ML18026A418

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Requests Approval to Use Clam-trol CT-1 as Replacement for Gaseous Chlorine Used to Treat Microbiologically Induced Corrosion in Cws.Use of Clam-trol CT-1 for Zebra Mussels & Asiatic Clams Treatment Approved.Related Info Encl
ML18026A418
Person / Time
Site: Susquehanna  Talen Energy icon.png
Issue date: 04/23/1992
From: FIELDS J S
PENNSYLVANIA POWER & LIGHT CO.
To: SWERDON P M
PENNSYLVANIA, COMMONWEALTH OF
References
PLE-15525, NUDOCS 9205050275
Download: ML18026A418 (62)


Text

Pennsylvania Power 8 Light Company April 23, 1992 Two North Ninth Street o Allentown, PA 18101-1179

~2151774-5151 Mr.Paul H.Swerdon Chief, Facilities and Construction Grants Section Water Quality Management Pennsylvania Department of Environmental Resources 90 E.Union Street, 2nd Floor Wilkes-Barre, PA 18701-3296 FILE R9-8A/SUSQUEHANNA STEAM ELECTRIC STATION APPLICATION FOR CHANGE IN CHEMICAL USAGE RATE OF CLAM-TROL CT-1 NPDES PERMIT NO.PA 0047325 CCN 741326 PLE-15525

Dear Hr.Swerdon:

In response to the requirements of the Pennsylvania Department of Environmental Resources (PaDER)"Permitting Guidance on the Conditioned Water Discharges and Use of Chemical Additives," Pennsylvania Power&Light Company (PP&L)requests approval for the use of Clam-trol CT-1 as a replacement for gaseous chlorine at the Susquehanna SES.Gaseous chlorine is used daily to treat microbiologically induced corrosion in the Circulating Water System.The PaDER has previously approved, in the Susquehanna SES NPDES Permit No.0047325, the use of Betz Clam-trol CT-1 for treatment of Zebra mussels and Asiatic clams.Provided in the enclosed information in triplicate are responses to the 12 requirements of this guidance document.In addition, reference materials are provided in appendices.

If you have any questions or comments, please call me at (215)774-7889.PP&L would like to begin this treatment program by the end of June 1992.rome S.Fields r.Environmental Scientist-Nuclear jsf/mecl39c(25)

Enclosure-Triplicate cc: INRC Document Coot('ol Oes~k NRC Region I Hr.J.J.Raleigh, NRC Project Manager Hr.S.J.Lehman, PaDER~n 9205050275 920423 PDR ADDCK 08000387 P PD~R Cac I I[I

RESPONSES TO REQUIREMENTS OF"PERNITTING GUIDANCE ON THE CONDITIONED MATER DISCHARGES AND USE OF CHEMICAL ADDITIVES" INTRODUCTION PPKL has reviewed several alternatives for the replacement of gaseous chlorine at the Susquehanna SES because of health and safety concerns of station operators.

Betz Clam-trol CT-1 was selected because 1)it has been used as a general biocide at other power generating stations, 2)is approved for use at the Susquehanna SES for control of mussels and clams, 3)would not require a major engineering modification to station systems, and 4)would be detoxified prior to entering the Susquehanna River the receiving stream.Cl.am-trol CT-1 can be readily detoxified with river solids and Betz DTS, a bentonite slurry.(23X active Bentonite clay.)Comparing the use of Clam-trol CT-1 to gaseous chlorine for the STATION , (two units)is as follows: CIRCULATING MATER SYSTEM Biocide, Table 1 Treatment fre uenc In-system conc.Pounds er treatment Pounds er ear'Dischar e limits Presence of possible carcino ens in dischar e CLN-TROL CT-1 2 to 4 times wk 10-15m 1 750-1,125 lbs()118,000 lbs 0.2 m l roduct none expected GASEOUS CHLORINE dail hours 1-2m 1 625 lbs 182,500 lbs r 0.2 m 1 FAC halogenated or anics

Detoxicant, Table 2 Treatment fre uency"'lowdown Conc.Pounds er treatment Pounds per year'Dischar e limits Production of possible carcino ens in dischar e BETZ DTS BENTONITE SLURRY 2-4 times wk 0-40m 1 700-1,200 lbs da'27,300-46,800 lbs/yr active Bentonite 23X none none'SULFUR DIOXIDE dail 21 hours2.430556e-4 days <br />0.00583 hours <br />3.472222e-5 weeks <br />7.9905e-6 months <br /> 0.35-2m 1 50 lbs day 14,600 lbs/yr none none Spring and fall two Clam-trol CT-1 treatments a week per unit and in summer or winter one treatment a week per unit<<Only one unit treated any given day Based on 80X unit availability Respirable carcinogens II.DATA FOR CHANGES TO CHENICAL ADDITIVES OR USAGE RATES 2.3.4.5.Trade names of additive(s).

~Clam-Trol CT-1~Betz DTS Name and address of additive manufacturer

~Betz Laboratories, Inc.Somerton Road Trevose, PA 19053 Naterial Safety Data Sheet (NSDS)or other available information on mammalian or aquatic toxicological effects.See Appendix A for Material Safety Data Sheets for Clam-Trol CT-1 and Betz DTS.Also included are toxicological summary reports.Bioassay data including the 96-hour LC50 on the whole product.In addition to the 96-hour LC50s for Rainbow Trout and Fathead Minnows, Appendix 8 lists additional information on the acute and chronic toxicity of Clam-Trol CT-1 and detoxified Clam-Trol CT-l.Also included are the Bluegill Sunfish and Goniobasis sp.(snail)toxicity information.

Proposed average and maximum additive usage rates in lbs/day.Addi ti ves Clam-Trol CT-1 Betz DTS as active Bentonite cia 23K Average lbs day 750 700 Usage Rates Nax lbs day 1,125 1,200 , Usage;of Betz DTS could range from 0 to 1,200 lbs/day 6.A flow diagram showing the point of chemical addition and affected'outfalls.

See Figure 1, Flow Diagram for the location of chemical addition and discharge through Outfall 071.

7.8.The expected concentration of the product at the final outfall.The expected concentration of Clam-Trol CT-1 at the final outfall (071)is less than 0.2 mg/l.See Form 1 (PaDER),"Information on Chemical Additives Known or Expected to be Present in the Discharge," for additional information.

The product density for liquids (lb/gal)used to convert usage rate (gpd)to in-system concentrations (mg/1).Clam-Trol CT-1, DENSITY=8.51 lbs/gal Average quantity per treatment 89 gal Average weight of product per treatment=(8.51 x 89)757.4 lbs 757.4 lbs x 453,592 mg/lb 3.44 x 10 m er treatment Total system volume=9.1 x 10 gal 4.1 14 g 1 1.141 1/g 1.44 1~1i'1 volume Average in-system concentration (mg/l)3.44 x 0 er treatment..3.44 x 10 liters system volume 10 mg/l Betz DTS, a Bentonite slurry of which 23X is active Bentonite clay, is used to detoxify Clam-Trol CT-1.The amount of Bentonite clay used is based on cooling tower basin Clam-Trol CT-1 concentrations which are reduced by system demand and river water solids.The concentration of active Bentonite clay in the effluent is between 0 and 10 mg/1.Betz DTS will be added at a ratio of 1.1 lbs of active Bentonite clay to 1 lb of Clam-Trol CT-1 in the blowdown.9.The analytical test method that could-be used to verify final discharge concentrations when the product is in use and the associated minimum analytical detection level (mg/1).See Appendix C, Clam-Trol CT-1 Mollusk Control Agent, Methyl Orange Method for verification information.

10.Conditioned water discharge rate (blowdown rate)and duration (hours).The conditioned water discharge blowdbwn from the treated unit is diluted with discharge from the untreated unit prior to Outfall 071.The average blowdown of the conditioned water will be 3,500 gpm with a maximum of 6,000 gpm.The duration range for treatment is 12 to 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />.

11.Available data on the degradation or decomposition of the additive in the aquatic environment.

See Appendix 8, references-

~Abstract submitted for presentation at the Society of Environmental Toxicology, and Chemistry Meeting, November 1991 Determination of the Effect of Detoxified Clam-Trol CT-1-A 9-t di igF h dNi d0~li II 12.Any other data or information the permittee believes would be helpful to the Department in completing its review.See Appendix D, Betz Clam-Trol CT-1, Environmental Information Package for additional information.

