ML20101G100
| ML20101G100 | |
| Person / Time | |
|---|---|
| Site: | Hatch  |
| Issue date: | 05/31/1991 |
| From: | Bongers L, Burton D, Fisher D JOHNS HOPKINS UNIV., BALTIMORE, MD |
| To: | |
| Shared Package | |
| ML20101G087 | List: |
| References | |
| NUDOCS 9206250288 | |
| Download: ML20101G100 (69) | |
Text
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THE RELAilVE TOXICITIES OF CONTINUOUS AND INTERMITTENT EXPOSURES OF CHLORINE AND BROMINE TO AQUATIC ORGANISMS Prepared for The Sodium Bromide / Bromine Chloride Industry Panel i
Prept. red by Leonard H. Bongers, Ph.D B&B Environmental Services, Inc.
Baltimore, Maryland 21229 Dennis T. Burton, Ph.D Daniel J. Fisher, Ph.D The Johns Hopkins University Applied Phy:ics Laboratory-Shady Side, Maryland '20867 May 1991 l
Page 1 cf 69 9206250288 920611 PDR ADOCK 05000321 P-pop
4 FOREWORD A
he study was initiated at the request of he Sodium Bromide /Brornine Chloridi Industry Task Force under contract to B & B Environmental Services, Inc. on October 10, 1990.
2-De test program was performed in accordance with the " Protocol for Testing of the Effects of Sodium Bromide on the Toxicity of Chlorine to Fresh and Saltwater Organisms.'
2 (Appendix B) and as amended by Protocol Amendment #1 (Appendix C). The Test i
Protocol and Amendment #1 were agreed upon by he Sodium Dromide/ Bromine Chloride Industry Task Force, U.S. EPA, and B & B Environmental Services, Inc. He only deviation from the Test Protocol is the expression of oxidant as peq/L rather than ug/L oxidant in the report. The rationale for expressing the oxidants as peq/L rather than ug/L oxidant is i
given in the report.
In addition to the test program speci5ed above, a program wu developed by L Bongers and _W. Furth (iceluded as Appendix A), designed to w mate the relative emironmental impacts resulting from the application of chlorine and bromine for fouling control.
4 De undersigned certify that the test program was performed in accordance with the l
Test Protocol and Protocol Amendment #1.
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i ABSTRACT Sodium bromide can be used to convert hypochlorous acid into hypobromous acid.
1 Simultaneous addition of sodium bromide and chlorine to water used for powerplant condenser coolidg could significantly reduce chlorine application rates because bromine oxidants are generated and consilered more effective for controlling biofouling than chlorine oxidaan.
Since such a change in biofouling control strategy could Impact the environment, the biotoxicity characteristics of bromine oxidaan were evaluated in tarms of LCO values. In order to ucensin potendal effects of rasidual bromine oxidants on the environment, decay properties of bromine oxidanu were compared to r.hlorine oxidanu.
It was found that in four of six species tested, the bromine oxidants were about twice
~3 as toxic as the chlorine oxidants, while for two species the difference in toxicity was five fold.
J For continuous egosure to bromine oxidants, the 48.h LCO for daphnids and tha 76 h j
LCO for amphipods could not be calculated becaus: signiGennt mor.21ity occurred at the oxidant quantitation limit.
g Oxidant de=y propenies here significantly different as well Bromine oxidants k
decayed two to five times faster'than chletine oxidants.
f Biotoxicity and che=ical findings r.re in general agreement with data published 7
previously.
2 Present data suggest that environmental Snefits may result from the simult:neous application of sodium bromide with chlorint for biofouling control as compared to the application of chlorine without sodium bromid.:.
}
m Preliminary computations based on present data hdicate that these environmental benefits may be sighificant. The anticipated environmental benefits are attributable to the relatively rapid chemical decay of the bromine oxidants and also to the relatively lower 1
amount of biocide needed for the same degree of biofouling cor.rol. Further details are given in Appendix A.
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Page 3 of 69 d
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e TABLE OF CONTENTS P:ge FO REWO R D........................................
2 AB STR4CT.........................................
3 L
INTRO D UCUO N......................................
- -3 H.
MATERIALS AND METHODS..........................
10-15 TEST MATERIALS..............................
10-11
. Test Spe cies...................................
10 Test Co mpounds................................
10 Dilutio n Wate r.................................
11 TEST METHO D S................................
4-13 Treatment Conditions............................
11
. Exposure Syst e:n................................
12
. Excesure Protocol...............................
12
. Mhsure=ents of Oxidant Concentration..............
14
. Measure =ents of Oxicant Decay Rates............. '..
14
- A:nmonia Measurements..........................
13 HL RESULTS
...............l...................
15-13 CHLORINE AND BRO,MINE TOXICITIES...........
16-M DECAY OF CHLORINE AND BROMINE INDUCED O XID ANTS....................................
li IV.
D IS CUS SI O N........................................
19-20 V.
Ln ERATURE CITED.................................
21-2:
TABLES 23-3s FIGURES 39-40
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APPENDICES
'I Relative h$dronmen al Impact Es imates for Chlorine and A.
Bitmine Used For the Control of Blofouling Condenser Cooling Systems B.
Protocol for the Testing of the Effects of Sodium Bromide on the Toxicity of Chlorine to Fresh and Saltwater Organisms C.
Protocol Amendment #1.
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LIST OF TABLES Table j
Pap 1
Informanen on organisms used in testing '....................
23 2
Mean water quality (= SD) for the chlorine studies.............
24 i
3 Mean water quality (n SD) for the chlodne NaBr study.........
25 4
Toxidty of chlorine and bromine on freshwater and saltwater 25
- +*
5 Chlorine TRO concer.trations (ug/L chlorine TRO) expressed :s the mean (=SD) of all measurements made during the test period for each trest =ent 25 6
Bromine TRO concentr:tions in (ug/L bromine TRO) expressed in the mean (=SD) of all measurements made during the test period fo r each tre:une nt.....................................
30 7
Free available oxidant and total residual oxidant (values in parendesis) i:: chlorine test expressed as g/L chlorine oxidants...
32 8
Free avanable oxidant and total residual oxidant (values in -
parenthesis)in chlorine test Ltpressed as ug/L bromine oxidants..
23 9
FAO, measured during the a:n=enia exposures as gg/L chlorine or bromine 34 10 Oxidant decay, me:sured as total residual oxidant equivalents in freshwater and 20 ppt saltwater upon the addition of chlorine, and chlorine plus L5 times the stoichiometric amount of NaBr.......
35 11 Oxidant dec:y, me:sured as total residual oxidant (TRO) equivalents in freshwater................................
36 12 Oridant de=y, me:sured as total residu:1 oxid:nt (TRO) equivalents in 20 ppt saltwater..............'..............
37 13 Estim:tes of the rel:tive environment:1 imp:ct on a freshwater stre:m resulting from the tre:tment of cooling water by -
chlorination in the presence and the bsence of sodium bromide..
33 Page 6 cf 69
r LIST OF FIGURES Figure
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1 Oxidant,deeny as peq TRO la freshwater.................... -
39 2
Oxidant decay as peq 1RO in saltwater......'......'.........
40
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I. INTRODUCTION Chlorination by wutewster treatment plants and POTWs to eliminate the discharge of pathogenic orpnisms and the use of chlorine by electric utilities to inhibit biofouling are widespread practices. Laboratory research has shown, however, that chlorine induced exidr.nts are toxic to both freshwater and saltwater squatic organisms. Due to the relatively slow decsy rate of these oxidants, they may be toxic to squatic life when dischstged into rece:ving waters.
The use of sodium bromide in conjunction with chlorine has been proposed as an alternative method to routine chlorinttion. When applied with chlorine, sodium bromide is oxidised by hypochlorous acid (ROC 1) to hypobromous acid (HOBr) and sodium chloride. Due to the relatively low bond strengths, bromine residuals exhibit low stability and hence, should decay faster. In addition, they are more reactive than chlorine residus!s.
and should perform better as biocides. In cooling water containing ammonium salts.
application of sodium bromide with chlorine shold result in much lower levels of oxidant residuals because the slow decaying chloramines would not be genemted.
De objective of the present study was to provide a technical basis for assessing the potential environmental and operational benefits of using sodiure bromide in conjunction
'with chlorine for the control of biofouling in power plant cooling systems.
Comparative datawere obtained for both freshwater and saltwater organisms exposed to the two biofouling control options., The testing effort included:
Measurements of acute toxicity effects on representative fresh and saltwater organisms resulting from a continuous or intermittent exposure to chlorinsted or brorninsted fresh and saltwater.
Evaluation of the effecu of ammonia on the toxicity responses, and Measure =enu of decsy rates in fresh sad in saltwater of chlorine and bromine induced exidants.
Toxicity responses were e.tpressed :s 96 h LC50 values for all species tested with the exception of daphnids, for which 48 h LC50 values were estimated. Oxidant decsys were computed r.s quasi first order decay constanu.
Findings presented in this report suggest that the relative potency of bromine induced oxidants allows the amount of chlorine required for biofouling comrol to be reduced to about half the amount that is required in the absence of bromide.
Page B of 69 1
'Ibe relatively rapid decay of bromine _. induced' oxidann is another promising feature 1
resulting from the simultaneous addition of sodium bromide and chlorine. The combination -
of reduced blocide requiremenu for foullag contml and the rapid decay of residual bromine -
oxidants may result in a s'gnificant decrease in environmental impact. Using toxicity data for golden shiney' and rairden trout, and oxidant decay values determined as part of the present study, sample calculations of th: relative impacu of chlorine and bromine oxidanu were performed. (For details see Appendix A.): These calculations indicate significant reduction in environmental impact, depending on biocide use for fouling control, and the '
relative amount of the riverBow and for condenser coolin5 1,
s Page 9 of 69
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II.' MATERIALS AND METHODS
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TEST MATERIALS Test Species..
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- ... tTadcity tests were pe.rformed on four freshwater and two saltwater species. The freshwater species included two invertebrates, the daphnid Depnia magna and the amphipod Nycleffa c:reca, and two fish, the golden shiner Noremigonus crysoleucas and the rainbow trout Oncorhync/mr mykhr. The two saltwater species were an invertebrate, the mysid Mysidopsis behia, and a fish, the silverside Menidio berylls.u The life stage (length and weight, where appropriate) of each test species and the exposure conditions are given in Table L Daphnids and amphipods were obtained from in.Eouse cultures; common shiners from Perry's Fish Farm in Petersburg. VA: and Rainbow trout from the U.S. Fish and Wildlife Service's Erdn National Fish Hatchery in Erwin TN. Mysids were obtained from Chesapeake Cultures in Hayes, VA and silversides from Aquatic Indicators in St. Augustine.
FL Test Compounds Sodium hypochlorite (Lot #0276), was obtained from Lab Chem. Inc., Pittsburgh.
Pennsylvania; sodium bromide (Lot #020290) from Ethyl Corp., Baton Rouge, Louisiana.
All chlorine stock solutions were prepared from Lot #0276 containing 66 grams chlorine per liter. To prepare bromine stock solution, sodium bromide (NaBr) from Let
- 020290, containing 527 gra=s NaBr per liter,was added to a solution of hypochlorous acid.
In order to assee complete conversion of hypochlorous acid (HOC 1)into hypobromous acic (HOBr), sodium bromide was added at L5 times the staichio.etric concentration of chlorine, in accordance with equation:
HOCl + LS NaBr - HOBr + Nacl + 0.5 NsBr Thus. it is reasonable to assume that a stock solution containing chlorine and sodium bromide in the specified ratio will principa!!y contain hypebromous acid, and no
. hypochlorous acid. (In the text these solution are referred to as chlorine /NsBr mixtur-s or as bromine solutions.)
Page 10 of 69 l
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Dilution Water _,.
B Unchlorinated groundwater from an on site deep well was used for all tesu using'-
freshwater. For saltwater tests, esmarine water from the adjoWag Parrish Creek 5.as used ~
Both the freshwater and the saltwater wars Illtered to 1 km and stcred in 850 gallon holding tank The water in the holding tanks could be serated and heated (dtanium heaters) as necessary. For all organisms wi'h the except'on of rainbow trout the water ta'mperature was maintained at 2PC; for rainbow trout the temperature was maintained at IPC. For all saltwater tests the salinity of the estuarine water was increased to 20 ppt with Instant Ocean *. Water quality panmeters are recorded in Tables 2 and 3. The groundwater was also tested for organic priority pollutanut none were detected abcvs the level of detection. -
TEST METHODS Treatment Conditions.
