ML20148L692
| ML20148L692 | |
| Person / Time | |
|---|---|
| Site: | Sequoyah  |
| Issue date: | 03/30/1988 |
| From: | Brooks R TENNESSEE VALLEY AUTHORITY |
| To: | Sinclair R TENNESSEE, STATE OF |
| References | |
| NUDOCS 8804040076 | |
| Download: ML20148L692 (98) | |
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l TENN E3CEE VALLEY AUTHORITY KNOXVILLE. TENNESSEE 37o02 MAR 3 01988 Mr. Ralph M. Sinclair Manager, Permits Section Tennessee Department of Health and Environment TERRA Building 150 Ninth Avenue, North Nashville, Tennessee 37219-5404
Dear Mr. Sinclair:
SEQUOYAH NUCLEAR PLANT (SQN) - NPDES PERMIT NO. TN0026450 - NOTIFICATION OF USE OF CHLORINE / BROMINE TO CONTROL BIOFOULING In accordance with Pact III.D. of the NPDES permit, this is notification that TVA proposes to begin adding sodium bromide in addition to sodium hypochlorite to the essential raw cooling water (ERCW) system at SQN. In the past, sodium hypochlorite has been added to the ERCW system to control clams. TVA now believes it is necessary to treat the ERCW system to control biofouling and mitigate microbiological 1y induced c.orrosion (MIC). TVA proposes to use a chlorine-bromine mixture applied to the ERCW system continuously, year round. Industry experience has shown that a chlorine-bromine mixture is a mor9 effective blocide than chlorine alone.
Like chlorine, the bromine combines with organics to form bromamines, which are effective blocides and are less persistent than the chlorinated organics (chloramines) in the environment. The addition of bromine also reduces the amount of chlorine that is needed to provide the desired results. Therefore, the use of bromine reduces the total residual chlorine (TRC) and aids in compliance with the NPDES permit. In addition to the chlorine-bromine mixture, a biodispersant may also be added to increase penetration of the biofilm and thus make the blocide more effective.
TVA will likely contract with one of the following companies: NALCO, Betz Laboratories, or Calton to supply the chlorine, bromine, and biodispersant chemicals; assist with the feeding of these chemicals into the ERCW system; and determine the effectiveness of the treatment program. The chlorine-bromine biodispersant can be applied in a premixed form or the chemicals can be added individually to obtain the desired mixture. The actual forms used will depend on which vendor is selected.
The following products are being considered:
- 1. NALCO Company's Acti-brom 1338--Acti-brom 1338 is an aqueous solution containing sodium bromide and a blodispersant. Acti-brom 1338 would .
be injected simultaneously with sodium hypochlorite to obtain the '
desired bromine-chlorine mixture in the ERCW system.
- 2. Betz Laboratories' Slimicide C-78P--S11micide C-78P is an organic granular material (bromochlorodirtethyl hydantoin), that when dissolved in water releases both chlorine and bromine. No additional sodium hypochlorite is needed with this product.
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MAR 3 01988 Mr. Ralph M. Sinclair Betz Laboratories' Slimicide C-82--Slimicide C-82 is an aqueous solution of sodium bromide. It would be inje:ted simultaneously with sodium hypochlorite to obtain the desired bromine-chlorine mixture in the ERCW system. This is an alternative to Detz Laboratories' l Slimicide C-78P.
If this treatment is not fully effective, Betz Powerline 3690, a biodispersant, may also be used.
- 3. Calgon's H950--H950 is an aqueous solution of sodium bromide. H950 would be injected simultaneously with sodium hypochlorite to obtain the desired bromine-chlorine mixture in the ERCW system, i If this treatment is not fully effective, Calgen's CL-361, a !
surfactant, or TRC 233, a biodispersant, may also be injected. j Product-specific information provided by the vendors are given in Enclosures 1 through 6. Included with this information is the name and general composition of each product, toxicity data, recommended dosages, users of the product, and EPA registration number, if applicable.
Additional toxicity information complied from the literature on chlodne-bromine mixtures is given in Enclosure 7.
TVA proposes to upgrade the present sodium hypochlorite feed system; the l present system is unreliable and equipment problems have led to ineffective treatment. TVA also proposes to install a product-specific feed system for the bromide product ultimately selected. This will enable the feed rates for these chemicals to be closely controlled.
Until permanent feed systems can be designed and installed TVA plans to contract with one of the above-mentioned vendors for skid-mounted feed systems on a rental basis.
Actual dosage rates of sodium bromine and sodium hypochlorite are not known at this time. The specific dosages will vary depending upon the product selected, the number of ERCW pumps in operation, the water chemistry, and the severity of the biofouling. However, addition of the chlorine / bromine will be controlled such that the resulting TRC concentration in the diffuser discharge to the Tennessee River will not exceed 0.1 milligram per liter (mg/L). To help ensure that effective treatment is being provided and excess chemical is not added, the TRC level and microbiological activity will be monitored at various points within the ERCW system. The results of this monitoring program will be used to ninimize chemical usage and serve as an operational control to avoid exceedances of the TRC effluent limitation established in the NPDES permit. If a biodispersant or sur'actant is necessary for effective treatment, those additives would be fed at a rate of 3 to 10 mg/L depending on product selected and would pose no environmental threat due to low toxicity (as referenced in the enclosed literatura).
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Mr. Ralph M. Sinclair The initial goal will be to provide enough chlorine / bromine to maincain a 0.5 to 0.7 as/L total halogen residual at the ERCW heat exchant.ers. Once a vendor has been selected and a product-specific dosage rate determined, your office will be provided more specific data on the dosage rates. For example, Calgon estimates that the H-950 consumption would range from 32 to 190 pounds per day per ERCW pump in operation (ERCW pump rated at 9.85 MGD), depending on the feed ratio necessary to control the microbio-logical population, assuming an average chlorine demand of 0.4 mg/L, and maintaining a free residual of 0.5 to 0.7 mg/L total halogen. The estimated dosage rate for the Calgon product la considered representative of the dosage rate that would be required for any of the other products.
Of course, variability in the dosage rate will occur depending on the concentration of bromine and chlorine in the specific product.
TVA requests that this information be made a part of the permit appilcation for renewal of the SQN NPDES permit submitted October 1, 1987.
TVA further requests that SQN be permitted to continuously inject chlorine, bromine, and biodispersant (from the list above) year round into the ERCW system for cla control and prevention /raitigation of microbiological 1y induced corrosion with the following effluent limitation and monitoring requirement: TRC of 0.1 mg/L at the diffuser discharge i measured by multiple grab sample once per day. Multiple grab sample shall be defined ar not less than four equally spaced grab samples during a one-hour period.
From discussions with your staff, we understand that when the permit is reissued, toxicity testing of the plant effluent will most likely be required on a seasonal basis. We propose to begin toxicity testing of the diffuse 'ischarge shortly after the bromine /c'ilorine treatment begins. We wall provide a copy of the toxicity testing procedures for your approval prior to initiating the tests.
The skid-mounted system for chlorine addition should be installed in time to began treatment for clam control later this spring. TVA would like to install the skid-mounted, bromine and biodispersant feed system so that treatment for MIC can 'uegin as soon as poss.'ble. Therefore, we request that the permit be renewed or modified by July 1 to allow for the treatment of the ERCW system as described herein.
If your staff needs additional information or has any questions regarding this request, please have them call Madonna E. Martin at (615) 632-6695 in Knoxville.
Sincerely.
ORIGLN t.L Wim ni-M LPilIL Bnoagg Ralph H. Brooks, Director Environmental Quality Enclosures ec: See page 4 t
MAR 3 0 083 Mr. Ralph M. Sinclair ,
cc (Enclosures): 1 Mr. K. P. Barr, Acting Assistant Director 1 for Instection Programs TVA Projects Division U.S. Nucle.tr Regulatory Commission ;
Region II ;
101 Marietta Street, NW., Suito 2900 Atlanta, Georgia 30323 Mr. Bruce R. Barrett, Director Water Managetwnt Division U.S. Environnental Protection Agency Region IV 345 Courtland Street, NE. )
Atlanta, Georgie. 30365 U.S. Nuclear Regulatory Commission l Attention: Document Control Desk j Washington, D.C. 20555 Mr. Philip L. Stewart, Manager Chattanooga Field Office Division of Water Pollution Control 2501 Milne Street Chattanooga, Tennessee 37406-3399 Mr. G. G. Zech, Assistant Director for Projects TVA Projects Division U.S. Nuclear Regulatory Commission One White Flint, North 11555 Rockville Pike Rockville, Maryland 20852 l
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ENCLOSURE 1 Product Information for NALCO Company's Act!-brom 1338 (This information was provided by NALCO for TVA's use in obtaining regulatory approval for the use of the specific product.)
EPA Registration Nt-'er: The EPA registration number for Acti-brom in recirculating systems is 1706-168.
NALCO expects approval for the registration number for once-through systems any day.
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AQUATIC T0XICITY
SUMMARY
ACTI.8RON 1338 1 The acute 96 hour0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> static LC of Acti-Brom 1338 for the RainbowTroutandBluegillShnfishwasfoundtobegreaterthan 1000 mg/L (ppm) for oath species.
Corresponding 24 and 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> LC50's for Rainbow Trout were also greater than 1000 mg/L, respectively.
For Bluegill Sunfish the 24 and 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> LC50 values were also greater than 1000 mg/L.
Tne 96 nour observable no effdct concentration noted f'or botn Rainbow Trout and Bluegill Sunfish was 1000 mg/L.
Estimated Toxicity Rating = Essentially Non-Toxic Resp ctfully submitted,
/ I p J/1/>L)/__
claude H. Wolf /
Corporate Toxicologist l Maren 1984 l ABC/EH&S 279/F7903/84A209 I.
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NiATERIAL SAFETY DATA SHEET PRODUCT AcrI-aR* 1338 BIcoISPGsmr N ALC O Emergency Telephone Number Medical (31219201510(24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />)
SECTION 1 PRODUCT IDENTIFICATION TPAIE 10ME: ACTI-IROf 1338 BIDDISPDSANT IESCRIPTICN! An aqJoous M1*ims of brmiria salt and an oxyalkylate {
NFPA 704M RATDC 1 NEAllIH 1 FIA>HABILTIY 0 REACTIVITI O OIHER 0= Insignificant 1=611ght Miiiderata 3=High 4= Extreme SECTION 2 EAIARDOUS INGREDIENT 8 Cur hazard evaluaticn has 4M4fied the following hirmi !
ingredient (s) as hazardous under CSHA's Hazard rwmenication Rule, 29 l CFR 1910.1200. Censult Section 14 for the nature of the hazard (s).
DEREIIIDir(S) CAS # APPPOX.%
i Scdium brcanide 7647-15-6 40+ l SECTION 3 PRECAUTIONARY LABEL INFORMATION !
iaRNDC: Causes eye injury arti skin irritation. Do not get in eyes.
Avoid ccntact with skin ard clothin7 Wear gtrygles or face shield when ha:xiling. Avoid prolcoged or repeated breathirn of vapor. Use with adequata ventilaticr.. Do not take intarnally.
Dpty centainers may centain resMial product. Do not reuse container unless prcperly reocrditicned.
SECTION 4 FIRST AID INFORMATION EYES:
SKIN: Flush with water for 15 minutes. Call a physician.
Wash thoroughly with soap and rinse with vator. Call a physician.
ICIE TO IHYSICIAN: No specific antidote is krmn. Based on the irdivirttal reactions of the patient, the physician's juipent shoald be used to control syntas and clinical ec4xiition.
CAUTICH:
If unconscious, havirg trcuble breathing er in convulsiens, do not irduce vernitirq or give watar.
SECTION 5 HEALTH EFFECTS INFORMATION PRNARY PCUrE(S) CF DGCSURE: Eye, Skin EYE CNIACI:
Cal: cause trancient to Feriarate irritation.
PAGE 1 OF 6 NALCO CHEMICAL COMPANY ONE NALCO CENTER e NAPE AVILL E, ILLINOIS 60568-1024 AAEA 31.1 961 9500
MATER!AL SAFETY DATA SHEET PRODUCT AcrI-sam 1,338 BIODISPERSM N ALC O Emergency Telephone Number _
Medical (312) 920-1510 (24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />)
SECTION 5 NEALTE E/FECTS INFORMATION ( CONTINUED )
SKD( c2nacr: May cause irritatim with prolmced omtact.
SN OF EXEOSURE: A review of availahla data does not identify any synytams fri:n exposuru.
AGGRAVATICH OF EXISTDG Ct2iDITICNS: A review of available data does not identify ar.f worsening of existing ccaviiticos.
SECTIO 3r 6 TOZICOI4GY INFORMATION Acne ToxICm SWDIEs: Acca tcxicity sttrilas have been cx:nducted cx1 this product alcus with acuta toxicity shrilan en the hazardous )
inJredient(s) in Secticr. 2. The results are shown belcu.
PRIMM EYE IRRTIATIch TEST (AIBDC RABBITS)
EYE IRRTIATICH Di!E IRAIS RATDC: 10.8/110.0 Mininally irritating ctM< Des: No correal cpacity was noted. IriM al irritation which !
cleazwi three days a.ftar contact was noted. Slic,ht to ver4 rata conjunctivitis which citared 7 days aftar cxzeact was also nc+ad.
Results suggest transient irritaticn.
OIHER TOXICITY RESUIES: .
Sodium branide ID50 c.:al .in rats is believal to be betwen 3,500 and 5,000 ::q/kg.
SECTION 7 PHYSICAL AND CHEMICAL hROPERTIES CDIDR: Colorless FORM: Liglid OCER: Ncrw CEKSM: 12.2 lbs/ gal.
SOIUBILITY Di WATER: Ctr pletely SPECIFIC GRAVm: 1.46 @ 60 Cegres F pH (NEAT) = ASTM D-1298 7.1 AgIn g-70 VISCCG m : 5 cps 0 2 Degrees F ASTM D-2983 FRI22E 70DC: 16 Degre a F FIA5H ICDC: ASIM D-ll77 None (P!O.;)
AsqM o-93 l WIE: These physical p.WJ,es ars typical values for this prcduct.
DECTICN 8 FIRE AND EXPLOSION INFORMATION h
FIASH 70DC: None (ROC) ASTM D-93 EXTDCUISEDC XEDIA: Not applicable PME 2 OF 6 NALCO CHsMICAL COMf8ANY ONE NALCO CENT E A e NAPEPvlLLE. ILLINOIS 60588 1024 Asag A J
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MATERIAL SAFETY DATA SHEET PRODUCT AcrI-BRN 1p8 BIODISPERSANP N ALC C Emergency Telephone Number meewei (312)sto isio(24 wurs)
SECTION 9 REACTIVITY INFORMATION INCm PATIBILrfY: Avoid ocritect with stzt 1g mid4=a (eg. chlorine, ptrwi da=, dutmatas, nitric acid, perchloratas, ocncentrated cuygen, permanganatas) thich can generate heat, fires, explosicris and the release of emin fumes. ..
SECTION 10 PER8ONAL PROTECTION FQUIPMENT RESPIRAItStY PRomTICH: Respiratory grotecticn is not nm=11y ren.ind since the volatility ard twinity are low. If significant vapors, mists or aaresols are generated, wear a NIOSH approved or equivalent respirator, (ANSI Z 88.2, 1980 for requiruments and sedacticn).
Ibr large spille, entry into large tanka, v-la or arclosed *=m11 spaces with inadequats ventilation, a erld, self-ecntairend breathing apparatus is rar==rded.
VDirIIATICH: General ventilaticn is ree-nai,ded.
F&m.uVE EUIRE2(r Use 4= - ble gloves ard c W iral splesh -
geggles (ANSI Z 87.1 requirements and selecticn of gloves, geg31es, shoes, etc,) Wen att @ feeding equipment or doing mainten roe.
It clothing is contandratad, remove clothing and "Wy weah the affected area. Imundar contaminated clothing before rouse, alECTION 11 8 PILL AND DISPOSAL INFORMATION IN CASE OF TPANSKRIATICN ACCIDE2CS, CALL die EDIIIWDC 24-lEUR TEIEREtE hu!BER (312-92>1510)
CPIIL CQfIPOL AND RECOVER':
Small liquid spills: Certtain with ^W 1-is ::aterial, sch as saw i dust, clay, soil or any emrectally available absortent, shcual relai=4 dip 1 liquid ard absortent intr., W or salvage dru=s for Refer to C2RCIA in Sectico 14.
Iarge liquid spillst Dika to p.6 further nova:nnt ard reclaim into recmery or salvage drums or tank truck for disposal. Refer to CERCIA in Section 14.
DISP"GAL: If this product becxres a vasta, it does not rect the critaria of a hazarius vasta as dr. fined urdar the Resource Conservatim and Recovery Act (RCPA) 40 CF". 261, since it does not have PAGE 3 OF 6 PJALCO CHEMICAL COMPANY CNE NALCO CENTE A e NAPE AVILLE. ILLINOG OOSG6-10nd AAEA 310 981 3500
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MATERIAL SAFETY DATA SHEET PRODUCT AcrI-apcx 1338 BIODISPSSANT NALCO
. Emergen:y Telephone Number Medical (312) 9201510 (24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />)
SECTION 11 SPILL AND DISPOSAL INFORMATION ( CONTINUED )
the d'aracteristics of Subpart C, (i.e. D001 tJurugh D017) nor is it listed under Subpart D.
As a rx:n-hazardous liquid wasta,_it should be solidified before M 5=41 to a sanitary landfill. Can be deep-wall injected in hAx.i. with local, stata and federal regulaticns.
SECTION 12 RNVXRONMENTAL INFORMATION AQUATIC DATA:
96 hour0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> static acuta If50 to Bluegill Sunfish = Greater than 1,000 pps S hour no chamW affect wJation is 1,000 rps based on no mortality or arnormal affects.
NCIIY RATDG: Essentially ncn-tencic 96 hcur static acute IC50 to Rainbow TItut = Greater than 1,000 ppa 96 bo.tr no r+=avved affect ocncentration is 1,000 ppn based on no mortality or ainormal affacts.
'IOXICITY RATDG: Essentially rrn-toxic If ralamaari into the envim-6., see CERCIA in Secticn 14.
SECTION 13 TRANSPORTATION INFORMATION IX7T PROPG ShuvuG NAME,4'AZARD COCE - PRODLUr IS ?Or RS2XAIED CIJRDC TPNGPCRIATICtf SECTION'14 REGULATORY INFORMATION The follcwing regulatiens apply to thiu protact.
EIDGAL RD3AATICHS:
CGWS HAZARD CI2%NICATICH RUIE, 29 CFR 1910.1200:
Based cn cur hazarti evaluaticn, the follcwing i.Went in this product is hazardous and the reasce is shown 1:eicv.
Scdium brunida - Eye irritant PAGE 4 0F 6 NALCO CHsMICAL COMPANY ONE NALCO CEN rE A e NAPE AVILLE. ILLINOIS 60568-1024 A f4 E A 312961 3500
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MATERIAL SAFETY DATA SHEET PRODUCT ACrI-BRM 1338 BIODISPERSAMP N A LC O Emergency Telephone Number Medical (312) 9201510 (24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />)
SECTION 14 REGULATORY INFORMATION ( CONTINUED )
CERCIA/SUPERFUND, 40 CPR 117, 302:
Notificatim of spills of this product is not required.
'IOKIC SUBETIANCES ONIICL ACT (TSCA):
The cha=N1 ingredients in this product are cm the 8(b) Inventory List (40 CPR 710).
REBCURCE CCNSULVATIN AND RECIM3E ACI (RCRA), 40 CFR 261 SUBPART C & D:
If this product h a wasta, it does not meet the criteria of a hazardcus wasta.
FIEERAL HNIHL ICIllTTICH CINI5CL ACT, CIZAN WATER ACT, 40 CFR 401.15 (fnmarly Sec. 307), 40 C2R 116 (formerly Sec. 311):
Ncne of the ingrafiants are specifically listed.
CIDN AIR Acr, 40 CFF 60, SECTICH 111, 40 CIR 61. SErrICH 112:
'Ihis prcduct does nc; ocntain ingredients cwered by the Clean Air Act.
SIATE REGUIATICNS: -
MIQUGAN CRITICAL FAIERIAIS:
This product does. not ocntain ingredients listed m the Michigan Critical Materials Register.
SIAIE RICHT TO Moi IAWS 7, tc A.tA et does not ocntain ingredients listad by State Right Tb Fnow te n.
SECT!JN 15 ADDITIONAL INFORMATION Ncne SECTION 16 USER'S RESPONSIBILITY This product ratarial safety data sheet prt:vides health and safety information. The product is to be usai in applicatiens mnsistent with our prcduct literature. Iniivhls han:llirq this product cheuld be informai of the recccrendal safety precautiens and should have am to this information. For any other uses, expcsures should be evaluated so that apprcpriate handling practices ard trainirq progrs=s can be establishai to ensure safe workplace operations. Please censult your 1ccal sales representative for any further inforratien.
PAGE 5 0F 6 NALCO CHsMICAL COMPANY ONE NALCO CENTE A e NAPE AVILLE. ILLINOIS B056G 1024 AAEA 312 901 9500
- MATERIAL SAFETY DATA SHEET PRODUCT AcrI-an:n 133a amnrnanNr N A LC O Emergency Telephone Number Oedical (312) 9201510 (24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />)
SBCTION 17 BIBLIOGRAPLY AleERL REPCRT CN CMr Tiry:ns, U.S. Departasit of Health and Mut Services, Pelin Health Service, PB 33-135855, L983.
CNIAREIT AND DOULL'S 'IOKIO3[.OGY,_JHE BASIC SCIENCE OF ICISCNS, Doull, J.,
Elnamara), C. D. , and Adiarr, M. O. , eds. , 'M114m Publishing Ompany, Inc.,
N. Y., 2ni editics), 1980.
OIDCICAL 19.ZARDS OF 'IHE WG5PIACE, Proctor, N. H., ani lir3h es, J. P., eds. ,
J. P. Lipincott Ccapany, N.Y. ,1981.
DMCDCUS PICPERTIIS CF INEXBIRIAL MATERIAIS, Sax, N. Irving, ed., Van Nostrani Rainhold omparsy, N.Y., 6th editicr), 1984. ;
IAlt 1CNO@APHS CN 'IEE EVAIIRTICH OF 'INE CAPCDDINIC RISK OF QEMICAIS TO HAN, Geneva World Health Organizaticri, Internatiaal Agancy for Research cm) Cancer, 1972-1977. ,
PWIY'S INEUSTIRIAL fuGIINE AND ToxICOIcGY, Claytcri, G. D. , Claytcri, F. E.,
eds. , Jchn Wiley ard Scris, N. Y. , 3rd editien, Vol. 2 A-C,1981. 1 RD3ISIIDE OF TDXIC EFFTME CN QGMICAL SUNINGS, U.S. Department of Baalth ani Numan Servioso, Public Health Service, Center for Diseasc 0:sitrol, National Institute for occupational Safuty and Health,1983 -
supplement of 1981-1982 editicri, Vol.1-3, Qi,1984.
Title 29 Code of Fedaral Regulations Part 1910, Sul.part Z, Toxic ard Hazardous Substarces, Coxpaticnal Safety ard Ihlth Administration (OSHA).
'IHRE!ECID LIMIT VAllTES FCR QEMICAL SUNDWCES AND EHYSICAL MDmi Di THE W34GCQi DNIPCt0ERT WrIH DirDUD OR!GIS, American Conference of Governmental Irdustrial Hygienists, CH. j 1
PREPARED BY:
Jchn J. /.aspr, MSc., Manager Prcduct Safety
[A2E O RNGZD: 03/27/86 DA22 PRDTIED: 09/23/87 l
I PAGE 6 OF 6 NALCO CHEMICA7 COMptiNY C)NE NALCO CENTE A
- NAPE AvtLLE, ILLINOIS GOSEG-1024 A84EA 31J.969 3500 '
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( NALCO C H L' M I C A L COMPANY o N E. N AL.C L J E N T E r1 D N A A E A V a t .. L ".L.N Qiu 0050(1+?I.. 3 .4 o A H r. t. "J ' P 9 C ' . 4!, " ;
January 14, 1988 Mr. W. A. Nestel
' Tennessee Valley Authority 1N 54B Blue Ridge Place 1101 Market St.
Chattanooga, TN 37402-2801
Dear Mr. Nestal:
Thank you for invitilig us to the TVA-Sequoyah Plant to discuss Acti-Srom. We enjoyed meeting with all of you.
Listed below are the answers to the questions which came up during our discussions.
- 7) The use of bromine chemistry at Alcoa is still in the
- proposal stage-so there is no' reference available.
However, bromine chemistry is used at two (2) DuPont ,
i plants in the State of Tennessee. The contacts at these plants are: -
A) DuPont Chemical Co.- old Hickory, TN i Bob Berthold or Terry Barnes (Envir.)
(615)S47-6394 '
B) DuPont chemical Co. - Memphis, TN Larry Hordon or Steve Hodorowsky (Envir.)
(901)353-7100 If you need any further inforsation, please contact me.
Sincerely, .,
i,' ,~
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( Sandra M.tRoeplid-Call, Ph.D.
Utility Chemicals Group SMKG/ tim Enclosures t
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Reference List of Nuclear Plants 1
Using the Nalco Acti-Brom Program l l
Arizona Nuolear Power Project-Palo Verde Generating Station Philadelphia Electrio Company-Limerick Generating Station Commonwealth Edison Company-Byron Generating Station Commonwealth Edison Company-Dre= den Generating Station Houston Light and Power Compnay-South Texas Project Northern States Power Company-Monticello Generating Station Note: There are currently over 50 applications of Aoti-Brom 1338 at both fossil and nuclear generating stations in the United States.
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Utility Product Chemloals Bulletin ACTI-BROM" CHLORINE '
k N ALC O ENHANCER BIODISPERSANT Product Benefits e Helps maximize turbine e Can reduce chlorine residualin condenser #ficiency the discharge e Helps extend condenser tube lits e Minimizes chbrine usage e Can reduce maintenance costs Principal Uses ACTb8 ROM 1338 is used to tions where biological control can-enhance chlorine activity in utility not be obtained within the legal cooling water systems. This product chlorination time limits or where can be particularly usefulin situa- chlorine residuals are a problern Colorless 1. quid General Description ACThBROM 1338 is an aqueous Form solution containing a bromide salt
- Density 12.211Vgal and biodispersant designed to improve chlorine activity. Since pH (ideat) 8.0 (max.)
ACThBROM 1338 is not a blocide, Freese Point 16'F it is easy to handle and feed. g,,,g g 3.F) 5 cp ACTkBROM 1338 can be used Flash Point (PNCC) None with either gaseous chlorine or **
sodium hypochlorite.
Application ACTFBROM 1338 should be fed representative will recommend the directly from the drum or bulk optimum dosage necessary to storage tank to a location in the ensure maximum program chlorination system where it will be performance for your system.
uniformly mixed and thoroughly dis- Cl BRM 6 B mee tributed. The specific dosage of to materials normally used in feed-ACTb8 ROM 1338 will vary depend- g g ing upon the operaten;a character- and material compatibility instruo-istics of your system. the wate' tions. consult your Nalco represery chemistry, and the severity of prob- tahva lems encountered. Your Nalco Handling and Storage ACTFBROM 1338 should be eyes, also get medical attention. Do handled with caution. Do not get in not take internally. Keep out of eyes. Avoid contact with skin and reach of Childrett clothing. In case of contact, irty Recommended irkplant storage rnediately flush with large amounts is t-of water for at least 15 minutes, for (Continued on Reverse Sde)
NALCO CHEMICAL utiLiry cHeMicALa C O M IB A N Y ONE NA4.CO CENTE A e NAME AV4L L ALINOS 905e8 9 094 h=".1%'t"L"t '#'W"N"Waft ltiit'EP.02
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- returnable, lined steel drums weigh- housing facility, ;
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i ing approxirrately 670 pounds not or retumable stainless steel PORTA-FEED
- units with a maxi-mum capacity of 385 gations.
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Chlorine Minsmization with a Chlorine-Bromine-Biodispersant Mixture N
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1 Presented at the Amencan Poner Conference. 46m Annual Meeong.
Apnl 23-25.1984. Chicago, Ilknois CHLORINE MINIMlZATION WITH A CHLORINE BROMINE-BIODISPERSANT MIXTURE F. W. KRAEMER and A F. GEPHART Toledo Edison Company, To'edo, OH S. K0EPLIN GALL Natco Chemical Company ABSTRACT heat transfer losses due to this insulating layer, cor.
r si n and pitting can occur ander these deposita, Biofculing is a problem in every utility. ToTelo Edison-Bayshore Station has investigated several rnethods of caus slong unn damage to tb sysun biofouling control. The most effective method was an Biofouling is generally controlled by chlorination with netivated bromide chlorine mixture, either gaseous chlorine or liquid sodium hypochlorite.
Based upon Federal Power Commission data, about j The activated bromide chle ine mixture demonstrates 6M of the 842 steam electne plants in their data base enhar.:ed performanee over chlorination alone. The use chlorination for microbiological control Chlorination activated bromde mixture is more effective at alkahne practices have come under close scrut" 'rsm the pH values than chlorine. It provides similar system Environmental Protection Ageraies due L
- torie by- 1 performance at lower dosages and shorter treatment products which are believed to form. Electne utilities time periods than chlorine alone. Field studies have spddly have been singled out for elose regulation of shown an 54 estinated yearly decrease m total their chlorine discharges. This has forced the electric 1 oxidant uttlizing an activated bromide mieture instead of chlorine alone. In addition, the activated bromide utility industry to look at chlorine minimization and i mixture never exceeded a concentration of 0.2 mg/l i mhh2 h&hW !