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FORM 1 Pa DER)NPOKS Number PA 00l7325 NFOIMATION ON CHEVAL ADDITIVES KNONN EN EXPECTED TO IE RESENT IN THE DISCHAIGE anal OutfIN 5uiitaacem Ceayeae4~awP'laJWy Impalas I ENwal'Ualls Lowest~essive Arrelytjcal Lewl Qvytl)WhoIe pro&set OC Hr LCSI{eylle sINcles Whde+QAKl M Hr LC%IaayN)er eyecies 071 Clam-Trol Betz Laboratories CT-1 750-1a125 10<0.2 eg/1 Rainbow Daphnia Trout Nagna (li.7 ag/1)0.4 eg/l)Fathead Ninnow (3.0 Irg/1)Bluegill Sunfish (h.3 ag/1)Goniobasis sp, (11 eg/1)071 OTS<>>Betz Laboratories 0-1)200 0'-10 eg/1 N/A Fathead Oaphnia Ninnow Nagna (435 mg/1)(l35 ag/1)u>)in>s>tin>aine data requirement aiNpot5 permit applita'duo (2)During treatm<<l<>>Aa active Bentonite clay

-'DETOXIPICiTIOR POINT UNIT 2 COOLING TOUR UNIT 1 COOI ING TOOER CIRC.11TER SVSTEK CIRC.ViTER SVSTEK SERV.Q1TER SVSTHf SERV.11TER SVSTEH INJECTION POINT COMBINED OUTFhLL (071)Figure 1 FXOV DI1GR1M APPENDICES A Naterial Safety Data Sheets 8 Bioassay Data C Analytical Data 0 Betz Clam-Trol CT-1 APPENDIX A Material Safety Data Sheets~Clam-Trol CT-1~Betz DTS BETS LABORATORIES,INC.

4 6 3 6 SOMERTON ROAD I TREVOSE I PA 1 9 05 3 BETZ MATERIAL SAFETY DATA SHEET EMERGENCY TELEPHONE (HEALTH/ACCIDENT) 800-877-1940 (PAGE 1 OF 3)EFFECTIVE DATE 01-24-92 PRINTED: 28-Jan-1992 REVISIONS TO SECTIONS: APPENDIX PRODUCT: CLAM-TROL CT-1 PRODUCT APPLICATION

WATER-BASED MICROBIAL CONTROL AGENT.---SECTION 1----.-------HAZARDOUS INGREDIENTS---

ETHYLENE GLYCOL***CAS g 1 07 2 1 1 f LIVERY KI DNEY AND BLOOD TOXIN CNS DEPRESSANT;ANIMAL TERATOGEN(HIGH ORAL DOSES)g PEL/TLV:50PPM-C.(C12-16)ALKYL DIMETHYL BENZYL AMMONIUM CHLORIDE***CAS568424-85-1'ORROSIVE (EYES)g PEL: NONE p TLV: NONE.ISOPROPYL ALCOHOL (IPA)***CAS$67-63-0 r'LAMMABLE LIQUID'HRONIC OVEREXPOSURE MAY CAUSE LIVER AND KIDNEY TOXICITYgPEL/TLV:400PPM (500PPM-STEL).

DODECYLGUANIDINE HYDROCHLORIDE(DGH)***CAS013590-97-1;CORROSIVE'PEL:NONE'LV:NONE.

ETHYL ALCOHOL(ETHANOL)***CAS464-17-5'FLAMMABLEtEYE IRR1TANT MAY CAUSE DEPATTZNG DERMATZTZS,DZZZZNESS AND HEADACHE;PEL/TLU:

1000PPM.INFORMATION ON PHYSICAL HAZARDSP HEALTH HAZARDSP 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 POTENTIAL ACUTE AND CHRONIC HAZARDS OF THIS FORMULATION.

THIS PRODUCT IS SUBJECT TO THE PENNSYLVANIA AND NEW JERSEY WORKER AND COMMUNITY RIGHT TO KNOW LAW.NONHAZARD INGREDIENTS:

WATER (7732-18-5)

---SECTION 2-------TYPICAL PHYSICAL DATA PH'AS IS (APPROX.}5.3 ODOR: MILD FL.PT.(DEG.F):

116 SETA(CC)SP.GR (70F)OR DENSITY: 1.022 VAPOR PRESSURE(mmHG):

23 VAPOR DENSITY(AIR~1):

)1 VISC cps70P: 23%SOLUBILITY(WATER):

100 EVAP.RATE:

<1 ETHER 1 APPEUGKNCE:

COLORLESS PHYSICAL STATE lsIQQID FREEZE POINT(DEG.F):

<-30----SECTION 3-,---REACTIVITY DATA-------STABLE MAY REACT WITH STRONG OXIDIZERS.DO NOT CONTAMINATE.BETZ TANK CLEAN-OUT CATEGORY PBN THERMAL DECOMPOSITION (DESTRUCTIVE FIRES)YIELDS ELEMENTAL OXIDES.

BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3)PRODUCT: CLAM-TROL CT-1----SECTION 4---------HEALTH HAZARD EFFECTS ACUTE SKIN EFFECTS***PRIMARY ROUTE OF EXPOSURE CORROSIVE TO SKIN..JTE EYE EFFECTS***CORROSIVE TO THE EYES ACUTE RESPIRATORY EFFECTS***PRIMARY ROUTE OF EXPOSURE VAPORS~GASESgMISTS AND/OR AEROSOLS CAUSE IRRITATION TO UPPER RESPIRATORY TRACT CHRONIC EFFECTS OF OVEREXPOSURE***

PROLONGED OR REPEATED OVEREXPOSURES MAY CAUSE LIVER AND KIDNEY TOXICITY,MAY CAUSE REPRODUCTIVE SYSTEM TOXICITYgMAY CAUSE CNS DEPRESSZON/AND/OR MAY CAUSE TISSUE NECROSIS.MEDICAL CONDITIONS AGGRAVATED

      • NOT KNOWN SYMPTOMS OF EXPOSURE***INHALATION OF VAPORS/MI STS/AEROSOLS MAY CAUSE EYE g NOSE~THROAT AND LUNG ZRRITATIONgSKIN CONTACT MAY CAUSE SEVERE IRRITATION OR BURNS.PRECAUTIONARY STATEMENT BASED ON TESTING RESULTS***MAY BE TOXIC ZF ORALLY INGESTED.---SECTION 5 FIRST AID INSTRUCTIONS

SKIN CONTACT***

REMOVE CLOTHING.WASH AREA WITH LARGE AMOUNTS OF SOAP SOLUTION OR WATER 15 MZN.IMMEDIATELY CONTACT PHYSICIAN EYE CONTACT+**

IMMEDIATELY FLUSH EYES WITH WATER FOR 15 MINUTES IMMEDIATELY CONTACT A PHYSICIAN FOR ADDITIONAL TREATMENT INHALATION EXPOSURE***

REMOVE VICTIM FROM CONTAMINATED AREA.APPLY NECESSARY FIRST AID TREATMENT.IMMEDIATELY CONTACT A PHYSICIAN.

INGESTION**~

DO NOT FEED ANYTHING BY MOUTH TO AN UNCONSCIOUS OR CONVULSIVE VICTIM DO NOT INDUCE VOMITING.IMMEDIATELY CONTACT PHYSICIAN.

DILUTE CONTENTS OF STOMACH USING 3-4 GLASSES MILK OR WATER----SECTION 6--------SPILL, DISPOSAL AND FIRE INSTRUCTIONS-


SPILL INSTRUCTIONS***

VENTILATE AREA,USE SPECIFIED PROTECTIVE EQUIPMENT.

CONTAIN AND'BSORB ON ABSORBENT MATERIAL.PLACE IN WASTE DISPOSAL CONTAINER.

THE CONTAMINATED ABSORBENT SHOULD BE CONSIDERED A PESTICIDE AND DISPOSED OF IN AN APPROVED PESTICIDE LANDFILL.SEE PRODUCT LABEL STORAGE AND DISPOSAL INSTRUCTIONS REMOVE IGNITION SOURCES.FLUSH AREA WITH WATER.SPREAD SAND/GRIT.

DISPOSAL INSTRUCTIONS*+*

WATER CONTAMIHATED 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 PERMIT PRODUCT(AS IS)DISPOSE OF ZN APPROVED PESTICIDE FACILITY OR ACCORDING TO LABEL INSTRUCTIONS FIRE EXTINGUISHING INSTRUCTIONS***

FIREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING APPARATUS(FULL FACE-PIECE TYPE}.PROPER FIRE EXTINGUISHING MEDIA DRY CHEMICAL,CAISSON DIOXIDE, FOAM OR WATER e

BETZ MATERIAL SAFETY DATA SHEET (PAGE 3 OF 3)ODUCT: CLAM-TROL CT-1--SECTION 7------SPECIAL PROTECTIVE EQUIPMENT-USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITH 29CFR SECTION 1910.132-134.

USE RESPIRATORS WITHIN USE LIMITATIONS OR ELSE USE SUPPLIED AIR RESPIRATORS.

VENTILATION PROTECTION***

ADEQUATE VENTILATION TO MAINTAIN AIR CONTAMINANTS BELOW EXPOSURE LIMITS RECOMMENDED RESPIRATORY PROTECTION***

IF VENTILATION IS INADEQUATE OR SIGNIFICANT PRODUCT EXPOSURE ZS LIKELY, USE-A RESPIRATOR WITH ORGANIC VAPOR CARTRIDGE&DUST/MIST PREFZLTER RECOMMENDED SKIN.PROTECTION***

GAUNTLET-TYPE RUBBER GLOVES,CHEMICAL RESISTANT APRON WASH OFF AFTER EACH USE.REPLACE AS NECESSARY RECOMMENDED EYE PROTECTION***

SPLASH PROOF CHEMICAL GOGGLES-FACE SHIELD---SECTION 8-----------STORAGE AND HANDLING PRECAUTIONS-STORAGE INSTRUCTIONS***

KEEP DRUMS&PAILS CLOSED WHEN NOT IN USE.STORE IN COOL VENTILATED LOCATION.STORE AWAY FROM OXIDIZERS HANDLING INSTRUCTIONS***

COMBUSTIBLE.