All tests with the exception of rainbow trout, were conducted at 23*C = 2'Ct tests with rainbow trout were conducted at 15' z 11'C. Test temperatures were recorded continuously, and at no time did the te=perature exceed the specified limits.
Other conditions are as listed in Table 2 and Table 3.
The test organisms were exposed to either chlorine or bromine (i.e, chlorine /NaBr mixture) in a side by side !!ow-through exposure system. This. allowed direct toxicity comparisons between both oxidanu using the same dilution water. All organisms except the daphnids were exposed for 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br />. The daphnids were exposed for 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br />.
Two separate tesu were conducted on each species. In one test, organisms were exposed continuously to a dilution series of oxidanu. In the second test, orBanisms were exposed intermittently to a dilution series of oxidant for 40 minutes 'every 3 hours3.472222e-5 days <br />8.333333e-4 hours <br />4.960317e-6 weeks <br />1.1415e-6 months <br />.-- The organisms were maintained in oxidant free conditions for the periods between exposures.
Initially,. the method ' of. Brooks, et al. (1989) > was used-to maintain' oxidant concentratbus during the intermittent exposures. These investigators spiked the tanks with oxidant to obtain the desired exposure concentration. Then, a Gow-through toxicant delivery.
system was turned on to maintain that concentration during the intermiu'ent period. ' At the end of the pei 3e toxicant delivery system was turned off, and the tanks were flushed with diluent water. This procedure was used for tesu with the daphnids and the golden-
- shiner,
. r the rest of the intermittent tests conducted in the present study, the toxicant -
delivery ytem was maintained under constant conditions,.while the test-chambers, containing the organisms, were transferred between halogensted test aquaria and non -
halogensted Bow through holding tanks.- Immediately following transfer of the organisms Page 11 of 69 I
C to the holding tanks, the now rate of diluent water into the tanks was incressed to fhah any total residual'exidants (TRO) that may have been transferred from the test squais, ne rainbow trout were held in 1 mm mesh nitex baskets with petti dish bottoms during the latermittent exposure periods. The petri dishes allewed for a small amount of liquid to cover the Esh during tmnsfers between treatment comittions.
De smaller organisms were mted in the continuous expcsure ensmbers described i
below and transferred with a glass ladle between trestments. Th's allowed the organisms to remain immersed during the transfer. Although both intermitti nt procedures produced good
- square wave" intermittest exposure conditions, the latter tr insfer method appeared more' convenient than the spiking procedure.
An additions! continuous exposure study was conducted to compare the toxicity of chloramines and bromsmin-; a dsphnids and mysids. In the',e experimems, dilution water was dosed to 0.3 mg/L NH N with ammonium chlorice tdor to delivety to the test system.
This stoichiometric ratio of ammonia to oxidant; aso used by Brooks et al. n!!cws conversion of oxidants into amines.' Bio ssays c itoucted with these test selutions principsily evaluate the biotoxicity of chloramines and bromamines.
~
Exposure System A continuous flow delivery system similar to that used by Vant.etherst et al(1977) was used to create a stable oxidsm exposure environment. Water from the diluent holding tanks was pumped to s 200 gallon constant head tank located above the exposure wet table.
.The smaller head tank was temper:.ture controlled and sersted. The wet table holding the exposure squaris was also te=perature controlled. Diluent water was delivered by gravity through a 4 inch PVC delivery pipe suspended above the wet table. OverSow from the delivery pipe was divened back into the large holding tanks. The flow rate through the delivery pipe was comrolled by both a standpipe in the overhead tank and a PVC valve at the beginning of the delivery pipe. Excess water not used as dilution water was diverted from the overhead tank to the holding tanks through an overflow system. Diluent water was delivered from the delivery pipe to the test squaris by adjustable glass siphons as shown in Vanderhorst et al (1971). Esch siphon was inserted into a green nalgene stopper which was inserted into a hole drDied into the 4 inch delivery pipe. De Gow rate from each siphon was adjusted to 190 mL/ min for all halogensted treatments and 200 mL/ min for the control Chlorine and bromine stock solutions were delivered at a rate of 10 mL/ min to trestmem conditica by Masterfiex* pumps. Stocks of various TRO concentrations were made up using reverse osmosis water in 20 L glass carboys. NsBr was added to the Ns solution. stirred. and allowed to stand in the dark for 15 minutes prior to desing of the stocks. The stocks were mixed thoroughly and sllowed to stand for 1 to 2h prior to use.
During the exposure periods. the 20 L carboys were covered with blsch plastic. New stoc Page 12 of 69
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I solutions were made every'24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />. Glass' delivery tubes were ins stoppers to the bottom of the stock bottles.' C j,
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After mixing, the halogen funnels suspended below' the diluent water siphons -con volumes of treated or control water to two replicates per treatment.
'the exposure aquaria (93 L) contained 7 L of solution.- Flow in 100 mL/ min. This allowed for a 9096 molecular replacement tim hours. All tesu were conducted in these aquaria using theTsame G continuous exposure tests, daphnids, amphipods, mysids, and s glass chambers (5 cm diameter by 15 cm length) with nalge hich allowed test chambers were suspended in the test aquaria from a rocker. arm il l
as the chambers to move vertically through the t Rainbow trout -
throughout the test. Control organisms were I
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. and baskets (trout) were moved between exposure and o l
exposure tests.
F.xposure Protocol Each test (continuous or intermittent) consisted of five to six t plus a control. In the chloramine /bramamine studies an a added. Rainbow trout tesu were ebnducted at a temperature of 15' i
were conducted at 25'C. The light cycle for 211 the tests was 16 h lig were not fed during the tesu except for the mysids which require liv sutvive 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> and amphipods which were fed micro-encapsu i
i il to the start of each test the exposure system was operated untilTRO co i
h test aquaria stabilizedc The continuous flow resu were started by a stabilized test aquaria. To start the intermittent exposures for the
~
L and silversides, organisms were added to the exposure chambe all of the chambers were loaded they were transferred to the tes exposure. After 40 min, the chambers were transferred to.n As discussed above, daphnids and shiners were kept in the te and continuously dosed for 40 min, after which time chlorine was In the continuous exposure experiments, water samples
- at 1, 2, 4, 6, 8,10,12, 24, 36, 48, 60, 72, 84. an 1, 2. 4, 8.- 12. 24, 36, 48. 72, and 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> for th
- Organism mortalities were recorded at1. 2, 8,12,16,24, and every 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> thereafter unt.ilthe-4 h'
t continuous exposures, and atconclusion of the test. Free av
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treatment during every test Dissolved oxygen, conductivity or salinity, pH, alkalinity, and hardness were measured daily in each treatment. Temperature was recorded continuously I
l in one control replicate in all tests.
L During the chloramine /bromamine studies, total ammonia (NHrN) was measured in the diluent water holding tanks at the be5 nning and and of each tr.nk refill In addition, i
L FAO, mono., and di.halogensted amines were measured in each treatment tank once during L
each of these tests.
The b'ionssay test protocol was consistent with the test guidelines described in the Em'ironmental Protection Agency's,' Methods for Measuring the AcuteToxicity of Ef!!uents to Freshwater and Marine Organisms" (USEPA 1985), with the exception of temperature, l
The test temperature for all species, except rainbow trout, was 25'C rmher than 20*C. The rainbow trout test was conducted at 15'C rather than 12*C.
Measurements of Oxidant Concentration l
The amperometric titration method, described in StandardMethodt (Method 4500-CL D APHA et al.1989), was used to determine total residual oxidants (TRO) and fr'ee available oxidant (FAO). Fischer Porter amperometric titrators (Model #17T2000) were i
i used for all measure =ents. By using the high sensitivity mode, a forward titration, and a 200 mL sample,1RO quantitstions limits were 15 ug/LTRO as chlorine and 34 ug/L TRO as bromine. With this sample size,1 mL of PAO (0.00564N phenylarsene oxide) titrant equals 1 mg/L chlorine equivalents. Samples were analyzed immediately upon collection to avoid loss of oxidant due to holding. Total residual oxidant concentrations are presented as ug/L (ppb) TRO as chlorine or bromine.. LC50 values are reponed as ppb TRO as chlorine and as peq TRO/L for the chlorine exposures and as ppb TRO as bromine and as geq TRO/L for bromine exposures.: The TRO as ppb bromine was calculated by m"Itiplying the milliliters of titrant (PAO) used by W as described in the Fischer Porter utrator manual. LC50 values for the two treatments are compared on a peq TRO/L basis.
The concentration of TRO as ppb chlorine and bromine are converted to peq TRO/L by dividing by 35.5 for chlorine and 79.9 for bromine.
Measurements of Oxidant Decay These tests were conducted on the freshwater and saltwater used for the bicassay testing. The effects of sodium bromide on the decay of chlorine. induced oxidants were tested at 1.5 times the stoichiometric concentration of chlorine. Tr.e static decsy tests were Page 14 of 69 y
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- beskers at 2PC in the dark. TRO measurements-were made amperometrienlly by the same procedures described above for the blousay tests.
Ammonia Mansurements Ammonia (NH N) was measured using an ammonia. selective electrode :nd an Orion 3
Model 901 Ion Analynr. Method 4500 NH described in Standard Methods (APHA et al.
3 1989) was used for the analysis.
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UL RESULTS CHLORINE AND BROMINE TOXICITIES The toxicity data for continuous exposures are presented as LC50 and as ILC50 for intermittent exposures. These toxicity indicators are based on the average oxidant concentrar'.on per treatment. De LC50 represents the 30 concentration which is ledal to 50% of the test organisms exposed continuously over the test period. The ILC50 represents the 30 concentration which is lethal to 50% of the test organisms exposed, inter =ittently for 40 minutes every 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br />. The continuous exposure LC50 values are based on the average TRO concentrations over me entire length of the test period, while the ILC50 are based on the average TRO concentration for all of the 40. minute exposure periods duri.2g the test.
LC50 values are es!culated from the mortality data in accordance with EPA Manual 600/4-85/013 (USEPA 1985). Where possible, the probit method was used. If the str.tistical criteria for a probit analysis were not met, an LC50 value was calculated by the moving average angle method. An EPA computer program was used for calculating a!!
LC50 values (Stephan 1978).
The results of all toxicity tesu are summarized in Table 4, while oxidant
. concentration for all treatment conditions are summarized in Tables 5 and 6.
From the examination of the results it appears that bromine. induced exidants are more toxic than chlorine. induced oxidants when compared on a peq TRO/L basis (sen Table 4). On the other hand, when the comparisons are made on a weight basis (i.e., pg/L) l chlorine. induced exidants appear more toxic than bromine. induced oxidants in 12 of la c:ses tested. Dese apparent contradictions result from the difference in atomic weight of the two aSents involved.
We prefer to' express toxicity and chemical decay in terms of microcquivalents per liter (geq/L) for several reasons. One is that neither the speciation nor the relative contribution of indhidual oxidanu to biotoxicity are known; another is that the TRO measurement method determines TRO concentrations in terms of iodine eeuivMems per unit volume. And, since there are differences between the toxicities of chlorine induced and bromine. induced exidants, anc, their rates of decay,it would be misleading to convert TRO equivalents into either a weight. based chlorine value or a weight. based bromine value.
Also, to facilitate estimates of the relative environmentalimpacts of the two agents it is more convenient to perform cniculations based on TRO values expressed in terms of chemical equivalents per unit volume.
Page 16 of 69
Accordingly, in this teport comparisons between the agents will be based on geq chlorine TRO/L or~ueq bromine TRO/L Results recorded inTable 4 indicste that for continuous exposures, bromine oxidants-appear to be twice as toxic (1.93 = 035) as chlorine oxidants in four of the six organisms:
for the amphip6ds and silversides bromine oxidants are about five times u toxic (5.23 =
y 0.52). A 48.h LC50 for daphnids and a 96 h LC50 for amphipods could not be calculated l
i for continuous bromine exposure, because survival was less than 50% at the level of oxidant l
. quantitstion.
l l
For intermittent exposures, bromine oxidants 'were, on the aversge,1.7 times (1.67
= 034) as toxic; but there was little difference among species.
In freshwater, daphnids and nmphipods were most sensitive, both in continuous and intermittent exposures. In saltwater, the mysid was the most sensitive organism whe:t exposed continuously to chlorine oxidants. De mysid and silverside were equally sensitive to continuous bromine exposure and also to both oxidants, when they were exposed intermittently.
