutants,
~ ]y .
1972). For the most part, the several studies of POM in fly ash have indicated either
.,n .
i extremely low or undetectable levels (Cocraittee on Biological Effects of Atmospheric y/j Pollutants ,1972) . U5
- In a survey of fly ashes representing several coals and combustion conditions.
Aslund et al., (1978) found no individual species of POM te be present at concentrations 9C T'N. greater than 20 ng/g. A number of other unidentifled organic compounds were, however, 9)' observed at somewhat higher (10x) concentrations. It is important to note that all of g! these studies have considered fly ash collected in bulk from power plant control devices.
-Q[
Only a few studies have been made of PCM present in fly ash that was actually
'..s %. da emitted and collected from the atmosphere (Natusch,1978b; Tomkins,1978; Stahley,1976). ,,-fi However, all have indicated concentrations that are very much greater than encountered 1-Q.f, : --.
in fly ash collected within the plant. This apparent paradox has been explained by
- k. 9 Natusch and Tomkins (1977) who postulate that POM (and probably other organic species)
- W are present as gases at the temperatures encountered within a power plant but rapidly ano
. 3 I quantitatively adsorb onto surfaces of emitted fly ash particles as the temperature falls on leaving the stack. E,oth laboratory (Miguel et al.,1979) and field (Miguel,1976;
[. Natusch,1978b) studies support this hypothesis. g The actual compounds that have been identified in emitted fly ash are listed in
'?]
~- - ' Tables IX and X, which present the results of two separate studies in which specific LQ concentrations inside and outside the plant, and volume concentrations in the plume,
". M were determined. To our knowledge,~ only one study has actually measured _POM-__. concentra-
.3 . .y
?? tions as a function of particle size for emitted fly ash (Natusch,1978b). The results
,ff, indicated little $glehendenetof c concentration on aerodynamicJart.icle.-stae
! f y_J, over the range <1,1 to >7.0 m. However, the fly ash in question was derived from a
/-
small plant that employed a chain grate stoker, and the particles were found to be ex-Q ,]j tremely irregular in outline. Furthermore, there was very little change in specific _-i,(a
; surfacegea_ote_r the size range collected. We do not, therefore, consider these re-H .q. 4 suits to be conclusive.
Y ' In fact, if the temperature dependent adsorption mechanism proposed by Natusch and Tomkins (1977) is correct, dne would expect the specific concentration of organic species
,, to vary in proportion to the surface area of the fly ash particles. There is some in-d direct evidence for this behavior (Chrisp et al .,1978; Fisher et al.,1979c), but fy further work is clearly required. It has been established, however, that adsorption of p(,{j POM (pyrene) onto fly ash under laboratory conditions occurs, to significantly different extents, on different fly ashes and on cagnetic and nonmagnetic fractions of a given fly ash (Miguel,1976; Korfmacher et al.,1979a).
f.,!..@.,3. ?
~: 30 v: , =.A
1 Table IX. Measurement of Polycyclic Organic Matter Emitted Of from a Coal-Fired Power Plant Stacka 0) 3 4 Specific concentration (pg/g) N Inside stack Outside stack tg*f Compound
' D Trace Fluorene ND ND 9 Phenanthrene
~
i Fluroanthene ND 19 Pyrene ND 12 Benzofluorene ND 2 i 1-Methylpyrene ND 1 l.] " Benzophenanthrene MD 3
. Benzo [a} pyrene ND 5 Total fluorescence 3.61 x 10-3 units 3.68 units i a
- t. s From Tomkins (1978).
b Not detectable,
.)
e-t- ,
>i
Emission Factors for Polycyclic Organic, Matter from Coal Fired Table X.
Furnaces in (pounds / ton of coal) x 104 Pulverized Chain grate Species firing stoker Hand fired Benzo [alpyrene 0.2-0.52 0.3 3520 t . 0.8-1.6 3.5 5260
. Pyrene Benzolelpyrene 0 -2.3 1.1 880 l.
Perylene 0 -0.6 -- 526 I. 6.0 8800 Flucranthene --
'i
- Committee on Biological Effects of Atmospheric Pollutants.1972.
I l e
- 1 g
1 41 1 1
.,t a
lit ' i Finally, it should be mentioned that POM associated t ith fly ash may undergo
O chemical transformation following adsorption and emission. In this regard, Korfmacher et al., (1979b) have shown that adsorption onto coal fly ash effectively stabilized most P0M against photochemical decomposition, but actually prom)tes rapid (hours to days) non.
df photochemical oxidation of polycyclic aromatic compounds p;ssessing one benzylic carbon atom. Furthemore, Hughes and Natusch (1978) have shown tlat exposure of PCM adsorbed on fly ash to typical plume concentrations of sulfur dioxide and nitrogen oxides results in j very rapid formation of a variety of derivatives having sulfur or nitrogen containing substituents. It is possible, therefore, that the chenical nature of POM associated with coal fly ash emitted from a pow plant is likely to change dramatically with time I) . and distance from the plant.
' ;;l
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[2h , 42 N A
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i s
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47 4 i}}