DO NOT USE AROUND SPARKS OR FLAMES'OND CONTAINERS DURING FILLING OR DISCHARGE WHEN PERFORMED AT TEMPERATURES AT OR ABOVE THE PRODUCT FLASH POINT.**************************************************************************

THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD t***********************************************************************

APPENDIX: REGULATORY INFORMATION THE CONTENT OF THIS APPENDIX REPRESENTS INFORMATION KNOWN TO BETZ ON THE EFFECTIVE DATE OF THZS MSDS~THIS INFORMATION IS BELIEVED TO BE ACCURATE.ANY CHANGES IN REGULATIONS WILL RESULT IN UPDATED VERSIONS OF THIS DOCUMENT....TSCA THIS ZS AN EPA REGISTERED BIOCIDE AND IS EXEMPT FROM TSCA INVENTORY REQUIREMENTS

...-FIFRA(40CFR):EPA REG.NO.3876-'145...REPORTABLE QUANTITY(RQ)

FOR UNDILUTED PRODUCT: 0.4 GALLONS DUE TO ETHYLENE GLYCOL...RCRA: IF THIS PRODUCT IS DISCARDED AS A WASTE, THE RCRA HAZARDOUS WASTE IDENTIFICATION NUMBER IS: D001~IGNITABLEgD002~CORROSIVE(SKIN)

~~-DOT HAZARD/UN4/ER GUIDE4 IS: CORROSIVE TO SKIN.COMBUSTIBLE UN1760/$60~~~CALIFORNIA SAFE DRINKING WATER ACT (PROPOSITION 65)MATERIALS:

NONE~~~SARA SECTION 302 CHEMICALS:

NONE~~~SARA SECTION 313 CHEMICALS ETHYLENE GLYCOL(107 21 1)g 21'30 F 04~~..SARA SECTION 312 HAZARD CLASS: IMMEDIATE (ACUTE), DELAYED(CHRONIC)

AND FIRE...MZCHZGAN CRZTXCAL MATERIALS:

NONE NFPA/HMIS:

HEALTH-3 FIRE-2 REACTIVITY

-0 SPECIAL-CORR t PE-D BETZ LABORATORIES, INC.4 63 6 SOMERTON ROAD/TREVOSE g PA 1 9 047 PRODUCT: CLAM-TROL CT-1 4/02/92 AQUATIC TOXICOLOGY RAINBOW TROUT 04 MORTALITY:

10 MG/L 96 HR.LC50: 14.7 MG/L DAPHNIA MAGNA 04 MORTALITY:

0.16 MG/L 48 HR.LC50: 0.4 MG/L FATHEAD MINNOW 04 MORTALITY:

1.55 MG/L 96 HR.LC50: 3.0 MG/L 4/02/92 MAMMALIAN TOXICOLOGY ORAL LD50-RAT 3270, MG/KG DERMAL LD50-RAT: 9999~0 MG/KG SKIN IRRITATION SCORE-RABBIT: 5.1 EYE IRRITATION SCORE-RABBIT: 103 INHALATION-NO DATA BETZ LABORATORIES,ZNC.

4636 SOMERTON ROAD, TREVOSE, PA.19053 BETZ MATERIAL SAFETY DATA SHEET EMERGENCY TELEPHONE, (HEALTH/ACCIDENT) 800-877-1940 PRODUCT: BETZ DTS (PAGE 1 OF 3)EFFECTIVE DATE 11-13-91 PRINTED: 13-Nov-1991 REVISIONS TO SECTIONS: 1 PRODUCT APPLICATION

A DETOXIFYING AGENT.----SECTION 1---.-----HAZARDOUS INGREDIENTS---

--INFORMATION ON PHYS ICAL HAZARDS i HEALTH HAZARDS i PEL S AND TLV S FOR SPECI F IC PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIONS STANDARD IS LISTED.REFER TO SECTION 4 (PAGE 2)FOR OUR ASSESSMENT OF THE POTENTIAL ACUTE AND CHRONIC HAZARDS OF THIS FORMULATION.

THIS PRODUCT IS SUBJECT TO THE PENNSYLVANIA AND NEW JERSEY WORKER AND COMMUNITY RIGHT TO KNOW LAW.RESPIRABLE QUARTZ(CRYSTALLINE SILICA)***CAS¹14808-60-7;SUSPECT KBGQf CARCINOGEN (IARC=2A)MAY CAUSE LONG TERM LUNG DISEASE(SILICOSIS)

RESPIRATORY IRRITANT;PEL/TLV:0

'MG/M3~RESPIRABLE CRZSTOBALITE(CRYSTALLINE SILICA)***CAS¹14464-46-lgSUSPECT HUMAN CARCINOGEN(ZARC~2A)gMAY CAUSE LONG TERM LUNG DISEASE (SILICOSIS)i RESPIRATORY IRRZTANTgPEL/TLV:0.05MG/M3

~RESPIRABLE TRIDYMITE(CRYSTALLINE SILICA)***CAS¹15468-32-3iSUSPECT HUMAN CARCINOGEN(IARC=2A);MAY CAUSE LONG TERM LUNG DISEASE(SILICOSIS) g RESPIRATORY IRRITANT;PEL/TLV:0.05MG/M3.

TRIETHANOLAMINE***CAS¹102-71-6;IRRITANT POTENTIAL LIVER,AND KIDNEY TOXIN PEL/TLV:NONE.

NONHAZARD INGREDIENTS:

WATER(7732-18-5)

BENTONITE(1302-78-9) g 2-PROPENOIC ACID, HOMOPOLYMER (9003-01-4)

---SECTION 2-------TYPICAL PHYSICAL DATA------PH: AS IS (APPROX.)5.9 ODOR: SLIGHT FL.PT.(DEG.F)>200 P-M(CC)SP.GR.(70F)OR DENSITY 1 142 VAPOR PRESSURE (maHQ)18 VAPOR DENSITY (AIR~1):<1 VISC cps70F: 2 i 000%SOLUBILITY (WATER): 0 EVAP RATE: ND WATER 1 APPEAEULNCE:

GREEN-BROWN PHYSICAL STATE LIQUID FREEZE POINT(DEG.F):

32---SECTION 3-------REACTIVITY DATA-STABLE., BETZ TANK CLEANOUT CATEGORY'Bi THERMAL DECOMPOSITION (DESTRUCTIVE FIRES)YIELDS ELEMENTAL OXIDES'

BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3)PRODUCT: BETZ DTS----SECTION 4---------HEALTH HAZARD EFFECTS-ACUTE SKIN EFFECTS***PRIMARY ROUTE OF EXPOSURE SLIGHTLY IRRITATING TO THE SKIN JTE EYE EFFECTS***MODERATELY IRRITATING TO THE EYES ACUTE RESPIRATORY EFFECTS***MISTS/AEROSOLS MAY CAUSE IRRITATION TO UPPER RESPIRATORY TRACT CHRONIC EFFECTS OF OVEREXPOSURE***

PROLONGED OR REPEATED EXPOSURES MAY CAUSE LIVER AND KIDNEY TOXICITY.MEDICAL CONDITIONS AGGRAVATED

      • NOT KNOWN SYMPTOMS OF EXPOSURE***MAY CAUSE REDNESS OR ITCHING OF SKIN.----SECTION 5---------FIRST AZD INSTRUCTZONS-SKIN CONTACT***

REMOVE CONTAMINATED CLOTHING.WASH EXPOSED AREA WITH A LARGE QUANTITY OF SOAP SOLUTION OR WATER FOR 15 MINUTES EYE CONTACT***

IMMEDIATELY FLUSH EYES WITH WATER FOR 15 MINUTES IMMEDIATELY CONTACT A PHYSICIAN FOR ADDITIONAL TREATMENT INHALATION EXPOSURE*+*

REMOVE VICTIM FROM CONTAMINATED AREA TO FRESH AIR'APPLY APPROPRIATE FIRST AID TREATMENT AS NECESSARY INGESTION***

DO NOT FEED ANYTHING BY MOUTH TO AN UNCONSCIOUS OR CONVULSIVE VICTIM DILUTE CONTENTS OF STOMACH.INDUCE VOMITING BY ONE OF THE STANDARD METHODS.IMMEDIATELY CONTACT A PHYSICIAN---SECTION 6------SPILL, DISPOSAL AND FIRE INSTRUCTIONS


SPILL INSTRUCTIONS***

VENTILATE AREA,USE SPECIFIED PROTECTIVE EQUIPMENT CONTAIN AND ABSORB ON ABSORBENT MATERIAL.PLACE IN WASTE DISPOSAL CONTAINER.