Conversion of chlorine oxidants into chloramimines, and bromine oxidants into bromamines appeared to increase toxicity, although this effect was less pronounced in case of the bromamines. This increase in toxicity is attributable to amines, and not to the formation of unionized ammonia. Under prevailing test conditions, the concentration of unionised ammonia was estimated at less than 15 and 17 pbb during the mysid and dsphnid tests respectively. These levels are well below reported toxicity values (USEPA 1985,19S9).
During each treatment conditicn, one sample also was analyzed for free available oxidam (FAO), as well as total residual oxidant (TRO). The results of these analyses are l
recorded in Table 7 (chlorine), Table 8 (bromine), and Table 9 (ammonia test).
l FAO was observed more frequently at the high-concentration treatment conditiotu; with bromine as the treatment agent, FAO was also observed at tow-concentration treatments. To what extent free availabic oxidant did contribute to the observed mortalit I
l Is unclear from the available data.
In the presence of 03 mg/L ammonis nitrogen.FAO was not observed in chlorine treatments (Table 9). Addition of ammonia to bromine treatments did indicate the presence of relatively 1stge concentrations of FAO. According to a personal communicstion with Dr.
Franklin Handy of Great Lakes Chemical Corporation, West 1.nfsyette, Indiana, the FAO observations in bromine treatments with ammonia are erroneous. Apparently, under such Since conditions, the amperometric titration method measures bromamines as FAO.
ammonis was added in relative excess, we may assume complete conversion of bromine oxidants into bromamines. Thus, the observed toxicities reflect bromsmine toxicities.
l Page 17 of 69 i
DECAY OF CHLORINE AND BROMINE INDUCED OXID.WrS De effect of the addition of sodium bromide to a 5,ludon contsining chlorine on oxidant decsy is recorded in Table 10, and Illustrated in Fig.1, where the natural logarithm
.of the total residual oxidant concemrations are plotted against tim-for solutions containing chlorine and c!ilorine/ solutions to which sodium bromide is added. Figure 1 shows the decay in freshwater, in Fig. 2, similtr data are shown for the decsy in saltwater, l
ne test data reDect a two phase, qual first order oxidant decay, for both chlorine f
and bromine (i.e., chlorine / sodium bromide). In both cases.'the laidal reladvely fast deesy, defined as K1 (slope of in (peq TRO) vs time) was followed by a much slower decay, defined as K2.
i In freshwater, (Table 11), sodium bromide increased the fast decay by a factor of i
about three (0.054 vs 0.016), while K2 was increased by a factor of 5 (0.005 vs 0.001),
l t
In sainvater (Table 12) with, sodium bromide, the fast decay (K1=0.034) was, on the aversge, about twice as fast as the fast decay observed in the presence of chlorine (K1 = 0.M4). The slow decay (K2 = 0.009) was, on the aversge, about nine time l
1 value (K2=0.001).
These dats clearly indic:te significant ineresses in the rates of the fr.st and slow oxid=t decays when sodium bromide is applied simultaneously with chlorine.
As wQ1be discussed in the next section and in Appendix A the relatively rapid decay I
of bromine oxidants may signi5canti reduce the environments!' impact resulting from biofoulin5 control of powerpl=t cooling systems.
Page 18 of 69 Y
e
5 z?.4,'
4 d
IV. DISCUSSION LC50 values for chlorine TRO in the current study are consistent with toxicity values from the Envirgnmental Protecdon Agency's water quality criteria _for chlorine (USEPA-1984) when expressed as ppb chlorine TRO. The species mean acute values (SMAV) for Dopluda magna (27.7 ppb) and rainbow trout (62 ppb) reported m the water quality crit are identical to values from the current sudy. The SMAV. for amphipods of 267 ppb is similar to our value of 78 ppb considering the species (Cammarus pseudolimnaeur) and life stage differences. De somewhat lower SMAV of 127 ppb TRO for Notamigonus crysoleuc reported in the water quality criteria may be a factor of one low value (40 ppb) skewing SMAV and the fact that sewage ef!1uent was used as the dilution water in all the tesu used-to determine the SMAV.
There are no direedy comparable values for Mysidopsis bahia or Menidia beryllina in the water quality criteria.- The only mysid value reported was an LC50 of 162 ppb fer.
Neomysis sp. determined at 15'C and a salinity of 28 ppt. -. De temperature differer.ce between the two studies may explain the difference from our value of 62 ppb. There is one 96 h LC50 value of 54 ppb for Menidia peninsular and a 96-h LC50 value of 37 ppb fer Menidia menidia which form the basis for comparison with our present value of 143 ppb with Menidi beryllina. The value of 37 ppb was achieved using field collected adult silversides.
De 96 h LC50 value of 54 ppb is an unpublished value cited in a paper by Goodman et al (1983) for comparison with long term studies conducted with the same species. Comp to the no effects level of 40 ppb found by Goodman et al. for hatching success and survival, it seems likely that the 96 h LC50 of.54 ppb may be somewhat low.-
l I
Brooks et al. (1989) conducted an extensive study on continuous and intermitten:
toxicity of chloramines to a number of species.- Results from his studies'give comparable
~
LC50 values to the current studies (48 h LC50 of 24 ppb TRO for Daphnia magna and a-i 96-h LC50 of 111 ppb for rainbow trout).- Dese investigators also showed a 3.to 5 fold decrease in daphnid sensitivity _ during intermittent exposures (2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> / day) and a 7-fold-decrease in rainbcw sensitivity, again very comparable to the present study. The common -
shiner Norropis comurus was more sensitive to chloramines (96 h LC50 of 71 ppb) than the golden shiner was to eMorine in the present study. -Species and exposure dissimilaritie (ammonia vs no ammonia) could explain the differences in the LC50s.
Present tests indicate that continuous exposure to bromine oxidants appears to be
' about two times as toxic to four of the six species. compared to continuous exposure to chlorine oxidants. For the silversides and amphipods, the difference was five fold. For continuous exposures to bromine oxidants the 48 h LC50 for daphnids and the 96 h L for amphipods could not be calculated because their survival was less than 50% a of oxidant quantitation. With intermittent exposures, the difference in toxicity ws on th L
average 1.7 times.
Page 19 of 69 r
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,,w w,,-
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A similar differencein ' potency" was also observed in a study by Bongers et al.1971, and Liden et al,1980, when the effectiveness of biofouling control by bromine chloride was 4
compared to that of chlorine. These studies indicated that the more toxic bromine oxidants permitted the use of much lower amounts of biocide for fouling control. A 15 day trial, conducted on a powerplant cooling system using low.saliniry estuarine water for heat rejection, indicated that, on an equimolar basis, bromine oxidants were two to three times more effective than chlorine oxidams.
In light of the observed fouling control efficacy of bromine oxidants, and their relatively rapid decay characteristics, the conversion of hypochlorous acid into hypebromous acid and bromine oxidants could significantly reduce the impact on the squatic environment resulting from the control of biofouling of powerplant cooling systems. Beneficial effects from this conversion would be most pronounced at.tigh unblent water temperatures and when a relatively large portion of the riverflow is used for condenser cooling.
Preliminary estimates of a reduction in environmentalimpacts is shown in Table 13, where the benefits of using sodium bromide in conjunction with chlorine are estimated for heat rejection into a freshwater stienm. (Methodology, assumptions and calculation are given in Appendix A.)
This comparison which is based on rainbow trout et 3 golden shiner data, indicates that signifierait reduction in :nvironmental impact can be whieved, depending upon the amount of riverflow used for condenser cooling.
t 1
l l
Page 20 of 69 I
1 V. LITERATURE CITED APHA American Public Health Association. American Water Works Association, and Water Pollution Control Federation.1989. Standard methods for the examination of water'and wastewater.17th ed. Washington. D'.C Bongers. LH, T.P. O'Connor. D.T. Burton.1977. Bromine Chloride An alterative to Chlorine for facility control in condenser cooling systems. EPA-600/7 77 053.
Brooks. A.S, D.C S: mania and M.S. Goodrich.1989. A comparison of continuous and intennittent exposures of four species of aquatic organisms to chlorine. Final Research Report. Center for Great Lakes Studies and Department of Biological Sciences. University of Wisconsin Milwauken. Milwaukee, WL Liden. LH, D.T. Burton. LH. Bongers.1950. Estimation of ^'orine and bromine chloride dosages for biofouling controlin tow. salinity estuarine once through cooling systems.
J.F. Garey, R.M. Jefdan. A.H. Aitken. D.T. Burton, and R.H. Gray, eds. Condenser biofouling control symposium proceedings. In: Ann Arbor Sci.Publ.Inc Ann Arbor.
ML Goodnun. LR D.P. Middaugh, D.J. Hansen. P.K. Higdon and G.M. Cripe.1933. Early life stage toxicity with tidewater silversides (Menidia peninsulce) and chlorihe.
produced exidants. Environ. Toxicol. Chem. 5337 343.
l Stephan. CE.1978. LC50 Program. Unpublished data. U.S. Environmental Protecticn Agency Environme.tal Research Laboratory - Duluth Duluth, MN.
1 USEPA. 1984. Ambient water quality for chlorine - 1984. EPA 440/5 84-030. U.S.
Envirrnmental Protection Agency. Washington, D.C USEPA.1985. Methods for Measuring the Acute Toxicity of EfHuents to Freshwater and Marine Organisms. W.H. Peltier and CL Weber (eds.). U.S. Environmental i
Protection Agency, Wash, D.C EPA /600/4-85/013.
USEPA.1985. Ambient water quality criteria for ammonia 1984. U.S. Environmental Protection Aget.:y, EPA 440/5-85-001.
1 USEPA. 1989. Ambient water qual;;y criteria for ammonia (Saltwater) 19S9. U.S.
Environmental Protection Agency, EPA 440/5 88 004 Wndernorst. J.R., C L Gibson. L.J. Moore and P. Wilkinson.1977. Continuous flow l
apparatus for use in petroleum bionssay. Bull. Environ.Contam.Toxicol.17.577-534 o
Pr.ge 21 of 69
1-i 4
h j
1985. The acute toxicity of chlorine on freshwater
' l Wang, M.P. and S.A. Maisson.
I organisms: %ne concentration relationships of constant and intermittent exposu l
Eighth Symposium. ASTM STP891, Aquatic Toxicology and Hazard Assessment:R.C. Bahner and DJ l
Phil:.delphia. pp. 213 232.-
s s
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i Information on organisms used in testing
..i j
Table 1. -
Test l_ lie Stage f.ength nwn( 2 SD)
Weight isng 2S08 i
1 Species Wet Dry i
NA NA l
~ 48-h Continuous
- < 24h NA NA.
NA Daphnid (Da,,t i-ma,ns) -
48 h intermitterw
< 24h NA l
7 f.5(4.80) 318047141 890(2251 Go den shirier 96 h Continuous Young 3300(701)'
960(2298 l
s 74.916.09)'
(Notesnigonus 96-h intermittent '
Young i
I.
ctysoleucast '
98.O(11.91 17.2(2.011 f-Rainbow leout 96-h Coneinuous 15 day 24.011.23) 98.0(11.98-17.2(2.018 foncorhyncfws 96-h inteemhtent -
15 day 2 4.011.2 31 l
~
,y myhissi -
NA 0.4400.148 Amphipod -
98-h Conei nious.
),werwee NA NA 0.4400.148 e
g
(#4adeEs asteca/ :
96-h inocemissent -
luven'le NA 96-h Continuous 5 day -
NA.
NA-0.17100.0038 i
14&sk%ssis 96-h Intermissent '
Sday NA NA' O.16900.0031:
j R
4 P-g Mysed
- 2 Sdwersidas 96-h Continuous 8 day
.10.610.93) 4.81(2.08)-
0.9 600.4 23
- h beMel' v
96-h Insermittent 11 day -
1 1.640.7 68 8.24tt.575 1.6800.3 30 i
(AdamsEs l
A.i ""x.'
Daphnid 48 h Continous
< 24h' NA' NA --
NA 300po Anunanie
[
n toas** me,nes so-h Continuous 5 day J NA NA 0.18800.0058 l
taerstepsis 300 pod Aawnoale Mysis I
60
- f 1
i 4
f I
L
_s
... -..-. -.... - ~ -.
8 e
Tatste 2. Mean water cuaity (e50) for the chlorine studies n
Hard.