'ldC; whereas, chlorine alone did. Cormaion rates for I mits while maintaining adequats plant perforraance.
the activated bromide mixture were similar to chlorine The Toledo Edison Hayshore Station began a chlorine alone, but overall corrosion should he less due to the minim!4ation prugram in February of 1976. The Bay-shorter treatment time. ahore Station has 4 fossil fueled units. The intake bays This paper will discuss the laboratory and field studies are locateo directly act is fr m the City nf Toledo perfc:Tned at Toledo Edison.Bayshore Station to Sewage Treetment Plant. Each umt has a once through determine the effectiveness of an activated bmmide e nden.er which takes water from the Maumee River.
mixture. Studies involving biological control, total Hist rically, slime and algae growth nas been a problem m these condensers. Chlorine was necessary to control residual oxidant dwterminations and corrosion rates will be addressed. the microbiological gro .th. Analytical data gathered since 1980 have shown typical maximum TRC's of 1 INTRODUCTION to 3 mg/L Fouling caused by microorganisms is a problem in A chlorine minimization study resulted in a 27% redue-electrie utility systems. Extra fuel costs to the electric tion in the pounds of chlorine used per year. Honer, utility industry due to binfouling have been estimsted at this reduction did not reduce the Total Residual Chlor-
$<00 million a year. With the costs of plant operation ine (TRC) value to the 0.2 mg/1, which is specified in rising at a dramatic rate, any propm that improves USEP A Guidelines. Dechlorination by either ,odiuin effidency nead. to be implemented. sulfite or sulfur dioxide was considered. However, both The ondeser is me largest amgle area that can affect metho is were determined to be too expensive.
p; ara efficiency. The ;emperatures inalde a typice! Altertitives to chlormation which could reduce the condenser provide an ideal environme nt for the growth TRC value to 0.2 mg/l were investigatec;. Chlorine oimicroorganisms. Eve n a few Ihounandths cf an inch of dioxid i was tried durmg 1981 This program proved to slime deposit on a condenser tube - an almost invisiMe he eff. ctive but only at a cost equal to four times the layer - has been shown to affect condenser efficiency, currer.t chlorine cost s. In addition, high capital expendi.
plant heat rate and maintenance costa. The alime layer ts es v ould be needed for a permanent feed installation, forms a sticky surface which allows sitt and other and th safety of personnel and plant equip ne-t would particles to adhere to the tube surface. In addition to be jeo >ardized. Chlorine dioxide could pn.aably meet
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the TRC limits, but at an unjustifiably high cost. -
Conuquently, other alternatives were sought.
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A chlorine alternative, which und a chlorine, bromine
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and biodispersant mixture, was evaluated during 1962, his pmgram is referred to as an activated bromide
\i program since a bromide alt and biodispersant mixtun ] \ ]
are used in coniunction with chiorine to produce the ] so - n - ao y'
oxidsnt species. The biodispersant assists in penetra- I \ ]
tion of the biofilm. $ j his paper will discuss laboratory and field trial 14:ults 'o " " "
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obtained with the chlorine bromine biodispersant or i setivated bromide misture.
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EXPERIMENTAL -
\ l Chlorine is und to activate the bromide and bio- \
dispersant mixture according to the following reaction , i i i i A ,,,
HOCl + Br ~ HOBr + Cl-The chlorine residual to bromide ratio can be varied to
- obtain a system which contains anywhere from a total Figure 1 - Distribution broh som at sam,o/ aqueene uspHs chlorine h ad bromine neidual to a total chlorine ruidual. This is i panicularly important in systems with high ammonia ,,,
levela since bromamines degrade more rapidly, and ,
consequently, are not as persistent in the environment, This nduces the TRC and side m compliance. Per. 'O j j i ;
formance it also enhanced since bromamines are known , i to be men biologically active than erdoramines, Chlorine and bromine neiduals can exiat as either j -( ,
jc' - {i g
un ionized or ionized species in water. The conversion __.%,,..
from one species to another is pH dependent. This can i
be uen in rigure 1. on, . i ~ ~"" C' ,, * ',* ';i',';'i.****
At pH 7.5,50% of the available chlorine la HOCl and
- C*'"*'"'*****
50% is OCl Asthe pHisineressed moniunited OCl-k c ooi is present relative to HOCL OCl- is known to be only * ' ' ' ' ' ' ' ' ' 'O l
1/50 to 1/100 as effective a biocide as HOCL It is l important to use the most effective biocide possible, Flore 2 -- Percent s urrirai re dosage for chlorine j particularly in once through systems where centact ""# ' A #"# #'"# "U""d D'"#'
- M mmutes contact tm.e.
Figure 1 a'so shows the pH dependence of hypobmmous ico m .
acid. At pH ".5, o\er 901 of the exiuant is present as i HOBr. At pH8.7,over50% of themateriali presentas se \.
the un.lonited acid. There is abc evidence that obr- la \
a rnore effective biocide than OCl , which further
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snhrnees the effective pH range of bromine residuals.
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Performance dets generated in a laboratory compared the biocidal activity of chlorine alone and the activated
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bromide chlorine mixture. The<a data are showm in coot, , , j Figure 52 and 3. At a typical contact time of 15 minutes, e .. .
It takes 2.5 ppm of chlorine to achieve 0.001% survival.
Finn 3 -- Penent s urths t re doease jbr chlorine Under the ame conditions,it takes only 1.25 ppm of the and cAforsa, plus acrk ased 6romide aser s minutes activated bromide chlorine misture. contact time.
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0 i i i i i i i o g g g i g g 0 10 20 30 40 so so 70 0 7 4 s a to 12 on.caat octape (com) oncant Dosage (com)
Figure 4 - Laborosocy deka bm May 10. J983 Figure 5 - Imboratory data hem June 7,1883 This effect is more pronounced when the contact time is total oxidant usage based on concentration. In addition.
reduced to only 2 minutes. In this situation. a chlorine it was necessa27 to chlorinate Bay Shore Unit No. 2 for a dosage of 2.5 ppm allowed 75"A sunival Under the period of 60 minutes per day, or 3 times longer than same conditions with 2.5 ppm of the activated bromide- Unit No.1.
chlorine mixture essentially sterile conditions were Based on th'ese figures, a total of 584 lb of chlorine was achieved in only 2 mi: utes.
used on Bay Shore Unit No. 2 while 23.9 lb of total As can be seen from these data. the activated bmmide- oxidant was used on Bay Shore Unit No.1. This chloriae mixture provir 8tn faster kills at lower dosagen. representa a reduction of 95.9'T in the pounds of For thin reunon, a field trial of this program at the oxidant used per day.
Toledo EdiscreBayshore Station was undertakea In addnion to the cost savings realized by Toledo Edison. an estimated annual 409.5 ton reduction in PRELIMINARY FIELD TRIAL total oxidant munt also be considered as a benefit to the The initial r'ecommended treatment rate for this prelim- enviromnent.
inary program was to reduce the current chlorination dosage m half and feed for only half the time. In LABORATORY STUDIES 1
addition 0.85 pounds of the activated bromide mixture Laborsiiry studies during hiny and June of 1983, l was to be added per pound of chlorine used. This verified the effectiveness rif the activated bromide- '
resulted in an initial decrease m total vaidant of 46'4. chlorine mixture with hiaumee River water. These
- *" dI" The field trial at Toledo Edison. Bav Shore Unit No.1 dosa ge.!n nitored began in June 1982. cad was compic ted in .luly.1982. The e(feet of twototal plate different counta chlorine versus total to bromide Visual inspections verified that condenser cleanliness reti a ma aim investigated. These data et.n be seen in was maintained throughc.ut the period. The total dosage gwes I ac 5.
concentration of t'w setivated bromide chlonne mid In hiny of 1983 ! Figure 4), chlorine alone required 2.a ture over the entire period averaged 2.24 mg/l. During pp n to t ill 80'4 of the haeteria present in the make up ;
this sar.ie period, e sister unit. Ray Shore No. 2. was water. Only 0.5 ppm of a mixture it, a 2:1 ratio of ,
treatc d using chloru.e alone at an average concentration bmmide to. chlorine was required for comparable kilt A I cf 9.11 mg/1. This represents a reduction of 75.4'4 in mixture m a 1:1 bromide.to. chlorine ratio required o.7 l l
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- chlortee ve ehtonne ppm to accomplish the task. In this situation,3 4 times if the dosage is increased to 1000 times the normal more chlorine alone was regired than either of the two value. there will still be no substantial corrosion as long activated bromide. chlorine mixtures. as the treatment time is orie hour or less. 24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> treatment at 1000 times the normal dosage will incur This experiment was repeated again in June of 1983.
tremendous corrosiort These dosages would only be These data can be seen in Figure 5. In this situation, chlorine alone required about 7 times the dosage that sun h e neentrated chlorine ime. The system w uld n rmally dilute the chlorine wellbelowthislevel.
either of the chlorine activated bromide mixtures did.
These expenments clearly demonstrate the added efficacy which an activated bromide chlorine mixtun .
provides.
FIEI.D TRIAL The final test for the activated bromide chlorine mixture CORROSION STUDY waa n long term field trial on Unit No.1 at the Toledo n Ba# n Madon Mg Ws mal snnal Laboratory studies were also performed to determine pararnetern were m nit red. The condenser was phys-the corrosiveness of the activated bromide chlorine leall.Y inspected whenever possible. Back pressure and mixture versus chlorine alone. Mild steel, admiralty, wa ns a em va s wue m n u d. M and 304 stainless steel coupons were exposed to a ma . ma Nate e untn ere performed to determine chlorine and activated bromide. chlorine residual of 2 * ' N" ' N d'd tant n the microbiological times and 1000 times the normal expected value. The p Pulatiort I nue to the s n.i of contammation on the No.
results of these experiments are shown in Table 1. 2 side of Un t No. I condenser during chlorination of The dsta were taken for 24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> period. The corrosion Unit No. 2, only the Nr. I side of the No. I Unit rates are reported based ori 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> of continuous condenser w is used for tlas evaluation treatment. These data were then recalculated to allow Bayshore Sta tion No.1 Cc,ndenseris dual. pass and has for a typical treatment time of only 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> per day. thpdil ' of reversing flow. Side l was treated with These data are listed under the expected corrosion '
the setivated bromide chlanne mixture for 10 minutes
I'
per day. Bayshore Station Unit No. 2, a sister unit, was l If the treatment dosage remains below 2 times the tasted with geneous chlonne for s period of 60 minut es normal value for only 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> per day, there should be no per day. This trial will continue through May 1984. The substantial corrosion of any of these metallurgies. renulting dat.i. through December 1983, can be son m However,24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> continuous treatment at 2 times the Table II and Figures 6 and 7. Figure 6 shows a com- ,
normal dosage willincrease the corrosion to a marginally parison of th . de sage of an activated bromide chlorine l acceptable level. mixture vs. hlorine alone. Figure 7 shows that the l
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Table I ~ Corrosion results (s 70*F Table il - Results of aethsted bmide chlorine mi.rturs va ehtorine alone Aou' use 304 sai (movi (may) (mey) unit 1 side 1 unit No.
Aetivated BeemiaWChiertne Mlature 1000 times normalcosage See fee la Cl Total Total outdant ontdent 1 times ormaldoodge (expected) 01 11 00 6-7 27 0 00 78 040 2 times normat aosage 6-13 27 010 78 052 (24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />si 02 47 01 4 27 0 15 78 080 2 times normal cosage 5 27 0m 78 0 50 (especteni 00 01 00 G-16 27 0 05 78 0 36 Chlorine Alone o-17 27 0 05 78 040 6-20 20 005 78 035 1000 tsmes normaicosage e.?t 20 0 00 . 78 035 (24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />) 04 140.3 -- 03 6-22 10 78 1000 times normaicosage OL4 l 0 60 6-23 20 0 0'- 78 040 (expeclec) 00 58 00 2 times normal cosage +27 20 010 7.8 055 i24 hours) 02 51 00 GP8 27 005 -8 8 2 times normal cosage 6-30 27 0 00 78 063 tence:tec) 00 02 00 7-5 27 0 00 7.8 0 00 1-11 38 0 00 8 8
,[,, 7 20 55 0 00 91 032 estswess steri *3 I 0 00 'U# OIS E 10 20 0.00 91 0 60 F 17 20 000 91 0 50 F 23 31 0 00 9.1 025 t 31 20 0 00 8 s ac'ivated bromide chionne mixture never exceeded the 97 20 000 78 0.55 USEPA Guidelines of 0.2 mg/l TRC,in fact. it seldom 9 20 0 00 78 025 was above o.1 ppm TRC; wherean, chlorine was fre-quently above this value.
l, N y ] 04 1 *19 24 0 00 72 135 From June through December.190. the No. 2 Unit hed 1 '26 24 0 00 72 110 !
72 0 00 t an average chlorine dosage of 7.M mvl, whereas the No. I Unit had an average dosage of 2.38 mvl total M N fo'.3 .
i .is ?$ 0 00 oxidant (activated bromide chlorine). The activsted I
~
bromide chlorine mixture was fed for 10 minutes per day. The chlonne alone was fed to No. 2 Unit for 60
. .N i -i a N
37 0 00 N
65
['l 7
1 52
, minutes per day. This represents a yearly savings of i '21 37 0 01 65 c 33 l 170,000 pounds of oxidant per unit. In addition to a _i-' 28 37 007 65 037 significant savings of chemicals, it also allows the w isv<ec ar tne errivert s"ee, ouwr
' #' i station to change from gaseous chlorine to activated "#"*"** '
bromide and chlorine solutions at a cost savings.
l th.in chlorine alone. In addition, personnel safe ty would
, be jeopardized.
CONCLUSIONS An activated bromide chlorine mixture was found to be Chlonne minimiration alone will not provide adequate an effective biofouling control agent, Laboratory studiea biofouling control of the condenners at the Tnledo de'nonstrate the effectiveness of this program at alkaline Edison Bayshore Station. Field and laboratory studies pil saluen. Laboratory and field studies show the show that there would be frequent exceedances of the eft.etiveness of this program at lower dosages than 0.2 mg/l TRC USEPA Guidelinen. While a dechlorin. chlorine alone. In the eight month field trial, a system ation system woula prevent this, it would be expensin treated with an activated bromide biodispersant-from both a chemical and equipment standpoint. ebiorine mixture required 92"c less oxidant than a sitnilar s> stem treated with chlorine alone. In addition, Chlorine dioxide can provide adequate microbiological thi unit treated with the activated bromide mixture control However. this program would cost 4 times more nes er exc eeded the 0.2 mg/l TRC USEPA Guideline.
This reduction in total oxidant represents a 27.6% co.: much shorter time period. The overall corrosion should savings over chlorine gas alone. It la also a significant be less for this reason.
environmental adventage since approximately 170,000 lb less oxidant per unit would be used by the Bayshore Overall, an activated bromide chlorine mixture is the Station annually.
most roat effective method fer the Toledo Edison-Corrosion rates for chlorine and activated bromidc. Bayshore Station to meet the USEPA Guidelines of 0.2 chlorine mixtures are essentially the sene. However. .ng/ITRC and maintain a system free of microbiological the activated bromide mixture will be operated for a growth l
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ONa NAACO CaNTam o NAPERVA a. ALewora SOSee-iOP4 '
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ENCLOSURE 2 Product Information for Bett Laboratories' 511alcide C-78P r i
(This information was provided by Betz Laboratories for TVA's use in obtaining regulatory spproval for the use of the specific product.)
3 EPA Registration Numbor: 5785-65-3876 r
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l V V V VVV BETZ8 SLIMICIDE C 78P i MICROBIOCIDE l
e Long lasting proteatlerwec.ittelled l>locide re- washer by means of a plastic or stainless steel feed lease dev6ce, such as a mesh beg or perforated container that provx$es gradual solution. For larger applica-e Fast dissolving granular form tions, a by-pass feeder is recommended to echieve consistent product residuals throughout the system.
o Generates effective concentrations rapidly Betz Mfws a fun range d how systems fw @
e Effecitve on bacterial, fungal, and algal foullng ing S!hnicide C 78P.
Proper treatment levels for BETZ Siamicide C-78P DESCRIPTION AND USE depend on many sectors such as the nature and de-BETZ Slimicide C-78P is an of'ective, broad spec- gree of severity of the microbial problem, system retention time, temperature, and other operrt trum microblocide in a granular form. The product condrtbos. Typicany. enough BETZ SHmdde C 7 contains active bromine and chlorine h a stabilized is added to the ter" to maintain a 13 mg/t. total form; they are released into the water in a controlled halogen residual thw water for at least 4 hr daDy.
fashion as the granules dissolve, For oest results, your Betz lndustrini representative Bromme and chlonne work together to provide effec- should oJtermine the proper dosage for the specific tive control for a broad spectrum of shme-forming system and the problem to be treated, organisms. By controning alime accumulations, f%micide C 78P aucws cooling towers and host ex. In au cases, the product must be applied in accor-cuangers to operate at peak efficiency and r9 duces dance wrth the use estructions on the BETZ the tendency for underdepoort corrosco. Silmacide C 7&P container label.
S!!micide C 78P is particularly well suited for spotica-tions that require shock dosing. For example, the GENERAL PROPERTIES rapid dissolution rates typical of thts product make possible effectrve biofou!mg control of utikty surf ace Bromo-chloro hydantom . . . . . . . . . . . . . . . 93.5%
condensors without exceeding total residual oxicant inert ingfecients ......................6.5%
discharge limits. Appearance . . . . . . . . . . . . . . . . . . . white granules BETZ Shmicide C 78P may be used afternately wth Bulk Density . . . . . . . . . 64.5 ib/f t* (1033 kg.ma)
EPA Reg. No. ...... .......... 5785-05-3876 other BETZ Samiodes ef activeness by reducegto improve overall profram ine oeveiopment o erecrgani,m s,ra,ns tnat are resis, ant ,o a ungre gg*ge->ca)g -
biocidal agent.
SAFETY PRECAUTIONS Stimicide C 78P is registered with the Ermronmental Protection Agency foi the control of bactonal, fun ~ A Matertal Safety Data Sheet containing detailed in-gal, and algal slimes in industrial cooling towers- f formaton relatrve to thas product is available upon ,
once through coo..ng systems, brewery pastoun' request. ;
rers, air washers, influent water systems, such as 1 flow through filters and lagoons, and industrial water scruobing systems. PACXAGING INFORMATION j TREATMENT AND FEEDINf3 REQUIREMENTS BET 2 Shm cide C 78P comes in granular form. It is supphed in 6.5-gal (25 L). polyethylene containers. -
In small systems. BET 2 Slimicide C 78P can be fed Approximate not weight por container is 50 lb (23 directly to the cooling water. pasteurtzer, or air kg).
PFC 485 4712 e tggy BETZ LABORATORIES, INC. ALL NGHTS RESERVb I
i PETE LABORATORIES, INC.
4636 SOMERTON ROAD, TRIVOSE, PA 19047 PRODUCT: SLIMICIDE C-78P 1/12/88 AQUATIC T0XICOIDGY
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RAINBOW TROUT 96 HR. LC50 0.87 NG/L DAPHNIA MAGNA 48 HR. LC50 0.47 NG/L FATHEAD MINNOW 96 HR. LC50 0.25 MG/L DEHAIDGENATED SLIMICIDE C-78P RAINBOW TROUT 96 HR. LC50 6100 MG/L l DAPHNIA MAGNA 48 HR. LC50 1300 MG/L FATHEAD MINNOW 96 HR. LC50 8100 MG/L 1
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BETE MATERIAL SAFETY DATA SEEET 24 NOUR EMERGENCY TELEPEONE (NEALTR OR ACCIDENT) 215/355-3300 l (PAGE 1 OF ?)
PRODUCT SLIMICIDE C-78P EFFECTIV" DATE 07-14-87 REV.t SEC.9 PR$ DUCT APPLICATION : SOLID MICEOBIAL CONTROL AGENT, , l
GECTION 1-----------HAZARDOUS INGREDIENTS--------------- '
INFORMATION ON PHYSICAL HAZARDS, MEALTH HAZARDS, PEL'S AND TLV'S FOR SPECIFIC {'
PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIONS STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF THE POTF.WTIAL ACUTE AND CHRONIC HAZARDS OF THIS FORMUIATION. ;
1-BROMO-3 -CHI 4RO-5,5-DIMITHYLHYDANTOIN * *
S E CTION 2 ----- ------TY PI CAL PHYS ICAL DATA-------- 7---------------
PHI 5% DISP. (AFPROX.) 4.7 ODOR: HAIDGEN FL.PT.(DEG.F) >200 SETA(CC) SP.GR.(70F)OR DENSITY: 6 5 LSS . C'J . FT .
VAPOR PRESSURE (mmHG): NA VAPOR DENSITY (AIR =1): NA VISC cps 70Ft NA 4SQLUBILITY(WATER) 1 EVAP. RATE: NA WATER =1 APPEARANCE: WHITE PHYSICAL STATE: GRANULES FREEZE POINT (DEG.F): NA
SECTION 3-----------REACTIVITY DATA------------------------------ i I
OXIDIZING AGENT.D0 NOT STORE OR MIX WITH REDUCING AGENTS T1. dRL DECOMPOSIT70N (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES.
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RETS MATERIAL SAFETY DATA SEEET (PAGE 3 0F 3) )
'PRODJCT: SLIMICIDE 0-787
.....SECTIQN 4 -----------REAI/rg m m EFFECTS ----~~----------------
ACUTE SKIN EFFECTS *** FRIMARY FM7TE OF. EXPOSURE ,_ l "0DERATELY IRRITATING TO TBE SEIN.MAY BE CORROSIVE IN CONTACT WITE NOIST l KIN.
ACUTE EYE BFFECTS ***
SEV7RE IRRITANT TO THE EYES ACUTE RESPIRATORY EFFECTS ***
DUSTS CAUSE IRRITATION TO UPPER RESPIRATORY TRACT CHRONIC EFFICTS OF (IIREXPOSURE***
NO EVIDENCE OF POTENTIAL CERONIC EFFECTS.
MEDICAL CONDITIONS AGGRAVATED ***
NOT RNOWN l
SYMPTONS OF EXPOSURE *** -
.MAY CAUSE R2DNESS OR ITCHING OF SKIN.
i' PRECAUTIONARY STATEMENT BASED ON TESTING RESULTS ***
MAY B3 T0XIC IF ORALLY INGESTED.
SECTION 5------------FIRST AID INSTRUCTIONS----------------------
SKIN CONTACT ***
REMOVE CIDTHING. WASH AREA WITH LARGE AMOUNTS OF SOAP SOLUTION OR WATER l FOR 15 MIN.IMMEDIATELY CONTACT PHYSICIAN l EYE CONTACT *** l IMMEDIATELY FLUSH EYES WITH WATER FOR 15 MINUTES.IMMEDIATELY CONTACT A l PHYSICIAN FOR ADDITIONAL TREATMENT INHALATION EXPOSURE ***
EMOVE VICTIM FROM CONTAMINATED AREA. APPLY NECESSARY FIRST AID
.REATMENT.IMMEDIATELY CONTACT A PHYSICIAN. l INGESTION *** l DO NOT FIED ANYTHING BY MOUTH To AN UNCONSCIOUS OR CONVUIJIVE VICTIM ;
DILUTE CONTENTS OF STOMACH. INDUCE V0MITING BY ONE OF THE STANDARD l NETHODS.IMMEDIATELY CONTACT A PHYSICIAN l
.....gECTION 6-----------SPILL, DISPOSAL AND FIRE INSTRUCTIONS--------- l SPILL INSTRUCTIONS ***
VENTILATE AREA,USE SPECIFIED PROTECTIVE EQUIPMENT. SPILLED MATERIAL WHICH CAN NOT BE RECOVERED FOR RE-USE,SHOUID BE PLACED IN A WASTE DISPOSAL CONTAINER AND DISPOSED OF IN AN APPROVED PESTICIDE LANDFILL.SEE PRLDUCT LABEL STORAGE AN) DISPOSAL INSTRUCTIONS.
PRODUCT RELEASES CHIDRINE WHEN WET. SPILL RESIDUE MAY BE NTUTRALIZED WITH 3% HYDROGEN PEROXIDE SOLUTION.
DISPOSAL INSTRUCTIONS ***
WATER CONTAMINATED WITH THIS PRODUCT MAY BE SENT TO A SANITARY SEWER TREATMENT FACILITY,IN ACCORDANCE WITH ANY LOCAL AGREEMENT,A PERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES IIRMIT l PRODUCI(AS IS)-
LJRY IN AN APPROVED PESTICIDE FACILITY OR DISPOSE OF IN ACCORDAACE WITH LABEL INSTRUCTIONS 1' FIRE EXTINGUISHING INSIRUCTIONS***
FIREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SEIJ-CONTAINED BREATHING APPARATUS (FULL FACE-PIECE TYPE).
DRY CHEMICAL, CARBON DIOXIDE, FOAM OR WATER
IETS MATERIAL 8AFETY DATA SEEET (PAGE 3 OP 3) ]
- ~
ppm 10CT: SLIMICIDE C-78P l
.... 8ECTION,7-----------8PECIAL PROTECTIVE EQUIPNINT-----------------
VENTIIATION PROTICTION***
ADEQUATE VENTIIATION To MAINTAIN DUST CONCENTRATIONS BEI4W THE EXPOSURE LIMITS OF 10NG/M3 (TLV) AND 15NG/M3(PEL) FOR NUISANCE OR INERT DUSTC l RECOMMENDED RESPIRATORY PROTECTION *** j IF VENTIIATION IS INADEQUATE OR SIGNIFICANT PRODUCT EXPOSURE IS LIKELY, USE RESPIRATOR WITE ORGANIC VAPOR, ACID GAD 8E8 AND DUST / MIST CARTRIDGES.
RECOMMENDED SKIN PROTECTION ***
GAUNTLET-TYPE NE0 PRINE GI4VES, CHEMICAL RESISTANT ~ APRON WASH OFF AFTER EACM USE.REPIACE A8 NECESSARY RECOMMENDED EYE PROTECTION ***
AIRTIGHT CHEMICAL GOGGLES i
SECTION 8-----------STORAGE AND HANDLING PRECAUTIONS------------- i STORAGE INGTRUCTIONS*** i KEEP DRUMS & PAILS CIASED WHEN NOT IN USE. l DO NOT EXPOSE TO NOISTURE HANDLING INSTRUCTIONS ***
CENERAL-IMMEDIATELY REMOVE CONTAMINATED CI4 THING, WASH BEFORE REUSE S?ECIFIC- OXIDIZER. EMITS TOXIC FUMES WHEN WET.
-SECTION 9-----------FEDERAL REGtfLATIONS--------------------------
FIFRA(40CFR):BPA REG.NO. 5785-65-3876 OSHA (29CFR)-USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITH 29CFR SECTIONS i 1910.132-1910.134. USE RESPIRATORS WITHIN USE LIMITATIONS OR ELSE USE i SUPPLIED AIR RESPIRATORS.
~
j REPORTABLE QU'NTITY: AS IS PRODUCT (HAZARDOUS SUBSTANCE)
NOT APPLICABLE RCRA (40CFR): IF DISCARDED,THIS MATERIAL BEARS HWIf NOT APPLICABLE DOT (49CFR) CI. ASSIFICATION: OXIDIZER NFPA/HMIS : HEALTH - 3 ; FIRE - 1 ; REACTIVITY - 0 ; SPECIAL - OXY : PE - C oco*ee********eee**eeeee***********ee******eeeeeeeeeeeeeeeeeee********.**
l THIS DOCUMENT IC PROVIDED TO SUPPLY ALL THE INFORMATION NECESSARY TO COMPLY WITH OSHA HAZARD COMMUNICATIONS REGUIATIONS, AND RIGHT-TO-KNOW REQUIREMENTS.
WHILE TKE INFORMATION AND RECOMMENDATIONS SET FORTH HEREIN ARE BELIEVED TO BE ACCURATE AS OF *HZ DATE HEREOF, BETZ LABORATORIES MAKES NO WARRANTY WITH RESPECT THERETO AND DISCLAIMS ALL LIABILITY FROM RELIANCE THEREON.
l HAROLD M. HERSH ENVIRONMENTAL INFORMATION COORDINATOR l
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MCIlvt0 January 18, 1980 CHEem 31WeCH 3M) 2.o ' 99 TVA --- '
Lookout Place 5 "
South 61 E-C umu v
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1101 Market Street -
Chattanooga, TN 37402-2801 Attention: Mr. William Nestel j
Dear Mr. Nestel:
Enclosed is a package of information which addresse""' h -J questions you raised during our 1-14-88 meeting.
BIOCIDE REFERENCES We offer two industrial plants as references within the state of Tennessee. I should note that both plants are using C-77P, rather than C-78P. Both p:oducts contain 934 1-Bromo Chloro-5, 5-dimethylhydantion. The C-77P product is compressed into tablet form for slow dissolving while the C-78P is granular and recently made available for a higher maximum dissolution rate (i.e. shock dosing). ,
E. 7. DuPont de Nemours Mempnis, TN l Inland Container l
New Johnsonville, TN l
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MCLOSURE 3 j Product Infor ton for Betz Laboratories' j Slinictde C-82 s
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4636 SOMERTON ROAD, TREVOSE, PA.19047 PRODUCT: SLIMICIDE C-82 1/15/88 _ AQUATIC T0XICOLOGY FATHEAD MINNOW 96 HR. LC50 16,479 MG/L NaBr DAPHNIA MAGNA 48 MR. LC50 11,000 MG/L Br-POECILIA RETICULATA 96 HR. LC50 16,000 NG/L Br-ORYZIAS LATIPES 96 HR. LC501 24,000 MG/L Br-Data supplied by manufacturer t I . t i l l l e 1 t I i l 1 i . i f I .i
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- i Product Information for Bets Laboratories' l Powerline 3690 , ,
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! (This information was provided by Bets Laboratories j for TVA's use in obtaining regulatory approval i for the use of the spetilic product.)
1 - 4 1 EPA Registration Number Not Applicable ; I t 1 I i a ! i l b f i l f 3 e i i i a f l l i i I
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[ Trevees PA 19047 47a3 00Ddam80c080 M ine wow uen gement o,v on et seu uwnones. m. January 21, 1988 Mr. Wil; lam A. Nestel Program Manager, Chemistry TENNESSEE VALLEY AUTHORITY Lookout Place 5 South 61 E-C 1101 Market Street - Chattanooga, TN 37402-2801
Dear Mr. Nestel:
Attached for your referenet is a new Aquatic Toxicology data sheet for our blodispersant, 86tg Powerline 3690. The data sheet has been revised to include the results of the aquatic toxicity evaluation on Daphnia mogna conducted this week in order to provide TVA with a more complete envircn-mental affairs package. In our initial aquatic toxicity evaluation on rainbow trout conducted several years ago, Powerline 3690 exhibited such a low order of toxicity that no further studies were conducted on other aquatic organisms. Betz Powerline 3690 was shown to produce 0% mortality on Daphnia magna at a dosage of 500 mg/L, the highest level tested.' Normal application rates are on the or er of 5 to 10 mg/L. d Thank you for the opportunity to be of service. Very truly yours,
'BETZ INDUSTRI AL h=y ~/ . [
Raymond iA. Post Project Engineer RMP/bw Enc.