THE WASTE CHARACTERISTICS OF THE ABSORBED MATERIALgOR ANY CONTAMINATED SOIL/SHOULD BE DETERMINED ZN ACCORDANCE WITH RCRA REGULATIONS'LUSH AREA WITH WATER.WET AREA MAY BE SLIPPERY.SPREAD SAND/GRIT.

DISPOSAL INSTRUCTIONS***

WATER CONTAMINATED WITH THIS PRODUCT MAY BE SENT TO A SANITARY SEWER TREATMENT FACILITYgIN ACCORDANCE WITH ANY LOCAL AGREEMENT/A PERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT PRODUCT(AS IS)INCINERATE OR BURY IN APPROVED LANDFILL FIRE EXTINGUISHIH&

INSTRUCTIONS***

~FIREFZGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING APPARATUS(FULL PACE-PIECE TYPE)IMPROPER FIRE EXTINGUISHING MEDIA: DRY CHEMICAL, CARBON DIOXIDE, FOAM OR WATER BETZ MATERIAL SAFETY DATA SHEET (PAGE 3 OF 3)lDUCT: BETZ DTS--SECTION 7------SPECIAL PROTECTIVE EQUZPMENT-USE PROTECTIVE EQUIPMENT ZN ACCORDANCE WITH 29CFR SECTION 1910.132-134.

USE RESPIRATORS WITHIN USE LIMITATIONS OR ELSE USE SUPPLIED AZR RESPIRATORS.

VENTILATION PROTECTION***

ADEQUATE VENTILATION TO MAINTAIN AIR CONTAMINANTS BELOW EXPOSURE LIMITS RECOMMENDED RESPIRATORY PROTECTION***

IF VENTILATION IS INADEQUATE OR SIGNIFICANT PRODUCT EXPOSURE IS LIKELY, USE A RESPIRATOR WITH DUST/MIST FILTERS.RECOMMENDED SKIN-PROTECTION***

RUBBER GLOVES WASH OFF AFTER EACH USE.REPLACE AS NECESSARY RECOMMENDED EYE PROTECTION***

SPLASH PROOF CHEMICAL GOGGLES---SECTION 8---------STORAGE AND.HANDLING PRECAUTIONS------

--STORAGE INSTRUCTIONS***

KEEP DRUMS&PAILS CLOSED WHEN NOT IN USE.DO NOT FREEZE.IF FROZEN, THAW AND MIX COMPLETELY PRIOR TO USE HANDLING INSTRUCTIONS***

THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD APPENDIX: REGULATORY INFORMATION CONTENT OF THIS APPENDIX REPRESENTS INFORMATION KNOWN TO BETZ ON THE EFFECTIVE DATE OF THIS MSDS~THIS INFORMATION IS BELIEVED TO BE ACCURATE.ANY CHANGES ZN REGULATIONS WILL RESULT ZN UPDATED VERSIONS OF THIS DOCUMENT.~~.TSCA: ALL COMPONENTS OF THIS PRODUCT ARE LISTED ON THE TSCA INVENTORY~~.REPORTABLE QUANTITY(RQ)

FOR UNDILUTED PRODUCT: TREAT AS OIL SPILL.RCRA IF THIS PRODUCT IS DISCARDED AS A WASTE, THE RCRA HAZARDOUS WASTE IDENTIFICATION NUMBER IS: NOT APPLICABLE

~~DOT HAZARD/UN4/ER GUZDE4 IS: NOT APPLICABLE

...CALIFORNIA SAFE DRINKING WATER ACT (PROPOSITION 65)MATERIALS:

NONE~~~SARA SECTION 302 CHEMICALS:

NONE~~.SARA SECTION 313 CHEMICALS:

NONE~~.SARA SECTION 312 HAZARD CLASS: IMMEDIATE(ACUTE)

~~.MICHIGAN CRITICAL MATERIALS:

NONE NFPA/HMIS: HEAIsTH 1 g FIRE-1;REACTIVITY

-0;SPECIAL-NONE g PE-B BETZ LABORATORIES,INC.

4636 SOMERTON ROADgTREVOSEgPA 19047 PRODUCT-BETZ DTS 4/02/92 AQUATIC TOXICOLOGY DAPHNIA MAGNA 04 MORTALITY:

435 MG/L 48 HR.SCR.FATHEAD MINNOW 04 MORTALITY:

435 MG/L 96 HR.SCR.4/02/92 MAMMALIAN TOXICOLOGY ORAL LD50-NO DATA DERMAL LD50-NO DATA SKIN IRRITATION SCORE-NO DATA EYE IRRITATION SCORE-NO DATA INHALATION-NO DATA APPENDIX 8 Bioassay Data Abstract Submitted for Presentation at the Society of Environmental Toxicology and Chemistry Heeting, November 1991 Acute Toxicity (LC 50's)Clam-Trol CT-1 Chronic Toxicity of Clam-Trol CT-1 to Fathead Ninnow Chronic Toxicity of Clam-Trol CT-1 to Ceriodaphnia Determination of Effect of Detoxified Clam-Trol CT-1, A Long-Term StdylligFth dill delhi II Chronic Effect of Detoxified CT-1 on Fish Survival and Growth

ABSTRACT SUBMITl ED FOR PRESENTATION AT THE SOCIETY OF ENVIRONMENTAL TOXICOLOGY

&CHEMISTRY MEETING, NOVEMBER 1991 SHORT-TERM RATE OF A SURFACTANT BASED MOLLUSCICIDE AND ITS EFFECTS UPON A SEDIMENT DWELLLING ORGANISM.J.R.Bidwell, D.S.Chery, J.L.Farris, and L.A.Lyons.Virginia Polytechnic Institute and State University.

Blacksburg, VA 24061, and BETZ Laboratories, Trevose, PA 19047.The short-term fate of the cationic surfactant based molluscicide CT-1, and its effects on larvae of the midge, Chironomus

~ri arius were examined in laboratory and field studies.Levels of free CT-1 dropped sharply when solutions of the molluscicide were mixed with bentonite clay or placed over natural sediments, and were inversely related to the amount of suspended solids in raw river water.In suMhronic (10-d)btoassays with t.~ri arius the impact of CT-t upon the survival and growth of the organisms was reduced or eliminated in the presence of clay or natural sediment.These results were validated by field studies conducted during the spring and fall of 1990 when midge larvae were exposed to effluent containing CT-1'nd clay in ratios between 1:1 and 1:3 during a 24 hr on-site application at a power plant.Larvae were also tested in river sediments which were collected during dosing and up to 21 days after dosing from selected stations above and below the plant discharge.

No~significant effects on survival or growth of the larvae were associated with exposure to the CT-1 and clay in either the effluent or river sediments.

These data further Indicate that the adsorptive nature of the cationic surfactants in the mollusciclde can serve to mediate its toxicity to non-target organisms such as the midge.

LA,BQRATQRIES.

INC.AQUATIC TOX(COLOGY KO'ABORATORY SOMERTONROAO TREVOSE,PA19047 U.S.A.I TEL:215 355.3300 TELEX: 173148 FAX+355 2969 Effects of Detoxified clam-Trol CT-1 on Chironomus Survival and Qrowth The effect of.a 10-day exposure to Clam-Trol detoxified with Beta DT-1, a blend of highly adsorptive clays, on the survival and growth of CblÃQRQ*S 5 exposed to various ratios of Clam-Trol CT-1 and Bets DT-1 on both an artificial substrate of glass beads and natural substrate collected from the bottom of a stream.The midge larvae were exposed for 10 days to daily renewal of test solutions.

For the artificial substrate using glass beads, a significant growth impairment resulted from exposures.to CT-1 only and the CT-1:DT-1 ratio of 1:1 and 1:2.This growth impairment was mediated at the 1:3 ratio.Zt should be noted that the Midge larvae on the artificial substrate exhibited lower growth compared to organisms on the natural substrate.

This is probably both an artifact of the sterile nature of the glass beads and an illustration of the extent to which the natural sediment mediates CT-1 toxicity.For the natural substrate using river sediment, the survival of the midge larvae exposed to all test concentrations was not significantly different from the control.Zn addition, growth was only slightly impaired at.the CT-1 only and the 1:1 ratio of CT-1:DT-l.

Qrowth was not impaired at the 1:2 ratio.\Survival r CT-1/L: mg/Clay/L A N Mean Chironomid Dry Weight (mg+SE)A N 0 100 0 10 20 30 50 87 93 30 77 93 100 100 10 10 0 0'754(0.0343) 0 0~6779 (0~0478)'10 0~0641(0~0103)+0~2272 (0~0107)+10 0.3900(0.0534)

  • 0'476(0'443)10 0~5558 (0~0108)*Significantly different from Control (a~0.05, Fisher's LSD)0'347(0.0583) 0~8930 (0~0512)0.6782(0.0286)*

0'069(0'527)*0'585(0.0695) 0+8369(0.0252) 0.7916(0.0263)

A Artificial substrate N~Natural substrate LABORATORIES, INC.AQUATIC TOXICOLOGY LABORATORY SOMERTON ROAO+TREVOSE.