..Tes),,,,.. D O pH Cond/ Salinity
- Ak, (at mg/L (rng/Q (a8 mg/L :
- CACO)
CACO)-
FRESHWATER
~
I Daphnid 8.5 7J1 333.3 -
152J 144.4 Continuous W.2) 7.71 (17.0)
(1.51 (2.9)
Caphrtid 8.4 8.11 388.7 108.3 181.0 Inteett (0.1) 8.34 -
00.5) 94) 017)
Shiner 7.4 8.16 388.3 133.3 184.3 Continuous (0.2) 8.36 (25.3)
(18.5) -
(20.01 Shiner 8.8 7.41 350.0 100.0 145.5-Interm.'t (0.1) 7.68 M.51 (1 5.81 (5.1)
Trout 7.7 7.20 334.0 132.0
- 160.0 t
Continuous (0.1) 7.64 (6.5) -
(2.41 (3.31-Trout 7.7 --
7.20 334.0 132.0 100.0 Intermit (0.1) 7.64 -
-(6.5)'
(2.4).
(3.3)
Amphipod 8.0 -
7.84.~
363.0 '
'185.0 138.0 Continu:us (0.1) 8.00 p.4) p.1)
(4.3);.
Amphiped 8.0 7.84 333.0 165.0 138.0 Intermrt (0.1) 8.00 Q.4) p.1)
(4.3)
Daphnid 8.8 7.35 341.2 -
159.0 142.0 w/ Ammonia (0.1) -
7.90 (14.3)
(5.1)
- Q.2)
SALTWATER :
S3versides 7.2 8.36 20.7-Continuous
-(0.2) 8.52 (0.45)
Suversides -
7.2
- 8.33. -
20.$ -
Intermit (0.21 8.65 9.44)'
Mysid -
7.2 '
' 8.36. ~
20.7 Continuous (0.2)-
-3.52 W.45)
Mysid -
'7.2 8.33 20J.
Intermit (0.2) -
8.65 9.4J)
Mysid 7.7 '
8.00 21.0.
W/ Ammonia
-(0,1) 4.11 (0.82) -
- ConductMry expressed as unhos/cm; salinity expressed as pot -
i.
l Page 24 of 69 -
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Table 3.
Mean water cua!!ty (350) for the chlorine /NaBr stud /
Test DO pH Cond/ Salinity
- Ak.
Hard.
l l
.(mg/Q (as mg/L (as mg/L CICOJ CaCOJ l
I FRESHWATER Caphnid
'8.7 7.28 331.2 150.0 145.0 l
Continusus (0.1) 7.77 (14.3)
(5.0)
(3.0)
Cacnnkt l
8.4 8.21 366.7 110.0 178.7-l' Imermit l (0,1) 8.34 (20.5)
(4.01 (8.2)
Shiner 7.6 8.11-368.3 141.0 184.3 i
Cominuous (0.2) 8.33 (25.3)
(tSJ)
(20.0)
Shiner 8.8 7.41 350.0 100.0 145.5 Intarmit (0.1) 7.E8 (9.5)
(15.8)
(5.1)
Trout 7.5 7.24-334.0 132.0 160.0 Continueus (0.1) 7.41 (6.51 (2.4) c.3) i Treut 7.5 7.24-334.0 132.0 160.0 t
intermrt (0.1) 7.41 (6.5)
(2.4)
Q.3) h Amphipod 8.0 7.81-363.0 185.0..
138.0 Connnuous (0.t) 8.01 c.4)
(7.1)
(4.3) 1
' ~
Amphipod 8.0 7.81 353.0 185.0 138.0 Intermrt (0.1) 8.01 c.41 (7.1)
(4.3)
Daphnid 8.6 7.33-341.2 159.0 142.0 w/ Ammonia (0.1) 7.89 (14.31 (5.1)
Q.2)
I jj SALTWATER l
$3versides 7.2 8.35 20.7 Continueus (0.7) 8.51 (0.45) i l
20.5 SJversides 7.2 1.30-Intermit (0.2) 8.69 I (0.44)
Mysid 7.2 8.36-20.7 Continuous (0.21 8.51 (0.4 51 Mysid 7.2 8.30 20.5 Intermit (0.2) 8.69 (0.45)
Mysid 7.7 8.02-21.0 w/ Ammonta (0.1) 8.16 (0.82)
- Conductrvity expressed as umnos/cm; safintry expressed as got Page 25 of 69 l
l i
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'I' aide 4.
Toxicity of Chlorine amt 11:omine no Freslowater ami Saltwater animals k
1.C50 wish Cl, LC50 with Cl, + Nalir Common Name Species Name Toxicity peqTRO/L pg Chlorine /L pes!TilO/L sg Ilrimine/L a imlicator
- 95% Cl.
- 95% Cf.
195% Cl.'
95% C'I.
FitESilWNIT!R i
Daphnkt Dnphnia 48-h 0.90 32
< 0.4 0.*
<38 )
0 Continuous 0.03 & l.02 i & 30 magna Daphnki Dnphale 48-h 1.55 55.
0.76
~
61 Intermittent 1.27 & 1.92 45 & 68 0.56 & 0.96 45 & 76 negma Goklen Shiner Note:ntgeesus 96-h 8.57 304 3.61 288 m
rrysolenent Coneimenus 7.19 & 10 09 255 & 358 2.96 & 4.43 236 & 353 Gtiklen Shiner Noremigorms 96-h 16 13 572 9.90 790 to raysolenens Intermittent 14.24 & 18.44 505 & 654 880 & 1831 702 & 903 Amphhwul 11pktsre nraera
%-h 2.20 78
<039
<32fil m
Continuous 1.75 & 2.78 62 & 96 Amphipml 11ptegre naieca 96-h 8.49 301 4.17 333-Intermittent 7.14 & :*721 252 & 362 3.4 1 & 5.10 272 & 407
, 18
<039
<32"I 08 Daphnkt Onphnis 48.h
< 0.51 Contiminus pengem 300 pg/L Ammonia i
itaintww Trout Oncorhpr/ms 96.h I.66
- 5's 0 85 68 ngths Contimeous 3.41 & 2 00 50 & 78 0 68 & l.02*
54 & si i
Rainl== Trinet Onrerhynr/ms
%.h 10.55 8.374 fin 6 484 myilar Intermit! cat 8 57 &.12R.
304 & 449 5.22 & 7.02' 416 & SMI 4
Talite 4 (camtimsell l.C50 with Cl + NaDe 2
I.C50 with Cl, Common Name species Name Toxicity s eq TitOfL ses Chhwine/I.
i.eeg TilO/L pg Iltamine/L s Imficator s 95% Cl.
- 95% Cl.
a 95% Cl.
95% Cf.
m.,
sat:lY?ATER 96-h 1.75 62 1.16 92 klysid Afpklopsir 1.47 & 2.09 52 & 74 0.93 & l.41 74 & I13 bahka Contimeous 96.h 5.92 280 4I,0 367 3.95 & 5.36 315 & 428
&fyski Afysktopsis 4.77 & 7.25 169 & 257 _
Intermi':.
Inshke 143 0 82 65 I
4.03 Silversiiles AfenkIke
! 3.24 & 5.16 IIS & 181 -
0.62 & G.99 50 & 79 96 h ter3fthws.
Contimsous Q
Silversieles AlcnkIks '
96.h 5.44 193 4.33 344 3,,
293 & 410 intermittent 4.20 & 6.79 149 & 241 3.67 & 3.13 _
her>ffine
<50'8 l
96 h
<0.59
<2108
<ft.62 y
9.
Alysit!
Alyskfopsir brahke -
Continianus g
300 pg/L Ammamia Only 6 survivors at lowest conceatration lessett.
8 Only I survivier m Inwest concentration testett 2
8 No survivews at howest treatment.
Only 8 sestvivors at howest treatment.
4 Only 3 serviviws at lowest treatment.
8
' Only 2 survivews at howest treatment.
ki all test schulnes the concentration of total resklual osklants was measurest as TRO c
/ liter chkwine for all tests cemsluese.1 wish chlorine in the NOTE:
cepivalenes per liter (s cig/l.). The test resules are engwessol as microgramsabsenc To cimveis chhwine into 'twswnine cereivalents*
kity is czpresseil as micrograne/liser Iwamine. To 5
camvest Ivewnine into "c%eine espivalents" ellykle the twomine cimcentration ley 2.2.
mutilply she chhwine camcentration ley 't.25.
1
.5 4
i l
Chlorine TRO concespkations pn pg/t_-shforine TRO) ehwessed esdienevisan (sSO) of Table 5.
measurements madq during Ihe test period for each he alment n
e s
9 I, THFATMENT CONDITIONS:
l l
Test.
Hop 1
2
-t**
3-4 5
l
-l l
e FRESifwATER
i Daphnirl A
24 a 4.0 42 a 5.0 76 a 8.0
- C! a 8.0 308 a 15.0 Continuous B
2414.0 4Ia6.0 73 a 60 164 a 12.0 314 a 25.0 C
24 a 4.0 4Ia50 74 a 7.0 163 a 10.0 390 a 20.0 Daphnid A
25 a 4.8 40 a 9.5 76 a 7.9 153 a 20.5 P.A a 28.3 i
Intermit 8'
20 4 7.5 45 a $ 1.2 86aj4.4 J59 a.20.3 -
250 a 14.1
[.
7 C
2:: a 6.9 43 a 10.5-81 a 12.5 ISS a 20.0 285 a 99.8 '
s I
[
Shiner A-4I a 5.0 72 a 9.0 -
155 4 10.0 312 a 18.0 522 a 13A '
so m
Conhnuous B
4 1 a 6.0.
73 a 7.0 165 a 14.0 -
300 a 13.0..
528 a 99R E.
C '.
41 a 6.0 7348.0 160 a 13.0 380 a 15D 524 a16D Shiner A'
295 a 33.0 418 m39.0 l 670 a94.0 984 a $25.0 1547 a 40.0 f
4 m
lateemR 8"
295 a 30.0 4 f I a45.0 677 s 94.0 j 950 a 80.0 f477 a 6.0 I
4 I
C 295 a 31.17-496 a.40D 673 a93.0 967 a 907.0 1582 a 48D h
f.A; ='
A-18 a 4.4, '
35 a 4.5 84 a 8.9 -
158 a 8.1 '
390 a 20.7 '
-l Con 8nuous B:
14 a 4.4 -
38 a 5.0 -
82 a 8.6 '
f57 a 8.4 321 a 14.3 C
15 a 4.5 35 a 4.8 83 a 7.7 158 a 0.2 318 a 18.3 l
153 a 13.1 -
305 a 29.5 831 a 88.8
(
A.
38 a 5.5 8I a 7.7 153 13.2 302 a 27.4 826 a 92.0 a
Interrnit B.
35 a 53 78 a 11.2 C
35 a 5.4 80 a 8.8 153 s 13.0 304 a 27.8 SP9 a 87A -
i 20 a 3.0 35 a 5.0 79 s 9 0 -
i Daphnid A-Ammonia B.
16 a 3.0 -
35 a 6.0 69 a 5.0 '
l 0.3 mg/t. <
C 18a4R 35 a50 74 s90 F.-
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SRS E
2 D.
gi ass ass ass 565 sus una ts:
g p
~
a m
qqq Se0 *e s *s. :e b5 M ' --
Mnq
-M e. nz..e. ::: ~~~
-I l
.3y RER RRn -K R R KRR EUR *** EMS :
li an s
'sF
<mo<co
<mo '< m o <mo <mo<mo
'3 Page 30 of 69 t
. ~.--.,...-..,,...:.......-.. =........
,..k u~,~....---,.
F 4
h Tatdo 6.
Corh =d
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l 5
1 2
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hst Rep _
i~
Troul-A' M a 10.8 77 a 13.7 142 a 41.6 299 a65.0 623 a 65.0 2
Continuossa B
27 a SE 74 a f5.3 140 a44.1 313 a 75.4 608 a 61.0
- C-29 a 9.2 77 a 14.4 142 ; 4 IS 306 a 67.7 -
684 a57.8 Trond '
A 36 a 10.4 8 1 a 96.*r 380 a 37.4 392 a725 689 a55.R intennt B
29 a 8.1 77 a 12.8 164 a 4IR.
4I2 a 63.2 788 a 53.2 C
32a95 79 a 15.I 173 a 39.4 401 a 675 700 a 59 8 SAI' WATER T
- f. A 54 a 9.0 97 a SSE 180 a 36D 443 a 585 796 a 1305 I
f g
Mysed 1 B 52 a 10.3 tot a 88.0 880 a 405 407 a495 702 a 808.3 i
C 52 a i1.3 99 a 15 8 180 a 3e.3 425 a 56.3 70s a 4125 I
ao Cone maness i
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tea s 25.I_
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Intenuit 8
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a.