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i l BETE IADORATORIES,INC. 4636 SOMERTON ROAD,TRIVOSE,PA.19047 PRODUCT: POWERLINE 3690 1/21/88 ! AQUATIC TOXIC 010GY : DAPMNIA MAGNA 04 NORTALITY 500 MG/L 48 NR. SCR. RAINDOW TROUT 0% NORTALITY: 1000 NG/L 48 ER. SCR.- 1/21/88 wawwarvan T0XIC01DGY ORAL LD50 -No DATA - DERNAL LD50 -No DATA SEIN IRRITATION SCORE-No DATA EYE IRRITATION 80083-30 DATA INMAIATION-No DATA l l OXYGEN DEMAND (ppa) i PRODUCT CONCENTRATION (ppe) BOD COD TOC 1000 <4 356 201 l 1 1 1 l 1 ? l l J t I 1 1 , i
- BETZ LABORATORIES,INC.
4636 SOMERTON ROAD, TREVOSE, PA. 19047 . . BETZ MATERIAL SAFETY DATA SHIET 24 HOUR ENERGENCY TELEPHONE (HEALTH OR ACCIDENT) 215/355-3300
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PRODUCT POWERLINE 3690 ('8 M N b # CTIVE D E 11-11-87 SEC.8-MINOR CHANGE. PRODUCT APPLICATION : WATER-BASED DEPOSIT CONTROL AGENT.
-----SECTION 1-----------HAZARDOUS INGREDIENTS-----c---------
INFORMATION ON PHYSICAL HAZARDS, HEALTH H)ZARDS, PEL'S AND TLV'S FOR SPECIFIC PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA MAEARD COMMUNICATIONS STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF THE POTENTIAL ACUTE AND CHRONIC HAZARDS OF THIS FORMUIATION. THIS PRODUCT CONTAINS NO HAZARDOUS INGREDIENTS BY 05iMA REGULATION 3 OR ANY STATE RIGHT-TO-KNOW REGUIATIONS.
-----SECTION 2-----------TYPICAL PHYSICAL DATA-------------------------
PH: AS IS (APPROX.) 12.5 ODOR: NONE FL. PT. (DEG. F) : >200 SETA(CC) SP.GR. (70F)OR DENSITY: 1.019 VAPOR PRESSURE (mmHG): ND VAPOR DENSITY (AIR =1): ND VISC cps 70F 11.7 % SOLUBILITY (WATER): 100 EVAP. RATE: ND WATER =1 APPEARANCE: COI4RLESS PHYSICAL STATE 2 LIQUID FREEZE POINT (DEG.F): 31
-----SECTION 3-----------REACTIVITY DATA------------------------------
STABLE THERNAL DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES.
' BETS MATERIAL SAFETY DATA SHEET (PAGE 2 0F 3) PRODUCT: POWERLINE 3690 - i -----SECTION 4-----------HEALTH HAIARD EFFECTS---------------------- .. l ACUTE SKIN EFFECTS *** PRIMARY ROUTE OF EXPOSURE ! 4 SLIGHTLY IRRITATING To TNE SKIN ACUTE EYE EFFECTS *** NODERATELY IRRITATING TO THE EYES , ACUTE RESPIRATORY EFFECTS *** ! MISTS / AEROSOLS MAY CAUSE IRRITATION TO UPPER RESPIRATORY TRACT < CHRONIC EFFECTS OF OVEREXPOSURE *** i l No EVIDENCE OF POTENTIAL CHRONIC EFFECTS. MEDICAL CONDITIONS AGGRAVATED *** j NOT ENOWN 1 l !, l ) { SYMPTOMS OF EXPOSURE *** MAY CAUSE REDNESS OR ITCHING OF-SKIN. ~ i i
- . i
-----SECTION 3------------FIRST AID INSTRUCTIONS---------------------
I i SKIN CONTACT ***
! REMOVE CONTAMINATED CICTHING. WASH EXPOSED ARIA WITH A LARGE QUANTITY OF i SOAP SC WTION OR WATER FOR 15 MINUTES i EYE CONTACT *** '
- IMMEDIATELY FWSM EYES WITH WATER FOR 15 MINUTES.IMMEDIATELY CONTACT A I PHYSICIAN FOR ADDITIONAL TREATMENT INNAIATION EXPOSURI*** 1 REMOVE VICTIM FROM CONTAMINATED AREA TO FRESH AIR. APPLY APPROPRIATE '
FIRST AID TRIA'IDEENT AS NECTSSARY
- INGESTION *** ;
DO NOT FEED ANYTHING BY NOUTH To AN UNCONSCICUS OR CONVUIJIVE VICTIM ' DILUTE CONTENTS OF STOMACM. INDUCE VOMITING BY ONE OF TNI STANDARD I
- NETRODS.IMMEDIATELY CONTACT A PMYSICIAN
-----SECTION 4-----------SPILL, DISPOSAL AND FIRE INSTRUCTIONS--------- ;
- SPILL INSTRUCTION 8*** l
' VENTI! ATE AREA,USE b1ECIFIED PROTICTIVE EQUIPMENT.CONTAIN A90 AhSCRB ON ABSORSENT MATERIAL. PLACE IN WASTE DISPOSAL CONTAINER. TWE WASTE i j CHARACTERISTICS OF THE ABSORBED MATERIAL,0R ANY CONTAMINATED SOIL, l I SHOULD BE DETERMINED IN ACCORDANCE WITH RCRA REGU!ATIONS. FIDSM ARIA WITN WATER. WET AREA MAY BE SLIPPERT.IF SO, SPREAD , ! SAND OR GRIT.
- DISPOSAL INSTRUCTIONS ***
WATER CONTANINATED WITH THIS PRODUCT MAY BE SENT To A SANITARY l ! SEWER TREATMENT FACILITY,IN ACCORDANCE WITH ANY IOCAL AGREEMENT,A , I
- 7ERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT PRODUCT (AS IS)- 1 INCINERATE OR BURY IN APPROVED IANDFILL
! FIRE EXTINGUISNING INSTRUCTIONS *** ! j FIRIFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING
- APPARATUS (FULL FACE-PIECE TYPE) .
! DRY CHEMICAL, CARBON DIOXIDE, FOAM OR WATER ] l i i l l 1, !
l RETS MATERIAL SAFETY DATA SHEET (PAGE 3 0F 3) PRODUCT: POWERLINE 3690
-----SECTION 7-----------SPECIAL PROTECTIVE EOUIPMENT------,----------
VENTILATION PROTECTION *** ADEQUATE VENTILATION i RECOMMENDED RESPIRATORY PROTECTION *** IF VENTILATION IS INADEQUATE OR SIGNIFICANT PRODUCT EXPOSURE IS LIKELY, USE A RESPIRATOR WITH DUST / MIST FILTERS. RECOMMENDED SKIN PROTECTION *** RUBBER GI4VES WASH OFF AFTER EACM USE. REPLACE AS NECESSARY l
~
RECOMMENDED EYE PROTECTIONe** , SPLASH PROOF CHEMICAL GOGGLES
....l.8ECTION 8-----------STORAGE AND HANDLING PRECAUTIONS-------------
STORAGE INSTRUCTIONS *** KEEP DRUMS & PAIIA CIASED WKEN NOT IN USE. REASONABLE AND SAFE CHEMICAL STORAGE MANDLING INSTRUCTIONS *** GENERAL-IMMEDIATILY REMOVE CONTAMINATED CI4 THING, WASH BEFORE REUSE SPECIFIC- ALKALINE.D0 NOT MIX WITM ACIDIC MATERIAL.
-----SECTION 9-----------FEDERAL REGULATIONS--------------------------
OSHA (29CFR)-USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITH 29C1'R SRCTIONS . 1910.132-1910.134. ; REPORTABLE QUANTITY: AS IS PRODUCT (MA2ARDOUS SUBSTANCE) NOT APPLICABLE RCRA (40CFR): IF DISCARDED,rMIS NATERIAL REARS HWIf D002 DOT (49CFR) CLA38IFICATIOW t NOT APPLICABLE - NFPA/MMIS : MEALE - 1 ; FIRE - 1 ; REACTIVITY - 0 ; SPECIAL - ALK ; PE - B oeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee**eee****eee*****eeeeeeesee THIS DOCUMENT IS PROVIDED TO SUPPLY ALL TFE INFORMATION NECESSARY TO COMPLY WITM OSHA HAZARD COMMUNICATIONS REGULATIONS, AND RIGHT-TO-FNOW REQUIREMENTF. , WHILE THE INFORMATION AND RECOMMENDATIONS SET FORTH *iERFIN ARE BELIEVED TO : BE ACCURATE AS OF THE DATE MEREOF, BETZ IABORATORIES MAKES No WARRANTY WITH , RESPECT THERETO AND DISCLAIMS ALL LIABILITY FROM RELIANCE THEREON. ' HAROLD M. HERSH ENVIRONMENTAL INFORMATION C00RDINATC i i 1 . l j i
INCLOSURE 5 ,
,~
Product Information for Calgon's H950 (This information was provided by Calgon for TVA's use in obtaining regulatory approval ' for the use of the specific product.) EPA Registration Number: 5785-66-10445
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t yt: catoou COOLINGWATE r~. . . . ... ;21... . . . . . . . . . . . TRE ATMENT H-950 DESCRIPTION H 950 Microbiocide is a bromine-donating compound in liquid fora designed to supplement conventional chlorination for control of biofouling on heat exchange surfaces in.once-through and recirculating cooling systems. When introduced into a chlorinated water stream, H 950 releases two powerful oxidizing hypohalous acids providing superior biocidal effectiveness at costs that approximate chlorination. H-950 also controls the growth of microorganisms in the bulk water and removes existing biofouling from system surfaces. Residual chlorine concentrations are greatly reduced'so that discharge restrictions can be easily met. ADVANTAGE 5 More Effective than Chlorine Alone H-950 releases balanced amounts of hypobromous (HOBr) and hypochlorous (HOCl) acids. Lower total halogen is required to maintain microbiological control than when chlorine is used alone. Hypobromous acid is a more effective biocide than hypochlorous acid, producing greater kills in a shorter period of time. The hypobromous acid formed is about four times more active than hypochlorous acid. Effective Over a Wide oH Ranae H 950 effectively controls microorganisms in cooling water systems.over a pH range of 6.0 9.0. The hypobromite ion (obr') is nearly as effective as undissociated hypobromous acid. The hypochlorite ion (OC1'), which is the predominant form at pH >8.0, is significantly less effective than the hypochlorous acid. Therefore, at high pH, H-950 is more effective in maintaining microbiological control at lower treatment levels than chlorine fed alone. Low Caoital and Ooeratina Ceili H 950 provides superter results at costs comparable to traditional chlorination, lhe injection of H-950 is simply integrated into the existing chlorine feed system. Your Calgon representative will recommend the proper size feed system to meet your specific needs.
lyw i
., Reduces Toxic Rv-Product Discharoa Chlorine reacts with naturally occurring organics in water to form toxic compounds such as trihalomethanes (T}Ws). By using H-950, chlorine feed is typically cut in half, significantly reducing THM formation and discharge.
Broad Seactrum Activity H-950 provides broad spectrum control of slime producing microorganisms such as bacteria, fungi, and algae in open recirculatingcoolingwatersgtems. Unaffected in the Presence of Ammonia H-950 remains active in the presence of ammonia. When amonia is present in cooling waters, both chlnrine and bromine will react with it to form haloamines. The chloramines formed are less effective biocides. Brosamines have relatively the same blocidal effectiveness as hypobromous acid.
- No Adverse Effect on System Wood or Meta 11urav H-950 releases balanced amounts of hypobromous and hypochlorous acids. Because lower total halogen is required for microbiological control, there is reduced potential for wood delignification or corrosion of system metallurgy.
EPA REGISTRATION' H 950 is registered by the United States Environme'ntal Protection Agency (EPA Registration No. 5785 66-10445) as a biocide for use in recirculating ar.d once through cooling water systems. DIRECTIONS FOR USE Badly' fouled systems MUST BE cleaned before treatment is begun. I Feed H 950 after the oxidant injection point into the water to be treated. Be .<ure rapid mixing of the treated water, H 950, and oxidant is achieved. Your Calgon representative will recommend appropriate feed equipment to assure complete mixing of the material. 1 Dosace Rates Add H 950 to the system at 0.25 to 1.0 NaBr/C12 mole ratio. For example:
- 1. 0.06 0.26 gallons H 950 per pound chlorine gas (99.9%).
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- 2. 0.08 0.34 gallons H 950 per gallon sodium hypochlorite (12.5% available chlorine).
Initial Desm When the system is noticeably fouled, add 0.001 to 0.020 ga'lons H-950 per 1000 gallons of water in the system and oxidize with either gaseous chlorine (.008 to .15 lbs. per 1000 gallons) or sodium hypochlorite solution (.006 to .12 gallons per 1000 gallons). Maintain a free halogen residual (0.1-0.3 ppe as C13) for a sintaus of one hour. Repeat as necessary until control is evident. . Subsecuent Dose: When microbial control is evident, add 0.0005 to 0.020 gallons of H 950 per-1000 gallons of water in the system and oxidize with either gaseous chlorine (.004 to .15 lbs. per 1000 gallons) or sodium hypochlorite solution (.003 to
.12 gallons per 1000 gallons).
Once-Throuah Coolina Water Initial Dose: When the system is noticeably fouled, add 0.003 to 0.04 gallons of H 950 per 1000 gallons of water in the system and oxidir.e with either gaseous chlorine (0.02 to .30 lbs. per 1000 grilons) or sodium hypochlorite solution (.02 to
.25 gallons per 1000 gallons). Maintain a free halogen residual (0.1-0.3 ppm C12 ) for a minimum of one hour. Repeat as necessary until control is evident. .
Subsequent Dose: When microbial control is evident, add 0.001 to 0.04 gallons H-950 per 1000 gallons of water in the system and oxidize with either gaseous chlorine (.008 to .30 lbs. per 1000 gallons) or sodium hypochlorite solution (.006 to 0.25 gallons per 1000 gallons). CONTROL TESTING The best indication of the successful application of H 950 is visual inspection of tower surfaces or monitoring changes in heat transfer on metal surfaces or process equipment. Usually, a free ~ oxidant residual is require 6 to achieve biological control. Use of on site bacteria counts or microscopic examination provide relative indicators of system cleanliness and biological control. If bacteria counts are used., note that counts may be high trediately after biocide addition. Counts will lower as control is achieved. TYPICAL PROPERTIES Active Ingredient..................... Sodium Bromide 46% Appearance................................... Clear Liquid pH................................................... 7.3 1 Specific Gravity 9 77 F............................. 1.42 Densi ty, pounds per ga11on. . . . . . . . . . . . . . . . . . . . . . . . . . 11.8 0 dor............................................ 0dorless Freeze Point, F....................................... 50 l l
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~
PACKAGING , H-950 is available in 55 gallon drums or delivered to on-site storage facil Service-Plus.gies via bulk or Calgon Bulk Liquid STORAGE AND HANDLING . The recommended minimum storage temwrature is 50 F. H-950 should be stored in heat traced tants or in an enclosed facility capable of maintaini_n,9 50 F. PRECAUTIONS Hazards to humans and domestic animals. Harmful if swallowed. Avoid breathing vapors. Irritation may develop from eye and skin exposure. Wear gloves and safety goggles. Avoid contact with skin and eyes. Wash contaminated clothing before reuse. Environmental hazards. Do not discharge into lakes, streams, ponds, or public water unless in accordance with an NPDES permit. For guidance, contact your regional office of EPA. Physical and chemical hazards. H 950 is not flaisnable. However, ir, fires fueled by other materials, hydrogen bromide or bromine may be released. Wear self contaminated breathing apparatus. Storage. Keep product in tightly closed original container when not in use. Store in a dry, well-ventilated trea. Product should be stored at 50 F or above. Disposal. Wastes resulting ' rom the use of this product may be disposed of on site or at an approved waste disposal facility. Triple rinse the container (or equivalent). Then offer for recycling or reconditioning, or puncture and dispose of in a sanitary landfill, or incinerate. Burn only 1 Fallowed by state and local authorities, if burned, stay out of smoke. Information concerning human and environmental exposure may be reviewed on the Material Safety Data Sheet and label for this product. For additional information regarding incidents involving human ! and environmental exposure, call (412) 777 8000 and ask for the i Health and Environmental Affairs Department. For more information, contact your local Calgon Representative or write: Water Management Division, Calgon Corporation, P.O. i Box 1346, Pittsburgh, PA 15230. l l
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_; .... ,. . . s;.._ , . . , .;. f p.. ..!' Fi . AQUATIC T0XICITY l liQLi Trout: LC50, 96 Hr. 0.08-0.1 ppm Minnows: LC50, 96 Hr. 0.09 ppm Bltegill: LC50, 96 Hr. 0.18-0.33 ppm Daphnia: LC50, 48 Hr. 0.02-0.2 ppm HOBr2 Trout: LC50, 96 Hr. 0.23 ppm l 1 Bluegill: LC50, 96 Hr. 0.52 ppm
,9 p Daphnia: LC50, 48 Hr. 0.71 ppm 1 !
As Cl 2 h4a 2 # As Br2 . P
- __. _ - _ _ _ ~ _ -
L4
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. r: s. .ueerg sosM 1m n k@19!N t > e1*WW dt Mi%At4 e PMODUCT NAus HWO .
emesesure eP asessis a p (N . ..s ...._...4. - .a AnoREss " P.O. Sea 1344. TC% 7;_ ,; - 15230 CHEMICAL N AMg P OM MULA ANDSYNONYMs MMen GrornW M - M
^
, '. i t . l if lN 11 HA/A PRINCIP AL H A.Z AR DOUS COMPON E NT 18) % ORAL W OtRMAL LDgo TLV (UMed l Name W h C M M E M 5-e1 35 45 > 5000 ms/ks I > 2000 mehe i Estehtished
~
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so LING point (*PI > 212 SPECIPIC ORAvlTY (H2 0 11 1.34* 1 8 ' l PERCENT VOL ATILE l V APOR PRES 5URE immHs l N/A av VOLUML (%) 56 l l l V APCR C(NSITY ( AIR *1) N/A cH N/A SOLUBILITY IN WATIR Corftpitte , APP [ A A ANOE AND 0DCR Coloriets liquki, odorless
, 4 ,. y g .w p 7 ,, , , , , , , ,,,, , , , , , , , , , ,, , , , , , , , , , j l i'
F L ASH PQlNT IVetmoc Usect F L AMMA8Lt LIMITS Let Uet N/A N/A - t XTINGut$HiNG VE DI A Water, CO2, Foem, Dry Chemical setCi AL piRt SIGHTING PRoctoVAES Emertlie oeut6on when fi# ting any chemical fire. A self oontained breathing appetetus and protective tiothing ere essential. UNU5U AL FIRE ANO E KPLO$ TON H AZ ARDS None N/A = Not epolicable l W* e IN iato met on and eecommenost oni set 'onia berein are beneves to be scrweste si of tee este hereof, CALGON CORPOR ATION M AKES NO W ARR ANT Y WITH RE SFECT HER[TO AND DISCL AIM $ ALL LIABILITY FROM .' RE LI ANCE THEREON I
--- - ,,-,------,--,.---,.e, - - - - - - - - - - - - - - - - - - - -
Users of Calgon Chlorine / Bromine Chemistry in Tennessee Aluminum Company of America BASF Fibers l l I
. _ . . . . - . . . - . . _ - = - - - . - - . . - - - . .. _.
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ENCLOSURE 6 [ t f- Product Information for Calgon's I CL-361 l l l i< r (This information was provided by Calgon for ! TVA's use in obtaining regulatory approval ! for the use of the specific product.) I EPA Registration Number: Not Applicable ' f I i f l l I t
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^
i I CL-361 i Deposit Penetrant i _ oe n s ty, pou nd a pe r oallon...... ........................... 8.5 i DESCRIPTlON Fl a sh Poln t, ' F (TCC).. . ..... .... .. ................... > 200 I CL.361 is a unique liquid blend of deposit M eas u red Freeze Point.
- F..................... ........ ... 30 I penetrants, surfactants, and polymeric disper. Brookfield Viscosity @ 70* f, cps............. .........15 sants formulated to enhance scale, deposit and
*l corrosion control programs. PACKAGING ADVANTAGES CL.361 is available in 5 gallon plastic paus (40 lbs.
-! net, 43 lbs, gross), 55 gallon plastic drums (450
- Enhances Microblological Treatment Results Ibs, net, 474 lbs. gross), 275 gallon plaatic CL 361 et/ect/vely penettsfes st/me deposits disposable bina '2337 lbs. not,2512 lbs. gross), or permitting the microbloc/de to / unction cost el- delivered to on site storage facilltles via bulk or lect /vely. The low loaming action which results Calgon Bulk Liquid Service.Plussu.
from CL.367 feed facilitates slime penetration.
. Deposit Control SHIPPING Ct.367 IInctions as a dispersant keeping in. DOT Hazardous Class... . . .... . . ...Not Restricted
( organic and organic foulants fluidized to DOT Proper Shipping Name... .......Not Restricted minimize deposition on equipment and on heat un numygg_, , ,, ,, , ,, , ,,,,ygg gppllcagg, exchanger sullaces.
. Improves Corrosion Control riograms STORAGE AND HANDLING Ct.36f promots: system cleanliness, resuIting The recommended minimum storage temperature in increased heat transfer. Corrosion inh /bstors for CL 361 is within the range of 30 35'F, Best if function more ellect/vely when metal surfaces used within twelve (12) months from time of are / tee of foulants, improved system receist. Preferably, product should not be allowed cleanliness also minimizes under deposit cor. to f reeze, il freezing occurs. product may rosion. separate, it may be possible to restore product in.
l METHOD OF FEEDING [o t$ng ,
. CL.361 should be fed at a point in the system l i where turbulent flow will assure good mixing. The COMPATIBILITY J l product must be fed neat and must not be mixed Recommended materials for.
I with other water treatment chemicals prior to Bulk Storage Tanks . High density or cross linked feeding. CL 361 may be fed continuously or inter. polyethylene, fiberglass with bisphenol, I mittently depending on treatment objectives. Your isophthalle, or vinyl ester liner resins. #304 or #316 I Calgen representative will aslist you in stainless steet, epoxy phenolic, or vinyt ester
! establishing a treatment program to fit your lined steel.
l specific cost performance criteria. Pump "Liquid Ends" and Piping Polyethylene, polypropylene. PVC, 304SS, 316FS, Kynar, i CONTROL TESTING Hypaion, viton or Teflon
; Product performance is ultimately confirmed by periodic equipment inspections, as well as heat ,,,,m,on cone,, nog 3,,, , av en,,on,.w, e,posure mer oe i transfer and corrosion monitoring. revwo m ew ure.c sawy ore sneer for rms proover l w.wone ,nrormeen recovee .ncernes meeg nume, ens
.'1s 'provtment
****'* "" "' 8000 *^"* "* '* **o'r
( TYPlcAL. PROPERTIES Appearance..
... .. clear, colorless liquid
. 5.3 ay rr "'~*'
ae Arts D H .. ... .. . . . . . i Specific Gravity @ 77'F.. ... . . . .1.02 i i i Pstated te U 9 A SU509IM $l'Iea l 1
n = ica . MAN SMETY BATO ENK2 0 1.
****r" 2'"
9019-46 2842 579 Og9 PMOCUCT N _ . e. . _ ADDMIS8 P. C. tem 1848, Pteentwgh, Pennsykenis 15230 CHIWICAL Naut P OMeilVLA ANDSYNONYM4 Seriettent LM _ _ -.__-_ i i i _._ ~ _ ! l Standsed (29 CF R 1910,13001 1 1 Sf ( f ( IN let BOILING PCINT (*Pi > 2'I 3PgC4P ic GR A V6 TV (Hp tl 1.01 1.03 , PERCENT VOL ATILE l V APCR PRE SSURE tmmHg i SimWaf to Wate'- SY VOLUME (%) E l Similef to Water og 6.0 6,$ V APOR DE N5lT Y ( AIRel) SOLUB6LITY IN
- ATE R Complete APPE AR ANCE AND ODOR C16er colorless liquid with mild ofgenec odor
+ f P L ASM POINT tuetmoe Useal P Lauv Asti : iMIT5 Lei i vee Not fiammable Not 4put We { E E TINCul5MihG Ut 01 A Product is not flammable.
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$Pf CYAL FIRE FIGHTING Proct 0unts None UNU5U AL FIRE AND E M P LO510N H A2 A R DS N one
! A=.i.in.,.as o ,m.i.cn m .com,.c o..on. ,,, io,,, me.. .a ,,, e,n,* n to e., ec c ..ie ei ci ta, oei. n e,,os. c A L GnN PhWPOR AfiON Mat f $ NO A AHM Anis Alf6* HF tPF CT wf Rf f n
- 0 015C L AIM % All Ll&PILITY FAOY .
i
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't* F tCis OF OviRexPO5Usta ~The product is pesetitally non toale theou lagest6en and dormal N^2 The neute oral LD50 (rets)is > 3.0 g/kg. The neute dermal LD50 (rsbbi:3 )is > 2 ml/ks. It is not a prbnery skin irritent. The Primary levitation Inden la 2.04/8 (rabbits). The product produced silght conjunctival irritation in rebbit eyes (Score efter 24 hr . 2, Score efter 48 hr . 0).
e . EI4tRGENCY AND FIRST AlD PROCEDURES I Good First Aid should be followed in all casse of exposure, in cese of eye contact, flush with plenty of water for et least 15 minutes, if irritetson develops, call a physicien. l l( ( f( # N' - t i a 'l . i !WilY1)hIA
$ TABLE X COA DITiONS - !
U#0I' TO AVOID Unknown lUN5 TABLE l i INCOMP AT Atl LITY Strong h (Materials to Avoid) N A2 ARDOU$ Of COMPO51 TION Ur*nean PR00VCTs H AZ AROQU$ POLYME RIZATION CON 0lTIONS TO AVOID Unknousi M AY OCCUR l NO X e, vis .ee s e Ot ? I a T M '" W : ' ~t. s REPORTASLE OV ANT 6Titt IROI NOTIPY EPA OP PRODUCT SPILL 3 IN L85. OF EP A M AZ ARDOVS N/A (OV AL TO OR EXCEEDING
$US5T ANCES IN PRODUCT 1. -
N/A g,gg, 2. 3 STEPS TO 6E TAktN IN CASE M ATE AI AL 15 RE LE ASE D Dispose of in accordance with local, state and federed repletions. Dike eree to conteifi CR $PjLLEO es muCh spilled meiertoi se pose @e Remove erry rerneinmg meterial by absortMng on vermiculite or other tutte his shootting material and piase in a see6ed metal conteense for drepoesi. W ASTE DISPOS AL, Mt THOD Flush wtth p6enty of wetoe end dispose of lo sesorsinnse wie local, etoto end federel repletions. U95?? . ' , ' i '. . . g g . g g ., {' - t SON Vfts SI f t: tap F8 toll C flOly 4NFORMAf TON RE5?tR ATORY PROTECTION Not Regu6ted 850eoir Typel LOC AL E xH AUST ~htCI AL VENTILATION
-_M t CH ANIC AL OTHER Normal i o.,s., m Not Rowlred PROTECTivt GLOVE 5 EVE PROTECT'ON Not Requ. ired Not Rew.ired 1 bf ME R PROTECTlyt tOUIPMENT Not Required 6 . : .
, M C llON IX 'J'l f.l At Pf 4E (. AUlluly5 PREC AUTIONS TO st T AKEN IN H ANDLING AND STO'11NG Weeh thoro #y after handig Keep containet cdM Exercise caution in te stotees and band 6no of all ehemical subetences.
OTHER PREC AUTIONS None 578 PRtPARtDgy Janet Mostowy_ _ _ _ , _ _ l
ENCLOSURE 7 Toxicily Data for Chlorine / Bromine Mixtures (This information was compiled from the literature.)
'i l
1 1 1
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. .- ..~ .. .. .-. .-- .. . -. - _-
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l l i t "EFFICACY OF CHLORINE AND BROMINE MIXTURES A8 BDCIy"g AND , l SUBSEQUENT E.WIRONMENTAL CONSEQUENCES--A REVIEW i j -i 1 i Biocides are typically used in raw water systems of power , plants to control biological fouling in .various system components. Biofouling reduces system of ficiency by creating more resistance to j l flow and by decreasing 'ef fectiveness of heat transfer. Essentially l 1 '
', complete clogging can occur under extreme conditions. Biofouling can !
( also result in corrosion in the system to the point that leaks j , develop. ' } As a result of these probicas, power plants use toxic agents J , f (biocides) to control these growths. However, biocides cannot , 1 t i distinguish target from non-target' organisms. This creates environmental consequences once treated water is discharged to a - receiving stream. The resulting~ dilenusa is how to maintain plant ( efficiency and safety yet minimize environmental impar:ts ' f rom a 1 control program. i The most coreonly used biocido la chlorine because of its I
- l I historical use, effectiveness, and low expense. It is usus11y l j injected as chlorine gas (CL ) r as a hypochlorite such as sodium 2
f hypochlorite (Na001). Once injected into the sys. tem, there usuaaly ] { ; will be two forms of f ree chlorine--hypochlorous acid (H001) and the A l hypochlorite ion (0C1~). In the presence of anunonia (NH ) 4 two 1 t l , forme l l I l I 1 j l This review was based on abstracts from various abstracting i i - services. , I t I 1 I i l ) t
- l i' J l' 1
( I of combined chlorine can exist--monochloramine (NK2 01) and dichloramine (NHC12 ). All of these are quite toxic to aquatic organisms (EPA, 1985). The relatively long life of the combined forms (approximately 20 hours) adds to the concern for environmental impact (2eh, 1984). Toxicity of chlorine from power plant use has been thoroughly studied and will not be detailed here because of its extensive documentation (Heinle,19761 Cherry et al.,1977; Morgan and a Prince, 1978: Anderson et al., 1979 Fandrei and Collins, 1979 Seegret et al.,1979; Bean et al.,1980 Brooks et al., 1982; Howells,
; 1983 Brooks and Barton, 19841 Wang and Hanson, 1984; Hidaka and Tatsakawa, 1985: Moss et al., 1985).