PA 1 9047iU.S.A.

1 TEL: 21 Si355 3300'ELEX:

1 73 1 48iF AX sr 355.2969 The term"benthic" refers to organisms that live in the bottom sediments of lakes and streams.Aquatic insects such as the midge tcaix'.~-'s used to study the effects of materials on bottom-living organisms.'idge larvae were exposed for 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> to 10 mg/L of Clam-Trol cT-1 and to Clam&rol CT-1 which was detoxified by the addition of Betz DT-1, a blend of highly adsorbent clays.The results, shown in Table 5, indicate that the Clam-Trol CT-1 by itself produced an 804 mortality without detoxification.

Treatment with Betz DT-1 in ratios of 1:1 to 1:10, successfully eliminated any effects of c-1 on the mortality and growth rate of the midge larvae.i 7"~CbiDU Zillk11llh 2-day exposure to ratios of Betz.Clam<rol CT-3.and Betz DT-1 followed by recovery for 8 days in dechlorinated laboratory wata at ZOoC.(n~30)mg CT-1/L mg DT-1/L Mean Chironomid Mortality (0)Dry Weight (mg+SE)10 10 10 10;10:.0 100 0 10 30 50 100 80*10 0 0 9048 0 9789 0.8121 0.8748 0.9164 0'278 0 9502 (0~0121)(0 0136)(0 0135)*(0'122)(0.0112)(0 0115)(0.0180)*Significantly different from controls (a~0.05, Dunnett's test)

LABQRATQRIES, INC.AQUATIC TOXICOLOGY LABORATORY SOMEATON AOAO~TAEVOSE, PA 1 9047oU S A./TEL:21 5+355.33OO~TELEX:

1 73 1 46~FAX c 355.2869 Acute Toxicity (LC5p~s)Clam-Trol CT-1 eswte 0s s Rainbow Trout 96 hr LC5p~14.7 mg/L Bluegill Sunfish 96 hr LC50 4.3 mg/L Fathead Minnow 96 hr LC5p 2.9 mg/L 48 hr LC50 0.4 mg/L 48 hr LC5p~0~45 mg/L Chironomus riparius: 48 hr LC50~6.5 mg/L (Midge Larvae)Goniobaata sp (Snail)96 hr LC50~11.0 mg/L Note: The above LC50 values represent toxicity levels for Clam-Trol CT-1 when 1004 of the"free" activas are available to the acgxatic organism (that is, no suspended solids for adsorption of the actives).

LABQRATC3RIES, INC.AauATIC TOXICOLOGY LABORATORY SOMERTON ROAOiTREVOSE.

PA 1 9047iU.S.A.

/TEL: 21 5+355 3300iTELEX:

1 73 1 48iFAX 355 6669 C c To c t of C am-T o CT-1 to Fat ead Minnow A 7-day static toxicity test was conducted to estimate the chronic toxicity of Clam-Trol CT-1 to the Fathead Minnow, using larvae less than 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> old.The endpoints of this toxicity test are based on adverse effects on survival and growth.This toxicity test was conducted following EPA protocol as described in"Short-Term Methods For Estimating the Chronic Toxicity of Effluents and Receiving to Freshwater Organisms, EPA/600/4-89/001.<<

For Clam-Trol CT-1, growth was.the most sensitive endpoint producing a lowest observed effect concentration (LOEC)of 3.2 mg/L and a no observed effect concentration (NOEC)of 1.6 mg/L.The chronic value, the estimated<<safe<<or<<no effect<<concentration, for Clam-Trol CT-1 is 1.3 mg/L.Dividing the chronic value generated during this study (1.3 mg/L)into the acute value (2.9 mg/L)results in an acute/chronic

'ratio of 2.2.Mortality and Growth of the Fathead Minnow after a 7-day chronic exposure to Clam-Trol CT-1.CT-1 Concentration 0~0 0.4 0'1.6 3'6'12'Mortality 5'2'0 7'12.5 100'*100'*~e 0'90 0.296 0.292 0'68 0.029*We S.D~0~032 0.029 0.029 0.022 0'19 m F s 0'54-0.329 0.261-0.333 0.259-0.324 0.245-0.291 0.186-0.225*Significantly different from Control (a 0.05, Dunnett's test)

AaUATIC TOXICOLOGY LABORATORY SOMERTON ROAOiTREVOSE.

PA 1 9047'U.S.A,/TEL: 21 5i355.3300'ELEX:

1 73 1 46iFAX 355.6669 Ch on ox'c t of Clam-Trol CT-to Cer oda A 7-day static renewal toxicity test was conducted to estimate the v**c""~dubia, using neonates less than 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> old.The endpoints of this toxicity test are based on adverse effects on survival and reproduction.

This toxicity test was conducted following EPA protocol as described in"Short-Term Methods For Estimating the Chronic Toxicity of Effluent and Receiving Waters to Freshwater Organisms.

The lowest observed effect concentration (LOEC)for a 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> exposure to Clam-Trol CT-1 for both survival and reproduction was 0.80 mg/L.The no, observed effect concentration (NOEC)for survival and reproduction was 0.40 mg/L Clam-Trol CT-1.The chronic value, the estimated"safe<<or"no effect" concentration for Clam-Trol CT-1 is 0.56 mg/L.Mortality and Growth of the ce oda n a du exposure to Clam-Trol CT-1.7-day after a 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> CT-1 Concentration m 0.0 0.05 0'0 0'0 0'0 0.80 1.60 Mortality 0 0 0 0 10 9 0*100 Average 0 of e oduc 25'28'23'24'22'18 total neonates**Significantly different from Control (a 0.05, Dunnatt's test)

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1 73 1 48iF AX e 355 2869 Aquatic Toxicity Report Determination of the Effect of Detoxified Clam-Trol CT-1-A Long Term Study Using Fathead Minnows and gy~~g~~Study Conducted By: Aquatic Toxicology Laboratory Betz Laboratories, Inc.Trevose, PA

Objective:

The purpose of this study was to determine if any acute toxicity would be exhibited from long term exposures of Clam-Trol CT-1 detoxified with bentonite clay to fathead minnows and~~g macon and to determine any evidence of desorption of the actives to a toxic form under these test conditions.

Test Type/'onditions:

The detoxification of the biocidal activity of Clam-Trol CT-1 is readily achieved by adsorption with a variety of materials and substrates.

Once the two cationic actives present in Clam-Trol CT-1 are adsorbed, they no longer exhibit toxicity.The intent of this study was to detoxify toxic levels of Clam-Trol cT-1 and expose aquatic organisms for an extended period to evaluate any acute toxic effects of the detoxified solutions and if any potential desorption of the actives resulted to cause toxicity.URltlalR-Source: SP Engineering, MA-Total length (mean): 3.5+0.34 cm-Wet weight, (mean): 0.42+0.19 g QxpJ~L MQGiL Source: Stock culture Age: 12+12 hr.old neonates Fathead minnow and Q.]~ggL were exposed to the following five treatments and test conditions for 30 days.-"control 0 mg/1 Clam-Zro'1'T-1

-25'mg/1 Clam-Trol'CT-'1-25 mg/1 Clam-Trol/250'mg/1 bentonite clay-250 mg/1 bentonite clay only-Continuously aerated 25 mg/1 Clam-Trol CT-3./250 mg/1 bentonite clay.

Method: 's es Detoxxfied Clam-Trol CT-1 solutions were prepared by mixin 25 mg/l Clam-Trol CT-1 solution with 250/l ite clay (a CT-1 to clay ratio of 1:10).mg of bentonite The two materials vere mixed with a mechanical t'ca s xrrer at mixed in rp or 30 minutes.All treatments vith cl y the same manner.Fifteen liters of solution were c ay were prepared for each treatment.

replicate.

Twenty fish vere e o a d xp sed to each treatment-two replicate an 10 fish per 15 liter of solution.All treatments with.exception of th ti 25 ppm C3.am-Tro3.

CT-1:250 ppm bentonite clay were renewed e cont nuousl aerated vith freshly prepared solutions on the followin da s sol test vas initiated on day one.Du utions, only the supernatant was si honed r ng the reneval of test container and the s di t ti ip one from each test retained in the containe th t e men a on of cia on the con a ner e test.Fresh test solution vas added after siphoning and.mixed ith th umulated clay.Fish were fed comme', f w e existing daily.Observations of mortality and behavio ercxa flake food were assessed daily.n e av oz response Standard 48 hr acute Qg'~" ia e only on days that solution renewals vere made in the fish test.Daphniids were exposed to subsamples of test solution taken from the fish test containers.

During each reneval period,,toxicity tests were performed vith the freshly made test solutions and vith the aged solutions taken from each test container.

Trent y Q gg~were exposed to each treatment, 10 ind1viduals per replicate.