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54aSA 97 a *5A 180 a 98.0 473 a225 784a338 i
Continesonas 8-52 a 18.3
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52 a 11.3 -
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SI e 94.2 200 a 35 8 374 a53.8 898 a 42A 3200 a ISS C
92 a 17.1 213 a 37.s 394 a 57A 747 a $4.4 1325 a 77.4 -
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52 a S.3 asaSE 205 a 13.1 382a453 GS3 a 1485 i-0.3 g.
C 52 a 7.0 60a92 200a88.7 35e i 44.3 577 a 124.2 le conuse e,emene se eseossie :;
- c. aba se av 2 &
k Hese:
' ase-weasse me aussese Tao eenennessene ser. ace esse==ss ans e.
e l
c; eseino a
s:r - w.
j-I 1
1 I
l I
I Table 7, Free available oxidant' and total residual oxidant (values in parenthesis) in l
chlorine test exorossed as ag/t.chlonne oxidants.
j 1 *.
i
- TREATMENT CONDITIONS
~
1 3
3' 4
5 Rep i
Test E
PRESHWA1ER Daphnid A
0 (10) 0 90) 0 (60) 30 (140) 60 930)
Continuous 5
0 (15) 0 (40) -
0 (to) to (145) to Q25) f Daphnid A
0 90) 0 (40) 0180) 20 (160) 160 (290)
Intermit s
0 (20) 0 (30) 0 160) 0(1s0) too (2:0)
A 0 90) 0 (40) 0 (75) 0(160) 0 Q30)
Shiner Centinuous s
0 (20) 0 (45) 0 170) 0 (145) 0 Q201 Shiner A
0 (230) 40 960) 440 (590) 900 (1010)
Intermit
,5 0 (2to) 150 (340) 460 (600)-
,860(950) i Trcut A
0 (20) 0 90) 0 (65) __
0 (140) 0(300)
Cent!nuous B
- 0 (10) 0 (40)
. 0 (60) 0 (140) 0(200)
Ttout A
0 (20) -
0 90) 0 (65) 0 (140) 0(200)
-- I Intermit B
i 0 (10) 0 (40) 0 (60) 0 (140) 0 000)
Amphiped A
0 (10) 0 90) 0 (80) 30 (140) _
60 (330)
Centinueus 5
0 (15) 0 (40) 0 (80) 20 (145) 60 m25)
Amphiped A
0 (10) 0 (30) 0 (to) -
30 (140)
SO (330)
Intermit B
0 (1 51 0 (40) 0 (80) 20 (145) 80 (325) 5At.TWATER Mysid A
0 (25) 0 (40) 0 (90) 40 (160)-
210 (315)
Continuous
, s, 0 (20) 0 (45) 0 (90) 30 (170) 220 Q25)
Mysid A
0 (30) 0(60) 0(160) 210 (380) 340 (670)
Intermit B
0 00) 0 (60) 0(1Fs 230 (360) 380 (700)
0 (25) 0 (40) 0190) 40 (160)'
210 pts)
Centinuous i 5 0 (20) 0 (45) 0 (90) 30 (170) 220 Q25)-
0 (30) 0 (60) 0 (160) 210 990) 3Ms(670)
Intermit 8
0 00) 0 (60)-
0 (t40) 230 Q80) 3801700)
A value of 0 ug/Lindicates FAO, as not detected et quantinable.
w C-Page 32 of 69
,, e r,$m.- w m,.e ee-em....l.-&.--,,.,w-n w w n. s.A w u n-e w-w.4
,,,.r.,
e m
.,-,en,,w,,An,&,m.,m,-a-wv,,ew,,.--,.,
,,r,q, a nn v e,,-m v ~ w n s,-
.,-,+w,-
B Table 8. Free available oxidant and total residual oxidant (values in parenthesis) in chlorine /NaBr test excrossed a8 ug/L bromine oxidant 8'.
TREATMENT CONDITIONS l
Tant Reo l 1
2 3'
4 5
i i
l FRESHWATER Daphnid A
0(23) 23 (113) 113 (203) 203 (460) 485 (898)
Continuous 8
0(23) 23 (124) 113 (233) 225 (4281 450 (co)
Daphnid A
0 (56) 0(90) 0 (180) 88 (450) 473 (855)
Imermit 5
0 (45) 0 (113) 0 (158) 0(473) 338(788)
Shiner A
0 (45) 0 (79) 45 (146) 113 (315) 495 (898)
Continuous 8
0 (56) 0(90) 45 (120) 124 (338) 450 (630)
SNner A
135 (350) 135 (360) 495 (675) 830 (900) 1193 (1395) i' 180 (405) 450 (525) 720 (968) 1418 (17101 Imermit 8
93 (360)
Trout A
0(23) 0(68)
SS (180) 158 (270) 540 (6981 l'
Continuous 8
0(23) 0(68) 88 (191) 180 (3381 5 85 (7201 Trout A
0(23)
'O (8/.)
Es (14;,;
154 (270)
$40 (658) 1 I
intermit B
0(23) 0 (E8) 88 (191) 180 (338) 585 (720) '
~
Amphipod A
0(23) 0 (113) 113 (203) 203 (450) 495 (698) i't Continuous 8
0(23) 0 (124) 113 (203) 225 (4281 450 (co)
Amonipod A
0 (23) 23 (113)-
113 (203) 203 (450) 455 (6981 j
Interma 8
0(23) 23 (124) 113 (2J3) 225 (428) 450 (630)
Sat.TWATEM Mysid A
23 (45) 45 (113) 158 (203) 338 (450) 853 (788)
Continuous 8
23 (45) 56 (101)-
189 (100) 293 (383) 675 (731) l Mysd A
0 (113) 0(270) 135 (405) 830 (810) 1328 (1575)
Intermit 8
0(68) 0 (203) 45 (383) 473 (743) 1818 (1530) 53versides A
23 (45) 45 (113) 158 (203) 338 (450) 853 (788)
Continuous 8
23 (45) 56 (101) 189 (180) 293 (383) 675 (731)
Siversides A
0 (113) 0(270) 135 (405) 830 (810) 1328 (1575)
Interma 8
0(681 0(203) 45 (383) 473 (743) t 418 (1533)
To cormrt bromine to cNonne scuNalems dkide by 2.25.
Page 33 of 69 I
-w
- +,
s
~,,
.,,>c--,g
-e--~
- - - - - ~ ~ - - - + - - -
4 Table 9., FAO, mesured during the asumoala esposures u WL chlorias or bromina (ug/L Bromlns/2.25 = g/L chlorias equivsteau)
Q "C '" *
- ge,i;,angs* * -
FAD "
ll TRO 1
Daphald 1(A) 0 30 i
Chlorine 1(B) 0 10 2(A) 0 35 2(s) 0 30 3(A) 0 70 3(B) 0 65 Daphnid 1(A) 34 34 Ch!crine/Nast 1(B) 34 45 2(A) 68 79 2(3) 45 56 3(A)
US 13 8 3(3)
US 146 M nid 1(A) 0 20 Chlorine 1(B) 0 20 2(A) 0 40 I
2fB) 0 40 l
3(A) 0 15 3(B) 0 80 4(A) 0 160 4(B) 10 165 5(A)'
0 270 5(B) 0 234
. Mpid 1(A) 45 45 Chlorine /NaBr 1(B) 56 56 2(A) 44 68 2(B) 19 79 3(A) 158 141 3(n) us 191
(
4(A) 3U 360 4(B) 293 349 5(A) 515 475 i
5(Bi-630 810 f
Page 34 of 69 Y'wm
1 i
l 7
Table 10.
oxidant de sy,' measured u total residual oxidant equkalents Ipeq. TRO) in fresh water and 20 ppt salt water upon the addition of chlorine. and chlorine plus t.5 times the stoichiometric amove' of NsBr.
Decay TRO TRO
. Decay TRO TRO Time Time (min)
(pec/L1 LN (ueq/L1 (min)
(peq/t.)
LN [ waft) t C
c,+ Ns8r i
FRESH WATER f
1 0
l 25.35 L 3.233 0
25.35 3.233 5'
'21.27 -
3.057 5
15.41 2.735 15 19.01 2.945 l
10 14.65 2.684 l
l 30 18.31 l1907 l
30 13.10 1573 85 11.27 2.421 l
90 l 15.21 2.722 i
170 l 13.38 l 2.594 160 10.48 l 2.349 l
270 13.1 8 2.579 i260 8.39 2.189 l
2.029 l
l 2.540 350 -
7.6i.
360 12.68 SALT WATER' l
l0 28.17 3.338 0
l 28.17 l 3.338 5
20.85 3.037 4
14.93 2.703 10 19.15 2.952 10 12.96 2.562 l
20 17.32 2.852 18 11.83 2.471 50 15.77 2.758 30 9.72 2.274 110 13.52 2.604 90 6.48 1.869 2.551 150 5.07 1.623 170 12.82 f
260 10.85 2.384 240 3.38 1.218 380 9.01 1198 360 125 0.811 These observations are fitted to a two. phase first order model and plotted in Figure 1 (fresh water) and Figure 2 (salt water).
Page 35 of 69 l
l 4.-,.-
&z.1.. a s -
Gaidant Decay,* Measured as Total Residual Orlant (TRO) Equivalents In j P.r'e it.
l Freshwater i
8 Tut Time TRO Range 5
r 5
r 8
i L
. (min.)..
s4L Chlorine (min )
(min )
d Chlorine 240 900 495 0.0 15 0.848 0.001 0.988 a
360 900 450 0.010 0.775 0.001 0J06 1
1290 727 275 0.023 0.947 0.001 0.998 1345 840 250 0.017 0J12 0.001 0.983 Av8 a SD 0.016 e 0.005 0.00t e 0.000 TRO Range
-
- Chlorine Plus 8mmide. -~~~-
pg/L Bromine 350 2025 608 0.055 0.818 0.002 0.986 380 1901 90 0.0$0 0.819 0.006 0.983 TOS
'2036' 338 0.0'61
O.839 0.003 0.983
~
525 1530 <23 0.050 0.864 0.007 0.980 Avs. SD 0.054 s 0.005
- 0.005 0.002 The test ruults are expressed as microgram / liter (ug/1.) chlorine for all tests conducted with chlorine in the absence of added bromides. For teru with bromides. added the stoichiometri amount of chlorine. residualTRO concentratios.
- tre expressed as ug/L bromine. The observations were fitted to a two. phase first order model i
1 1
1 Page 36 of 69 I
1 Table 12.
0aldant decay,' measured as Total Residual Ostdant (TRO) equivalents in j
20 ppt saltwater 8
Test Time TRO Range r
r 8
(min) ut/L Chlorine (min )
(min *)
d 1
Chintine l
i 380 1000 320 0.039 0.905 0.002 0.984 4 13 1000 350 0.055 0289 0.001 0.387 0.810 0.001 0253 705 1000 315 0.035 0.936 720 1000 310 0.048 0.926 0.ML Avg a SD 0.044 a 0.009 0.00t a 0.00t TRO Range ug/L Bromine Chinrine Plus Bromide
~.035 0.873 0.003 0.998 i
0 120 2205 360 240 2183 45 0.094 0.9 t0 0.0 13 0.994 360 2250 180 0.073 0.798 0.005 0.972 395 22t6 22 0.083
,,0 473,
0.m9 0.9 64 Avg SD 0.084 a 0.009 0.009 0.003 The test results are expressed as microgram / liter (ug/L) chlorine for all tests condue:ed with chlorine in the absence of added bromides. For tests with bromides, added at IJ times the stoichiometric amount of chlorine, residualTRO concentrations are expressed as ug/L bromine. "Ihe observations were Gtted to a two. phase first order model.
I 1
Page 37 of 69 1
i
I I
Table 13. Estimates
- of the relative environmentalImpact on a freshwater nream resulting o
from from the treatment of cooling water by chlorination in the presence and the absence of sodiurh bromide.
~
2 E!Duent Flow as Rainbow Trout Golden Shiner
%*of RJverCow Impact Ratio.
Impact Rath, Chlorine / Bromine Chlorine /Eromine 0
1.19 2.21 i
1.45 337 10 25 2.38 5.15 I
50 6.71 22.9 l
......... 100 ' * * ' "
' "' l *
- 9A1 97.1 I
t Eiilmates foTrainbow tr'out ire bued on the Est!mstes for golden shiner Erfili*e'd'en the fouowing inpuu:
fouowing inputs:
b m mine, _3.61 bmmine, _0.85 gg_g (c5g ;
96-h LCEO :
chlonna 1.66 chicnne
'8.57 D**I"'
I *"
bem/ne, _0.16-96-h LCf:
=
96-h LCf:
chicnne 0.48 chicnna 2.06 K, bromine -
0.051 K,bromino 0'05s 0xidant decay.
=-
Oxidant decay * :
K,chicnne 0.016 K, chicnne
- 0.016
=
K, bromine 0.00s K, bromine 0.005-
.Kgchlenne 0.001 Kg chlorine 0.001 Further details are given in Appendix A Ps9e 38 of 69
Fipte 1. Oxid:mt demy u peq TRO la frubwater 3.5 k,
3.0
//g J
Ci 2
~
2.5 -
o CI +NcBr 2
O 2.0 g
I c
a)
- 1.