Other implications f rom use of chlorine include formation of organochlorine compounds. Formation of these compounds is a concern because incorporation of chlorine into an organic molecule increases its 11pophilic character and at the same time increases toxicity or ! bioaccumulation, or both (Kapperman et al., 1976). Another concern for formation of organochlorines is that they have been found to be l 1 carcinogenic and mutagenic and, if present in a drinking water supply, have potential to af f ect human health (Bean et al.,1983 Bull, 19843 Meier and Bull,1984t). I Because of the problems associated with use of chlorine as a j ! biocide, power plants, weste water treatment facilities, and drinking water supplies have investigated use of alternative ' biofouling/ disinfection control techniques. One of the more promising j alternatives is use of bromine in place of or in addition to chlorine, t i 1 2- I
Bromine is injected into the system as either bromine chloride (BrC1), j a fuming red liquid potentially hasardous to the user (Nalco, 1982); sodium bromide (NaBr), a salt solution typically used in addition to chlorinet or 1-Bromo-3-chloro-5,5 dimethylhydantoin (BCDMH), a slow i release biocide (Soracco et al., 1985). Most available. literature deals with efficacy and/or i environmental impacts of using BrC1. Because the active bromine species should be the same regardless of the donor (Nalco, 1982), study results should be applicable to one another. Although some studies have found that bromine is a better biocide than chlorine : Mills, 1973a and 1973b), most have found a combination of bromine 2nd chlorino to be more effective than using either alone (Nalco, 1932; Zeh, 1984). Toxicity of bromine has been ' found to be roughly equ.il to that of chlorine for copepods (Bradley, 1977) and benthic invertebrates (Venosa and Ward, 1978). Venosa and Ward also found chlorine to be more toxic to fathead minnows than bromine, yet bromine war more toxic to salmonid fishes than chlorine. ! Tests on chlorine residi als and bromine residuals have shown chlorine residuals reduce growth of fathead minnows at substantially lower levels than bromine residuals (0.033 compared to 0.34 mg/L, respective 1yt Ward and lieGraeve, 1978) and are more acutely toxic than bromine to juvenile ye. not adult fathead minnows (Wilde et al., , 1983). However, Wilde et al. also found that bluegill were more tolerant of chtnrine thaii bromine residuals.
- It appears bromine is an effective biocide and is more desirable environmentally because of its short life compared to 4
i chlorine- approximately 10 minutes for bromine compared to 20 hours t for similar chlorine compounds (Zeh, 1984). Bromine apparently of fers another advantage when used in combination with chlorine in that it enhances the decomposition of the . toxic chloramines by formation of , hHBrC1 (Trofe et al., 1980a and b). Most researchers concluded that the tnvironmental consequences of bromine were less than chlorine (Mills, 1973a and 1973bt Wackenhuth and 1.evine , 1974 croninger et al., 1978 Ward and DeGraeve, 19781 Zeh, 1984 ). > l Although bioaccumulation of brominated compounds has been investigated much less extensively than chlorinated compounds, results of a study by Kuehl et al. (1978) suggest bioaccumulation of organobromine compounds in fish. A study by Hohlf feld et al. (1983) also indicated potential for organobromine compounds to bioaccumulate, . although they found levels less than 100 ppb in fish exposed to BrC1 ] i , treated watert a level which they concluded posed no risk to human j i health. t FAEB 10123
, l 1 .
l l
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1 1 4
l Literature Cited ! Anderson, D. A., R. M. lean, C. J. Gibson, and P. R. Reed. 1979. !
"Biocide by-Products in Aquatic Environments. Quarterly Progress Report, January 1-March 31, 1979." Battelle Pacific Northwest Labs., Richmond, WA. May 1979. 55p.
Bean, R. M., D. C. Mann, B. W. Wilson, R. G. Riley, E. W. Lusty, and ! T. O. Thatcher. 1980. "Organohalogen Production from Chorination i of Natural Waters Under Simulated Diofouling Control Conditions." i Water Chlorination: E,nviron. Impact Mealth Effects. 3, 369-77. [ Bean, R. M., D. C. Mann, and D. A. Neitsel. 1983. "Organohalogens in I Chlorinated Cooling Waters Discharged from Nuclear Power Stations." Water Chic ination: Environ. Impact and Nealth Effects. Vol. 4. Book 1: Chemistry and Water Treatment. j p. 383-390. Ann Arbor Science, Ann Arbor, MI. , I i Bradley, B. P. 1977. "Comparison of Residual Biotoxicity of Chlorine ' and Bromine Chloride to Copepods." Water Resources Research Center, University of Maryland, College Park, MD. Report No. W78-11378, OWRT-A-040-MD(1). TR-47. j Brooks, A. S., J. M. Bartos, and P. T. Danos. 1982. "Effects of Chlorine on Freshwattr Fish Under Various Time and Chemical
- Conditions
- Toxicity of Chlorine to Freshwater Fish." Wisconsin i Univ.-Milwaukee. Center for Creat Lakes Studies. EPRI-EA-2481, July.
Brooks, A. S. and J. M. 'lartos. 1984. "Effects of Free and Combined l Chlorine and Exposuro Duration on l<ainbow Trout Channel Catfish, i and Emerald Shiners." Trans. Am. Fish. Soc., Vol. 113 No. 6, ;
- p. 786-793. !
Bull, R. J. 1984. "Toxicology of Natural and Manmade Toxicants in j' Drinking Water." Health Effects Research Lab., Cincinnati, OH. j EPA Report No. EPA-600/D-84-222. September. i Che'rry, D. S., S. R. Larrick, K. L. Dickson, and J. Cairns, Jr. [ 1977. "Response of Eurythermal and Stenothermal Fish Species to Chlorinated Discharges." In: Trace Substances in Environmental Realth-XI, p. 413-418. D. D. Hemphill, Ed. Univ. of Missouri, Columbia. , i
- Environmental Protection Agency. 1985. Arbient Water Quality. l Criteria for Chlorine-1984 Report No. EPA 440/5-84-030. .
I l 1
Tandrei, G. and E. L. Collins. 1979. "Total Residual Chlorinet The Ef fects of Short-Term Exposure on the Emerald Shiner Notropis atherinoides (Rafinesque)." Bull. of Environ. Contam. and Tox1. Vol. 23, p. 262-268. Groninger, G. D., D. R. Martin, and J. F. Mills. 1978. "Bromine Chloride - An Alternative to Chlorination As An Antifoulant in Once-Through Cooling Waters." Proc. Int. Water Conf., Eng. Soc. West. Pa., Volume Date 1977, 38, 347-51. Reinte D. R. 1976. "E(fects of Passage Through Power Plant Cooling
. Systems on Estuarine Copepods." Environ. Pollution. Vol. 11.
- p. 39-57.
Hidaka, H. and R. Tatsukawa. 1985. "Avoidance Test of a Fish, Medaka (Oryzias latipes), to Aquatic Contaminants, with Special Reference to Monochloramine." Arch. of Environ. Contam. and Tox1. Vol.
- 14. No. 5. p. 565-571. September.
g Howells, G. D. 1983. "Ef fects of Power Station Cooling Water Discharges on Aquatic Ecology." Water Poll. Control. Vol. 32. No. 1. p. 10-17. Kt 9perman H. L. , D. W. Kuehl, and C. E. Glass. 1976. "Chlorinated Compounds Pound in Faste-Treatment Effluents and Their Capacity to 31oacc umulate ." Environ. Impact. Water Chlorination. Proc. Conf. Mseting Date 1975, Issue CONT-751096, 327-45. R. L. Jolley, Ed. Kuehl, D. W. , C. D. Veith, and E. N. Leonard. 1978. "Brominated Compour.4s Tound in Waste-Treatment Effluents and Their Ability to Bioaccumclato." Water Chlorination: Environ. Impact Health Ef f ects, h voc. Conf. , Meeting Date 1977 Vol. 2,175-92. R. L. Jolley, H. Sorchev, and H. D. Hamilton, Jr., Eds. Meier, J. R. and k. J. lull. 1984. "Mutagenic Properties of Drinking Water Disinfectsnts and By-Products." Helath Effects Research . Lab., Cincinnati, OH. EPA Report No. EPA-600/D-84-224 September. Mills, J. T. 1973a. "chemistry of Bromine chloride in Waste Water Disinfection." Pet pr. Pap. Natl. Meet. . Div. Environ. Chem. , Am. Chem. Soc., 13(2), .37-43. Mills, J. F. 1973b. "Disinf ection of Sewage by Chlorobromination." Prepr. Pap. Natl. Meet., Div. Water, Air Waste Chem., Am. Chem. l Soc., 13(1), 65-75. I Morgan, R. P. Jr. and R. D. Prince. 1978. "Chlorine Effects on larval Development of Striped Bass (Morone saxatilis), White Perch l (M. americana) and Blueback Herring (Aless aestivalis). Trans. i Am. Fish. Soc. Vol. 107. No. 4. p. 636-641. I l 4
f
- Moss, R. D., S. P. Gautney, and P. A. March. 1985. "Targeted [
Chlorination is Viable and Environmentally Acceptable." Power. l Vol. 129. he. 2. p. 79-41. February._ , , i I Nalco. 1982. Questions and Answers - Chlorine Alternatives. Malco l Chemical Company, 2901 Butterfield Road, Oak Brook, Illinois
- 40521. ;
i Seegert, G. L., A. S. Brooks, J. R. V. Castle, and K. Grada11. 1979. ! ] "The Effects of Monochlorasine on Selected Riverine Fishes." [ Trans. Am. Fish. Soc., Vol. 108, p. 88-96. , l 4 Soracco, R. J., E. W. Wilde. L. A. Mayack, D. H. Pope. 1985. ! i Nomwrative Ef f activeness of Antifoulin8 Treatment Regimes 11 sing ?
; Chlorine or Slow-Releasing Bromine 31ocide." Water Research, L 4
Vol. 19. No. 6. p. 763-766. I t ( Trofe. T. W., J. D. Johnson, and G. W. Inman, Jr. 1980a. "The ' Einetics of Monochlorine Decomposition in the Presence of . Bromide." Energy Res. Abstr. 1941, 6(3). Abstr. No. 4143. ! l Trofe. T. W. , G. W. Inman, Jr. , and J. D. Johnson. 1980b. "Kinetics I
- of Monochloramine Decomposition in the Presence of Bromide." i
- Environ. Sci. and Techno., Vol. 14 No. 5. p. 544-549. May.
Vanosa A. D. and R. W. Ward. 1978. "A Study of Alternatives to Chlorination for Disinfection of' Wastewater." Water i
- Chlorination. Environ. Impact Health Effects, Proc. Conf., !
] Meeting Date 1977. Vol. 2, 625-8. R. L. Jolley, R. Gorchev, R. D. l Hamilton Jr., Eds. . 4 t
- Wackenhuth. E. C. and G. Levine. 1974. "An Investigation of Bromine j i Chloride as a Biocide in Condenser Cooling Water." Proc. Int.
Water Conf., Eng. Soc. West Pa., 35, 1-14. ) l l
, Wang. M. P. and S. A. Hansan. 1985. "Acute Toxicity of Chlorine on l
{ Freshwater Organisaat Time-Concentration Relationships of i constant and Intermittent Exposures." In: Aquatic Tox1. and i 'Rasard Assess.: Eighth Symposium. Fort Mitchell, KY. April ! 15-17, 1984 ASTM Tech. Special Publ. 891, 1985., p. 213-232. Wilde. E. W., R. J. Soracco, L. A. Mayack, R. L. Shealy, and T. L.
- Broadwell. 1983. "Acute Toxicity of Chlorine and Oromine to j Tathead Minnows and Bluegills." Bull, of Environ. Contam. and Tox1., Vol. 31, No. 3. p. 309-314. September.
l Ward, R. W. and G. M. DeGraeve. 1978. "Residual Toxicity of Several Disinfectants in Domestic Wastewater." ' J. Water Pollut. Control Fed. Vol. 50 No. 1. p. 46-50. i
- Zeh. T. G. Jr. 1984. '%sstewater Disinfection with Bromine j Chloride." Public Works, Vol. 115, No. 10. p. 56-57. October.
.1 ] TAEB 10153
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s
N N A LC O , , ACUTE TOXICITY OF CHLOROBROMINATED I AND CHLORINATED EFFLUENTS TO VARIOUS SPECIES Chlorobrominated Chlorinated
- Effluent Effluent 96 Hour 96 Hour TL50 (mg/1) _TL50 (mg/1)
Fathead Minnes 0.133-0.185 0.082-0.095 Pimechales cronelas Northern Common Shiner 0.120-0.140 0.051 Notronis cornutus Pugnose Shiner 0.109-0.136 0.045 Notropis anocensus Western Golden Shiner 0.090 0.040 Notemiconus crysoleucas Lake Trout Salvelinus namaveush 0.102 0.060 Chinook Salmon Oncorhynchus tschavytscha 0.059 Northern Yellow Bullhead Letalurus nat slis 0.177 Northern black Bullhead inialurus melas 0.233 Daehnia Maana 0.047-0.0!i5 0.017 1 Disenfection Efficiency and Residual Toxicity of Several Wastewater Disenfectants - Volume I, EPA-600/2-76-156, 10/76.
%^.h." , S.". ? 5..'.f.^h",2.F.f. ' 1T ~
.g 'Y ( Bull. Environm. Contam. Tmed 27.126.t.14 HW H 1 y .
L gi< ) Statle Acute Toxicity of Sodlum Bromido i -
\
" ~~
t 1 , to Fathead Minnows' l, H. C. Alexander.' J. A. Owek. Jr .' cnd E. A. Barren 8
'Research Assoc >te 'P?oiect Leeder sne 'Rese srch Chemist invironments t
! Sciences Research Ls00rstory. The Cow Chernest Co.. Mictand. MIU640 j Q ;.
t th
\ v.s D
3 % g , b < I This study was the first phase of a research program g designed to examine the dynamics of sodium bromide i ;., r uptake, biotransforfration, and depuration in fish. l
- i. j This investigation was dest ned to determine the
'h'I . acute static toxf city nf snktum bromI(le to the te:.t $
v E Species, Pimephales promelus Rafines ue. These data
- b. . '
were used to select exposure levelr. or later long-sx .{
& J term sodium bremide exposures, )
ua h i. ' w MATl;M1 Al.S
- d
%P '
l Test _ Material. The NaBr used was analyzed 99.9*4 pure h
, trom Lot 090G9, Halogens Research, Michigan Division, I t.m.' . The Dow Chemical Company, Midland, MI. i. @
i a l Dilution Water. Lake Huron water which had been N
%. passed through a carbon contactor and ultraviolet dh-11 he sterilizer was used.
?.' g ' .
134 difutionwateraregiveninTables1andDetailed anal ses of this 'i l 2
)
(HUNEMORDER 1979). p @ (% ;. Fish. Fathead minnows (original stock from U.S. EPA
' m
-(, ; O :
. G'5 oratory Duluth, MN) were hatched and reared ! N' . 'i y ;~ in the Environmental Sciences Research (ESR) Labora- 1 h
- l '. , tory. These animals were reared at 25 + 2'C untti
- d9 about 60 days of age (subadults) and then slowly
.i d
(11'C/ day) acclimated to 12 + 1'C. Typical holding
, (;h. a andrearing15-2044 period at conditions lux andwere a water T6 h 11ght/
flow rate day >2 photo- h. , l1 l 6./ min. Fish were fed onto or twice daily, "ad y{ i l i b i t uan . The specially fortnulated diet mix Ts shown in Table 3 (MEHRLE 1976).
,i f, .i.' I j ',
METHODS y,L j t* i A range-finding test was run in which two fish were ' 1 2 placed in 1 L of each of seven widely varying concen- 1" . ) , y trations of NaBr at 12 + 1'C. This test indicated ! .- the LCSO was between 10!C00-23,000 mg/L. I fl
- thw Chemkol Company D400.owst I !.
$ 0007 4 6lil1/0027 0326 501.20 1 O 19RI Springer.Verl.ig New York Inc, i
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i I ..h k Y .. ,i M -% . in W P.".- G" '! T2.'+ %7-94;cr y o w .v . . .. l i l i TABLE 1. CARBON FILTERED RAW LAKE HURON WATER ANALYSES { i
\
l Alka!initv i Conductivity Hardness Date pH .mhos/cm eg/L as CACO 3 eng/L as CACO 3
. t
,9 l l 4/5/79 7.7 158 110 .
l
*- f i 134 85 5/29/79 7.7 200
?/2/79 7.7 190 110 87 95 7/18/79 7.6 200 77 -
] 9/10/79 7.9 188 103 86 j , 4 10/12/79 8.0 198 102 73 i . 1 11/20/79 8.1 185 105 80 i j l 1/1/80 7.8 155 97 80 l i 1 i 1 . i l i 1
* 'O .
l -
)
1 i j . .
i i * '
)
)' ,
i ! s TABL i-' \
- s. TABLE 2. ,
Dry s p.hetic j CARBON TILTERED AAW. LAKE HURON WATER ANALYS i [l k ,' i
- 2 8 *. ( !
157. I i g i Chemical Quality 2 87. t rat /L i ("l Alky1 benzene sulfonate 47. r I Arsenic ND (0.1) i N' r3 , Sarium ND (0.001) ' j k ' Cadmium SD (1) f N' 94 { Calcium ND (0.01) h, ; 20 Mix for 15 at Chloride 9.9 Hix equal wei Chromium Huron water & s.' Copper ND t J.05) 4 a
$.P Cyanide NC (0.011 This was foll CAL COMPANY 1 y?
Fluoride ND (0.01) W'" C * *
\ tron 0.09 with concentt ; t)! Lead 0 01 For this test dilution wate Magnesium ND (0 05) i seration was 7
of water to b Manganese vessel at the Mercury SD (0.05) for 96 h at 1 animals remov Nitrate ND (0.005) during the te Phenols 0.20 in the testin SD (0.001) fluoroscent i Polychlorinated Biphenyls absence of op Selentum ND (0.010 x 10*)I prodding. He SD (0.01) concluston sh
' Stiver '
weight to be Sulfate 50 (0 05). 19 - statistical C Total Filterabic Residue tests were us Zine 146 the toxicant the test orga-ND (0 5) was done usin of probic ana i j of moving avo: j method thTEEL ND =detectable Parameter was not detected followed by mintm amount um val (a range t in parenthesen. the reat LC50 results are cc i and are report
! gram requirem.
moving average l' n i
\ \
l i 4 a I
\ \ .
'. TABLC 3. 00RMut.Attu SYNTHr.T!C Dir.T [f I
l i try synthette diet centains: , 9ES 28% casoin - 280 g per kg dry mix 15. geis t in - 150 g per kg mix ! I l 28% dextrin - 280 g per kg etx i 4% mineral mix - 40 g per kg mix
- 97. vitamin mix - 90 g per k,; mix ;
.d l
t 11% corn ott - 110 g per kg mix j , 5?. salmon oil - 50 g per kg mix .. d
.i s
Mix for 15 minutes and package. ,;
- Mix equal weights of dry mix and dechiirina:ed Loko ,g l '. ,,,
Huron water and refrigera,te, , g This was followed by a daftnitive test (THE DOW CHE.MI-e- CAL COMPANY 1978) in which the concentrations of NaBr l were set close together usin a 907. ditution factor. .;
- with concentrations ranging rom 8.610-20.000 mg/L. '
4 For this test, ten fish were placed in 8After L of 24 h. ,, i
- dilution water f or 24 h with aeration.
I aeration was discontinued and toxicant added with 2 L '- of water to bring the total volumeFis3 to 10 L in each were exposed i- , vessel at the start of the test. , for 96 h at 12 + 1 C with effects No recorded and dead food was provided . animala removed every 24 h. during the test. The 16-h photoperted was also used in the testin area at 915-1345 lux cool white fluorescent i lumination. Death was confirmed by i absence of opercular movement and lack of response to ( predding. Measurement of surviving iish at test = conclusionshowedtheavera!estandardlengthand weight to be 26.8 mm and 0. $$ g. [ l j statistical l 1culations. The results from toxicity i.e. ? Iests were used to calcGlace the LC50 value,50*. el .i
,s
' the toxicant concentratton which would kill i j the test organisms in a specified time period. This s was done using a computer p gram of Finnoy's method ,' l of probit analysis (FINNEY 52). Thoepann a method of moving averages (THOMPSON 1947). and the binomial i i cethod (STEEL et al. 1960). The 9D. confidence inter-i C val (a range within which there is 95'4 probability ) i che real LC50 value lies) was also determined. Probic ' results are considered the most accurate IPARK 1979), and 'aro reported when data fulfilled the probit pro-Otterwise LC50's r;alculated by l gram requirements. j noving average are reported. , n, . 1 1 k . i l I i
\ : l ..l \ . f RESULTS AND DISCUSSION
IINNEhsh.
1- { The acute toxicity of sodium bromide to the fathead THOM
- 7,7 .
minnow is sunmarized below: . i . TEEL., R. G. Exposure Procedu
! Period 1 Method of i
_ (Hours) . _LC50 feg/L) Calculation ). ' j > gARK, C. N.t l 24 18,441 (17,879-19,140)* Hoving Avg. Dow Che communt
; 48 17,757 (16,929-18,668) Compan)
Probit ,
- 8ARTLETTi E.
72 17,019 (16,034-18.1373 from 84 Probit (1978).
' N 96 16,479'(15.614-17.428) y' . Probit P,} 3ecepsco M*
( p The noving average value for the 24-h LC50 is reported because the data did not fulfill the requirement for 1 K 6. M i the probic analysis which requires at least two par. 5 L tial kills to achieve statisticat.ly valid results. 2 (Ji There was a sufficient range of mortality during the y remainder ses. of the test to perform valid probit analy-3 . 4-D h' Sodium bromide has a low toxicity to fathesd minnows that is sinitar to that of sodium chloride. The 96-h 4 6 LC50 for sodium chloride on fathead ninnows has been
! [, reported mg/L by our 1978).
(BARTLETT laboratory as 10,610 (10,423-10,846) moles This is 0.181 (0.178-0.185) per L. per L or 0.362 (0.356-0.370) tenic equivalents . (p,# The 96-h LC50 16.479 (15,614-17 428) value for sodium bromide of m
'M * . molesperLor0.$20(0.g/Lis0.160(0.152-0.169) 304-0.338) lonic equivalents per L.
! $( 'g These nificanti different toxicity values are close but still sig.
*>p on the 95 confidence interval.at P 0.05 because of no overlap -
td b D n. ( j REFERENCES y' t HUNEMORDER, E. J., I K. J. KELLY, D. KRUECER, K. R.
' ' SCHMECK, N. J. SMITH and D. WEACE: Analysis of , '-.} raw Huron water used at 1707 But1fing fish lab.
l J ML-AL.79-50491 (1979). HEHALE, P. M.:
"..g bia, MO. USDI Fish and Wilditfe Service, Colum.
6: Personal com unication to E. A. i }; Bartlett, (1976). The Dow Chemical Compane, Midland, MI
- .' THE DOW CHEMICAL COMPANY:
Standard st itic acute fish
.( i toxicity test rethod.
Research Laboratory, Midland, Environmen*al Sciences MI i1978). y
'95% confidence intervals 310 d'.
( t. L s i
1 1 Statistical metheds in biological ! T!NNEY, assay. D. J.:Canbridge University Press (19521. e W. R.: Bacteriologicst Fev. 11;115 !
. iBCMPSOS,7).
(194 i Csd . Principles and ,,
$ TEEL, :'.. G. D. and J . H. TORRIE:McGraw-Hill Book Cov.-
Procedures of Statistics. l 3g ,' 1 pany, Inc., New York, Sew York. pp. 389-394 l ton (1960). Hasich and Environmental Sciences, The , l PARK, C. N.: Dow Che:nic.n Company, Midland. Hi. Personal l l l jg, ' cone.unicatLon to D. C. Dill, The Dow Chemical i I d (1979). **. ' I Company, Midland, MIEvaluation of a RONNE@ spent bio ch l pRT1.ETT, E. A.: ,,, i j from 840 Butiding. ESR Letter Report ES-69t. . J j
. (1978).
, l d - :::
> y..n.3 w . is seit ,
I orted *. , l-(C r ' '?' ar. I [ .
; the 4s ,
t ly-e- i dbs ;
! 90-h *
-en g
'6) 1 i
'ts I
( in i 9t s ( ' sig- , ' ' lap * , I 8 I i 8 , of i i ID.
. tun- ,
H1 .
'Lsh
- I
} i l j 311 i I . J' \ ,
\
I L: . 5 5 ' i i I
.s D
( t___ _ ._--__ - -- - - _ _ _ _ _ _ _ . _- - - - _ . _ . _ _ _ - - - - _ _ _ _ --
l l gun, gavvem. Cantase. Tea 6cel. II 30s.)la (IM)) O IM) 3pnnest YeMad New Yort lac. 6 0 d. M l Acute Toxicity of Chlorine and Bromine { to Fathead Minnows and Bluegills 1 E. W. WJce.' R. J. Soracco.3 L A Mayeck.8 R. L Shoaly.I and i T. L Stosowo43
' G.
- 3Mensseteer Pyy10thnie Instrtute. frey, NY tittf
- and Erownght Laborato Ine. Orwentle. SC 29000 .
l
.1 +
l j T?ie iet e*"megntal acceptability of we(ng shlerise as an antifeut-i ' aoos todustrial eeolies systems is a subject C ineesseing pror, s everal alteressives to chlorisas ten have recent y been I 3-th' studing the use of a breatne-beesd blocide, O bromo-2 +$ edly ,$-disethylhydantela (ICD 40t). Dile coeposed has report
- Od geerformed chlorine in several cooling tower applicatione (MACCHsAAOLC, et s
al.1980! KATSCM & CMARACKLIS 1942). Inevever e inferisation on the use of SCDNR la ooce-through coolitig systems ! and the relative envirennental acceptability of SCCMR in taa3ari. l tt son to chlorine are lacking. } The objective of this study was to uusr ' the relative temicity v of chlorina and SCOMH to three typee system used for cooling a nuclear reacter. ..sh in a freshwater METH003 APO MAftt! ALS i i flow-through 14.h teattity tests were conducted in March 1932
! all using e metite laboratory toested adjacent to far Fond, a reakter l
cooling
- 3. C. reservoir at the Savaanah River plant (t u) near Anken, Two solenoid.attivated propertional, flow-through diluter j syntesaof testing asesidast described by PtLT!!B (1973) were weed for simultaneous
! rt ICO*0t additions. teendual tositity resulting f rom chlorine and j 401, 331, 201, 22 Each systes delivered apprestaately 1001, 711,
- trol tsocide te duplicate test citambers using Par Fond water asand O! of stock solutten of i
diluent. I I i I A Hydrelab 8000 system was weed to make daily sessuremente of: I dissolved orygen, temperature, eenductivity, and pH it the test
- thacers receiving 1001, 351, !!, and 01 bioside solu
- (one .
1 Alkatioity was mesaured by APPA standard methode (MKg 1980) . Jweenile (sia-week-old) and yearling fathead sinnews i Pinephales I Leone s sa) and young-of.the ye ar hlweg s tl e (Le pent e sei reen t ew s ) 4 were us ed as test organises. j water for tes days prior to theD.e teste. fl o ts were acclamated to far Fond
' dally during the sealisation and Juvenile einneve were fed i three types of fish were placed in test eachpersede. Ten of each of the l
} Io leading gate of (3.0 g fish /1 af water).of the duplicate chanters N.0 te deep and had a tapacity of l$ L. Each test t h e sa e r wta I Jwventle f at%e&A einnewa 309
)
I 1
- - _ _ . - - - - - - - , - - - - - - - _ . - . ------.-a-wv,e we__,,.--_,_w,-,...,,,n-, -
I were placed in small glass holding chambers (0.2 cm a 20.0 ce a 13.5 ra) which were suspended in the test chambers. These holding chambers had a 3.0 cm x 8.2 cs Niten screen (#0 mesh, 0.30$ een l sperature) et each end to allow circulation through the chamber and prevent predation by the other test organises. Two 80 L stock solutions of each blacide were prepared daily. ' Chloriae stock solutions were prepared by adding reagens grade $1 sodius hypochlorite. DCDMM solutions were prepared by adding Sreeicide* (Crest Lakes Chemical Corp., Laf ayette, lodiana). Stock biecide solutieaa were addsd to their respective diluter systema for 1 h/ day, 0, 24, 44, and 72 h af ter testies begas. Water samples (ca. 20 n!) were cellected from each of the test shambers and tanka soetaining steek solutions at 10-eleute inter-vale during.the periods (ca. 2 h/ day) that bioside residuals were esasurable is the test aheshers. Levels of total and free resid-ual chlories (TEC and FRC) were determined by the DfD opoetre-photometric method ( APEA 1980). Ouidaat residuals resulting from SWfu treatment were aise routinely seasured as chlorias by the DPD sethedl however, the DPD dif ferentiation mothed (uslag glycloe) was performed oe a few representative samples to distin-guish between bromine and chlorine residuals (VNITE 1978). Median lethat concantrations (96-h LCgo's) were deterslaed by the probit, moving average, and binceial sethods (STEPHAN,1977). Los
- transformations of dose values were set used because a better goodness of fit was obtained is the majority of cases by asing actual dose values. Biocide dosages were calculated as follows:
(1) 96-h peak = the single highes.t blocide residual detected durint the four days of testing. (2) 96-h aseen maximus = the average seminus blocide residual detected during the four days of testing. (3) 96-h in termit t ent esposure s'.an = the essa biocide residual level during the four *2-h exposure periods. (4) 96-h secueulative exposure = the total 96-h biocide esposure in ag/L residual a misuces of exposure (area under a time-concentration curve) . LC50's for TEC and T18 (total residual bromine measured as chlo-rina) espeeurs were statistically compared. Dif ferences were coa-sidered significant if: greater LC50/ sas11er LC50 > 1.96 sgeger (AFRA, 1980). RESULT 3 M 3 DISCUSSION The DPo dif ferentiation seasureeents showed that > 952 of the oxidant residual resulting free SCDMH treatment was bromine. l l 110 l
1 Therefora, residuals from this treatment were considered total and I f ree residual brosine (T1t.5 and FR5). l LC50 values computed by the three methods (probit, bicoelat and moving average) were sletter. Values obtained by tLs, moving aver-age method are presented in Table 1. Juvenile L.:nead alsoove were significantly more tolerant of TR5 the . TEC. TEC and TRS - 96-h LC50 values for adult fathead sinnews t ar* not significant ly differest. Bluegills were significantly acte 7.elerant of TBC than T15. Table 1. Comparative toxicity (LC o's $ and 95% confidene,a intervals) of intermittent (ca. 2 h/ day) esposure to residual chlorine or bromine _- Type of bioside dose Siocide - computation and fish TRC TER 96-h peak (as/L) Juv. fatheads 0.44(0.22-0.62) 1.21(0.96-1.42)* Adult fatheads 1.56(1.34-1.79) 1.83(1.59-2.10) _ 81uegills 2.48(2.20-2.64) 2.35(1.92-2.73) - 96-b saan max. (ag/L) Juv. fatheada 0.39(0.21-0.53) 0.81(0.65-0.94)* Adult fathesda 1.37(1.lb t.35) 1.17(1.03-1.31) _ i 81uegills 2.13(1.93-2.34) 1.43(1.28-1,62)* ' 96-h Inc esp. sean (ag/L) , l Juv. fatheads 0.18(0.11-43.24) 0.35(0.28-0.41)* , Adult fatheada 0.58(0.51-0.65) 0.51(0.46-0.57) 81uegilla 0.88(0.81-0.98) 0.65(0.36-0.71)* = 9 6-h ac c um. (es/L a ain) - Juv. fatheads 85(48-113) 164(132-194)* = Adult fathesda 274(240-304) 244(221-276) M, l alues(11s 421(387-465) 301(271-338)* _-
- Lc50's for T,E and Tis significantly dif ferent at 0.05 level.