Mortality was assessed at 1-2 24, 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br />.t Summary of Results Detoxified Clam-Trol CT-1 solutions were prepared by mixing 25 mg/1 Clam-Trol CT-1 solutions with 250 mg/l of bentonite clay (a CT-1 to clay ratio of 1:10).No mortality or stress was exhibited to fathead minnows that vere continuously exposed for 30 days to detoxified Clam-Trol cT-1 solutions.

No mortality was exhibited to'~~gag~that were exposed for 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> periods to renewed or aged detoxified Clam-Trol CT-1 solutions.

0 0

~BQRATQRIES, INC.AQUATIC TOXICOLOGY LABORATORY SQME+TQN RQAQiTAEVQSE.

PA 1 9Q47+U S A.I TEL: 21 5~355.33QQ'TELEX!

1 73 1 48~t-AX=355 2969 The chronic effect of Clam-Trol CT-1 detoxified with Betz DT-1 was studied using the standard 7&ay chronic fathead minnow survivability and growth rate test.The data presented in Table 6 show that 10 mg/L of CT-1 resulted in 100%mortality of the minnows.The addition of Betz DT-1 at a 1:1 ratio with CT-1 completely eliminated chronic mortality effects on fathead minnows, hut allowed some growth rate impairment.

Ratios of DT-1 to'CT-1 of 3:1 or greater completely eliminated any effect of CT-1 on both minnow survivability and growth.y~(~I after a 7-day exposure to ratios of Betz Clam-Trol CT-1 and Betz DT-1.mg CT-1/L mg DT-1/L Mean Fathead Mortality (4)Dry Weight (mg+sE)0 0 10 10 10 10 10 0 100 0 10 30 50 100 100+13 7 18 10 0~3101 (0 0157)0 2855 (0.0015)mmmmmmmmmmmm~mm*

0~1881 (0~0242)*0'032 (0'158)0.3355 (0.0046)0.2811 (0~0112)*Significantly different from control.s (a~0.05, Dunnett's test)

APPENDIX C Analytical Data J4~Clam-Trol CT-1, Hollusk Control Agent, Hethyl Orange Hethod CLAM-TROL CT-1 Mollusk Control Agent METHYL ORANGE METHOD APPARATUS REQUIRED Beaker, glass, 50 mL (2 required)Code Cylinder, graduated, 25 mL 2622 Funnel Rack, separatory 936 Funnel, separatory, with a Teflon stopcock, 250 mL (2 required)Glass Rod Optical Cell, (2 required)Safety Bulb, rubber 1575 Spectrophotometer GENERAl APPARATUS~121 917 935 140 888 CHEMICALS REQUIRED 1, 2-Dlchloroethane (reagent Code 1668 grade or equivalent)

Cylinder, graduated, 100 mL Code Cylinder, graduated.

250 mL Rask, volumetric, 1 L, glass (4 required)Pipet, glass, graduated, 1 mL Pipet, glass, volumetric, 1 mt.Plpet, glass, voltanetric, 3 mL pipet.glass, volunehc, 5 ml 124 Pipet, glass, volianetk, 10 ml 123 Pipet, glass, volwatlc, 15 mL 861 Pipet, glass, vollneirlc, 20 mL 1278'ipet, glass, voltxnetric, 25 mL 117 Pipet, glass, volumetric, 30 mL The general apparatus required for the test Is deter-mined by the specific test procedtxe used.'~Apparatus not available through Betz Lab Supply should be obtained through a local supplier.CT-1 Buffer Reagent Methanol (reagent grade or equivalent)

Drying Reagent.with a plastic dipper

SUMMARY

OF METHOD i591 322 I27t Use a weI-ventmated or hooded area to run the test.Always use a safety bulb when pipetting liquids.1,2-Dlchioroethane (also known as Ethylene Dichlo-ride)Is a pretty pollutant and a specifically-Iisted RCR&regutatedmaterial SubjeCt tO SPeCifiC diSpOSal re-strictions andlor prohibitions.

For this reason, aII used 1,2-dichloroethane should be segregated from other waste streams.Dispose of waste 1,2-dichloroelhane in an approved manner (e.g., labpacking or incinerationi In thIs procedure the dye in the CT1 Buffer Reagent com-plexes with the active ingredients in Clam-Trol CT-1>is complex is extracted into 1, 2-dlchloroethane.

The cr-ganlc layer containing the complex is separated from:r:e aqueous layer and drtedwlth a drying reagent containing anhydrous sodltxn sulfate.The color intensity of the I.2 dichloroethane layer ls then measured in a spectropho-tometer at 415 rxn.This methodmust be customizecf to each specific aocii-cation.Vary the voitxnes of sample, CT-1 Buffer Reagent.and 1, 2-dichloroethane according to the test range (see Tttbte 1).If a higher absorbance is needed, increase the vokane of sample or decrease the volume of t.2-dichloroelhane.

When increasing the sample volume it may be necessary to Increase the volixne of CT-1 Buffer Reagent used.For samples<150mluse 10ml of CT-I Buffer Reagent;for samples between 150 and 300 mL use 15 mL of CT-1 Buffer Reagent.Make sure that enough 1, 2-dlchloroethane Is used to leave a smail Plug Of SOIVent In the SeParatOry funnel When the OOItcm layer of solvent ls removed and to fill the optical celt properly~GENERALPROCEDURE AP 35S 9000~1QO BETZ LASORATOAIES.

INC.ALL AIGHTS RESERVED.oage i 1.Refer to Table 1 for the appropriate range and vol-umes to use in this procedure.

Transfer an aliquot of the water sample to a separatory funnel (the sam-ple).Transfer the same volume of distilled (or deion-ized)water to a second separatory funnel (the blank).Run the blank once for each set of samples tested(see Notes1,2, and 3).2.Add CT-1 Buffer Reagent to both the sample and the blank.3.Using a pipet;add 1, 2-dichloroethane to both se-paratory funnels.4.Insert the stoppers in each of the separatoiy funnels.invert and briefly open the stopcock to vent the fun-nels (see Notes 4 and 5).When venting the funnels, point the tip of the funnel away from yourself and others.5.Shake the funnels moderately for 30 sec, vent the funnels, then allow them to stand for 10 min (but no longer than 15 min).6.Collect the lower layer (1, 2-dlchloroethane) from each funnel in 50mL beakers leaving about 1-2 mL.in the funnel.This will prevent significant removal of water.7.Using the plastic dipper, add 2 scoops of Drying Re-agent to eachbeaker and stir with a glass rod for 15 sec (but no longer than 30 sec).8.Wait approximately 1 to 2 min (but not more than 5 min).Then carefully decant the extract off of the dry-ing reagent Into an optical cell.1,2-dlchloroethane.

Measure and record the absor-bance of the blank and the sample (see Note 6).10.The sample absorbance minus the blank absor-bance is used to determine the concentration of CT-1 ln the sample.From a prepared calibration cuve, determine the CT-1 concentration In the sam-ple (see Calibration Curve Preparation).

11.Clean the cells alter each meaarement (see Note 7).Concentration CT-1 Desired (mg/L)0.2 0.4 0.6 0.8 1.0 5.0 10.0 15.0 20.0 25.0 CT-1 Stock Sciu-tion Added to Make 1 L (mL)02 04 06 08 1.0 5.0 10.0 15.0 20.0 25.0 CALIBRATION CURVE PREPARATION 1.Prepare a 1000 mg/L CT-1 stock soluticn by ac=-rately Weighing 1.00 g Of CT-1 intO 1 L Of aiStiaea,=r deionized) water.2.pipet designated volumes of the stock solution ir:o 1-L volumetnc flasks.These are the stancar" s="~tions used in preparing a calibration curie Lee Table 2 to make appropriate dilutions cf:ne s',c=k solution for each specific application, 3.Follow the General Procedure using the spec..c s-Iution volumes',hat have been determinea!cr;.".e application ano prepare a calibration c ive Deter-mine the absorbance of a blank solution using".s.tilled (or deionized) water.This blank can ce suc-tracted from the sample absorbance cr csea:c zero the spectrophotometer so that the calibra.: r, curve goes through the origin.The caiibra:icn curve should be linear over the incica!=" ranges.Table 2.DI!utions for Calibration Curve Prepara-tion Based on a Final Solution Volume of1L.Table 1.Suggee&d Voturttee for Verfous Ranges of CT-1.Range CT-1 (mg/L)0.2-3.0 1.0-25.0 0.2-1.0 Voltatto CT-1 Buffer (mL)10 15 Volume Dlchloroethane (mL)10 Volume Sample (mL)Optical Cell Size t 0crn 5 cm~~5,0cm"~Thet.&an cell (code 1312)can be used with Hach spectrophotometers using a 1~cell adapter (code 2776ct~The 2.&cm cell Is the standard Hach 1-In.cell (Betz Code 2601).FIve centimeter cells are not available for use with the Hach photometers.