1.5 l
I Z
(
A Cl Cl2 + NoBr 2
-2
-2
~
k = -5.49X10 i
3*o k, = -1.81X10
~
r = 0.902 r = 0.819
-2
-2
.k
= -1.61X10 k2 = -0.10X10
~
0.5 2r = 0.790 r = 0.790 0.0 O
60 120 180 240 300 360 420 TIME (Minutes)
Page 39 of 69
Figure 2. Oxidant decay u peq TRO 8,n saltwater IBW g;2 3.5 m
=
.86X10 2
r = 0.905 3.0 2 = -0.18X10'*
k 2
k
/
= Oh84 o
Cl r
2 2.5 -
o r-,
O
~
Q::
2.0 -
E-o Cl + NcBr J
2 I
C4 1.5
.cd I2 + NaBr
~
1.0 i = -7.33X10 *
~
k l
r = 0.797 k2 = -0.47X10 0.5 2 = 0.972 r
0 60 120 180 240 300 350 420 0.0 TIME (Minutes)
Page 40 of 69 t
l i
I l
I t
l I
l APPDfDIX A Relative Envirentantal Is'act Estimates for Chlorina and Bror.ine Used for Me control of Siofouling Condenser cooling s,' stems I
hy l
L. Bongers W. Furth B&B Environmental' services Inc.
Baltimore, MD.
l-l l
!t-Js..a 1991' Page 41 of 69 1'
l m'
.-+e,..--,,
---s
,.r e
+[e w-c,v -, w-
-em-----or
--~...,-.-yn-.,,,
,we-c, - - < -,..,.,,. -
..---w-
,-_s--
m rr,
- w-*.-
1 ABSTRACT When used in combinaden with chlorine, sodlum bromide can signif application requirements because the bromine oxidants generat centrol biefoullng more effeedvefy. Also, since l
less.
e
- Therefore, although the LCis for bromine oxid sign!!icantly reduce the environmentallmpact of blefouting control.
To evaluate the extent of the impact redueden and the factors aff relative menality risks were estimated for rainb d
to centinuous bloc!de applications, ft was further assumed that the e varying amcunts of the flew of a freshwater stream for heat rejection.
Ccmputatiens indicate that a significant reduction in impact can sodium bremide is used in cenjunction with c penien cf the river flow is used by the electric facility for heat rejection These findings indicate that the anticipated I
lower amcunt cf bromine oxidants needed for the same degree
(
l' l
l Page 42 of 69 r
+..-w..%
,. = _..
l l
iM A.
PROBLEM STATEMINT since there is a viable alternative to chlorine for controlling'-
biofouling of power plant cooling systems, the environmental consequences of changinc' from chlorina to the alternative must ha ascertained.' The alternative considered hora is bromina, which is ganarated from chlorine when sodium bromida is simultaneously added i
to chlorina in the cooling watar.
one way of avaluating the environmental impact of such a are subjected when they are entrained in chlorinated or brominated water which flows through the cooling system. The impact estinata would also include the effects in the receiving waters which nix with the discharge.
are based on mortality and The sa=ple calculations, shown below, chemical decay infor=ation co 3
The calculations provida a eenearative impact estimata for rainbow l
trout and goldan shiner.
The mathed is based upon a si=ple and understandable.s et of ec=putations. Similar calculations can be made for other available.
3.
ASSUMPTIONE Throughout this appendix va shall use a Lagrangian approach; that and follow it through the with a parcal of water, in the and the transport and mixing river. The oxidant is, va star:
is the concentration in that parcel of water, as a function time, plant the time integral of concentration defined in this manner. Further, integral. Since this the concentration is also such a lagrangian va assu=a that the integral will be used to estimate the impact, exposed organisms af fectively follow the flow.
l
'Please saa text for added discussion.
3Please saa text.
Page 43 of 69 i
_. - ~,, _.. _.
l
- 1. Physical Arrangament 1
The following sequence of events is assumed:
l The biocide is introduced into the once-through cooling sy s tas,.*
1 It passes through the system, with no dilution, until it is returned to the river.
This river flows steadily away from the cooling water intaka.
In the river, the concentration of the biocide in the cooling vatar i,s diluted with the river water.
After a cartain time, this dilution is affectively ec=pisted (i.e.,
the river is laterally well mixed): this mixed fiev proceeds downstream with no additions or losses u the vatar.
- 2. cha=ical Reactions Based upon experimental data, it is assumed that the che:ical (i.e.
biocida) undergoes' a two-phase quasi-first order decay process. That is, if M(t) is the mass remaining at time t, 3
l exp (-k c) o s es:3 s
- 03 exp(-k e ) exp (-k (c-c ) ) e s:<=
is 3
s 1
Let c(t) be the concentration', define e,s e ( o ) a h 's The concentration, including chemical decay and dilution, is et c)
Mt c' divided by dilucion fac:c:
clo)
N(0) 4 3please see text.
l
'A notation table is providad at the and of this appendix Page 44 of 69
. - -. - -.. - - - -. ~ -.
b i
i t
j
- 3. Mortality *R'elatihnships r-one 'of
- thh key assumptions it that the time integral of the concentration above a threshold concentration is a sensure of the r
of course, is the Largest l
impact.. The threshold concentration, concentratibW Vhich a specified organisa can withstand for a long timepetibd*withoutsuf{aringacutetoxiceffects.Inabsenceof value may be used in the computations.
other. info y tion, a Lcg concentrations, as a functicn For seIn~e $~rk'an' isms, the Lc or Lc reasonaEy accurately described by a
y of exposur.e time X, are hyperbo tA... > *..,.
's * ::'
.1 y, aX ~ b y y gy X-c
).....
wherea','b',' and c are constants'. In such a representatica, the threshold is the concentration as X goes to infinity, that is, the c nstant a. This c nstant, even though it depends'upon'the organis:
l and*the Biocide, should be reasonably independent of the mortality is the constant c, which has dimensions of time, leve). Also.,
such as 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br />.
usuallyfs.=all'c = pared to times of interest, W ch..~**:.~:h si=piify this equation, as follows
~
T T = constant where T = Concentration above threshold T=
Tine beyond c and where the c',nstant depends upon mortality level and, of course, the biocide and species considered. This equation is c=nsistant with a dosa-above-a-threshold evaluation approac.%
- 4. Mixing The hydrological mixing of the affluent with the receiving stress is complex and dependt on site specific features. Even though this phencuena may be-one of the'few aspects of the over-all pronte=
which is " solvable" from first or second principles we shall use-only a very simple way of estimating the-dilution. pres 1
the' concentration which - results in XX% -
Seu e t- - r*) is seant mortality wKen exposed for T time.- If T is not specified, assume it to be 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br />.
'Please see Wang and Hanson,1985, as re!!srenced in the text-Page 45 of 69
is 7aasonable to asshms that the genearative impact of tvo biocidas is not significantly influenced by the exact natara of the mixing.
consequarc,$.y, va shall assume that the amount of river vatar mixed with the affluent increases proportional with time, until all of the rivar flow is involved. It is further assumed that during this mixing the af fluent is completely mixed lateral to it's flow (i.e.,
that it is independant of space, in the Lagrangian systas), and W
that longitudinal mixing is negligibia.
The dilution f actor?, with the above assumptions, is l
MIN ( Y, MAX ( 1, 1* (T - 1),'* ',', ) )
5.MeasureohImpact The ti=a integral of the concentration over the threshold is t
Z=
cz.x ( ( c( c) - ca),01dc
- f. (c(c) -c l dc
=
a is the threshold
= c and where en
. here t* is the tima when c(t) w u
concentration.
To cbtain the relative i= pact, va calculate Z' = c,s #
-cn where e is the concentration for % g at 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br />. The quantity Z*
has the dimension of time. The relative impact batvaan biocidas 1 n
and 2 (namely, chlorine oxidants and bromine oxidants) vill be the ratio of the above quantity calculated for each bio <,ide, or g
c',e - c'w Z8 c',.-c5,
where the superscripts ref er to biocida 1 and 2. This ratio has no biocida 1 has a larger impact dimension. If it is largar than 1, than biocida 2. This ratio say reflect tha comparative mortality.
'Please saa notation section for definition of the sy=bols Page 46 of 69
l a
C.
SPE;IAL CASES 1
Some special cases can be solved simply. For example, if va have no
{
mixing with the river vatar, as would happen if all of the river l
vatar is use,d for cooling, we have i
- l. e(0) -e ifc#se" N
h Ce-cn e
Z' +
=
"' 8 ~ #8
( c ( 0 ) - e,) k, * ( e,- c.,,) A
- 8 44 ( c,e - c,)
In contrast, if the river flow is verf large as compared to the
- affluent, and the concentration is immediately diluted to i
negligibla levels.as soon as the affluent reachas the river, than e.r..,1 c(0) g
,.g t,)
- g.,
h c,,-ca en cre provided only that the concentration in the affluent just prior to entering the river is largar than either c, or e *n D.
CALC'." ATED CASES l
1.
Impact of Decay Times several computations vara made for the chlorine oxidants (biocida 1) and bromina oxidants (biocida 2),
with the emphasis on determining the impact of their different chemical decay times. The ratio of the total river flow to the affluent flow was used as a paramatar.
The physical paramatars are shown in Table 1, and the chemical and biological paramatars are shown in Table 2a. The organism for which impact is calculated is the Rainbow Trout. In order to evaluate the impact of the chemical decay times, the initial concentration in the cooling vatar is twice the %, concentration for both biocides.
j The impacts, t'*, and - the impact ratio were calculated f o r t.'.a various amounts of affluent flow, as compared to the river flow, with these parameters. The results are shown in Table 3a. In that table, both. t' and t' have the dimensions of minutes.
Trom these corputations it is evident that bromine ha less of an 1
advarse impant than chlorina. For exampia, 'if the coesing systa=
borrows 25% of the river flow, the impact of bromine is only about 40% of the impact of chlorina. Additional compu';ation vara nada 1
Page 47 ci 69
that the benefits of bromine over chlorine increases which showed as both initial concentrations are increased. With hindsight, this is what one would expect.
Not surprisingly, the larger the fraction of the river that is used for cooling, the larger the relative benefits of bromine. The for the advantage, in all cases, is the more rapid N
" reason" chemical decay of bromine as compared to chlorine.
k.
cashined Zapaat t
The computations discussdd~abdVe ' dealt ' principally with the dif ference in the decay times. Additional computations, to include the impact of ditf arent initial concentrations relative to the Leg levels, ha,va to be mada.
computations were made for tha Golden Shiner. Ter this Sample concentration are shown-organism the chlorine and the bramine Lcin Table 2b. The no-ef fect thresho n
selected concentrations arr also shown in that table. It should be values noted that the ratio of the initial concentration to-the LCu for the two biecides. These initial concentrations are different were selsetad on the basis of a methodology developed by Bengers g The stated biocida concentratiens 11 1977 and Liden at al 1980.
would control biofculing'to operationally ~ acceptable levels at an a:3ient ta=parature of 25 C. The results of the sample calculations are shown in Table 3b.
E.
CONCLUSIONS Thess sampla computations indicate that a significant reduction in the environmental impact may result from using bromine instead of chlorina for biofculing control. This - anticipated reduction is attributable to the relatively rapid chemical decay of the bromine oxidants, and also to the relatively lower. amount of bromine necdad for the same degram of biofouling control.
Tor the chemical and toxicity data used,'the " benefits" of brcaina (i.e., reduced mortality) would have' a tendency to increase as biocida demand increases and/or the ecoling water flow increases-relative to the river flow.
this is what one would expect. Thus qualitative With hindsight, common sense is matched by _ the computational method, which hat the added advantage of being _both unamotional and quantitative, critical issues not addressed aret -
The ef fects of changes in oxidant do;.ay which may rasult frem changes in water qualityr values signiticantly dif f erant from those used in these Lcw sampia computations; Page 48 of 69
i "Statianary" organisms, such as benthics which reside in the mixing tone, and organisms which e.nter the cooling vatar after it is dischargedt and Intermittant biocide applications instead of the continucus applica, tion as used in the present computations.