~
Stuagills were significantly more tolerant of both blecides than were fathead sinnove. Adult minnove were significant ly more cot-erant of both blocides than juvenile sianows. {__ Water quality data are svsessrized in Table 2. All values for - parsseters sonitored during the tests were within acceptable testing Ilmits (FELT!st.1978), and variability over time or _m between test chambers was not substantial. - The percentage of total residual osidant (T1to) consisting of free _ residual osidant (FR0) was greatest at times of eatinum exposure y 311 [--
=- =A. w .
1 l 3. . Table 2. Sueimary of water quality measurements made in
- Al' conjunction with the toxicity tests. c i' co' Parameter Mean + SE tange to.
Temp (*C) 21.1 "" + 0.1 19.9 - 22.9 *i
. ch pH 7.0 + ~
0.1 6.7 - 7.1 el h3' Do (ag/L) 7.8 + ~ 0.1 6.5 - 9.1 83 cl Cond (ushes/cs) 64.6 ~+ 0.1 63 - 71
. T Alkaltaity (as/L) 15.3 f,0.1 14 - 16 e o
D w
- s. In tests with both biecides. The FRC and Ft.3 contributions to TEC 3 Na W and T1.5 in test chambers receiving 1002 stock biocide solutions
~
averaged 83.21 and 62.21, respec tively during the 30 min periode ! o f san ianas e s po su re. FRC and yta contributed 64.81 and 50.42, '
-espectively to TEC and TRS during all exposure periode in the test chambers reesiving 1001 blocide stock solution.
This was the second of two studies coopering ef fluent toxicity with chlorination and chlorination alternativen in an SR.P reactor heat exchanger cooling systes. The first study (WII.0E et . al. 198 3) showed that osident residuals f rom ch lorine dioxi_d.g_urg
/g-yg 2-4 times more tonic to three trees of fish then those from chlo-rinetion. The presset s tud y showed t h at_.on_the b a s i.s_o f 9 6-h
~
LC50 values for halogen resj ,d. gds. chio.rine and BCDFJi additions _r_e su l t ed to s aat t ar overall toxicity to fish. Compared To7hT6-
~
,. rine, BCDMH was acto toxic to bluegills and less toxic to juvenile g , f athead minnows.
The LC$o values for TEC were substaatially higher in this study than in the previous $17 study wheru nearly identical sethods were
-A used. However, the pattern of relative TEC textcity with regard $^.37 k A A 7 ~
to fish type was the same juvenile f athead sinnove were least tolerant, and btvegills were most tolerant. Two factors which V
% 1h probably cont ributed to the greate7 tolerance to TRC la the pres-
[Nfiti _o eat teste compared to previous tests were: 1) a longer acclimation period to the test water (10 days compared to 3 days), and 2) a
&l40
~'
A: lower average water toeparature (21.1'C compared to 27.7'C). NhN-d ago ! HE.ATR (1977) and IA.S$ and KIATM (1977) concluded that water teir= perature did not significantly influence the 96-h LC$0 values for MkN. j ghy.g bluegills interuittently esposed to chlorine. However, toxicity testing of several fish species by 880CES and SEECERT (1977) and tjg; M SE.ZCERT and BROCK 3 (1978) clearly demonstrated the existence of a fgfs f* 'fj < direct relationship between chlorine toxicity and temperature. DICKSCM et al. (1977) also showed that chlorine was more toxic to
@n y ,y m~ [: .
goldfish at higher temperatures, 3 I 312 ne O h68 .Sh9 h 94 . Ne$Mh N We
f %Qk site a.nd time ape-Although all fish tonicity studies are soeevhatbiocida regies and relatively high per-cific, the intermittent results more applicable contage of FR0 in the TRO sake the presentthan to domestic wastewater treat-to power plant cooling systems al. (1982) have recently demonstrated eent systems. 550013 et toxicities among various forms of residual significantly different chlorios to three species of fish. MATTtG et al. (1981) deter-four times as toxic as 1 eined that hyposhloreue acid was aboutOther workers (ZILLIG,1972:
- I hypeentortte Los to aosquitofish. free st?Ums,1973; EASS 4 M1ATM,1977) previously concluded that chierine La more tosis to fish than sonbined chlorine.
There are no previous studies comparing BCDMM tonicity with , chlorine toxicity. 8romine chloride has been shawn to be similar of elightly less toxic than chlorine al., (BURTCN & MARCaZY,1979; 1980). These re s ult s along CECIAKVg & WAAD, 1977; LIDEN et bromine with those of the current study indicate that~ ~ chlorine
'pr5Iuce eisitar residual hafogeo tEtcitTto TGC' ~ y Ac knowl ed g eeta t e . The informatico contained in this article was 2- ,
Eloped dursos the course of work under Contract No. DE-AC09-765100001 with the U.S. Department of teergy. , RIFERENCIS i4 AMZ1tCM FUSLIC MZALTH ASSOCIATICH: 15 t hStand ard, sethods for the ed . APHA examination of water and wastewater, Washington, D.C. (1980). S AS S , M. L . , and A . G . HT.ATH : Bull. Environ. Cont aa. Tou tc ol . 17, ~ 416 (1977). ~106-
, 278~
3 ROCK 3, A. 5,, and C. L. $EECERT: Trans. km. Flah. Soc. (1977). The ef fect s of 8 t0C K3, A. S . , J . H. PASTOS , and F . T . D AN OS : time and cionic al chlorina ao f reshwater fish under various EA-2481 conditions. Electric Power Research Institue Report < (1982). J. Vater Pollut. Control Fed. 45, 134 (1973). SR!lNCS, W. A.: Enviten. sci ~ Technet. ,1){, 684 E RTCM , D. T . , and 5. L. MAAC RIY : (1979). J. Vater Follut. Contret Fed. 10, CECRAzVt , C. M., and 1. W. WAAD: 2172 (1977). D ICK SO N , E . L . , J . J r . CAIRN S , B . C. C RICC , D . 1. NZ S S ENG E R . J. L. PLATEIN, and W. H. VAN DER SKALTE: J. Vater P ollut. Control Fed. 49, 35 (1977). RIATH, A. C.: HydEbiologia 5,6, 6 39 (1977). L ID EN , L . H . , D . T . SURTON , L . H . 50% E RS , a nd A . F. RCLI MD : J, Water Follut. Control red. 52, 173 (1980). MACCHI AACLO , N , T , , C. R . J OHN SCM , Tnd R . 3. HORBACY.: Cc ol in g Tower tastitute Paper TF-219A Kousten Texas (1980). l MATSON, J. V., and W. C. CHAAACKt!S: Cooling Tower Institute Paper T7-250A, Hous ton, Te xa s (1982) . KATTI CE , J . S . , $ . C . T S A 1, a nd M . B. BURCH: Tr an s . hs. Fis h . Soc. 11_0,$19(1981). m w
. =sr -% ...m___ - - _1 _
N1 i _ _ _ _ _ . - . _ _ , _ - _ _ . _ , - _ __ . , _ . ~ . . . , _ _ ._ .-_--.--,.-..I-- . - - - - _ - - I
, _m.
7 PELTIER. W.: US EPA SEECERT. G. L., and A. Ecol. Res. Ser. EPA-600/4-78-012 (1978). (1978). S. BROOKS: Trane. Am. Fish. Soc.107, 346 - STEPHAN, C. E.: Methods for calculating en LC$ o. ASTM, Aquatic Toxicology and Hazard Evaluation. ASTM STP 6%. F. L. Mayer and J. L. Heselink, (eds.) pp. 65-84 (1977). I WHITE. C. F.: Disinfection of wastewater and water for reuse. WIlht.New York: E. W. , R Van Nostrand Reinhold. (1978). J. 50RACCD, L. A. MAYACE, R. L. SRIALT, T. L. J. ZlLLICM, BROADVE1.L. A.: and R. F. STEFFEN: Water Res. (in press). J. Water Pollut. Centrol Fed. 44, 212 (1972). Accepted May 4,1983. t' r 6
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l STt'lW ON Tile TOXICITY 01 SODIUM lillOMilW. TO
. .Dil:13EllENT lillESliWATI.it OltGANISMS
- L 11. Cntiv,15. W. Wlot a" nnd I!. A. M. MAistisw s NmAU
%tunuveil of II. irohi..l..pkal w Tinicok.gy and
'I .its.i at.w3 4 l'.ith etogg Naisemal Inunnie 1
of puhhe llealth, p.O. Ilog 1. tMr1 ltA flititu.ss1s. Itw Nsihetf.unts . i s tt o a.I llu. i..ss.tii ..I s.stwiin liii. iinte f..e tit slis.itei ..in itsisois was ersiI k&inhw sl insn.s .ile se i Ani fsnm..ua us t. o psiacans (18.pluu.e pneems t and fnts tr.n ont t!te st%ws tosint the ih;ute 404: tabo)sh,e si s= uma Ilis No uf.es.# aini inte. Obvesed I;tfA1 Conwntrattims (NOliC culics)in the Louig. terne toh vanol frews 7 II in 2.4n eng lit tiroinkte ion m.n kny) iiutuisent ieprishidisul sei hsHli cima. swans aml fnls. llatadop* "My mi elfdts utte syplasia s.f ibi: idwesol m Llw toup.terni sot uttis Ory/tas. t*ut in flee reiwislisthwi t.si wille piii*"
. Y setwuluctaw shp.mt. anoidir ami depesser.down of ilee nunctature aist irgivwne chanys '
trast acie of wersal. As a nitenon of maier stual.ty. I sup ler thtse lues 1%vu imalstel. seu ti.e lum i.f reg.i.sluetn e tvrfonmn.v in tint l'hiia tol.'l he nuwvutt.iti.ms foiusi its suifaw water Istuetuly swswt ilus s.iloe ,in i noineimies re.wh tewis at which .seule stiwu on water organiuns e.in h: espettal, attaestlwtic MS., ' ISaridor AG. Iluset. Swit/erland) introduellroo , uial the length umt weight of euch fish was deter. Chemkal analpo liate shown that brontide ion is mined. Normally a .twwk tot witti Dup /mia enurnu ur.d present conevntrations in l)aich surface waters tWegman. II.imalerintilrelatiwly de llwr. high nn eggdarval tot with n fish, comhined with a 1%tl. Ilowoer, as d.ita on the toskity of bromide tot with nfgae. may give a reasonaNe improdon to water org.mNns aiv lacking. it h imisonible to uhout the powihle wotoxicological ctrwts of u com-caluate thoe anal 3tical data with ropeel to the pound ( AdoTd. Cnnton SisutIT A Hurtstreit. IWil. ethvt oss the a.Inatk ceosplem, ikvame ivpraluetion proval to he u very senutise in thi. slo.h. shoit term and long term tosivity criterion m the tot with Daphnia the cliech on the tok were caront out with ditierent sovies of froh. l'i, und Us gerwratium were uletudicit.To esamine water owannim to get an imprewini about the alw repristuction ofihh as well. an addiusmal tot wn Iwnuble ensiromnental e'Nts of biomide and to entriot out with /biri## retirwlata, otabbsh a wateinpialh> criterion. 1'urt herinore. All not org.amsnm were uhtainal from standard-anemum n as niid to smel4 histopithologgat irollaboratory cuburo.'lhe'onupersilium of the tot I?nha wetc as destdul previously (Catitort & Shiof f, etTA1s m lhlt. l'Nal, etept fue the mediunt med in the re.
- 13p timcatal pn=hietion tot with 1%viha. Ihh test was per.
lornel sonw )vais upi wtwn unothei standardi/al Test m. acrid. t he punts of the sonie of sothum tot nulmin wm inal for thh (for the n.mpanition, bionuite nv.1 as ihr iot ci.mnion.t m ilus un.h was %v Canton A van fiwk. l'or.l. W V It was obtanwsl Irom 1. I'. llales Llwmicah 'llw ouncentratioit rubos in the short.tstm and long.ter))t. tests were haul on a rutio of { lli (l.sl tikieger, t h: Nedies t.uals). /lti (.Uh ropniiWly emnpt for the re.
"' 1,H ul iletho'I' - pibhbion tots with D.iphni.i emd 1%vdia.*Hw pil
%hoit.teim iown> toh were carnol out with rom anil oqpen content ol'ths tot udulmrw were chaked inifvicut tiohwates esp.nuum glaNe 1): the alga immohately twt' ore the Ivyinn uga of espinme mal M rncilemun pimsnimini. a etniawan tild/> luna when l'rch tot wdutkut wan introdum! or at Ihe end magno s and tuo thh Ll'on stia reth ulata umt Ury:la- of the tot (in the case of a static 1o41. llecame of the I. aire,i 1.ony.ieim teh were performal unh l>aph- high staNiity of widium kumide in aqueouwfution<
ma. L'.mba and t tr3 nas i1alN 11. Itor h nuns and Wnce no adsorption on glaw owurs (L II. Cantmr , dei.nlal deceipnon of the loi protoeoh and esperi J: H. C. C. WegmJn. unpuhhshal datal, the actual mem.d sondniom ued woh %nntomus. l)aphm. conventratium were not msasured during the tot, and 1%viha, the rule of the 1)utsh 5tanstardi/ahon. At the end of the repre. duction tot with 1%vdia Ospanitahon i14.so; Ni N 0S11. 6S12 tiSt4 & tiSit.: anil the tot with Orytt.n afi unimah uvre emnwrcl in Ikium Hautive aner being Lilled with MS f1 . I' rom
.an lv med as seteience.
'I he kmjt. term tots with 1%vilia aiwl Orvias were the nmirol group and the group cupined to aho eatpol ont awouhng to th.ese into. .\t ihe enil hti mr. Ilr .htre m ihe on with Orvnas, ten Hsh avre et lite l uWL tot willi l'.u tle 1 aiml llw s %WL less cHds'dddl ici ame giaial!in bI.nl aus! Mirtsitol Wint*
nuh tin snas the i.nt.unmr Inh nele Ldled with the wnall,o in the tot with p n1.sha. .ill Ir.4 mue em.
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$hortw seses Sissic - Growth (b. oar 6 ass) 30*ccitusal 0 IS 2312 Mortality, atmormal ,-
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rae.de seem tese H mt E. s'o*1h Fwiaung 2 MortaE y. immy. to M. SF 30 2312 abnorinal behaviour. S-9 anoashs I24 . 8 , soproduction, hissopathology 2312 hshaces 2-3 , MortaE y. upmy. 30 1 abeovanI behaviour.
> a hr (eggs) 34 Orr: ass toeps heart rase.haschine.
{' growth. W . 3
. . > S000 teak Wein 12hr Eght. Ash B4 hr Egbe. -
*Lighsing sas ese a Eghudert cycle for as organuma eassya S. paumaniner gr .
1 Test unlution was venc=ed once encry 2. 2-3 or 7 days as udscaerd. l - - .. l **. i 6
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- 0.2$ 0.25 0.25 0.21 NOr.C! ,
NOl'44.)C = No oNrval b. 96ulmJi relae sunswultaten .
- r. . grow th. .
tl nunialey. lti montahty am! :iheustnut heIutiimr. % was 7.lt mglir slitre, which was derived from th) . twidal imlisishtally aner being cut in uigittal or reproshielive performanet of I)ufelvila nuerms.und wseral transserv nueet. Sections were stainal with Ihvilia rrtiradats. In the tot with duphnids there was haentitosylin arsJ codn. a cotuxntmtionarci. tied decrease in the total number
- of eggn priuliieol per fetruk per hatch in the brood.
b uhs vliamtwr. us well us a onuxntrution.related dectense in the siabihty of thew elp (Tahk 4). This phertom. Tlw routts on" the s!hirt. term tonioty tots are enoil w.is alw obwtml in the tests with the F , und i summarinst in Table 2. twiilia retin, lain was the . 3' tilent vnsitih' orpJIlistit ilT,,, .s at4 ing llr ,littel. ls Feasradotts. Al flie three highot leu omeentratiims (710. WWI w heie.ts the other tot org.mams promt to tw f.er less nnil 73'tlilingilr /litts) tlw fertility of Poes. illa was . suveptihfe (by a f.ietor of 10 c.100). ihit lfuji.iilt'il tlurillg ihe llrst 3 %WIs o[CRposturg, hy[ , IlW reslilts ot* tIW lootg terit1 litsisity lots strn' sho% ft ill Table ,I. IIW lowest b(ll.C 4;ihe (No in a few caws picin.iture were lern uru! ilw newborn
- lish stere immobile or dixid. Aner,this period 'no i
()b,erged 1:tTwt Coreentration) from these stusties LMe 1 Sumanary of the tvswitt ol' the liust.lcrvit tothly tests awn sadioen httunide LCt!"Ci" LesrC1.i LCll'.C). NorC Nor.C a Eye.ure is tir 3ilfel Ig tir liitivi (a Br lidtvl LNICl. fe t orpmsm time (J.ipt Cruction A n=reme 2.4 bleprishstan 0.fu;71 0.0Ni ii.f ans a all 0.0D P generaiam p oln 0.02.1 01su7s c.at:54 F, gener.nion F 3yeneratum l' nt h U.uD 0.ulfi 0.011
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i at.: J 1 6 i.u of ihe ici a o..n sc { wnri "d' ki'dIdkl@I #Vd b7 481 IN* b ,,ue.u tp wer noni cumat to soshmn lwomide _". 'UN il' lb!ID fI ' g Cunmbine sto..leni.ile ' (NaWililuantity of fiillielo of varying die mat d maimnsshape. s ta , of emun.t s.wel toe sometimo eghjhititig tidital or multilayetv la WWral anmaali, mame ure:n of thyroid epo ni umew . i go and neuhmns Newivrns~ thelium were preent, with few small colloidal spaws tmg htret ,a a 3 The epithelium was pencrally vuhok! to adumnar. N y[., o 34 with nuclear enlargement, intrueytoplasmic hyaline
' 3 r.1 13.r.
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1 _ uptwarauw.or was even neurw or abw orgatt was tml invariably preent in the wetions from
- 3 all (!w attimals q repr.shwtion swurrol at .tll and Lillot as, the alleranimals Myopathy Wegs 2 7c .1) was ohwrved in high stereriorated all fisit m thew groups wvre inciderwy its the .Wix). and 7Nul.mg Ilr / litre groups uhout tti wwks of esposure aial priwswd for besto. whereas a minimal myopathy was prewnt inand a
.YA1
/ pathologict! namin.ttum. The animals in the few caws in the omitid utal 70 other d 750 mg Itr /htre groups atul there wn one marked
'l sos poups tf 8 up to .Mimg ils ,hird saw inwere the 7.Lmg nam.med Ilr / litre group. for TheISta) lesion con. olv ure ivin elfects on reprAf twtiott. Up to 7N mg Ilr ; litre, only usted of patchy or dilTre Zenkers d i the numivr of newivrn myotibrils, thefoez!isolated necrosis and invnsion by r muero.
ij .Mi mg (tr titre group tlwre waslish alsomis the birthreduwd: ot' phap. irt (lsually libro or groups e libres wete alfatol in a more or new symmetrical pattern prem.nutes in luo enwn. was condderably und the lesiott osuisl iveur in any klcletal muscle. but
't he Non* vtne fm Uryriashire ott the hm of mot. Aas found naist onen in alw tait muwlo. Itegen-higher nameh Dalmg (trtahl) and ahnormal cration waslvhanour. poor or ubentt No strats were depawrutive changes romat
'. at any of the testol conwntr.tlions (from 7.M up to were usually awmnistnied by atruphy of mwwls
- 7xud mg th hire) mi the be.ut rate or the hatching libres and hhrods of the endompium. The spinal
( of the embr)iw atwl neither were any deaths ohotri;. encd. panglia und nerve roots showed no relevant
.\tter hawhing. no etreds were found up to cha iges.
Ud mg Ilr in re. At higher ouwentrations thh in pewtia. th. viviparous guppy. ruprisluctive 4 f showed abnmmal tvhauour ma l ewet l > 7Ni ntg gwrSemanw can tv unewed from alw histopatholog of the fentale terrodudive tract. Thus in the groups y ltr htro died. .t'A*> or 7NKimg itt /htre, a During the toucit3 tests no influeisv on till or opoet to .t'*8. 7xt). i( I I ongen consem of ilw te.1 s.dmions omid be oh. makol redudson in llw number of foetuses mn tiowl. along with regressive or degenerative changes ierwd. h'l jj l II".'dloe r of the npWeiw truch usch as ovarian utrophy. systic fothelo and alw ocenilmal resorption of an I
.\ part from twkgioimd pathology le.g. f.dt) adentt%wl. stupe fodus. No treatment.relatal chan ges L f mlihr.ition of the ther. nephrosis, incidental hepalih5 were oNerval in the male tvptn.lustiw organs.
or ytanulomail. the povolia subjwtol to long selm In Oryrian. #m treatment.retated histopathological h lewom wvre detnted, smi cett in orgsm systems olwure damed three m.ijor pathological toions.n.mwly thstost hyt ch.mp m the rentale repristuctin trut ll'ahle 3). t atinni I: i lAv s I.ot.ise of In.h tuiNdopal stuuri, I= oos.+ en /% As arisadohs .stto leing tons otuus l "" 3 ' Wu. parunioJ or anntisl pilvr a Jtt osmure tourtheres or: ' 78n .M ai 7atst
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&& h-l.'$~f trg.
i J. K.sgiital %Woon si the tail musks or /.u til.: reriodas er stru s4 to 7906 mg lir /litte, showing liyalme depwe.itnut mto.is ami phopetosis 64 inslividual mumlc i;bevs. II/C x 233. I I
# e.- t
. o= ,
. e b
I e
* . tis l I
w ~ . . ..
, = . . .
,a j n.o.% te i..mu y to a rt.tne wt i.e r u" O out m ian Int diets oint.uning sothum honnhte bun Imenwinn . , Irrien. Wohtuns. ftniasI 'M er '"ed4 1974 8'" " ""liw"'"'
animals
- P" 'h" I"Ch"i I"'"""I#
sh.., s .rce,a r.. u. s t r i t" /..
- scho sulltuently and etlubild stysn s>f nlotor slette.
Ikpenshng on llw froltu. net orgamuih usof, the Menanon of the lond hmbs. Ai IlN etwongnis wnh Daphnia, inytnred rou:b of the shoes.wrm sancl t%ttL6l(). f.tilgi'ig ft,e mt, tinioij M to tots !!%, saluo)MInit " reproduction %m noted in the estwrnm
!!r litre (Talhe 2). In itwre tsuig or&r of sus. P c li u Aipinem bh. In both orgunnnn the aw MiiC vahw (7.K mgIlr /litrcl was found and ecptibility the test, orgamsms can he arranged "
folkmv ta) Piwtha, th) Or> nas andi,a (elhromide 1)aphn! pnned to tuve an embryotosic clTect. The logettwr with Avpalesmus Ahmat no dwieaw us WF.C vahmt! si nimlin and NMviemr) from this ku is of the s.nne order of magnitude us (he NOliC LCtlT). salues niukt be observed during the tests. V escept for the IL v: duo for pawiha. \, ith this fish TN .m. ihiun) (v.m A. duni. tom W. a la(sor of 10 mas fomulivinvoi the l!( .at ,24 tmur rdeon m olhpiing mittelato wdh the , n' rmive hsphserved in alw ovariew As degen. mxt at 96 Imur in the short wrm tots wuh thh. abnormal behasicur prtned to tw n ytry sensitive craivond utrophic &nges were found.un etreet of eriterion: the 1:Cs, values (h - mortaluy atul beha." Wium hme em sivsn fuswtion is sugetd iour) were about N) 4410 times to,wer than the f.(
- und is Amsistent with ovarian chastges values; in the tot with daphrudtthn ditkreno. no No I.open es of.1974 Tiw roults of the hntiepuludosW eumimuion of Pmilia indicule imohed a f.wtor of ahmt 2. IWilwrnmre u elar eEwt usin thyniid imirphology Alesattder. Quk-k .% lla s. lor omrplades prome. und herwe presumably upon its functice.This mor.
16 g hire as the 9t* hour L(,ytlett (19x1) ouhhshed phologient change corresponds with.the thyroid hy.
/uv. a value comparahte to the LCs. values found in p.rpt:nia observalin the rat (van legten ct n/,1974h the proent study. a spwies in which in addithm scrum thyrusine was reduced along with a dwreuse in the umount of
- thyrodne in the thyroit follicles las evidenced by un'
- 1. meg.rerm InvWry son /ic' immmioperoslase tevhnkl ue) wtwrcas the'sentrn Dap!, nut. &slium bromide prosal to reluw thyrotropin level was vlevated llacher 1'runken &
strong 13 the iquishwinm cap.wity of / Asp / min vari 1.wimvn.1910).11 kyetwrally anvpied,that the nureno thpming inw li, amt uho ilw l! generathm. inh thyrowlis largely owniurable.no the manmulian e tw nei. did iuu te.wl to lower Nult saho. Ah have Iwn' publishal im gLm.L Sveral pywrs though the Nttl A' triun the tot with Ilw it, gener. shysoid hyperplada or even thyroid tumours hufuwd ution was slighd.s lugher (Tahk .4 tlin n not a realntie dit1'erenw Iw.inse the repnsinchihty or of imkmiwnof in netiols1.y thh by hwlitw ddiewswy tilarsidurrer. 1979 or unlehyto 1.mpwim tots wnh liof./,ma maena is no twtter than Sblumtwrger,19M; Winsthead & lillet.1967). A a factor ol' .t.: trant.ui & Adenu.19ht, llW simple Imt natisfaery esplination for thyroid hytwr. concentration strwt curso of the P. 6 urwi lh gener. plasia aml hygothyioidiwn aller wslium hnmtide atams were also approdnutelv the zanw Nv ilw espnurc e:m lw Tomslin the cimitwtilnw hetwwn the if,.. ir. rathw in t able .tl. Companng the M)lf two halogens, hromine und hslitw. with restwt to (!! = reprishwthmt fror's the test woh the l' gener- th3rosine synihois. athm ami the NOl (* tl = mortalit)l. a remaekahle T)w myoguthy. shuraeterlm) ley myolibri!!ar de. l ddkreiw can Iw noint tahout a fxtor of 40t11. Newh genernlion. myophagia and utrophy. roemblo I u marked etTwt im repnshwteoit h;n not hwn found nutritismal myopathy demeribal by Cowsy & Rotwrts in previous studies (Ailema er u/.1951; C.intim & (1978). llolwrh (197x) and lleider (1979), in the j hir.1952a.h; Canton .t Wegman,195.th Com. proens stinly, however. the myopithy was not aswi. ' turing the NOll' aint NUIT satuo front the long. eiJlal with IipiNd liver depefwruthm alMI stealitt% l tertti test wills thin fristit the sholt lerm test it enit Iw his suggots that vitamin 11 &licietiey was amt a omehntal that there is a m.tiLal dilkreiw he wwn nulor uvindogkul fastor in this owulition. Sindlar ow Mil t's aho.but piolongatn.u or the short.lerm muwle lohms have Iwn idwrvnt in llw rut aller act t6t did not ivendtji . hmer Nil C vahse. .nlmiantruham.,of wshum ie=Inte trantin. lot.7s. In l'wi elu, in the 4.wM set ,w th l'.wdm rcri. sdard a nurLed esta1 on the wmim ng (whasumr of the eats porn untiuyi bromkle motor irwo j thh was not61. This citat sarwd from rahsvd Iwn iepiutal. hut withoui hntins.nhidom.d lohu An N)lf in Llw muscukiture ,14an 1.opten et u/.19741 xtisily to immohikt3 of the animals. (try .lat. in llw long. term tot. (/rnia, taripes salue of 2.4 mg Ilr hire was l'omat. A pawNe 3esisla. pnWeil to IV nhmt 10 .t0 limo los sendtiw llmn nation for thm phenomenon mJy IV the m)o(Mlh obsersol microscopioily. t Mtw the elTwt The im ume lwhas* , Piweis dinkience w;n alsowith foundroiwt to llw in the dwut NulT vaho ( ternt mur dal not imp.nr the pouth of the aninub m the tob. the Mitt vuhw lM0 mp lit htielisidentwal
- 5. aint ! At mg tir htte groups tihe NH C for to ill Lt IDun thg' sheri. tern) luhoty tot. ug was pro %llt 1%fnp al%ml llt illon lif el417. the Ioi%) udake obwtsol in tlw tot with Pmilia.
was appaiemh not .utated at these unwntratnms % laihue of Ihpias to stoelop pulado6ul t he abnoimal w numuy Ivluuont was also poinwl sabNs loan s at 7stimgItr hire may tw attnhutal to llw en the sh.uineim toi amt the M H l' .md shig wg espi,me tmw .ont the towet tot unwen. it' nun talin .md tvhau..ml m the sh.ui. inith.m when comp.ned wdh the rqmhnlion tot in long.lerm lots woe the ume l'lfun on Iwha,siour weie%o ob enof m a un it.o tousits .tinly c.o riol Piw ha O
- i, 1
------.s d l W .i.t& [ K Q f d h n dl Q .p fg M g ,V
. ..;;i A V W vpi n . i W JI N W. .-
s
. .,g g
,n g i 11. t wim e ..t l*rops.nid for a waterninalai e rits ro.un Vanion i U k Akins W W W UW Mnul'MMar ,
.h , ,
'*r'"J us t a
- h a 'ei '*nh w *1 J
, Toe Nol C.taloo iiom ihis stud) <*hini. .mir "n'.,'Mi f.i,,.,i, den"
, ,c ..'.*. *.ind cienpan.in or'wroia the r <* mr=".'ii> ct .
long term tests) can be stunpared with thnw estah,- p,,f,f,,,,,,,,g,,,,,, woh fx,p,,,,, p,,p,.5 and Aspluei s s uc ullees e i lished for other freshw ater org;inisms uwh as haetera . j I@f in sh wi.ierm carvrnisnts ll.nhu6adier M. l.15. 11%cenhnimesin thuecernl. cyanobacteria 1.lliq'8- c. mum J. H. A siniilf W. IlgN). A pmpinal tai dawfy . e1,Ih er axin.nu 1, plahtx th arn.: minor 1. inweis IC"
- om't=*mh anst t.. estabhdi water snutity 6ntersa lueel Il4 or, tahnrann y daia. I' #,uic. .wv. .v.ef, 3.1:r T i /ix piricen). h)dawans lilohn enligm tM. molluses it.ytemativs sing,uil, ) and amlihibians(Xerassius Ascrh)-Canton i -J.11. - Aa"> shadt-W.- tivu2ak
"- Tuseoly aind uwerou.
t tw. m ,if a . n. cam in.Impeh m i dami. in deere.tsing order of losieny hsn the bads of NOl'C uilues). the org.inisms enn lie utrongol as ibliows: {"["" '#N"' '* k* "" *" A p,,,n,3, g g,3 %qr w, g g.,n: tis. snewtitvIes for pinnphate l
;d. Pwnarmonas. Mienie)us. sanedomus. I.ennu e.,,o.,mi,,, raa... , en.a m u.eir ins u y .mi h - I i
'.[ (Nt)l!C: 2.4111 W liJ tre). ilptra (7Mi rugilit reh gygi.nlah.hty in the aputic envirimmn:nt. Carnweepeevr ;
i it, ws. I ?, Or> rias (2.41 mg litre). Cules 173 nig littel. Nenopus i 8 (l.4 mg litre) atul l)aphni.t. l'i%Niha and lJnmaca Cain.m A II. A un bsh (i. J. (197ti). 'lhe sluirt.tvrun
- h'anny if mane ikJ addits to different freshester b' (7.5 mg litre). In the L)mnava test reproductiort was n'y**% #"# ""* 0'ahan. Ta rdr ed. ift. 731.