Many laboratoy spectropnoioi e'=s require an adapter to accommodate Sam cells.Check with the instnxnent manufacturer NOTES 1.For maximln ocaracy the calibration cthe should be checked by every operator using this test and shouldbe verNed a mlnimmn of twice per monthus-ing a freshly prepared CT-1 standard.2.A blank meastsement (the blank should be a sam-ple of the system water prior to CT-I treatment) must be recorded for each set of samples.The blank reading may vary slightly;however, the absolute dif-ference between the sample and the blank remains relatively constant.3.Chlorine causes a negative interference in the test.This can be eliminated by adding 0.1 N Sodium Thiosulfate (Code 235)to the water sample before running the test.The amount added is based on the concentration of chlorine in the system.For a 100mL water sample containing 0.3 mg/L chlorine, add 10 drops of 0.1 N Sodium Thiosulfate to remove the interference.

4.A slight emulsionmay form whenuslng natural water samples.When this happens, vary step 5 of the procedure.

Shake the funnel for 30 sec, vent it, then allow It to stand for 5 min.Gently invert the funnel once then allow the funnel to stand for 5 min.5.It Is Impotant to vent the separatly funnel both be-fore and after shaking it.Otherwise, a pret+we will build up in the funnel that can cause the stopper to be forced out of the top of the funnel.6.Use caution when Inserting or removing the sample cell In the photometer.

The 1,2-dlchloroethane can damage the cell compartment.

7.It Is imperative that the sample cells are kept clean during the nmnlng of the test.It is recommended ttiat the cells are cleaned after each measurement using the following procedure:

a)Rinse the cell three times with distilled (cr deionized) water.b)Rinse the cell three times with methanol.C)RinSe the Cell three timeS With I, 2-diChlarO.ethane to remove methanol from the cell.8.Itxbidlty can i.iterfere with this test prcceaure Ibrbldity may:~Create an emulSiOn in the 1.2,-diCRICrO-ethane layer that does not separate atter standing for 10 min when the funnel is shaken.~create a positive interference.

(A yellow color is extracted into the 1,2-dichloro-ethane layer.)These probloms can be removed by centrifuging II;e sample (10mkt at 3500rpm or 30min at 2500 rpm)betore performing step 1 of the procedure.

9.Ifyouneedto change test conditions(l.e., use differ-ent volumes than those in Table 1), contact the Ana-lytical Testing and Development Group in Trevcse for assistance 10.This method is adapted from Wang, L K.: Lai.aiy.3 F.Ind.Eng.Chem., Prod.Res.Dev., 1975.14, 3 210-212.RAT RIES.INC.ALL d3gd 3 A PENDIX D Betz Clam-Trol CT-1~Betz Clam-Trol CT-1, Environmental Information Package 10 LABORATORIES, INC.AQUATIC TOXICOLOGY LABORATORY SPMERTPN)PAPaTPEVPSE.PA19047>USA./

TE{-.215~355.33OO~TSI E~'f X;1 73 945aFAX 4355-cBS BETZ CLAM-TROL CT-1 ENVIRONMENTAL INFORMATION PACKAGE Clam-Trol CT-1 is an effective molluscicide for controlling Asiatic clam macrofouling problems in both once-through and recirculating cooling systems.The unique molluscicide applications can be used for exterminating adult Asiatic clams which cause advanced stage fouling conditions in cooling systems and can also be used as part of a preventative program for eliminating larvae and juvenile clams before they attain the adult fouling size which can cause advanced fouling conditions.

Clam-Trol CT-1 can also be used as a broad spectrum microbiocide for the control of bacterial, fungal and algal slimes.Clam-Trol CT-1 contains 13%active ingredients of two cationic surfactants and 87%inert materials.

The two cationic surfactants are n-alkyl dimethyl benzyl ammonium chloride{Qual)anddodecytguanidine hydrochloride

{DGH).CH3 I n-C14H29-N+-CH2 Cl I CH3 NH II n-C1zH25-NH-C-NH2HCI Quat DGH Both straight chain hydrocarbon containing molecules are referred to as surface active agents and have a hydrophobic tail and positively charged moiety that readily attaches to membranes to induce biocidal activity.The inert materials of this formulation

-ethylene glycol, isopropyl alcohol, and water-are relatively non-toxic to aquatic organisms.

Several studies on the adsorptive characteristics, aquatic toxicity, biodegradation, environmental fate and detoxification processes have been conducted for these cationic surfactants.

The results of these studies are summarized herein.

ge h ni m a A r i n Rat A~~i of cationic surfactants result from a st<<The toxic proPer'membrane proteins are essential f with membrane P ding various sPecific ion transport channels.The alkyl mechanisms

'ncl" tives becomes imbedded in these membranes.

In effqcg od biocidal performers but the cationic surfacta">s neutralized upon adsorption to various their positive charge var ous surfaces.xtremely strong affinities for many kinds of suspended OGH and ruat hav tes.A series of laboratory and field studies conducted b material and su'd ComPany evaluated the degree and rate that OGH is electrostatically boun the~r-Cy""'to suspended matter and other substrates I t d weighed portions of sludge containing 5.2%solids obtained from a In one stud , t lant were inoculated with 10 ppm and 20 ppm of OGH (Ip~active)and thoroughly mixed.After 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> and 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />, duplicate samples of the mixtures were centrifuged to seParate the solids.OGH was analyzed in the supernatant.

The results in the table below show that less than 2 PPm of OCH remained in the supernatant OGH added Contact Time OGH F ound in Supernatant 10 10 10 10 10 20 20 20 20 20 1 1 24 24 (Control;water only)1 1 24 24 (Control;water only)1.2 1.6 1.0 1.2 11.0 1.1 1.7 1.6 1.3 23.5 Other laboratory studies utilizing cooling tower water samples from Utah Power and Light demonstrated a loss of 95%OGH in 1/2 hour or less contact time after initial OGH concentrations of 350 ppm, 700 ppm, and 1,750 ppm were added to the samples.The residual OGH (ppm)in the supernatant after precipitates were filtered out and the 5 loss are provided in the table below: OGH added 350 350 700 700 1750 1750 Residual OGH (ppm)in n n 19 17 24 31 52 85 95 95 97 96 97 95 The rate of adsorption (loss of OGH to the cooling tower solids)was also determined from the above sample.Results are presented below: OGH added Contact time Residual OGH (ppm)350 1750 1 6 24 1 6 24 28 16 12 82 61 42 Field studies have also demonstrated that OGH is rapidly removed from cooling water systems.The two tables below show the concentration of DGH detected in the cooling tower effluents on two different occasions.

Sam Tim Oil and Grease OGH Content in Effluent Addition of OGH 8:15 am (16-17 ppm)9:30 am 10.15 am 12:00 pm makeup Mater added 158 1300 700 1500 14 0 0 0.4 0.9 0 Samples from cooling tower operation submitted by Chevron Oil, Salt Lake City, Utah, on Oecember 20, 1972.Tower has contained volume ef 350,000 gallons and a blowdown of 400 gpm.m l Suspended Solids Organ)c Carbon OGH Content in Effluent Before addition OGH addition 13 ppm After addition 1:30 pm 17 3:00 pm 280 16 (233 organic)(filtered) 4 00 pm 16 5:00 pm 15 Radioactive labelled ruat solutions at concentrations of.01 to.1 ppm were used for studies conducted by Rohm and Haas Company (Krezeminski, SF, et.al., 1977)to (IItermine adsorptive characteristics to different types oy material.In these C studies, adsorption was measured by the loss of radioactivity from the labelled solutions exposed to three different types of adsorbent material-river silt, and aquatic plant, and alum floe.Results are reported below: Adsorptive characteristics of Hyamine 3500 (504 Active ruat)Concentration in Water (ppm)Adsorbent Contact Time (hr)Ini ti al Final 1e Adsorbed River Silt Aquatic Plant (Azol'la Caroliniana)

Alum Floca 1/60 24 1/2 0.070 0.006 0.056 0.008 0.094.0 91 86 100 a)400 ppm turbidity 30 ppm alum concentration

As with the OGH studies, fiel'd studies conducted by Rohm and Haas have determined the residual ruat concentrations in cooling tower blowdown water at various intervals following biocide application.

The adsorptive nature of the active to the surfaces of the cooling system and to particulate material caused a substantial loss.Hyamine 3500 (5@A Active ruat)in Cooling Tower Blowdown Water as a Function of Time After Oosinga Concentration of Hyamine 3500 (ppm)Time After Oosing (hrs)1 2.5 5 8" 72 120 168 Oose 1 (60 ppm)60.0 52.2 44.8 26.5 5.18 2.50 1.16 Oose 2 (30 ppm)26.8 21.1 14.8 10.6 0.25 0.011 0.008 Oose 3 (30 ppm)31.6 21.0 14.2 9.9 0.041 NOR NOR a)Three consecutive dosings (60, 30, 30 ppm)at one-week intervals b)NOR no detectable residue;less than 0.005 ppm Cooling tower capacity 40,000 gallons Blowdown rate 30 gpm A i T A v Fr Acute toxicity tests determining LC50 values for Clam-Trol CT-1 with 13K'ctive ingredients is provided as follows:~Oa+r~i m~: 48 hr LC50 0.41 mg/1 (.37-.49 T.L.)Fathead minnow: 96 hr LC50 2.9 mg/1 (2.5-3.3 T.L.)Bluegill Sunfish: 96 hr LC50 4.3 mg/1 (4.2-6.6 T.L.)Rainbow trout: 96 hr LC50 14.7 mg/1 (10-15.5 T.L.)The above LC~>values represent toxicity levels for the neat formulation when 10%of the Free" actives are available to the aquatic organism (that is, no suspended solids for adsorption of the actives).However, when the formulation is exposed to adsorbent material (i.e., bentonite clay or activated carbon), acute toxicity is greatly reduced due to the adsorption properties of the active ingredients.