4 A
i Page 49 of 69 -
-~.
i i
1 2
Table 1 Physical Ineuts i
l t
o 60 minutes t,
5 minutes 1.lf*uent Flov/ River Flow 0, 10%, 25%, 50%, and 100%
1 i
Table 2a chemical and Bit teeical intut j
Rainbow Trout Ch],0:ine Bremine c(0) 3.32 1.70 pet /l s
e,.
1.66 0.85 p eq/l 2
2 s.
j
{
c 0.48 0.16 p eg/l u
k 0.,016 0.054 min *1 g
k 0.001 0.005 min **
3 c
15 15 min 3
l Table 2b chemieni and nieleefeal intut Golden Shiners I
i Chic:$ne 8tcmine i
j c(0) 9.44 2.66 pog/l e,.
8.57 3.61 p sy/J 1.10
.7 37 4e e
2.06 1.11 p og/l m
k 0.016 0.054 min **
g k
0.001 0.005 min't g
i e
15 15; min t
l r
Page 50 of 69
. j.
_. _ _ _ _ _. _. _ -.. _.. - ~. _ _.
..-.m i
j i
i i
TR.ble 34 Results of Connutatiefin' i
Rainbow Trout 4
1 1
9 chlorine stomlae.
Jt.s s
E' C*
Z*
C*
0 11.4 5
9.61 5
1.19
]
0.10 24.0
. 32 16.5 26 1.45 0.25 61.0 323 25.6 57 2.38 i
0.50 336 1010 50.1 III 6.71 1
1.00 1148-1709 122; 326 9.41 I
j Table 3b Results of Centutations l
colden shiners 4
2 T *1 C,':1ctine Bramine Es,s 2'
c' j!'
c' 1
0 5.39 5
2.44 5.
2.21 0.10 9.95 21 2.96 8.5 3.37 0.25
'17.6 50 3.41 11 5.15 0.50 88.3 604 3.85 14 22.9 I
1.00 433.
1297
'4.46 28 97.1
'l Page 51 of 69 f
i
...~,
,._,.y,
..-,.h-,.,
,.y,
,,,m.m,-
,.,. m + % w m
,,,.,5 r
34-
~ _ _.. - - -.- _- _ - _. _-
l 1
l i
i Notation symbol Definicion Dimension a, b, c Constants va:Lous l
c(c),
Concent:a cion yegl1 e
c,e
!.C,, concenc: scion, 96 h:2 peq/1 o
c, c(0)e***'6 yeq/1 c
Threshold concent:acion p eq/1
=
m ks,s Exponents in chemical decay mLn
l N( c)
Nass measure 9'1 Racio of effluenc flow to cocal rive flow l
R,s Racio of Z* for blacide 1 l
s cc z' for blacide 2 c
Time, time = 0 is ac min inc:oduccion of blacide e
Break cine, chemical equation min s
c, Tine when mixing complace mLn c,
Tinewhen e!!1penc :enches :ive:
min c'
Time when c(c) = e min m
T X-c time X
Exposure cine in eg cica b:s Y
concenc:aclon, specifled mo:cality og/1 i
Y-c conc.
a Z
Defined in coxc cine conc. =
z*
Defined in texc cime Noces supe:sc:1pcs refer co blacifes 9
Page 52 ef 69 I
APPENDIX B Retstive EnvironmentalImpact Estimates for Chlorine and Bromine Used for the Control of Biofouling Condenser Cooling Systems i
l Page 53 of 69
- _.. ~.
i P
i t
i i
PROTOCOL FOR THE' TESTING OF THE EFFECTS OF SODIUM BROMIDE ON THE TOXICITY OF CHLORINE TO FRESH AND SA!!! WATER ORGANISMS i
4 Prepared for The Sodum Bromide /Brendt.: Chloride Task Force Prepared by Leonard H. Bongen, Ph.D.
Dennis T. Burton, Ph.D.
4 August 1990 Page 54 of 69
~.,. - :.,n e,,
4...
, -,-,..r...
,.w,
.....f.
,y.
,,e a
,.7..r-~-
,y.y,
-e,
,,,sg.,,
,,,ry,
,.w y,,_w,,y.,
,.w.-rv e
w y m e-
- w e r -. m + m.,
,wr-
1 i
70 REWORD This protocol was prepared at the request of ths Sodlum Bromide / Bromine Chlodds Tuk Force by taonard H. Bongen, Ph.D, R&B f.nvironmental services, Inc. and Deards T. Bunen.
Ph.D, Johns Hopkins Urdv.h/s Applied Physics Laboratory,Invironmental sciences Group.-The tut protocolis daigned in accordance wkh suggadons submhted by EPA (Mr. Charles Kaplas's memo (,f Much 16, 1990) to the Task Force.
i 4
i
)
.Page 55 of 69
TABLE OF CONTi$1TS
}
k FO REWO RD........................................'.. '......
I DirRO D U CD O N..............................................
e PROG RAM O BJECTIVE........................................
TECHNICAL APPROdCH AND METHODS...................
Oxid an: Analysis........................................... 5 7 Exp e rs e Pro c edure,...... '.................................... 5 8 Tut Organisms and Experce Cond:icn
..........................61 Trez:=en: Cendi:!c ns.........................................'. 6 2 Qua!!:7 Asrm.ce and Quallr/ Conc cl............................
6 4
.RIPCRTU4G PROCIDURES.......................................
65 Total Residual Oxidant Rep er:ing................................
6 5 LC5 0 Rep e r:in g............................................
6 5 PRCG Pet SCHEDUll..........................................
6 6 P
PageE6cf69 l
1
~
INT"AODUCT10N Chlorinaden of wutewater by PC1Ws to diminate the discharge of pathogenic orruds:.s and the use ci chlorine by electric util!du to inhibit biefouling are a widupread praedce.
Rescuth has sho*wn, howeve, that chlorine Induced oddana, eines they decay talativdy slowly, may be toxic to aquatic life when dhcharged into recdving wates.
ne use of sedum brotnide in corduneden with chiedne may solve thh problem. When applied with chlorine, sodlum bror.lde h exidhed by hypochlerous add (HOC 1) to hypebremous add (HOBr) and sodlum chieride. Due to the rdadvely low bond reengths, bromine ruidads exh! bit low stabil!ty, ney un more reac:ive than chlodne residuah and, thus, should pe:f:r=
better.
In cooling water contdr.!ng a==cnium saltr, application of sodium bromide with ch!cri e should resuh ta much lower leveh of oxidant ruiduah because the slow de::sying ch!ctr.:.i.es would not bc genented.
The protocol out!!ned here h designed to evaluate the decay of oxidan:s ger.ented by ch!c:ine 's huh and sah wate in the pruence and in the absence of sedum bromide and to deter =ine the effect of sedum bremide on the biotoxicity.
t PD.OGMM OBRCTTVE The objecive of the proposed test program is to comput residual bletoxidties to representative huh wate and salt watu organisms exposed to water chlorinated in the pruen:e of sedum brer:dde with r"4 wate chlorinsted in the absence of added sedum bromide.
TTC*3NIC11 AP'90 ACH AND METHODS Oddsnt Mshns ne chlorinaden of hesh ?nd salt water may result in the formaden of a luge num):er cf reaction products having varying kinetic constanu and oxiddag espadty. The amperomeci:
dtradon method, de. scribed in Standard W.1, 408C (APHA 1985), will be selected to determine tot:d residusi exidants (TRO). Since it is essennal to preserve the chemic-1 condidens as of the moment of sampling, a back.d:rsden amperometric end. point detection method will be selected. Fixaden of oxidants at the time of sampling.ny be necessary because free oxidant, and especially bromine esidsnts, decay relsdvely rapidy. Otnerwise, the mensurements could resuh in a substantial over. estimate of toxidty.
Page 57 of 69
To implement the mened, euess phenylarsine odde (PAO) wul be added to the samp to fix available oxidant. Unreacted PA0 wi!!be detu=ined by back dcradon with fodhu so of known concentraden using an amperometdc dzrator for endpoint detecdon.
Potendomecie methods also wu1 be evaluated to determine whethe If performance subdes meuurements prodde suf5 dent sensitivity, accuracy and preciden.
I progtun objecdves, the technique wm be employed for roudne TRO mordtering.
We andcipate the amperome=ic back desdon taethod to be able to toudnely detect TRO e
Icvels.of 0.01 mga and quandfy levels of 0.0 mgA of chlorine equivalents.
~
e msm Er-erm r
In view of the antidpated rapid exidant decay, spedal provisions were necusuy to ceste a reuenably stable environment for.anhnal expos.ne. The dulgn selected, muscated in F wC1. at constant blodde feed rate, obtain steady. state oxidant decay along the length o channel. Withdrawal of test fluid at a given locadon along the decay channel wCl %:Jd constant total residual ondant level.
Duuent watu (fresh or salt water) (A; Fig.1) and stock halogen solutier (chlorine or chlorine plus sodium bromide) (B; Fig.1) wu1 be continually mixed in a mixing umbe (C; Fig.1), The hal en stock soludens, the concencadons of which wC1 be deter the inidal phasu of the study, wG be held in rius containes wrspred in black plasd M
Waru leaving the mbing eMmber wG1 Sow through the PVC decay moduk of all light.
seedens (D; Fig.1) to allow for decay of the oxidants. Halogensted water wC1 be d the decay module to rep!Icate test aquaria (F; Fig.1) at points widch provide a ge of Eve test concencadens. We will attempt to include one concentradenin the geome=
that kills 84 to 100% of the tut organ!sms and one concencadon that kms between 0 to 1 of the test organisms. Obsuvadcas wul be made at a minf=um cf 1,2,4,8,12,24,36,48 and 96 houn. Observadens of shnermal behavior, immobEt', loss of equmbrium, etc. w
/
recorded.
The test aquuia wC1 be sited so that loading of the Esh wm not exceed 0.5 g/L wC1 be less for the imtztebrates. All test aquada wG be held in a constant temperature water bath (E; Fig.1). All matuials for both the chlorine and chlorine / sodium bromide test sy wG1 be PVC, sGeon, or gins. Dhselved crygen and temper nue wG be measured in a chamben in replie 's A during the peded To to T24 and T48 to T72 houn of the st B du:ing the ; cried T24 to T48 and T72 to T96. Conduedviry or saliniry and pH me:sured b st:ndud procedures at the beginrdng and end of esch test and every all cond.s. and the high, medium, and low halogen concentr: dons. Tors! Residual O (TF % concenesdons are to be measured, as a minimum, at 1,2,4,6,8,10<12 7" 84, and 96 houn. 30 is to be messured in each test chamber for a!! replicates.
Page 58 of 69
~-
Test procedures and statistical analyses wQ1 be performed in accordance with EP.V600/4.
85/013 with the ic!1owing exceptions: 1) a!! test temperatures wG1 be 2512*C except for i
if i
- sinbow trout which wC1 be run at 15 i IT., and 2) reference tox cant n ormat on w21 be supplied for dsphrJds and mysids only.
d t
Page 59 of 69
)
B A
l 1
c l
3 D
t l
1 i
i r,
r, i
o n
E F
Figure 1.
Sche =sde of oxidant decsy channel used for side by side compuison of test solutions contai:dng chletine in one channel while the parallel channel (not shown) cen sins a mix:ure of chierine and sodium bromide. The decay modules wG1 be conscuc:ed from PVC schedule 40 pipe with inside diameter of 2,3, or 4 -
inches.
Module Diluent Wate:
D
=
A
=
Water Bath Halogen Tank E
=
B
=
Test Aquards Mixing Chs=ber F
=
C
=
Page 60 of 69 l
i
Test Orrerdsms arid beerure CondJdens Flow through tests wS1 be performed on early life stages of the following orfan!.s=s:
Fresh wat'er organisms:
g,pgj; igg Ate er Slie Rainbow trout (Oneethvnehus uniigg) 15 30 days old i 48 h Common shiner (Netrevis sp.)
I to 2 inches Amphipod (Gara.marus sp. or HvalleDa sp.)
Juvenue Watedea (Daeh-in mgng)
< 24 hr old Salt water ortsnis=s:
Adsstic suverside (Meridin rnerldis)*
711 days old i 24 h Mysid sh:i=p (Mwideeris ).g}sa).
15 days old 124 h Biotexicides wG1 be expresed as:
Rainbow trout 96.h LC50 Com=en shiner 96.h LC50 A=phiped 96.h LC50 Watedea 48.h LC50" At1sntic sUve=ide 96 h LC50 Mysid sbhp 96.h LC50.