# M ngain the most sensitiw criterkin. Thus it appears O N NM "" N Y. that bromide has .: sunt Led elTest wt the repnsitNtiost C8"h* tossay l d'orAtribrotovethane.
N"d" M' C'eystubesens and hamn > 1IT g of water organsms. Reproduction has prowd to he g. m dih fruh @isen. %ser L' a sensitive eriterion Idso in the r.it Won Leeuwen. den p,.s. 37,141 Tontelaar .t san I.ogien. IMll Coney C.18. A RAtts l(. J. Il97xt Nutrithmal pattniingy or ielones. In &4 l'ustmlanr. I:ahkii hy L J. Ruherts. p.
%;q l* rom the esivriments with vurious freshwater 21h. nainiere Tindall. London.
orpnkms it is concluded th.it Daphni.i and Poecilia ""I" '" E~l appe.tr to lY highl) sensitiw to bromide. the U"'5hNd*Id*8E* M
- UN N Nt)lIC l%'itig 7.!t til$ IIr litre. !I% a (9re%'i"'Is J
""""'"*"N'"""#'"'"*F*d"P'""""N*
Sud) LCuuon .t stooiT.,1. 197m. ihe tom es: -Mai ': Ikternurialmeet ad moste loskzty will 1%urilms refn - t ahA' ints pi"p'^nt j N()l.tl?)C % l.Cll'C).s I.Cil% as a criteriott for m aict sgualil.t. l or bromu, te sfus ut.a.a. N4.N f W; lkienmnalnut esf .luaicity wille uni. agg,o ,,in,,, gg g ein,, h g,ilne is I any llt htte on the b. asis of the elTo ts ll.naAn,.e, J, r. gig 79g Ao;meieg Hsy.,rg, geyha,y id olwertol sin repristnetimt in Pi%vilia (Table .1h l'uomuus in lowr Auimals suppionenti snuthumisan < l - F
)) 'the higitest goshYttirations of bromide in surfNe Inshtutism. Washington, DC.
water sistermitel hv Wegman s't id. Il%.li ist ille llAls*r 't h. Il% M yotuthy ami sleatitis in llst somsmm
,J
Itad nehalt % atm* eil plout rutYt . /*** * *l*d il'W'v'l frf4 8'lah8 81Yiff 48. Idd* .4888a
**l'oell%.l lvi .1
,i lii tog lia hite aihl . ma gtmu ni of aIh ull * *
- I"* E u* I "*" * ^* E A "" Id8*'" E' E E M 40 mN llt litre. The high vahics w the main fumig.ttien Ettort.,1hus, (141.11.12.llwis nf wshuin hnuniels ten ereilternne piirusse.
.ere Ibutst during Q it e.tn lv et(Wtytl ten in the fut as Mudeal by inununmykh% W
@ that th.e uw ol,meth>l bromste as a soit fumigant m f.stioi.unn,.n,iwy rd (Lee. Tveit.. H , y#l.
% glanlbtuw u tiught hate an adnefte elTW1 tm tht' Mielwels K. J. ll47Ek 'lhe puthophymnslogy and systomalie a61tt.ttle entirimmetu. The oitsviiinitions of brotuide pathology id seleiwes. In Min l',nanksy. 041; ice by L J.
[ in surf.iW water .ne softwtimes so high that mn (Wm p. 33. Itaittirv 11=dalt. lammion.
,I n O ;Nule effects Ctn IV espW1W!. SMutalk rptr ll. (s. (193)L Npnnlanineus psiiter snel unawr
[ of the tit} heed in anisuals O&Jee J. .Tif. M. 23. fb i tan law =en l' X. R den Toeikstear IL M. A van 1.ngten . hl. J 4 8'8313). 'lutkity of eintieuse hawnliig; s@g get {[+ i, mnmu owhvnne sysion and reptuihstion. Td Cisgu. Tatir. 31. t - 32.l. ' Ad.ina D. %l %).. C.asuost J. Il . %df W. A ltimsitet v.in 1 oglen M. J., Wolthe M Raves A. (1 Knii s R ska
'h'* ; A 11 (l' Hill Ihalevi.wk naaf wu l'.eisbkle Comuk:st%' TimLdaar l'. kl.. lbktras ll. A van lMe (), J. ller74.
liwtunethi*n ter Itetuhng un ee Aquahwies tosm Hot 59tuehnuue latiofy shaly' of meleetm hnemk in rats 1.1 un Nhlamperay.beke bikn. %1pustry id l'nhtee llealth Tann e er 1. 237. M anal l*nt th*nmetu.rM't.*to%ws. Rqert No. C1, 31 liti WeymJe R 48. C llamAr l'h A de lle:r 11. ligIL.tk RIV fdlil3 iHl Hill U1lll sl ll, liftmmk.i m Ju!Jr%Y iaf a (s.kigt shstrkt with laryy.ss.sk
,I, . Alew%ter 11. C.. t.bu J. A .tr A Ilirtten l'. A. (I"slL uw 98 metint bhmmk for sial funuptmas. r4 noe.
%1.the .seule soshiit ol sistmnt h6m ide to fallm'.nl 6.un. l'eu s. 21 tail.
en eu .. Ilu# . m n . I *.*t.nw. I' n e. :4 27. i.*f., Wi"Ilie.hl A II A I lkt N tl'Jhl). A muse usi liar slos4 [3 C miin M. t l'ai.)l. 5keletal muste new.un m mstste.ne. dol oiwnene et th> t.ml lucumis in alie setute gepp). louse, [ I r.d . . p. A l'.,44. fl.t. Mt. rokal.esan (PeteriL inct Genant. 2. 7.1, t
. t fr.
i l
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), i -
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;A _
8 t i ' ' Y*j Y* Y h M R: n ?ON l A*""2"! i Acclimation of fathead minnows well water (14'
! and lake trout to residual chlorine .t,eams r:W l
;;d ;..%. . of3
-I and brornine chlon.de ul .m.-
,y g, randomly selecte, p!p,, ,mc ,, ,,,.
G. blichcel DeGraevo, Bonald W. Ward "" * - rubber, and glas
-]I Grand Valley State Collegeo 'Allendale, hilch. construction of t
'l .~00 H. Em bers were 600 :
glass aquaria whi
'y' t 2.6 hours, or 9.
of inc during acclimation, and degree of ac. period. Althoug o Chlorine lui tven med for many years at a chnution achieved by fathead minnows. i made in the tant g wastewater dninfectant, and the tmicity ni %nt these tests were ennducted as a sup. ' measurements in chbrinated uasiewater is ucli dommented.'s ph ment in higher priority rnearch, theth,author jire eyej, , a
,,j Reently bromine chloride has been onnidered efent oxygen su were not able to explore this phenomenon as pp; an a poinble alternate method of disinfecting wonhl have been desirabit to test animala.
- - i wastewater " $ but Lnnuledge of the toxicity mmpletely as linu n ct, it wemed that the previatufy un. Signf8eant di g . ,I of chlorubrominated emnent in arputiv life wa< reportnl natnic of this data made any in.
limited to static, amte Imicity te<t< with fat. innnation t1ut enkt he obtained worthwhile, rposd andups Q.f
).
head minnows in chlorobrominated emnents hlore recent research by the authors. whleh METilODS AND M ATERIAI S g,is 3 y,, to test the relatd' y' j. usi enmhicted ming a finw.through system. 9 j
. shnued that although chlornbrominated efRuent ul!c. Mish.. Waitewater Treatment Plant as Tloc studies were conduded at the Crand.
bhd[ g
' j was tone to inme types of aquatic hfe. it was part ni a larger project concerning ef!!uentthe test chambe' connderably less tosie than chlorinated ihsinfection and residual toaleity.' The
*h emnent.r n
Whde condoning acute and life escle im. Gramhdle W.ntewater Plant is an setivated shulge plant which receive < wastewater pri. using 10 fathea ioty studin,it wa< noened that if total residual ***and **nd"#
, }- thlorine (Tue) nr total iesidual bromine chla. nunty finmemnent. domestic sonre,es usually j
ihnc< a high spuhty During the " 4 ride (tmu.) Inch ucre n latneh low initialh- twiinal nf thew studict, the treatment ! anti l'8" M i f *M and then gradually inctea<cd fnh scemed to
.fI be ahic to tolcrate higher rc<idual icvch than ellbent was chlorinated with a manua feed "series I'*" " o su I'*"" "d '
- d. they unnkt have been ahic to iniciate without minn adimted with the aid of !
a continuou In other u nrds. they opnating inidual (blorine monitor. Five and 3 pr evinm cywsn c. snen tenthi hten per minute (1.5 spm) of tinud unt eac seemed in he able en an hmate to the inc or thinonaint Gn.t emnent, which normally had g g i
.A vnue in the emocnt. Past ec.carth h.n indi. 1 o in 15 : 03 mg ; inc. was pumped from f fI her than th y ' catnt thit (hh .ne ahic to ao knute in alunen Ilm ihhnine contait shamber in the blessity 'I"*d *i"" **
m uater temperat ac
- and dn<nhed mvgen '
t tonientratum."' a!though niecmc. nf tal.natmv af terOne appiotimately Imndred arvl15 minutes # thirty.two of # #" nr Jm) either parameter can be !cthal. Became no moi.n t lunc. N "" " : #
~
data were available enmenung the abihte of was lismpomped twr nnnote (30plant's gpm)fina) ; unesposed ' f of nonditinfected
,~
l cilhwns from the d the 9' fnh in ardimate in Tuc nr inne in emnent. wtiling tanti to the s%nent treatment budding { tank an g'
<everal e penment< ucre enndneted to tot uhcre 2.5 ms'l of bromine chloride was sp. 8"*N 8#
this pn<ubihiv. The nhicctives were: 1. to pl.nl. After a $bminute contact time, $,7 wat WW e determine d fatle,ul nunnows aml late tront 1 min (1.5 gpm) was pumped to the bioassay incam e or h' . presinmlr npn<cd to inh!ctha) leveh of Tne lalunalnry for tmi<ity tettmg. [ aml tune in c(llucnt ucre ahic (n arvlimate Tl c dilution water inr the hioastay labora. '"1#' "^' [ and sonne m emucol h.ning Inch of inc or ton u a. acraint well water pawed throuch as
* .. A second gr inne ahnc their vnpcetive rii.hnur T L..
O in.n en nwal 6her. This water was of suf!icient cond 9 4 volun, 2. to orinnune the masionnn Ic cl of quahn in nuble fathead ininnnws and D@.
,, T O '
vne m emneni that f athc.nt minnmu can toler.nin mu na to enm aini repn= luce tathiscionh. ef!!uent, in t ate Im 7 dau af tn pininn np mne in sub. The el iminalnl emucut and well water were esposd to st lethal Toc in ch .un! .1 to deten nne relation. heatn1 en 2YC for Ints with fathead minnog g,ncentrations slup hetun n ao knutmn inne, onn entian m<
.f(. ,
W 2172 Jnurnal WPci' p % ket '
- r
~; j.
h I ,. - . . , . _ , _ . _ _ _ _ _ _ _ , . _ _ _ . _.____y-_ . . . , . - _ _ . _ , , _ _ . , , _ . _ _ , _ _ . _ _ _ _ ~ - _ _ _ . _ , . _ _ , , _ _ , _ _ _ _ . , _ . _ _ . _ _ , _ _ _ . _ _ _ . . _ - _ , . _ , - - , _ _ . _ . _ . . _
I
. kh h. .
g ne chlorobeoeninated eGumt%es tre unc eht5ed to 4 tE9' "siid$ise MlinIYfY
~
-t- "
wd above their 96.hr T!4evenues. . LQQM i spproximately the temperature ot smheated had no espesure ~; wD water (14' = 1'C) for tests with take The fourth group to rtsidual (cce*rol) bromine chlorkl# before being
. trout. Proportional diluters u with sorne re-hIon*ne .' -s were used e deuver de, w e nud in em-t -ammg iu ec.ce t,a-streams of 100 percen; eR!uent and well water tiom of nne. The mean une espesure level 4
snd e intermediate emuent concentrations of amt the mean survival time was calculated for* 60, 30. 2J.0,13.0, 7.8. and 4.7 percent to each test group. . randomly seleded test chambers. Only PVC A tidrd group of tests was conducted to e i pipe. silicone cement, stainless steel, neoprene determine the time required for fathead min-i rubber, and glass materials were used in the uuws to acelimate to ehlorinated eBuent, and r i 3 -. construction of the diluters. The test cham- to determine what levels of nc were most . 8 bers were 600 x 290 x 300 mm (28.41) moducive to acclimation. (See Table III to 1 gbss aquaria which received one vohtme every facilitate a better understanding of this portion . I-
!$ hours, or 9.2 tank vehimes per 24 hour of the study.) Two groups of 10 fathead min- ' L j
.n. atxl degree of ae- pmod. Although Do meuurements were not nows were acclimated for 1 and 2 hours to [.
1, cad minnows. sude in the tanks used in these tetts, daily Do 0 070 mg/l ne in eGuent, and then placed in h [ inoducted as a sup- neasurements in eqtdvalent corteentrations of cilhicnt having mean uc levelt of 0.302 to
.:i ,
incatch the authors the life cycle study tanks indicated that suiTi- 0 319 mg/1. A third (control) group of 10 d ,
~
. d.is phenomenon u cent ongen supplies were always available umntlimated fathead minnows were concur- 1I hoc t urn desirable. to test animals. renth placed in ellinent having mean nc ,,
at the previssly un. SigmAcant differences between previnody Irsch of 0.312 mg/l. In addition, fathead q 6 n > ; data made any in. esposed and previously unesposed (wntrol) minnmn were acclimated for 3 to 6 hours at
- 1. hour intervah in chlorinated efliner.1 having 1b nhtained worthwhile- ppt were determined using the two sample il sest." A linear regression analysis was used ine leveh of 0.030 to 0.049 mg/1, which was ,
3 I ltl M.S = test the relationship between survival times near half of the calmlated 96. hour T6 value for that species, and 0.074 to 0.095 mg/1,
)
'$ t ndort..d at the Crand- si acebnated and nonacetimated fah.n t i i Trr itment Plant u Leseh of ne and unc were measured in w hich wat near the previously determined 96- L
.i ou4crning emuent the tett chambers with a polarograph using the hour TL vahics (0.082 and 0.015 mg/1) ' .u
.in.d tmioty. The aperometric titration method." Af ter cath group of 10 Ash was expoted for I d
plant h an setivated The Arst study consisted of 4 duplicate tests the incoRed length of time,it was placed in a 'y
/,;
. iin wastewater pri- ,;smg 10 fathead minnows each. These tests sontrotration of chlorinated esuent having
.in n and n ually pro. .ere condmted over a 7.weet period. Each im. Icseh wc!) above their 96 hour TL.n. .
9.
. nio, st . During the .rst group u nt randomly espnted to one of a Concurrently,10 previously unexposed (con.
. k, the treatment plants enes of tuhteih.d chlorinated emuent concen- trol) imemle fathead minnows were placed i with a manual feed ranons (4.7 to 13 perernt) for I week, then in duphrate tett chambers having similarly
'O
. a,a of a continuously mshned in a dichth higher enneentration high nu lesch. The mortality and ne levels M
n,. . n , miinr. Five and far the next week. This procedure was con. ucie monitnred in each tank until all of the U niinme (1.5 gpm) of med until e.nh group of Ash was Anally sub. piesioml> exposed and control Ash were dead. .j
- a. ul uh normally had ected to thlonne concentratinnt which were lhe mean Tuc lesel and mean survival timc n . was pumped from yher than the 90.hnur T6 values for f at. was calculated for caeh test and control group. t '
n onb. r in the bioassay bd minnows (0.082 and 0 095 mg'l) which Our pievious studies i showed that the efilu- I s naati lt 35 minutes of m calculited from Aow through bioastay ent tuntaining both Tuc and use was not in- 1.b
,on.he il and thirty.two ist results.' At that time, a control group of hetently acuttly totic to either fathead min-
'."e geni of nonditinfected perposed Ash was itolated in the same test onu s or tale trout. Therefore, there were no '
Inom the plant : Sns! yk and the mortahty of both groups was lah espowtl to similar nondisinfected eIIluent ' t.., nt neatment buildint gatored. If the previondy exposed gioup t unientiations in sene as a control. ' non a c hloride was ap. , ed for I week, it was trantlerred to the n.on sontatt time, 5.7 w higher concentration. The mean (all Ill'.S U LT S po ni ed to the biossssy reans sie at thmetic means) n c esposure Fathrad rniunowt previously esposed to tub. !
' ' ' ' H ', L Ine) and sunival time for each neel was cal. Icthal Tuc !cseh tolerated higher nc levels o.
tac h.inauay labore. cr,bted for each sample group. than om observed 00-hr TL.e. values (0.082 to . m i p.med throu h s^ A second grnop of four aethmatino tests wat own mol) inc at least 7 days (Table I).
,"Ni$hn < an D . *docted uzing iske trout in thlorohrominated Fathc.nl minnows survived with no mortality
! ,, p .ince satisfactorily, thent. In the Arnt three tetts,18 Ath were for i ucek 0.1.11, at nemg/1.
and 0.133 levelsallofof0.113. which0.116. were 0.110,
.o d well water were aposed to sublethal (0 011 in 0 063 mg/l) i, u n i f athead minno.,s geentrations of chlorobrommated ellinent for hicher than our previously determined TLa October 1977 2171 -..--r--.
I - . - , _ _ f" k
l
.khkJh hffh.f 'hh h k Halogen Acehmetion
. d> ,
ire to chlorinated - htively high nac concentration (1.066 TABLEIL Siirvint of lake treet Isr
..s, ,g/1). Of the 18 Ash,22 percent were still chlorobresalasted odhseat.'
. slive after 5 hours. Although the time to total Tot Nunibn 1 3 , tahty was not known, C,4 4 Ssh remaining ,
~ ~ ,
sliw after 5 hours of exposure were stressed 1 tune cmrentmtion to which nah '%
" I sed probably tlied within the next hour. A s. *rre Da'v3=dy al..<d om mg/l ,
1.cngth al pnvioup erjiumum 4 days , anning that the remaining Ash died after 6 umtuni ni which fish it hoors of exposure, the mean survival time of I T""# ',s[m , t}gs groua was 3.7 hours. By comparison,18 : ,,,y;y,i ,;,nc at te.t n.4 dual .t.7 hourst,t .-
" i prestously unexposed (control) lake trout that Tc.t Numler 2 '5 [g lf
' sere placed in effluent having considerably k*er Tasc levels (0.647 mg/1) had a mean 1 tunc iuncentmtiun tu mhich fidi survival time of 2.1 hours (Table II). Our were previuuay expecd 0.029 mg/l l k' ;u , -
l.cngth ed previous expo ure 9 days
$ hour Tl u vahie determined in earlier flow.
- Tenc runrentration in which 64i Arough tests with lake trout in chlorobromi.
(:y
' "C'"'"I N '"8/3 g3ted effluent was 0.102 mgA) 7he second t ev irst subjected late trout to mean usc levels tinw at w il 3 h w il . 'ty i .
f 4 0.029 mg'l for 9 days before they were in- Tne Numler .1 . yoduced into a tank having 0.001 mgA noc. g ,,,nc y,,,,n.,umihin in .hich ti h I De mean sur ival time of this test group wat g , n p,c,;,,nay ng ,el H.nll mg/l .f 10 $ hours. Test three inbiette were exposed L.m i h ,,t pn t;,,n. ni. -ur,- v itar. 1 te 0 0ll mg l Tium for 9 days and then placed 2 tm>.c concentration in w hic h li h f4 y e?!uent containing 0.641 mg/l noc. "Their m e re Ir=in t U.HI mir/l ' ill
- t *m vival linw ,a int tr.idual 7.1houral
. iran sunid ti .m was 7.2 hours. These data *
,p . hat Test 2 !bl, were able to tolerate enn u,,3 "
e,:nbr residual levels for a Innger period of "'"*"'"'"U ' ' 3U rre because of prior expature to a slightly "*#I Qber Tnuc concentration (0.020 mg'l) than " ""# "y" n.",y, , '
, , "[f['[f , , , , ,
, i
'b
'M Oroup 3 (0.011 mgel). Croops 2 and 3 sur- g n uc n ,,n , .n ,,a;,,n in . h;, h na,
,ned signincantly (p = 0.05) longer than . ..n. i r ,nt o.647 mg/l M
aicit controb in similar Tnoc concentrations. t =wrsival tinw at ti,.t re idual 2.1 huur. [ ",4 Table !!! presents tun n al enmparisont be-b)
',,, cen 14 gmunt of 10 fathead minnows. each . iwhin.n Like in=>t more nel in ras h tr i (t '
int..i i, nuik m mm. t .whi n.7 ut ,- o ..i 0.359 Amated to iblonnated elfinent for 1 in 8 t iWiel.ii.nn luid ut.ni aH b4: kivinit din] by ' d;i;l
.o 60 igs, and tlnir respet tise stnitrol genitps ,
' l.. i aln) 25.6!
Ahn 5 huur i4 upu urr 4 y 'J!
;)nch lacled presinos emotore to chlorinateil 6 of I"o'w"i s"In al h nc *' urr.
tm abws ahhough they mere d'i 4 33 ,6ent. Thnw ridi svuoudy esposed to '""*I '""I P " d " U F 'N'I """" ' h'""I'"- 4I
' " "U
-- -- en T1tc levels of 0.0.'J mg'1 for 1 and 2 """"d Y I""8" 'h*" '" " I wn showed little thfferente in mean sunival t,a, $","[j"*
3
'f' i-
,, . hen compared with controls exposed to
,c,,mlar test concentration. Of the 12 remain- t me of 5 0 hours). Also, those Ash acclimated gb i
- i. , , i . ,i -, snoa ance. si pwps of test 6th. O uere prenously et. to ine concentrations of 0.038 to 0.049 mg/l o,.. t.ni. 2d rninnc, ped to mean "c Imli hasing a range of thmsed a creater difference in mean survival : Q l'
, . .. , . .t i .e m c %e nt ) n% to 0 040 rug I for 3 in S hnurs, while the tinw wben tempared to control 6sh than did '] 4
,,uning G croups of tett fah were previondv the fish aulimated to mean ne lesels of 0.074 ** i
,,,, atin 3 weeks d oF5ed in hichn tur lcsch of R074 in nrry maanse, to otic m to oe m m e 1. Wah the exception of the test ). I
. L u h. Ilowes er. la stIfor3to hoor t en pre ind expused to 0.070 rng/1 for 1 ' '
n,, noon t tunived fa, p that had prennut evnsure to residual .md 2 Imts, and those pieviously exposed to .
. , , sp., sal to 0.306 ud elk"'d 5"'"*I I"" E" I *#"" '"" #I 'I*' 'I 0.0a m I w for 3. hours. all other test
,, i uitts of exposyr, t hours) than did nmtrol Ash (mean survival in eiW iidaml>- h did ,
i ni number 4 show, we of 4 houish tuntrul lish (p = 0 05). i.
~~
Tuse 6sh p.esinndy esiwed in the 0 lowest in addhim a linear regre ssion analysis per.
,, npised to subletha s lesels f 0 0% in 0 019 mg 1) for 3 in 8 fnonut latween length of sechmation and ~
. .mniar abihty to se. gn were able in innive in Ingh ne levelt Ic,uah of sunival when exposed to high nc *
, t .,1,lo ll). The int keger (men sunn al time of 01 hnurt) than leul, nuhvatnl that there was a statistleally
,,, mo,n touc lesels d p that Sail previnnt emo< ore to mean W iigmficant (0 001 level of signtScance) linear ,;
pi u n to cwosure to a g of 0.074 to 0 095 mg I (mean survnal erl.aiombip lwtween those two variables. The October 1977 2175 m
- - _ . , - . , . , - - - - , , , _ , . , ,,-,--g - - . , ,__,_ _ . _ ,, ,% , , , _ . _ , , , , , , _ _ , , , , , , , _ _
__y.__,,_y.._-__.___-.,m, , , - _ _, _ ,,,_,,,,,wy
. . . .q . e. . , , 7 ,. . . . .
. ., , , c.
g Decreeve and Ward . l TABLEI. Survival of fathead minnows
- with and without previous arposure to chlorinated relative}y b wastewater. ing4). Of f
Week of Test anortahty wt 6 alive after 5
"] Duplicate Test Numtier I 2 3 4 5 7
_ and probabh u.I4.1 0.504 suming thet I hlg/l tac 0.u36 ti. I 1.4 i r4 F.muvnt Com entration 13 21.6 M M bours of erp
*; i Survival Timet N\ll N .\l N.\1 17.51 this group w s Nurvival Time! 14 1.1 previously ur
.j i hig/lTuc H.032 15.064 U.116 U.312 were placed
., 1* '
r/. Ef!Inent Concentration !? 21.6 M 60 lower nac '
; i Survival Timet N.l
\ N.li N.1 \ 19.31 survival time a Survival Time! - - . 56 3 1.4 96-hour Ti ,
} 2 k!g/ltac u.uji n.uh n or.4 n.214 through tests y % Ehinent Concentrati.in 7M l.1 11 r* M nated eRuen W '
, t 5nnival Timet N .\l N11 N .\l .49.7 s test subjectec
_ , a snevivat 7""r! of 0.029 mg/
.. . .\lg /l i n e U Ul A n ul? H il69 u.213 uCed ido
~
r; i:Murni Cuncinitati ni 7.8 f .i li r. M t Survival Timet N31 N31 Nil .17.6, The mean su:
# 10.8 hours.
1 Survival Timt!
; to 0.011 mg/l 3 .lg/ lime
\ U nni n.oi r, o u t.l n.100 0.106 i
in eSuent cc
! Si M&ent Conecmr.ni.wi 4.7 7.8 1.4 21.r. .l6 mean survival 15urvual Tiruct N \1 N TI N \1 N 11 62M suggest b m .