Tables 1 to 4 provide t litt t ftt d~I d~, f'lam Trol CT-1 which has been exposed to various concentrations of either bentonite clay or activated carbon.Even the most sensitive test species, lybaULmm.ff d I fft I t I I I 11 tl adsorb the free actives.A ppm ratio of 1 to 1 of clay to Clam-Trol CT-1 and 2 to 1 of activated carbon to Clam-Trol CT-1 resulted in the reduction of acute toxicity to fathead minnows to the point that the water becomes essentially non-toxic.

Both the LC50 bioassays and the detoxification studies were conducted by the Aquatic Toxicology Laboratory of Betz Laboratories.

I

The rate of biodegradation of the quat active was evaluated in both acclimated and unacclimated microbial cultures (Gawel, L.J.2 Huddlestown, R.L., Continental Oil Company, 1972).The microorganisms used for the biodegradation tests were derived from both soil and raw city sewage, and which grew on a defined medium.Rates of biodegradation were determined analytically using an extraction procedure to remove all unde-graded ruat.The results reported below present biodegradation data from cultures acclimated for different time intervals to the ruat (ION active).T A Acclimation Incubation Period Percent Oegraded~N 24 hr/48 hr 24 hr/48 hr 24 hr/48 hr 24 hr/48hr 37 95 60 97 60 97 15 50 The, reduced rate of biodegradation at 9 days was attributed to the additional transfers of ruat causing an increased biocidal effect upon the cultures.1 The Rohm and Haas investigation, previous1~4cited, reported biodegradation studies of ruat conducted by exposing the C labelled active to activated sludge.Fresh synthetic sewage (nutrients) and labelled ruat were renewed daily except weekends to a closed culture system durf~g a 24 day study period.Biological activity was determined by measuring the C02 that was generated from the labelled ruat.In order to allow for acclimation and any toxic effect, dosing of the labelled active started at I ppm and increased gradually over period of days to 10 ppm.Figure I presents the results as the percent C detected in the supernatant a~unde-graded active removed from the closed system and the present C as C02 converted during biological degradation of the ruat.guring the first f~o weeks, ggg of all labelled guet added to the culture unit was converted to C02.This activity increased to a 9'onversion after a two week accumulation period.It was concluded from this study that biodegradation of the quat was, after a short period of microbial acclimation, quite rapitk-and complete.

Biodegradation of OGH was examined in 1989 using the OECD Screening Test according to EC Directive 79/831.For the DECO study, a OGH solution was diluted with nutritive salt solutions and mud from the biological part of a clarification plant to nearly 40 mg/L OOC in water.The system was shaken at 24 C in the dark for 28 days.Dissolved Organic Carbon (OOC)determinations were used to monitor biodegradability of the OGH compound.Test results are presented in the table below.Day 0 1 4 7 14 18 22 26 29 31 i n DOC mg/L 34 39 26 26 17 16 18.13 10 9 Pr%Degradation 0 33 33 56 59 54'7 74 77 Thy OGH exhibited a OOC removal of greater than 70%within 28 days enabling it to be reported as"easily biodegradable" according to the test standard.In another study (Goldberg, M.C., et.al., 1969), dodecylguanidine acetate (DGA), an agricultural fungicide, was investigated to evaluate the biodegradation potential by microorganisms originating from soil and river muds.Two species of soil bacteria, one an aerobe and another an anaerobe that were isolated on agar plates and then transferred to dodine (DGA)salt media, grew profusely after a 7 day lag period.When these bacterial species were transferred back to dodine-free medium, growth of the organisms was poor.This study provided a demonstration that certain organisms were quite capable of utilizing OGA as the sole source of carbon.

Bioaccumulation studies (Rohm and Haas study)with bluegill sunfish determined the st~~dy state interval, which is the time when adsorption equals elimination using C labelled ruat.The steady state interval occurred in the fish after 2 weeks of continuous exposure at sublethal levels at which time the carbon 14 residues in the carcass and the viscera reached a plateau.The concentration of the biocide in the carcass of the fish at the steady state was 42 times that of the concentration of water.It was also found that the biologicaT half-life of the accumulated residues was short, about 7 days, which was determined by the elimination of the carbon 14 residues when the fish were placed in a biocide-free aquarium.

The bioc1dal activ1ty of Clam-Trol CT-I results from the two cationic surface active agents (DGH and ruat)in this formulation.

The product's efficacy is based on its ability to alter or disrupt various membrane systems of the biofouling organisms.

These same inherent properties of these agents which provide b1ocidal efficacy are rapidly neutralized upon adsorption to many types of naturally occurring materials thus reducing or eliminat1ng acute toxicity to non target organisms.

Several key characteristics of Clam-Trol CT-I will minimize its environmental impact following its application to cooling systems.These include: Adsorption rates of both actives are rapid and thus biocidal activity is short-lived.

Both actives readily adsorb to suspend material, sediments, and the surfaces within a cooling system.Both of the active components in the formulation are readily biodegradable.

Solutions of ruat have been show to biodegrade by more than 90%in 2 days while solutions of DGH exhibited 7(C biodegration in 28 days.Clam-, Trol CT-I provides an alternat1ve to chlorine or a number of halogenated organic or metal containing biocides that are considerably less environmentally desirable.

Bioaccumulation of the ruat active has been determined by continuous exposure of low levels of free actives to fish, as reaching a steady state after 2 weeks.The half-life of this accumulated material is short once exposure ceases.An analytical field method is available for determining the presence of the actives in a treated cooling system.The method is also useful for monitor1ng discharges.

Biofouling treatment programs to cooling systems need to employ innovative technology that will direct applications in a most effective manner to the target organisms.

Applications of Clam-Trol CT-I can serve to protect cooling systems from both macrofouling and microfouling problems using state-of-the-art technology.

Ho other treatment program exists that can protect a system from infestation by adult mollusks and larvae by employing seasonal applicat1ons.

Effective control and protection can be accomplished within a 24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> applicatioe.

In addition, Claa-Trol CT-I applications can provide microfouling protection to safety-related cooling systems due to 1ts unique fast-act1ng properties and its ability to permeate slime formations.

These are applications that will not cause the corrosive problems that develop from'continuous chlorination nor require extensive treatment periods for control.

TABLE 1'able 1: Oetoxification of Clam-Trol CT-1 with Bentonite Clay Clam-Trol CT-1 Control 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L Active Clay 100 mg/L 10 mg/L 20 mg/L 30 mg/L 50 mg/L 100 mg/L Clay: Fathead Minnow-Cumulative

%Mortality 4hr h 4 h 0 0 0 100 100 100 0 0.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 TABLE 2 Table 2: Oetoxification of Clam-Trol CT-1 with Bentonite Clay Clam-Trol CT-1 Control 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L 10 mg/L Active Clay 100 mg/L 10 mg/L 20 mg/L 30 mg/L 50 mg/L 100 mg/L Cl ay: 1 1:1 2:1 3:1 5:1 10:1 Oaphnia magna-Cumulative

%Mortality h 4 hr 48 hr 0 0 0 100 100 100 0 0 0 35 100 100 0 85 100 0 30 30 0 0 0

TABLE 3 Table 3: Oetoxification of Clam-Trol CT-1 with Activated Carbon Clam-Trol CT-1 Activated Carbon Carbon: W Fathead Minnow-Cumulative

%Hortality 4 h Control 10 mg/L 10 mg/L 10 mg/L 25 mg/L 25 mg/L 12.5 mg/L 25 mg/L 12.5 mg/L 25 mg/L 12.5 mg/L 25, mg/L 1.25:1 2.5:1 1:2 1:1 0 0 0 0 0 0.100 100 0 0.0 0 0 0 0 0 0 0 0 100 0 0 0 0 TABLE 4 Table 4: Oetoxification of Clam-Trol CT-1 with Activated Carbon Clam-Trol CT-1 Activated Carbon Carbon: Oaphnia magna-Cumulative

%Mortality 4 r Control 10 mg/L 10 mg/L 10 mg/L 25 mg/L 25 mg/L 12.5 mg/L 25 mg/L 12.5 mg/L 25 mg/L 12.5 mg/L 25 mg/L 1.25:1 2.5:1 1:2 1:1 0 0 0 5 0 0 100 100 0 100 0 0 90 100 100 100 0 5 10 100 100 20 100 100 0