The watedes and mysid shri=p wD1 be obtained from the Johns Hepki.s Univenity/ Applied physics Laboratory (JHU/APL) Culn:re Facuiry located at Shady Side. Mar /tsnd, where the studies wEl be condue:ed. Rainbow trout, common shiner, amphipod, and Atlan:ic suvenide wul be obtained from various supplies.- Each species wC1 be exposed to chlorinated water and chlorinated /brc=inated water in separata systems run side by side.
All species wS1 be tested by definitive condnuous flow acute toxiciry test procedures descibed above. Brie!!y, five test concentrations plus contro1 with two replicates of 10 organisms minimum per replicate wDl be used. All caposures wC1 be 96 ho:as with the exception of the water flea which wS1 be 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br />. The acclimation and test temperarat for an of the test ani=als, with the exception of rainbow trout, wC1 be 25 ( 2)*C. Rainbow trout will be ace"mted and tested at 15 1*C. Non. chlorinated deep well water, which has an averste alk:!!nity of =156 mg/L ss CACO, hardness of =190 mg/L as CACO, and pH of =7J, wul be used 3
3
- In the event that the At1:ntic sDverside' minnows are not avaEsble commercially,- the inl:nd suverside minnow (Me-Jdis bervilinmi may be substituted.
" An attempt will be made to provide a 96.h LC50.
Page 61 of 69 1
-t for the freshwater orpnisms. Futend Chesapeake Bay water 812 ppt augmented with sea salts -
to a salinity of m 20 ppt will be used forf the salt water organisms. Dissolved orygen.
concentradons w01 be maintained at a minimum of 4.0 mg/L at 25'C and 6.0 mg/L at 15'C. The'--
photo period wD1 be held at 16 hours1.851852e-4 days <br />0.00444 hours <br />2.645503e-5 weeks <br />6.088e-6 months <br /> light,8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> dark for an studies.
Trescent condidens For each orpnism tested, each 4et of paired treatment condidons 1.A and 1J; 2.A and 2.B; 3.A and 3.B shall be conducted-simultaneously.
Using test'orgsnisms and exposure procedure idend5ed above, the foDowing trest ent cond! dons wi:1 be tested:
Trennent Cond! den 1.At Continuous application of C1, and C,/NaBr; rainbow tr.,ut, common shiner, amphipod, wateriles; groundware..
Two test runs wG1 be made with the listed fresh watu organisms._ Groundwater wn! be used in this test series. For uch test run, a constant rate of chlorine without sodium bromide wC1 be fed to or.e decay channel whereas.sdium bromide wD1 be added to the second channel at 1.5 times the stoichiometric concentradon of chlorine. The animals _ 0lbe exposed to biocide w
concentrations from approximately 1 mg/L TRO to the residua 11 eve 1 remaining after a deeny time of approximately 90 minutes. Ninetysix.h LC50s will be' determined for all animals with the
. possfole excepden of the _watefles.
I i
Tresment Condiden 1.B:
Continuous _applicadon of-Q _and C1/NaBr; Adande Everside and mysid shtimp; 20 ppt' salt water l
o i:
Two test runs wC1 be made with the marine organisms listed earlic.cF.stuarine wate (20 :
ppt salinity) wul be used for this test series. Biocide applications wC1 be as in Tremenant i
Condidon 1.A. Ninetysix.h LC50s wC1 be determined. =
- Trescent CondMen 1At Intemittent applicadon of C _and C1/NaBr; common-shiner and water flea; groundwater. -
To evaluate the effect of intermittent biocide applicadon, elevated levels of blecide wQ1:
I be applied for 40 minutes at 8.h latervals. Chlorine wC1 be injected in both chann Is,. whenas one channel wG1 receive, in addition, NaBr 'at 1.5 times the stoichiometric concentradon of chlorine.- Intermittent LC50s wC1 be calculated.
Page 62 of 69 '
/L...
. ua a-
..__...-.~_a._w.a.__._,,___._
.~
s
- o T
l 4
Trestment Condiden 1B:
Inter =ittant application of Cl, and CWaBr; Adande t-
- silvanide and mysid shtimp; 20 ppt salt ware.
e The test run will be as desc hd under Treatment Condidon 2.A. except that salt ware win be used.
Treatment cendiden 1A:
Ammonia; C1,; waterfles; groundwater.
l To evaluate the efect of chloramines on biotoxiciry, watafleas win be exposed to--
1
_ groundwater chlorinated in the pruence of ammonia. The test ^=v=h described earlier will be used for this test series as well A fortyeight.h !.C50 will be calculated. In adddon to TRO. FAO shan be dete=ined-on a 12.h interval in the stock solution and the-highut exposure 4
concentradon tested.
Trescent Cendiden 3.B:
Ammer.ia; C1/NaBr; mysid; 20 ppt salt water.
To evaluate the efec:s of brommmbes on biotoxicity, the test procedure dese:foed under 3.A will be repeated using chlodne in combinaden with sodum bromide. 7ds w' include the l
dete=inaden of FAO as in 3.A.
Mdide.nl Tem i
^
1 l
Die.nway Tem t
l These tests will be designed to measure oxidant decay.with time in the dark.L TKO j
measurements win be started at approximately 0.3 mg/L and measuremests shall be' continue?. -
)
undl a concentraden of approximately 0.02 mg/L or less is obtained. -- A sufficient numbe of-measurements shan be ohmined to allow a reasonable plot of the data. A toen1 of four rests will -
be performed as follows:
i i
Freshwater with chletine i sedum bromide Salt water with chlorine i sedum bromide.
At predete=ined intervals, a 200.m1 aliquot will be taken, fhted with PAO, and analped for residual oxidant.--
4-i Page 63 of 69 e
vsm.
4 r
.,-.,,+.c.-c-
~ =
+e.-,.-m-r re--m+.
- +,mw+..,
'.--r-,,...-+,r4.~r>.
r' e +
~. _ _ _..
i t
Free' Avaunble Oddant Mensure nents.
Using Standard Methods 408C (1985), FAO wC1 be determined in addition a TRO, once during a test run when sodium bromide is added to the groundwater, and once during a test i
i run when sodium bromide is absent. -
i Table 1. Summary Test Resuks
(
L l
Trea~ ant Condition Test Number of j
Fluid
- Cone Controls Sp' cies Runs f.xposure e
Chambers 1
1A C2 vs C2/NaBr GW 2 5
1 4-2-
88 IB C2 vs C2/NaBr SW 2 5
1 2
2
~44 2A C2 vs 02/NaBr GW 2 5
1 2
2 44 2B C2 vs C2/NaBr SW 2
.5 1
2 2
44 3A C2 vs C2+NH4 GW 2 5
1 1 --
2 22 3b C2/NaBr vs GW 2 5
1 1
2 22 C2/NaBr+NH4 4
- GW: groundwater SW: sah water QuaUtv Assmnee and OuaUtv Cent-el 5
- The Toxicity Testing Group of JHU/APL has'a quality assurance / quality control prog:2m.
for all phases of its toxicity projects. The objecdve of the program is to assure that: 1) all results
- are representative and valid; 2) provisions are made to identify and correct any de5ciencies in.
testing procedures or repotts; 3) results' of aH studies previde a satisfactory basis for comparison.
with other studies; and 4) confidence in the resuhs of the Toxicity Testing Group se.. ices is suf5cient to assure their tallability to the sponsor, regulatory agencias ed the public. For further details see the JHU/APL manual endtled JStandard Operating Procedures for Acute Emuent Toxicity Tests with Freshwater and Salt Water Organisms.* - July 1987. : This SOP manual is--
submitted to provide quality assurance and quality controlinformadon for this study. However.-
' this manual dated July 1987, is incomplete insofar as it does not reflect all condidons planned for this study. To the extent that any condidon in the SOP is inconsistent with the condidon.
stated in the protocol, the condidon in the protocol shall govern.
Page 64 of 69 yr,-
--g e
gev'
-gs't-s en-N v
- e w W urere FT=s*=t'ww g
'-*+-Fm-rar-yv
- --f t
4W
?
g-g" #
$-y-'gi e yMw-p P'
't y h
4 i
j REDORTTNG PROCEDURrg Ters1 Reddust Oxidant Reer'nr 4
1 All ondant measurements wEl be reported in mg/L When bromide (Br ) is added to
{
chlorinated water, the oxidizing capacity of the soludon wC1 be expressed as ag/1. oxidant, or as chlorine equivalents. No attempt or speculador. wG1 be made on what ek =!cM species 4
, consti:ute the oxidants. *
~
LCIO Reerdne The def.nidve acute toxicity data wC1 be analyzed stadsdca!!y in acccrdance with' lea doe.:=e.nt 600/4-85/013.:
1 4
9 4
e f
9 Page 65 of 69
. ~,. _. _
8 & B ENVIRONMENTAL SERVICES, INC.
Tel. (301) 566 8109
.'431 Drury Lane Fan. (301) 342 2371 Saltimore, Marylens ::-
THE TESTING OF TEE ETTECTS OF SCDIUM RROMIDE ON TEE TOXICITY OF CILORINE TO FRESE AND.5'ALTWATER ORGANISMS
~ " ' ~ ' " ' '
Test Schedule
- 1. Design, Installation, a Testing of set-up 1.1
- Order and receive control equipment c==pletion 10/15/90 1.2
- Design and asse=bly of medules:-
ccmpletion 10/15/90 1.3. Installation of control equipment ce=pletion 10/31/90~
14
- Pre-op test runs; completion 11/15/90 1.5
- Program checkout, including analytical 11/15/90-2.-Biotoxicity Test Runs 2.1
- Treatment ondition lA and/or 1Br-3 species 11/16 c= 12/31 2.1
- Treatment condition lA and/or las 3 species 1/1 to 1/31 2.3
- Treatment condition 2A and 23 2 /1-to 3/8 2.4
- Treatment condition 3A and 3B 3/11 to 3/31
- 3. Die-away Test 12/1/90 to 1/3;
- 4. Final Draft Report 5/1/91 l
l Page 66 of 69 I -
i i
i J
l 4
i APPENDLX C Protocol Amendment #1 4
Page 67 of 69
i 1
1 December 3, 1)90 PROTOCOL AMENDMENT $ 1 The following three revision to the protocol entitled " Protocol for l
the Testing of the Effects of sodium Bromide on the Toxici;y of Chlo-rine to Fresh and Saltwater Organisms" were discussed and approved by USEPA representatives.
- 1. Test spe'cies The protocol specified the common shiner as one of the test animals for treatment conditions 1A and 2A.
Because of availability pro-blems, the golden shiner will be used in stead of. the cermon shinar for treatment conditions lA and 2A.
-2.
Size of the Shiner The protocol specified the size of the shiner as 1 to 2 ' inches.
Since test animals of that size were not available from commercial, dealers, a larger size will be tested.
Thus, for treat =ent con-ditions lA and 2A, golden shiners in the size range of 2.5 to 3.5 inches will be used.
1
- 3. Oxidant Delivery system Because of the size of the golden shiner, the oxidant delivery system described and illustrated in figure 1 of the protocol, cannot be employed.
Instead,'a continuous-flow oxidant-delivery system will be used,-which is similar to.the system described by J.R. Vanderherst et al. in Bull. Environ. Contam. Toxicol.:17:
577-584; 1977.- This systam-consists of individual stock solutions for each halogen concentration.
Each stock solution is metered via a-Masterflex pump to a. mixing chamber and mixed with deluent water.
The halogenated-feed from each mixing chamber will then be split to each treatment rep.acate.
The aquaria, housing the
. test animals, will be submerged in a constant temperature bath.
There will be.no changes to the analytical procedures speci*ied in the protocol.
All analyses will be performed as described in the protocol.-
Program anagement:.
Progr a sponsor (th Dennis T.
Burton, Pn.D.
Louise L. Wen, Ph.D.
Chairperson, NaBr/3rC1 Panel Leonarc M.
songers, en.D.
Page 68 of 69 I
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1 i
i ETHYL CORPORATION Heahh and Environment Depanment temesseyene asive v.--
n.,-,==.
et masse swest aww i
December 7, 1990 Dr. Leonard H. Bongers B&B Inviron= ental Services, Inc.
431 Drury Lane Baltimore, MD 21229 Daar Leonard:
Enclosed is a signed protocol amendment for.ths' NaBr test.
Please include it as an addendum in-the final study report.
Looking forward to saa you next vaak.
Sincerely, e
i Louise L. Wan, Ph.D.
Chairperson NaBr/Br Industry Panel LLW:ab o80LLW90 Enclosure Page 69 of 69 l
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