2 Surviv.il Ton. ! .l.6
.i ' Xf g/l ue o.ini7 u nJ9 u ni t 0,114 ILil y similar resku
'y '; Emnent Conenor.n ..n 4.7 7.M .11 21 6 .th time be.'ause Y s sun iv.d Tim. t N \t N \1 N \1 N \1 26.31 higher Tnse i f a sun .v.d lion ! 2.r. Group 3 (0.0 3 n.Ja l vived signi$c 4 .\l01 i m e nimm o n!I n o41 n. s .4 4 d ' 1:Mneni C. .enir.on.n
, 4.7 7M it 11 r. % their controls
-I t 5urviv.d 'l me. t N \1 AY N A1 N 31 77.43 Table III T t 5unival Tinw! 2.1 tween 14 groi
- q' .\lg/l tac u ni f u nJJ u.uiu o. l .ts u.224 0 359 sechmated to q r; FMornt Con. . .o r.o .n 4.7 7M l .i 21.6 x 6u bours, and t j . t survival l'imet N \1 N 31 N .\i N .\1 Jyi 5lnraatity 25.6]
.3 which lacked
, , a survival Timo! 1.3 gg g rnean Tnc les 2:
, ; .'l'J *t \lca t insatn nn I. ival ngikenne .i14 0mm. .n,.it .ofsin n.74 3 prn .. ".n.i.ry.~41 i. h' hours showed y 1 Slran .urvit al Umr t hour.) <4 $ pro svu.1) inw sin .I h h. time when co:
I No mnrialo3 elunne that un L a similar test c
# Aun n al innr .ic mi.. anile i.,oger lh.in pr. s i..soh snu y. d h.h at t he U li3 leve i e4 migniferance. ing groups of
. e L . oni r..I h 5 ry ~,i. it'rn s..n.is . ..o.h .,: ... ni. i..u. i> nu. ind.raint iliat fan.casi nun % posed to mea h nl a nwan .orvival time of 9 31wn.r. m b. n . y.. 41 in umt ir in 19M mg /lJ riuu tuttat uun uliac in e%est.) 0.036 to 0.049 remaining 8 gr
( salnes for that spetici. Alto, at higher rnid. 0.2D aml 0 215 mg i inc after 3 weeb d etP05'd 80 hiF ual icsch (0 215 in 0312 mgcl). piruoush esp nme in iubleth.tl inc levels. However. fa inFI I0f 3 'O opmed lathead mmuou s inevivesl for 10 to Tists 5 .uul 7. fatheail minnema surshed f , Esh that had
,{ -
37 umt. limger (17.5 to 77.3 honri) than ihd 02 6 aml 77.3 honn w hen eywed to 0.306 a4 chlo.ine survn their respcs tne unnp.nul tonhol ginnpi (1.1 0 Oli mg l Tiu folhming 4 weeks of espoig,, 8 hours) than i to 3 0 honn), to sohlethal Tnc leseli. Test number 4 show time of 4 hou There aho appe.ui to be a treint foi fathcail a smul.n Iremi, Those Ash p
] . . ,. minnou s to shnu imicawd tolciante Int high l.de tenut ubich ucre cyuned to subjet),gl gite levelt (O L Tate tontentratannt at length OI c\posine to suh. Irwls of iniW' slum ed a simdJr abahty to ac. bours werc ah 2,1 ! lethal vnt icsch increases. For cumple. in s tonaic in lethal leveh (Table 11). The Arn bnger (mean i
Tot 2 (Tahle 1). fathead minnons survised test gioup was cywned in mean Tuc levels d (sh that had 7, for 39.7 and 37.0 hours when subjected to 0 0m mg I for 4 dan prior to erposure to a j, vel, of 0.07 xp,i .y. 2174 journal WPCF
.1 6,h ,
a l , :
-i _.
I
-..__---_,_--..-,.,,-.__n._ - . . _ . - . _ _ - - . _ - . _ . - - - - . . . . . ~ - _ . . . . , , - - - . , . , - - _ _ , .
s.
?
O $,q . & Asa previously unexposed Ash. A similae has been observed might fadhtste.sveidense e phenomenon has been observed in a life cycle adions by lengthening the time interval avad- .. inicity test with fathead minnows in chlori. able for Ashes exposed to high halogen concen-seed emuent. While 96 h TL values for trations to and a more .'soepItable environment, i '
"' fghead minnous are 0.082 and 0.095 mg/l and might sho be on explanation for the lack ;
ne,100 percent of the test fish survived for of observed fhh kills when ne concentrations
- 106 days at mean ync wncentrations of 0.129 are umuually high.
- i eg ). One explanation for this long survival Studies to determine the lethality of chlo- ,
a e relatively high Tnc concentraticos is that rinated efflucuts generally use test animals -j ibe test animals acclimated to residual chlorine whleh have never been exposed to, and thus l '.; kring the early days of the life cycle test when have no increased tolerance for residual chlo- I ricantred Tric salues were low.' rine. If halogen acclimation does occur in
- In addition, esperiente has indiented that hih populations living in environments where 'E .
m]crance to Tnne concentrations above the they aie regularly exposed to low residual N, level decreases after several days of ex- chlorine tomcentrations then it is possible that '} psure to halogen free water. For exaInple, in the chlorine tolerance limits determined in q J. We cycle toxicity tests with fathead minnows many studies do not apply to those regularly < 9 e chlorobrominated eRuent, a decreated tolee exposed resident fish, but rather to fish which ge to tunc uas obu'n ed following 13.5-day rnay be tramient and have not had recent ! 'i y penod whcu. because of mechanical fadure, the halogen exposure, t il rst artimals were not expoted to re<idual ' f, wenine <bloride.' CONCLiiSIONS Whde halugen acclimation was observed in This undy leads to conclusions regarding the , f" pt two species, other Ashes probably aho aestimati m of juvenile fathead minnows and - poco thn tapabihty, which rnight base int- late trnor in ne and inne in secondary . nst value in natural conditions. For instance, elliuent.
. situations u here low levels of resiihul chlo. '
- 1. Fa head minnows and late trout with s,e are continuously added to a stream, such previons esptnnre (longer than 2 hours) te 4 4
g below the discharge of a chlorinated emu. t hlorinate d or thlorobrominated emuent re- i
,it, resident populations might develop an spet fivel> were capable of tolerating high messed tolerance for residual chlorine. This lesch of rm: ne nnc for longer periods of time j ,
ge.aed tolerance might enable the animals than Ash that were not presiously esposed to . i y
- is ranwe in, or escape unuinally high chlorine either haMgen.
3 dals such at rmght otrur u hen the treat. 2. Foi fathead minnows there was a linear '
; wit plant dncharge< efiluent with high ne relationship between duration of previous ex- '{
,cer.tratium or during peruuh of low stream posure .nnl toler.une to residnal halogen levels '
_ g An cumple of high Tnc leveh in a in cum of !XI.l.nnr TL:, vahies. .t
.. ......n), wening stream was reportetl hs jackson " 3. The atshmation of fathead minnows to f ibe found ne levels ranging at high as 1.40 nc was most apparent after 4 or rnore hours v
.i3 ng at 12 hourt gg i in retening w ater below the Howell of expouire to k w ne concentrations.
a l ' hours. 3id.) Watteu ater Treatment Plant. It is
- 4. Es cu af ter long. term exposure to sub.
pble. honeser. that Ash reading in water lethalloch of Tt c m effluent, fathead minnows lJ l
- of the fish se. pg uc les ch below their Thw saIne ruight une not aMe t a sunite high nc concen- {}
i n . .: I nc uen der some adse se inWthal cuests, soth as h a boni. h-
- m .nc for IL5 aced abibi) in amd piedatms ur redused
... Smet cal, 9,Aetne capmoci. ACK NOu LEDG\lENTS I
. ; ,n yving g Harr " ihicocci the f.u t that emprisinciv Credits We u nh to expreu our appreciation ij l
' hh Lih bas e becu olneneil u icie the Im fal a n .. t on as,nt.nue and cooperation to l $Nd $ nnated elfinents of waitewater catruent Trnt Cenian. Dale DeKrater. Irwin Jousema, He Paturia .Withno, and llomue White. Fund-l'l t be grT M8 8 .
.'gi... , .gtm'e thatdmh.n ge,1reason one powhie into natur.d waten.
for the latL ing for tl.is rnearch was provided by EPA ' f y g,rprted Ash Ldh in that thh .ne capable of Grant Number S.502292.
; we.og an1 avniding potentiallt lethat con. A nt hon. At the time this paper was written.
!, gj, and 1d, rowns of tmic '"ateriah Sprague and C. \lisluel lhCaeve ami Ronald W. Ward ; p
. . oom
. sp.. ed to c.s p y n and Sonimerfelt and Lewn " sho were in the Department of Biology at .the l J [
. on,c exiab.S wed asoidame re.atnun of Ashes to ter. Cr.nni Valley State Col'ege Allendale. Mich. ;
h '
.p. s in e halopa p cherninh. The h.do,:en anlinunon that IM;raeve k ennently in the Department of October 1977 2177 y
i , i
..sM i n
( . 1 d l l d P 1 v-- e-- -
---m-re--em-wwv -+e ywi-w-egrw--wr--iy--=--ww-- 9-w-in-e ------y w s*-- e --
-m--e *------*----------w -------e- + = - - - - - - - - - - - - -
- m. .
x:e p~a.>..-,.......,. ,[ - q$
~
..+.b Fry and Finsarlings? Prog. Fish CrJid
- Zoology and Physiology at the UrJversity of 814 (lW3)- l $
' Wyoming, I.aramie. 9. Chavin, W., "Asspenses el Fisb 18 EN ;
mental Chamens? Queries C7% Re ikm d ' ' f A, "Literature Review of the 10, S ss U" I' k.i,fg[' y,. four ese F C ikFed45 }8I
- f I"*' N#* N* Y P 883'03' N).
'" #* ", M UoM cl Califort
- 2. Tsa , C. F fests d Sewage Treatment II' Plant Eslt ents un Fish: A Rev6ew of Liters. Stmlics." Wese Ase., I, 30 (leM j'i 3Y,,,'A'* Bnsng ,,
! eure? ChmeA Raearch Consortiusa, I"' N l i II' T'* N Westeweter,.Ememimaales dflath 34) I for Alt- Methods Water and i Assa, Washinget
- 3. Wi , ,
);,ing ed l I rrda !
R idust obey , En h',"*d gju ,
' the population pressure. I-gi rms Sodefy of Baltimore, (Nev.14, 13. Afrmk nhall, W., "Intru Imilon to Pre % isode to degrade wate ami hiainths? (4th Ed.) Dumbury pg N. Stituate, Mass., p. 222 226 (IME), trot that in many are
- 4. Al lis, J'. F., "The Disinfection of Sewage '
i
' Erbent by Chlorobromination? Presented 3 4 IM'"u, C., "Catol Fhh Study at the H =el ' potable. Responsible W8dr*diff I'WI""*"8 Mkh. Weser 3, g, reed not only with l cfore the Dwasion of Water, Air and Waste Chemistry, American Chemical Society U"*"* O"mty Drain., Plant on Afarten and y ggg hfertina. Dallas. Tesas ( April 1973). *'"' 0"nns. (lW I). @ges In watw quall i t
' 3. .%Ils. J. F., "The Chemistry of limruine 15. Ilarr. Tlmanas E.,"Ibklual Chlorine in Wea,. One such area is Si
' Chionde in Wastewater Dismfection." Pr,. "dire M'a nte liesuh6ns Innn Disiedection,.
sentalleinte tlar Divn6nn uf Water, Air sml Talmini l' aper No. 38. New Yout stei, towneastern the !de of the of Bishop, Calif Waste Chemistry, Ameriesn Chernical So. Dept. of Envmmmental Conservation, tot p ' i , ekty Afeeting. Chicsgo, !!hoois ( August ( luT5 ). fall of 1974. a team o I 1073), in. Sp..unn . J. B., aml D. E. Drury, "Amidane luulty from the Env ' l 6 '/.d!nh, J.'A., "Prvliminarv Inseitletion i4 the licamna of Salnumid 1% to Repressata. Engineering program c ' Relatise Tusicitics of Chlorine Bromine and riir lbliutants." In S. II. Jenkins (Ed Mies of water quali Brnmine Chloride? hiidland, In House " Aih auns tu Water Pollution %.lreaches of DisheP Cri Pnw. 4th Int. Cn J . Prague, % Oi Report, The Dow Chemical Company st4 8 bcMd 4 a (1971). Prai. New York and Oxford, p.10313 biological characterias
' l*
e
- 7. Ward, R. W., and C. Af. DeCraeve. "Residual (It/19).
Tosicity of Sortal Wantewater DistrJec. 17. Sumnwrfch. R. C., and W. St. Lewis, ~3,,4 l' taminate assessment of contan i t a nt s." In press, /our. Werrr Folf. CoMrol enn of Owen EmRih liy Certain he recreation related tasag Fril. (1977 ). "Rates of Tempersture Ac. femr. Wofrr full. Control Fed, 30, 3 gag Planned manageme , 8 Das ers. W. D., (1907). chmation fut llatthery Reared 5tnped Bass Basin's water resource y the South Lahontan '
- i. -
Control Baard (an < l / , state Water Resourer ' 4 , the U. S. Forest Ser l 9 ; ander IInc mandates o i ktion Control Act At lI
; / to abate po!!ution an,
. iter in water bodii
[ l* enable to predict watt from the rnanagement f the agencies feel tha i
- ethin the area will he or in what way is not
. t OBJECTIVES The primary object
-j p[rovide e
a tornput water stuality indice Creek. This simulati
', 1. Allow predktion quality- indises on t 2178 journal WPCP
, i
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l J
,n i ---.-ie- - - - - - - - - - - - - - . , - - - - . - , , - - . -.. ..,--r-w.----e---. .-..--.rm%m-.,,.,-,,-.---_--,.,-_m.--_----~-,-.--,,,._..._,.----.--,.,.-.--,e
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~
Ufects of chlorolmrominated and chlorinated cooling waters on estuarine organisms laurence 11. Liden. Dennf> T. Ilurtnn Academy of Natural Selences of Philadelphia. Benedlet. Af aryland te nard II. Bongers. Alexander F. liniland
- 11. tin h1arietta Corporation, llaltimnre. Af aryland The environmental acceptahlhty of chl6ffMe is available hourver, enncerning the tmietty as a unhersal disinfection agent for both in.
dastrial and munitipal water and unttewater of brnmine chloride and its chemnteaction by. prewintti to cituarine floral and faunal species. treatment processes recently has beenme the A preliminary repnrt of BrCbCl3 toxicity to epic of considerable diseuulnn. The wide. Thh " and the resuht of a detailed compara. pread me of chlorine Int the treahnent of 'th e BrCl.Cl; hintenicity undy " comprise the brge volumes of enohng waters in thermn. nn!.s such unik pnhhthed concerning ettnarine eleitric pmwr plants has beenme a primary species. ca - of enneern.' The chronic and acute rf Continunm.fime hinasses s were conducted
*t of chlorine and its reaction by.prndnett during Augmt 1976 to compare the eIIcets of ni .piatic crc.mium has e been rniew ed et.
te, chlornbrominatol and chlnrinated condenter s cly by Tsai.' 8 ftcungt.o ' and Besker cw.hne elliuents on sneral selected estuarine
.oul lhalther.' Imesticatinns by Jolley ' and f,= =l.t hain ru canisme Twn fish .epecies. At.
Cluc .ind lictulcrum ' have further identified I.mtse menh.elen flhn nortid ftponnue) and
,n.m3 t hlonnated organit .nul innreanic cr.m.
rn.meh frnm chlorine.freated municipal and spot (f.rinifomut son +huren) two hivah c spe. cies. Ainerie.in oyster (Crnitneftra tircinicot nahntii.d ornnocenis u to nten atres that are pntentialh- and bratkish unter elam (flancia cunrefa). nun. 1 hut incrat alterni. .nia ihr copep<=1.trarfin fonsa u cre chosen lis n to c hlorine h.nc 1.cen sucentets hs bec ame nf their imrattance either iL tu enm. ; P. S. 1:nure mr.nial Protection Acont n,ettial or rn reatini .d fishinc or at fond.
. I N 1
- for u .ni, w ater tre.on.cnt. T he U. S.
A L. .. flee.daton enmmi d.m e and n"*"
. i b.on tienn in caurni l'. S. runarinc reginm.
Liden n h.n - unnm.n vol the c hlorma %ont.dh nr.urrine i ytophnkton h conununi. J on n e i for I, ..fooline c..ntrni in pim er. Ns ne sr med hir r imparaiu. pr.idiirinity i i evnulemt t t m hng u siemt. . id n.pii.m on u m be s g ome pinpmed e hlorine alternath e e inctnt!c p g I .* Ln4nmc chlornie. ninne. i bl.a me donute. hs. r Sim dn.cen perpside. nitt.n iuh t r.u h a t ion. :.nd I k ' ' h'c #H oli""-
'8 " l 100 monenun other enitines and phs ucal or t hem. I"'ul forlod p" s er pl .nt. I = alc.1 no the Pn.
W. twin unih i d tre.oment.n ni thne. be. none rbh.n.le i+nat Ilh rt. ( h.n in e 'mmt > . N!d. Compa ri. IlhCl) h.n emerg, d .n a prnre e .nuluhte as a son of the reudnal 1intrairitics ni nell at subc onte bb<ide .llrnmine l c hl.nide hu been 1.n.fonhne omtrol ciliatin " of the haln.
.how n to he an climin e i ninin t.mt of u.e tc. genatnl rfiks m , was ununph Ind by chlor ~
u ater " in adddio i, %cLenhoth and I.nin," brominating the rinina water of one unit atul It cert rf al ." " and thirton .nul hlarcrcy " iblorinatinc the cooln.g uater nf the sunnd I. o
' elemomtratnl benmmt (bloride's eRec. mut. The two biocidct ucre appbcil contime.
h ons u a bioficihne omin>l .n.cnt in ther. ennh at o.1 n,c ! ne ten in the respective It%tne pmt er pl.mt tooling tuteint using etHulenter rewnhng sinicturn thirine the fuld sarme u alers Itchtstelv hllte inInrmation trialt. January 10SO 173 i
i
, l.nlen et al.
hil-TiltilM AND hf ATF. RIALS u cre 78A (
- M>l9) mm mn! 59 (t 2.90) g llinassay apparatus. Chinrnlunminated and for all menhaden, aml 75.0 ( 14.03) men and a hLirmated entwlenter dittharge watett were 8.8 (* 2.31) g (ne all spot, pmnped nintimumily en large. 0 75 m high x Rh ah es. Jmenile sperimcen. with sheg 1.22.m. wide x 2.44.in.hmg ermight enn. Ictigthe $ 7.5 cm, nf American nyster (Cees.
strmtnl of 1.km. thick marinc plywnnd em amtren cfrainica) and brackith water elen, i enti with pnlyester.rctin.hnpregnated Rher. (Reincia comerita) were obtained frnrn th. gl.m. The _ troughs were partitioned with mcmhahne (5 to IR 'J, salinity) reginn of th, bmr 0.04.em.thic.k methyl methacryl te poly. Potomac Rner. The shellfish were antimated nwr dniders, which were spareil nguklittantly Inr at least 2 werkt lwifore esperimentation, h ai rms the enoght. F.ach was sceured in op. 200d tankt retei ing dcchherinated condemer pnite emit of the trinigh to forni a 12.m.Inng owding ellIncuts. Basic water egnality of ac. wrpentine chamiel. Cmling water inRow rates climation water was identical to that med for utre maintained at 0141/s. renitinc in h). fnh nahmathm. drauhr er sidente perirxh of apprmimately 60 Crrmpt of 20 nytters and 25 clamt were nanntes m all tremphs, simulating cooling water retained in vertically sittp.nded, nylon mesh retenthm times obtened in the plant's dis- "unks" located at the 5., 30, and 80.mirmte i h rge s.m:d A third treatch, supplied with pnitinen in the cipmure trrmghz. licfore im. elea bleu mated (tmlium thimnllate) Minling menkm. In epiantitate new shcIl depntition, w ater. vrs el m a referew e np..uire trnuch. the noter shell matghi of all tasters un Idad h, all sombes test organnnn uce retained in un,wh h: a 3. min rmtt h was fded in the shet I the t r. .ni t n at p mt imit uheir the innling matum ni cach (lam. Test animalt were it.. w alen b.nl "agnl*' apprmimatch 5. 30. aml spetted for mortahties three thnes cach ucel. fin minntn af ter halocenat.on. during the 15-day npante. New shell dep+ 1%h. Jm enika Atlantic toenh ulen ( Bret o. uthm wat measured after the end of the orten terrinennel and spit (1,cirutomos stinth. nperiment. , nrro l u ric seined frnm the Putnmat flis er Copepoda. Arartid toma from a 1.dunatory. ; near the \lorgantnun plant. The lhh urie maintained odture ucre utilired to determine )
.n ilunate d f or 30 d.n s in wparatc. 10001 ihe clice ti of firmniin. t hloride mal chl<irier. nei !
t.mL that ucre uipphni omimunmly niih sunival at Imth condenser ellinent (31'Cl - deshtorinated (uwhom thimulfate) diteharce aml ambient (22'C) temperaturet The cope. I water at flow rates of apprmimatelv 019 I 5. pwli urre unhmatirnl to the test ternpera l B nn u aici eptabty e4 the .u thmatinn uater. torn ins 2 day before me, in v rcennl cm, nuwnturnt dady. um n follems (mcan : stan- tainen hwcatnl he the reference trnnght. Test 41 erd deuate.n): temperature r 30 0 (e 1.311 neganium ucre omtainnl in 500.ml hhntas
't; pil = 74 (- 0 62): dim h ed ot> gen th.unbers, uldch urre screened at both inikm (i=0 = 3 A (- 1.21) me l; amnumia - N n aeol smillmv pniti to prevciit escape rif A 03i= 0.29 mg 1, and saluni) a 2.1 ( c: tonwe .uwl intriuhuiism of undnirabic orcan.
0 71) '!. . .\lamtetiante dicts of termt rhnw ium. If aloccuatetl water wat tiphoned ren. Im n.i nhad. n and linh Iner13 Imppnl men- tuntninly hnm the onngin' three pmtinen to hailen Int the spd ucre apputhmed tn the the reipccine ospepnt chambert Total sur. Inh im a tu ne. daily $rheilnic, during loth tital of A. Innw we determined after 24.hnur an innation and test periemh. npame periods. I.'nh ucre transferred in submergul minn Ph3 toplankinn. Entrained phsinplanktan ragn (0.ls m x 0.33 m x 0Jl m) turated nunnunntiet were med to evahiate the tmic m tla. smugin at lwmbos of 5, 30. aml (10 tilei t s of brmnine tbloride and chlorine on inmutn of balogen detav. at desor hed alwne. energ3 lising and respiratory prntruct of pri
\pprmimatel3 30 menh.ulen aml 20 spot were mar) pnuluurs. ' Cooling water samples were dntnhntnl randomly to segrrgated, r aired nhiained at tarium thnes during the day from t cagn Ohsenathms of Ash rnortahtv were the Plant intale emba> ment (reference) and j m.nic at hmus 1. 2. 4.10. ain! 24 tharin4 the from tle discharge ends of the hintmicit first 24 lumrs. atal tu tte d.ntv thereafter dur. Inmcht. Portium of thetc samples were med 4 me the 10 day (mciihaden) awl 20. day bptd) in determinc mygen cuilotion and m) gen .
esp ante pern=h. Total length a ml w et. omunnptnm (rnpirathm) rate acent.fing to I unght data of dead menhaden atwl tpnt were the ph>toplankttm metahohc rate meature. ' rnneded at each intpettkm. klean (2 stan. ment tethnirpice given in "Starwlard kleth- l darit desintinn) total lengths and wet weights ods." " Dissnived mygen determinatinnt
- 1 IN journal WPCI, Yid. $2. No. 1 I 1
1 Italogen Cennpuunit Tmicities procedures detailed hi "Standard Slethnd,"is r[B. 41. Total esidual osident nmi hv Snintanm (ammonia - N1,r' Total
.,,o atrations of chlorobrominated, rnnhul mklant enintuttatinus shawn in Tahle i d condenser I were measured twiec daily aint varied rinring
'i,lormated, and dechlor nate
.ghng waters during fish and bivalve thetc ttndies brw anw of plant npiipment mal.
l,ging periods, "" I'*P"'"T E' ' " d d"*"' I""'""" Halogen Concentrations (mg/I) Int equipment ecpair mturred,'"during which perinds the midant inels of < 0.002 mg1 Mean ( eStandard were reforded. Ilmen er, the downtime in. Jtartge Deviation) terruption intaled less th.m it hemes. Hah, gen f re strnent. -
~ deteaninatinm were enir.fneted U<ing a modi.
nt o m t #* n nt2 4 <nm2n90-
< n on2.H o; t Red ampernmetric technkpic detailed in n os t (*n on; ;)
im <n.nnlauw< Bongers et af." i 1o n H2n (
- n.ht ! 4) e f uw,2 ( en orn 1) < n.m2.n.nt o um2 ( *n.nv. ti <n m2.u n 4 BESULTS AND DISCUS $1DN Fish. Juvemie H. ti,rarmm and L sant/mru, i .o o nia (*mnit o) <njut2 Um2 tm were huth tolerant of the test ennehtinnt. Sur.
kt
<nnn; vsval ni menhaden aml sped espmed for 19
~
R nn < nun! - and 20 dass. retperthcly. In chlornbrnminated khn < n M! and chlorinated enndemet cIllnents nteeded 701 in all groups f Table It,t. Stathtical I i _a ll = Ilt('t. C = t I,. 't = Referenre, ilechtnei. anah e, n( ghr. menhaden d.da nting Inith aul; 4 (n. and #ai f..tl . ing le ttere elen..te ap.
- AN uy4 and gindtng',ggeg,g: gghg a,,,g th3g
- a. uvute halmen ein e tone. (nnnute l.
there ucre nn ddlerentes (P - 0.uU m ur.
, sival between brnnone chloride, cidorine, and t
; .ro made h3 the titration procedures de. reference ttratmenn tsunhal dat Innu con.
I we d hs Carlwnter? Chintophyll n and centrahnm of each halocen were peded for
'.e n.in ai n .n ("C1 det erminattnnt were unalyn became of un.dl s.nrple Wed. No ,
o itteil woh the methods of Stnekland and ddleremes urte found in sun hal of thloro. i l'.n . .m a All water sampics med for phorn. l.innonated ipos enmpared in niher (li nrin. l .n.ihesn. rnpiration. c hinenphsil a. mni car, Sun n al cf chin. i..n aunnilation innhn here inenbated for aled ne refensp.it emc.treatol nte w croups. as ienifh anti- e r < 0 0U I h.aus before analpk in a shallmv tub re. i o n me a inninnu n mpply .,f arnhn nt tw leu than that of the refereme fi h it h inter. esur.c in m itr inmru v. that a i ne.n el telatire spot i Lanas liner u ater. Th3toplantinine m3 :en dup 1.ctu ren halocen ngaent dwi e inh d u m ainl inpiratinn s alon u cre en sursis al u as rudent. Ihat is dn re.nni nwidual
, ;'emnl .n nntheram 0; por mithtram at C1,14 nulli.nsid mt in e h m s nmp.n.'e d la d- n .ni .1 inc.
, per hour and cathon. Asation values thal, ami that no un h relatinmlop w as fmmd m "C per mdh; ram Chi a per henir.
l 3 for the menh.nlen dsra.
" ater epiality. Anahsis of the chlornbro. I'. w und.e h n e t..cn nanir t. .I ownpar.
' .nl. ihinnnated, and erferem e (dn hin. . htnile and a
b.c the smu nns ni l en.r .c 'l l .e it . ad n 4ti ownlemer c(Ibient Inv lunc water t hbun.c in ntn.u me oveamun. 1 . pasarnetra indu ated small tuo inn. 9rt.hnus ihrt n.. d. m 1. th .! . nno ntration
"* a ihtference hetueen treatmente dming (Lehil n ahtes le portol In liehriti .md CIcf.
dl ph.nh of tha studi. The mean tempera. um " for nu nh nh n t h 22 n.: 11 nut <pnt Nrc i31.2'
- 12YCl of the iblonnated aml (u 22 and 0.21 my li une non h hhhcr th m wirreme stations. receninc 1.' nit 11 condenier the total residq il enulant lescle thed (n this
'Im har ges, w as contntently higher (O.I'C) than the mean temperature of Ibe chlnro. ilud3 (Tahic li t. u!.rer relatn els nonor mor.
tahts was ol-ned. Hnberts and Gleeson " hnwnmaird statum at l'nd I (SON :.: funnd that hmmnn. stdurole na . ~nuh rabh 151'C). Nn sigmResnt differences w ere ico emic to m50niuden ilun cbioime. based on hinul among other mean hacie water quihty 96.lumr Cl,. sahn, reported hs the \*in par meters. hetween all stathm; the pa am. hinmeh smla State M ater Contrul Biurd.h ob h .t:$ pil weic
= 7.1at inllemt 12 0.40); (mean no =&4.1 standard d vfa. the Water h nuni thunt le vt salon were f r. smperled to he underntim..tnl. . Gull m< et n I) me hr ammonia - N = 0.2 (+ 0 30) rdo reported ihat a inf al rnkhul chforint* cve
!!aile n 1. . nut satunn a 2 0 (
- 0 M) r!,. centratum (ti 12 mg n, ulnib u m donhlc the water quabt> analpes acre conducted ming f annary 19w ITS i
i litlen et al. i TA BLE II. Mean survival of selected estuarine species esposed to chlorobrominated, chlorinated, and dechlorinated (reference) s ondenser cooling eHluents.* Mean Survival at Gnen Mean Hologen Concentrations in mg/l (<A) t BrCI Ch Reference' ' Species 0.0s1 0.045 0.020 0.062 0.0J2 0.014 R$ R30 Rik l etcoit' g Fert nertie h r.# o m m s Ms.I tinin Qf th Qre ,c lb1) O
' Qr3. ) llN) t) ltM[H Q L,j Lesesteerars ader& mens AU.9 T3 0 7.s. t I A.3 f ra.U 7.l.9 22.3 .-
M;,rj i lG ah ed Crassestree cirgentre tinto vn o ltttu lotto 92.0 lento - - Inu u - Rangie r==reis s tat.H 90 n no loitu 80.o t ot).o - puto - s .\ lean m ater tensperatures 30*-3 t'C. 6 R t, R to. Rho refer to gositions in bioassay troughe curresirending to ennline m ater "aecs" of..4 .to, a,,g tal rninutre Residual niidaftf*tet els at atl re(cren.e statieans mere <0 tws) mg iduring studies.
' 14. anil 20 day espesures for M. f)ta==ms anst 4, saetamres. ress rtis ch .
- lbda s espesur,s.
maumoni Cl, residual otidant level used in this mente. There was a positive relationship be. ilmh fo no2 mg/l. Table 11), caused 50r; tu een shell depmition und total residual nst. mortaht) anusng menhaden after 90 hours at 'd.mt onnentration for both chlornhnmiinated
.hP C.
and thhrrinated nisters. A significant di[Ier. Simhn timdmini by hliddJugh rf GId eme it' < 0.05) uithin halogen treatments shoued that 50'; mortality of jusenile spot was finnid only hetueen oysters exposed to had ucentred af ter 8 day espotures to 0.t56 0 002 and 0.014 me 1 Clf tntal residual rni. tug I total rnidual chlonne at 15'C. No dant. No signifkant dderenw in depmitirm deaths were ninened anumg fish subjectMI to among litCI onnentrations was fenmd. Crowth either 0 04 nr 0 02 rns I total residual c hlorine of flancia. lsmner.was apparently undeterred at 10' nr 15'C int temperatures.85 in the by eithn chlorolmuninated or chlorinated ef?lu. present studv. imemic 1. rantimern were nf. ents (Table lill, as all test animah survi ipe freed at all Cl total f inidual oxidant con. had o.mpletely reidled the 3.mm nntch that centranons (Table Ill sesulting in siginfleanth had hn n hini in the shell perimeter. 1.mcr mean sunival of chlorinc treated feh W!nic BrCh or Cl,. residual midants do t omparni uoh relesniu . Ihm ever, the not appear to be austely lethal in C. rircinica anab ses imbrated that neither h.shtgen treat. or /I tidur ntst eat reuduJI Otidatd (oncentra.' me nt u.n owne dtleterunn thatt the other to tiena ** 0.1 Ing 1. the roults slirw an ethletit the virin al ol nther snenhadne or spot. .oh' ethal cfin t. Sheral other authurt hat e lih als o. Sun n.d of pncmic outcri and d,= imented oute r shell crim th supprosion
<lann w as unafinted after 15 day espnorre in hn.mme i ht.nole and iblorine in nntames to the ibl.nohonnmated or thinnnated om. of wblethai npanrn. IbJacrti and Clectim o de mer efilnenti ( Table Ill. All nn.rtalitin repoetal clh on e onntnuathna (te%) of rni.rded hn C. i ncuorn and 11 rum nts w ere 0.10 .un! O Ifi mg i 16:C1 aml 0.021 rug I Cl .
annlmtr-d in apparent sufhwaHon of nuin hl. w hn h ininhitnl imemte C tircInica she l uah that h.nl neapul insu the retainimt gr mih alter 9ti fumes. Shell depnition ahn "u= 1.nrrLC and m prnent hadthefallen tue:h6nin botham.the onacroinc was nmholk,1 among outen npani up to 12tl lumes en n.til me I thlorine produced osi-lintintrd shcIl denmtmn,imhcatne of wh. dant. 1.nne term ll.ureL nomure of inue. lethal strew. was rud. nt among bn enile u h sprobahh 31onhn) to 0.2 me I Cl re m acn opnini in the halogenated elliuents sulinlin 99; wrinal attinnpanied by < ,Inq
- (Tah'c llit An anahih of s ari3nte of inercain m mean dwil lengtht et the data mme the f. test 88 hnheated that 1 he rnerkted shcll depmition olacn ed ulule siemfhantly note (P < 0.05) thcli ,um.ng optres in this study probahh can he was centrated amon referem e nyter, com attnhuted in a onnhination of "avoidane" of parnt in edher halogenated group no ddict. the t hlornbrenninat eti and (ldorinated efflu-rme w as found hetucen DiCl and Cl, treat. enti19 shcIl closme and pasuble impairment 170 Journal WPCF, Yul. 52, No.1
-~
llalogen Cennpinmd Toticities hetueen 11:C1 ilmage mini sunival, that is, f r St.E !!!. Mesa shell deposition by fenile American oysters and brackish with hmrt IhCl.lutal residual midant (oncen. tratkun. !<mer snnival ociurrc<l. Conversely, ester clams esposed to chlorobrominated an opcoted indirect relathmship between Cl, ad chlorinated condenser emuents." nr reference tuntentrations um) survival, with Mean Shell Depealtion . higher hunhal wrrespomling to lower midant man Halogen tman 2 standard error) I"Yeh. "an n1 nerved. Tlnse analyses do not
-. - . - ~ -
Conuntration R. evntete'. offer ait esplanation for these anomaluus (rng/l) C. sirpinies roults, Chlurnbrorninated solutinm also weie fotmd f _ n,t t u nal Jf
- p. l .l > .t.n to be lest .imic than chlnrinated waters to n.ti4 A 2.7
- p.1.4 2.t.n Attertin by linherts and Cleeson. The 48 o nJn 2.8
- 88.17 24.0 hour 4.c50 BrCl values reported by Roberts ,
i tL und Cleeuin " were 0.12 aml 0.11 rug /l at '
' 2T and 05'C. respet tively. Concurrent tests Nt. b t
""4 'hb""'c pridel 1450 t alues of 02
' O.014 1.0
- U.21 2 .t .0 ."und 0 029 mgil. indic ating that the 0.05 mg/l grreren,e 4 lmur t.r.50 Cl, valor previotnly reported by
/ N
- r. l..t
- o. l; , 2 4.u Roberts et al." was apparently an overestima.
l. I . Tr.: iluration of 15 it.n,
.tlon." Sinular tette iising freshwater Daphnfa
- Ul i fam r fdtril mq. hre in she lls, mnerut indicated that thlorohrominated was!c.
- R in rs'rs e in pmiti.m in 1.punit truush snrre. u ater cilhients were lett tutic to the coperods
..nalini; in shrre re.diot m atera mere .tn minut tlom thlnrinated ell!uenis after 48.hrn.t es.
.J ' ' Hefrrence total rrs.lualpm' lant truls urte pmu res. " Total ti sidnal bromine chloride o 'n1 ins I l.a the elurat' um of the stu ti . m Wilom d tLOli and 0.055 mir.1 and a int.d reshlnal chlntme CrPuentration of 0017 4 phuinlugkal and metahohe proccues mth. mg I Camed 50'i mnrtalitiet among Daphnid
.ntheoptert Chinrhic shell timure resp..mes 4 m* tert e nr dnruption of nther nntmalleed* T ABl.E IV. M ean survival of A. toriso ut: patterm, as shnu n with flahnnn." maF esposed to chlorobrominated and chlorinated mtritt the total intde of faux! matenJIt mer condenser cooling waters.'
me. tinn tegnitmg in Inuer fitnest of the Mean Sursis at at nt organann indicated hv net det te. net in Gun Test
*t er (undition and gonadal induct. i
' h.uites in phpinlogn al proccues tinnlar t.i Residual 18 lme reported in mtur in fish u " as u rll at Conuntration tnig/l) .t l C 22 C h n:rs m nietalmht- pithway of vuler' }lsugen 4 ed la halogen equnnres .nul re sulting m y,g g gyg g p . pp, b B 5 01 Jintnal filltess ahti ti).n hat e (on.
' 'ited in the latl ;,f gumth nl opters in n mi st 4 n w.t .s l . J
- 4* stud). n "LJ 88.4 Copepods. The efict ts of short.trrm 2 8 ""O' ' 8' I I l "n npante in firCl. aml Cletreated tmbnc ""N "
w ah rs nn Ilic annh al of Acorfin innin are 88 n't 8 l '- -- vinnn.nueil 6n Tahlc jV. Atorfin inhpettet! 88
""W "
'" thlornininninated waters at 31' And 22'C " " I" "I bd lui:ht r puran total sunh al than eilher 'nn **i 1:t U .onattwi (31'C) or refereme (31 and er . n. . ' l' M 'h J 4.2 U Cl groups, linutser, nu statistkally sig. k "" M" "I 5
'+'ta ant (P : 0.05) dinerences w ere finnul I"
- ern treatruentt usingt the $tndent's f. tot I N""8' 'sn aanr e r' n=1 1 nt e inmhn tnl u.ing Nu
' salmeans,ss uere IntmdNnamong signifitimt eitherthRerem BrPI nret in ' "'#" " ' ""I""'
- I " O d "d F'" "O"" " * *I'" '
I rente A. Inntre tested at 31' and 22'C.
- 1",Nid 'n,,i y y g., g, g,g,n, ;,, i,;,_n
~,,,,.c. , a .i, a mngh higher mean sunwnl was oh crvi,1 r , ,, n ,, ,, , ,, , ,n. ,,,,,. , ,, , ,, a ;n, . .n , ,
94"og hoth groups at 22'C (see Table IV). m, ,,n,i nn m,nnie, matual mi.l mi fruti at .iti lhelpectedly. a direct relationship uas Inund referrm e gan.ma mer.. <n.un! nm i during Mustws. january 1980 177 l i
m
-.n.
~~~ laden et al.-
during thnse Eheme init." 'l l u. rnults of t imely upprmimated the 0.5 mg/l apph the prnent stmly indicate that the residual rate. Studies by .Wtmn a and Centils
, imioit> of thhirnhnnninateti waters is leu than et al." have limtn that A. tonut subjeded t, l that of thlorinatnl waten, although at a 2A ing'l intal rnidual chlorine had 50r.; and I statidindly insignificant inel. < 10<,; total survival, respectively, aller 5 7.onplankton nmrtalitin re ulting from pmver mhmte expmnres. Gentde et el." shn inund pl.mt entrainment has c lw en niinhuted to that arenips of A. temus had 50',; nunival after inet h. mind. thermal, und bionde strnset at a 2.h.nir esposure to 1.0 mg,I total residual urli as unii;>inatiinis s>I the three. Work by chlorine. The effetts of initially applied tote l Carpenter et til." Inditatetl that enpepod mor. residual ntidant omeentratiemt between 0.5 tabten ucre runseil by hydranlle and mechan. utul 1.'s in 2.0 mu l may not etmtnbute dt, i ital stresm intnismg during thrnugh plJnt rettly in tbc inunedjate death el entraiggd l "
cut rannnent. Imt the relatitunhipt ni caceu pru> plankton, but may increate the pouibihty ten.gw.tature mini thharine in supepnil mortalitt of enethanically ranted nortality perurring omsid not he diuttned frtwn their experimental after the hnlial hincide slmek, depending om dnign. time of espneure and temperature. Residual Sescral authors have showThowever, that hincide enntentrations <0.1 mg/l total re. nn* plankton (oipermit) are tolerant of rela, s; dual niidant dischargeil into the rettiving titel> large changes in temperature and that stream wouhl probably has e rninimal effect on pun.pmg strets abn may contribute httle in natural sonplankton populatinnt. mor taht y. Davies and jensen " found that Phytoplankton. Severe depression of pho. topelwul innrtahty, enmparing intake and dit. imynt hetic processes and signincantly in. t h.nge canal s. unpin, was unaHected hv um. Creased inpiration rates of entrained phy. Inrid tempnalnen at Lake Norm.m and Indian t@lanknm communities necurred during both Itis er pourr plants, but that at the James (1.!nrolunenination and chlorination r4 con. lin e plant nu tehty of o,pepodt decreased detact imhng wa'ers (Table \'). Reductier.s unth unreased teniperature. Similarly. A. In prunan prrulucers' nsygen evnintion ranged tonw h.nl Ins than $P; total nmrtahty when hetueen 77 and 3WI heknv that of unen. npowd tu an ll*C thermal increase." lle. trainni referente s. unpin. Similarly, caibon. sults of nnade studies hv lleinte " demon. Inations rates ("C assimilation) were limbed strated that enpepod mortahties from circulator en l19 in GO'; of untreatetl sample salues pump strett w as haicmIIe.mt. Shear streu. f Table \') by Imth halogen treatments. En.
.ateletahon, and atuadonal fort'es in m mv t rainment also resuhed in increased phyto.
plant onifiguratium may he the majnr nin. plank ton respiration rates ranging between hinodal ne emnpumpmg contributors in ann. 56 and 12761 greater than ihme recorded plankteu nort.dit) during conlmg s)ttem en. Int reference samples. Analysis of the data 8 tranmw1d." t ANO\'A) dal not indicate any significant dil. Cl mation has I.cen identified 1,3 sneral firences (l'. > 0 01) in pinimenthet;e e,
.nd hon " n " .n the m uoi arent iau me es. rnpuatory pror eu < hanges lietween chloro.
- i. anne m plankton rnoriahon in pnu er pl.mts brononatol treatmentt Nn differemet in Omite' umhrs in I)auet and Jemen " shnu ed rate t hances w ere inund either among 11 C1-that i ilonnaimo ni o.nd. nwr conhnu u aters total ennloal owlant onnentratiems f u osa rnnhed in sigmficant evpepeal mortahtiet at aml 0 0D to 0 066 mc il or anmne Cletatal
. Intal teddual t hlorme c nntentrat ons < l.0 nsulnal snidavit omeentratinnt (0.067 and me 1. Ih nile " nhsen ed unnlar dec re2n m 0 0M in 0121 ma lh I'brwm>nthesis and c..prpmt snn n al donng i hlorinahnn nelet at ie.pirati m rain ut diffen ut sample timm dur.
\lanland pow er pl.mts Innlimu u intal re, niu cash slav (see Table Y) were erpially ninali ble,eme t onu ntratu nl Anahen of the dhited by all hmeide treatments and Inch thnhi from the pinent saml 3diil rme indicate Ch?nsinau m of a amlcmer ennhng waters has am usmhsant halogen.mnival eficett at rep. heen demomtrated in omtribute in sar>ing rnentain e thuharge Inlal residual enidant decreet in the mpptr%6cm of primary pro.
Inth < 0.1 mu I linu ner, higher sneplank. dm ta it> of entrahird phytoplankton. Some r inn nmetahty rates unohl have been espected omttmersy esists concerning the osmhined with tunhng water from within the ennling cfieds of hincides (thlorine or brnmine chin-s9 tem timer tu the point of hhicide introdue. tide) and thennal increase. Several studo tism feirndator puinps in this studv). w here ict " " clearly demomtratal depression of total rnidual malant enneentrations more productivity during perinds of chlorination, al 17R Journal WPCI'. Vol. 52. No.1 I l l
=- - ~. . . __
Halogen Onnpound Tnxicities Effects of bromine chloride and chlorine treatments on photosynthetic and 31 LE V.
,spiratory processes of entrained phytoplankton."
Oi censumption in Dark C Fination In Light 0, Evolution in Light (reg oC/mg Chi e h) (rng/mg Chi s.h)" (mg/mg Chi e b) Drte - - - + ~ - - - - o--- Refer. E s pe ti. and E s peri. R e f e r. Espert. dosage Refer. mental ente mental 31 ecce mental ence (mg/l) Time not 27.4 n.23 ' u th
- 0. 4'. 3.2 p.13 hl n%
n.twi two luto 17.3 26 t - 12.N 2.9 Jte.4 f 6.0
- u. M
.l.t .6 24.2 12.10 22 H f i .H u.41 u.12 Th.2 .43 in.3 n.1 t n on; twri
- 1. 4 44 8 U.3I 4Lu n.7 u.o13 in30 17.1 11.2 H.4 2 n.12
.11.2 u.03A titui 23.7
.12.2 30.2 0.41 u.13 II .40 9.6 - 27.6 33 x u.32 u.Il n'23 two J 7,3 - 30.E 4.7
,0.1H 0 .116 (1, - 12.7 SJ 33.N n.nhi llLIO 24.4 323 -- -
.t l.U ~ *1.1 21.4 1244 22,7 U.30 0.14 39.9 9.! 9.3 m /.60: two 1A 21.9 ft.32 0.1.4 U1 =,7 tn to 21.2 - 218l n.In o 12
- 3.t. A 16.3 10.3 n.121 1030 2 M.0 0.49 h 148
= 71.0 36.2 109.3 1830 47.l i .t. int .17' (Il' to 4t'n. krtervm e s alue. are Huuhe irulirate comt ne.1 efrecie nt I.iori.le trrat[uent amt rom ambient tenya ratures (24* in DT) ami nu liinriite.
' %gathe s alurs imlwate <lcercano in fl, os edulinn.
tlam shell depmithm between <hinnihromi. l ahn ninened in this study. Total ininbl. nated and chlnrin.Hed ellinent. . h further indl.
,ai n. a of phs toplankton attivity resultinc from eation of equhalence of the tun halogem' t di.irination t of oui!ing waters 3hc h.4< heen repnried " . " thme er. thermal inneases residual tmicitics. Shell enmth inhibition of hira%cs hsing in ure.n affetin) by de plant's (rnm h m' .nninnit temperaturet ( < 20*C) digh.nge wendd undnuhtediv ewn r during ,
h.n c rnnited in either nn effect *
- nr in. penods of hincide utihratinn for hinfwding i ircase<l primar3 pnidnetion.'8 Thermal stress omtnd, mually frinn late spring to mid fall.
fruen base te,nivratures > 20'C ahn has been nr in haie ihmner while enmth might in fact he denunuttatni to bas e nn c#eu t' deprewe d pnmary pn =Incthity.". " The mallimited growth pnihahhbr hiraides woukt during enume after thk &ws.period, nnr. innphne u hnne med in thh stmh ih l nos 411,m for iblierentiation betw een firCl and tion of bbn ole me. l'hh enummtering bnnno. linu m er hawd shhninatni nr t hintmatnl omdemcr on. ling 01 sttren and .17 t-'C). ellinern in the d wharge area of reiching n ihe reinin ni sonilar'studws 8 . " it appears . il t the nlarnni c h.mgi. in phriop!miton streann prnbabh wendd be unafhunt in stie l f e hitics in thh stodv ucre primardy t.uned hm.lmel halnern f ru inals .uul w.mkl bc In the nonal neanm to the apphnt US ma i lach to mnkl umathf.n tore inniht6nm If pasible. BrCh ni (*l,.tnLil trudnal rul<hnt. The ennits ni tin. umh donomtraird that hrinnuie thintnic appt us to be Irw tmic to
#""P " d '"" N' "' "'.l"".'I""' b ' b "I 'I'I"fI#*
mgetg.qc3q ; The tmic clicah of thinnJnominatnl and ahhough de difico nn was statniaah inug. I iblorinatnl power plmt ennhng u aters em nWi. nit Tie ilata (nun un simh, prohahh ntnanne nicanhna appear to he umilar wuh d"' " ' " " i*I" dh"' "I "" d'dI "I '"""P "I' rnpett to the lethal aml sublethal respose and oder sinnla innptaitton et in huw imbrators med in this studv. Siimlar f. val mi"' 'I'I"ride or sidorine rnidna in de mh. wrshal of menh.uk n aml sp4. at wen as ing areas of dw plant,s dacharge where n itm and Nngin esp <acd in firCl. and Cl'., residual midant leuls wimk1 bc < 0.1 mg 1. 1 ated eninent imlinites that the imitifics sil t .c rnidnal midants were simdar (et lagh .\lottahty rates ni miplantit ri nmmntenna halogem. I.mk of dinimdarities in opter and initial hintide GrC) or Cld om&utrattien Jennary IONI l'u l l 4 .
I.iden et al.
' O.5 mg l during primary phaics of thmugh. Euen. Drinm AlacDonald, and J. Afills d plant entralument pmbably would he higher valuable suggestions. Brian Bradley, g th.m those r.,tes obsen cd in this stud 3 Soh. O'Connor. Ann Caurens Daley Hills, and 14 se<pwsa enethauiral mul physitsd streuct ahn uinwl ifall, Jr., ankted during varitsus phate.
unild be espected in imreasc death and in. of this work. Potmnae Ekstric Power Cem. Int 3 to entr.uned orgJ tistm. pany prrwided the study site, Biodde effetis on entrained phytoplankton This paper is Cemtributhm No.13 of the utihity appear to be identical regardless M Oyster House Publishing Institute and Seg lulocen treatment. Ahhoiigh the data inm3 tific Society d Estuarine Research. 11m simly did not delhicate the reparate roles Autheses. Lawreixe H. Liden and Dennis of hineidal, mechanteal, and physical streites T. Burton are, respetth ely, ficacerch Biologii
, in phytoplanktonic procenes, it is apparent and itesearch Assneinte Curatne, Academy o r Natural Sciences of Phdadelph:a, Benedici inen these d.ita and the hterature that in ti.
alh apphed minimum cimeentrations of BrCl Ettuarine Research Lalmratory. Benediet. Md or Cl3which effectively control biofouling in Leonard H. Bongers and Aleunder F. Holland estuarine :.whng systems, would contribute are Research Scientists with Martin Af arietta substantially to the inhibition *d photn9n. Corporathm. Envinmmental Center, Bahimort, thetic processes of entralned phytoplankton Md. onnmunitiet. Increased respiration rates oh.
, tened in this stud > may have been caused by REFERENCES uudathe haeterial activity, stimulated by the 1. Zritnun, l. II, and Rc3nolds, J. Z.. "Pose, sudden availabiht) of organic material, pre. Plant Chlorination? Entiron. On. 6
. Tre lmaf., 12. 30 (197M.
unnablv fnun dead phytoplankton. 2. Tsai. Cal., "tfletts of Chintination Sewage The ellmts im phstoplankton of residual "' " ' midant dntharges int'n reeching streams, al. ih,meh m4 imntigated as part of this study, h, ,#"('g,""lan
, ggg y,
, C S 'k$
appiar to be ormhned in an area within sev. i 1,,s c.,g,, gryn g, ng g n , ace Tu atment cral Lihom teis of the ihubarge point." Out. plant grum.nis on nihr A Review of the side of this area. Fos ami Mn>cr" reported 1.Heraturer chrisped, Research Crvs. i,unplete verm erv of phnton nthetic pnicenet u>rHum. Inc. Cn!!cse Park, Sfd. (1975).
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p., duhts of thew reemere prmesses are esl. trol Fed., 43, 2140 (1973), elent in the tarbon&ation data presented in tim simh ubere nnh partial inhibition of 4 n e nnes. W. A.,
- Effects nf Wastewster and W Chinrinatine on Aqushe Oawnndatum in (trCl and Cl af ter 4 h.nirs C""Il"8 Life. U.'S.' F.PA , Ecolerical, h seat h imuhathm succetts that intal ' destruction of the philoplankton uunnoniils chil not octor. c 39 6 1he esideme presented in this tin 13 and by n Des ker, C. D., and Thatdier. T. D., "Tatie-other imnticatnis en=cnts that the effriis on it s ni Power Plant Chemicals to Ariuatic
.oputw organisms of chlornhninonate<1 nou er 1.if e " l'. S. Ainmic F.ncrey Cama m6na.
plant o=4mg uaters are unnlar amt in inme De pt Nn. WA%Ibl:10. Washinston, D C
, aw, not a in tre as the cflects of cegun alent I1973) c hleumaint waten. Binunne chloride's mnrc I I"U.% lt 1. . "Chhirinat ure Eifnts on Or-
- raput deras rate may make it a more desirable 88"'r C"'"hh'ents in EfRucnts f ram Dn.
*"'"' ""d'" "**'"
anof,ndme afternatn e io eld. wine. f lou n tr. U"* d l.Treatnn
' ""*' * *neE Plants
"""'II' ,,
it n important that inme ownparatier testi he iin d.n icd to define am dint remet in tmkitiet n gg,,, y f'"
- g. R. and llendoson, L E., B'
...I Inommr i hhu nic ,o c himine raudnal mi. ..h mahnn i4 Ore.machlorine Can pounds dants ,rhete tests unnhl bc neceuarv before (,,,m ihr cid.,rinaia n of a NlunWpal Sec.
c hloinbronunat um can he enmide, at an inwi m i Chu nt? Jour Water roll. Cea. t ounomientally acceptable alternath e in tent Fert, 47, till (1075), thlorme for dninfecN and hidnuhng contnd. 9 l'. N Emironmental Prneceilon Agency, "Dis. Infection af Waitew ster. Task Force Re. part ." Special Rept. No. EPA.co n.75 012. Wehmaton. D. C. (1W76), M(NNOu.lEDUMENTS credits. Tim research was supported by in ti, ( gn,1,,, Resulatary Commluinn. Chem-
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3
...m a....._ ~
' llalogeti Ciminnmd Ti.sletties inty C=nmi d.m Dusket Nn. 50 4t$0, Wash. 22. Noknanan. L. *Detenninannn of Amnwnia in '
Natural W.iten hs Phennl llywa hlorite Inghe, D. C. ( 14751. Metin= h" Lle+md. ' 6 On sned., 14. 700 L linrton, D. T., aml Liike. I. fl., "Didemhna ( IU(8lb Omim! Ahnnathrs to Odorine for Pnwer al. MMMlenh4H. W.. "Intreulnethm to Prbhability 1%r t Onding Watcr Snttius An Oser. aml Stausuts." 3rd Ed., Dnsimry Presa, Hew." In "Water Chlorinattan Endron. Melmewt Cahf. (IMI). nwntal Imped and lleakh Effees." R. L 21. Virginia Starr Water Cantml Ikierd.
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Chinmlw.milnation." Chlormation en White Perth (Meroac j Ifdth Natamal Meeting. American Chem. menenruns) and Atlant6e hhmhaden (8teco,. , leal S<ac., Div. Water, Alt, and Waste orfe rurannus) at Two Temperatures. Clwmistry, Dalle. Tex. llM3). Ann. Southeatent Biol. S ull., 24, 55 11 hkenhuth. E. C., and Levine, C., **En th (1977). nw in the Une <4 Brnmine Chindde fa, 26. hHiulaush. D. P, et ek '"Tmisiiy 'nf Chineirw Antifrmhna at hicam Eledric Generettns to jmenile Spot. Leimtemon rentliurve. -
%t atienn." In "Refnuhns Cnntral Prncedure W8'r' A . 3 b 3080 Il077 b Tnlww.lngy unel Einlosel Kliests." L D. 27. Bhrwirrkk,"J. C . d sl., "Ellrit. of Chkeina.
Jemen (Ed.), Martel Dekker, Inc., New Hon to the Anwetsan Optre. Ctenostree in L, N. I'.. Id ( 1977 h d'stnics at 'rm n Temperstnres." Ann. I lbmuen. L 11., it al "Brnmine Chlork!c. .
' I "# 8"II. 84 80 f l#'77 h an Alternatne to Chierrine far Fonhns Crm. A hte. S'"'N""'."R, W ""1le EHed of Isa.Irul Iml en Omelenser Cnnhns hysicms." U. S. "' I*"I' EPA. Interauemy Envimnmental Research Ud"d".'H""
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! 77 0M. Wehingt.m. D. C. (1977 ). N'I " "'D #' *N" 8 0"*"' b# "'
11 *mst n l.11.. rt of., "Bromine Chloride.an 2% Ca , nf @stic in Chlo.
. li e Va rc.fhn n 1 Va Hnahan L, . Fuh %,d,U fe y, b.
Chbmnahim Environroent al inmatt and Rilt n. IL Dept. M 1.tnor. % ashing. Il ahh 1; tin ts." n. L Jnth.v er el. (Eds.). N "* " ICI0'enns. W. C, *Cm. r w h. I 78) tnd Manna Fnnhne in We Me,nu.
- lbni.m. D. T. and Marguy k L, "Cnntrnt of ""E#""" '" ""'.
I"
)h"'"' APD I'
"'"I ""^* "I ' ,'"'."' I I"' "
l'eminic Orcanmm in Eunanne G =ihna Water Nutnm in Chintine and Denmine "" '" E' U"# ' i ni n..a $t t ' 6 in t.eint , 11-natumal Or.nw imt., Im . %pa. mc. N. 'L. . Cih,wgny* g n,ks" 156 IIMO 1.bk n. l. II., anel Ibmnn. D. T , "<nn n at of 1L Nuiu. C 1. Ed Middans. D. P. ",t.amnal Jm onle Atlant w Mi nh.uten ( lf ri ower ne Chenna 1mnin ni chhn man.. on tic fier emn) and % pit f l.nmtomni suntin.nn t gm ,ng,, o p,,,, gn,. g, g ,,y, ,e.Mioi u.m l' u rne. L wi d in linnnn.c (1 loride. and Chtinuc. nuut d inipu e .md Iti shh 1:st Ms." IL. L lo ated l'stuarhw Watrn " four. Enocim. Se e ll< alth, Alt, .115 t IM7), join , ,, ,,f, ggg4 g ,,l 3. Aim tdiner Sch i
,A nni= n . M 11 Jr.. and Clecenn. R A ., emc' publ. inc., Ann Ail.w. Mk h , 313
', Aiute Tmicity nf linannthh emate d Si a. ( pgs t,
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unter to Selected Estuathic hpeden with a Osunarono to Chineimiin) Senu atrr Tm. Indiu ol M..<uhh in I ish." Truen lect. int.v . Marine Enidron. Ret, 1,19 ( 107:D- i nh %, HH. MU P C.U . W * % amlard Methnik (nr the Enaminannn nf 11 pmLin. J. A , "3 nh 1,n.on of nr.idual Water and Wastewater." 14th Ed., Amer. Chinrinc in W1.tcu ah r in Gilui Nabnnn Poh llcalth Assn., Wahington, D. C. ( om neln,m inn ( nur. le . .n I %.mw Br. nnlfant llanatologu al Ch.tngn." Ismr. ( lilitil. I'ts. llet. Ifd. Cen. 11. 2 M I fl T 01.
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1414 (IWh 1 minu Esp ntr in snhh thal lssch of Tntal
!! strkMatal. J. D. IL aml Pannn. T. R., "A N udnal cdorine m sinnkspil Wade.
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. I I
i
l.itlt ti t'l al. M. Il.m L. N. E , aiul liliii L. It %I. "h.fhuin e ..f .ml I Nen.n en." t . s.1.l'.g, l'. t.l..;n. el he. Chh.chistim m Anaernhk Sletalniliun in w.irth her. Nu. EPA larV3 78.tn5. Wask, Anwenan Oyssers." Alneme Foll. liull, inuton.1) C. ( 197A), . Im peru).
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Stress on Eitnertne Insertebrates." frwr, 48. hinesen. R. P., II and Strans. R. C Water fell. Car'trni Fed 45, 417 (1973), "De. stnwiinn of Phunplenktan in the Crohne
- 11. Ih h.h.1) n. "Elints nl Papace Thronsh Wuter Nuppl.t ni n heram Firetrie %euine.-
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