Text

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
Issue date:	04/23/1992
From:	Fields J; PENNSYLVANIA POWER & LIGHT CO.
To:	Swerdon P; PENNSYLVANIA, COMMONWEALTH OF
References
	PLE-15525, NUDOCS 9205050275
	Download: ML18026A418 (62)
	v • d • e

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

/

SUSQUEHANNA STEAM ELECTRIC STATION APPLICATION FOR CHANGE IN CHEMICAL USAGE RATE OF CLAM-TROL CT-1 NPDES PERMIT NO. PA 0047325 CCN 741326 FILE R9-8A 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 P

ADDCK 08000387 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 CLN-TROL CT-1 GASEOUS CHLORINE Treatment fre uenc 2 to 4 times wk dail hours In-system conc.10-15m 1 1-2m 1 lbs( ) lbs Pounds er treatment 750 1,125 625 Pounds er ear' 118,000 lbs 182,500 lbs r Dischar e limits 0.2 m l roduct 0.2 m 1 FAC Presence of possible none expected halogenated carcino ens in dischar e or anics

Detoxicant, Table 2 BETZ DTS SULFUR DIOXIDE BENTONITE SLURRY Treatment fre 2 - 4 times wk dail 21 hours2.430556e-4 days 0.00583 hours 3.472222e-5 weeks 7.9905e-6 months 0-40m 0.35-2m uency"'lowdown Conc. 1 1 Pounds er treatment 700 - 1,200 lbs da ' 50 lbs day Pounds per year ' 27,300 - 46,800 lbs/yr 14,600 lbs/yr active Bentonite 23X Dischar e limits none none Production of possible none' none carcino ens in dischar e 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 Trade names of additive(s).

~ Clam-Trol CT-1

~ Betz DTS

2. Name and address of additive manufacturer

~ Betz Laboratories, Inc.

Somerton Road Trevose, PA 19053

3. 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.

4. 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.

5. Proposed average and maximum additive usage rates in lbs/day.

Usage Rates Average Nax Addi ti ves lbs day lbs day Clam-Trol CT-1 750 1,125 Betz DTS as active Bentonite 700 1,200 cia 23K 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. 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.

8. 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 4.1 volume 14 g 1

= 9. 1 x 10 gal 1.141 1/g 1 .44 1 ~1i '1 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 0.00667 hours 3.968254e-5 weeks 9.132e-6 months .

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 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.

jsf/rpcl40c(25)

FORM 1 Pa DER) NPOKS Number PA 00l7325 NFOIMATION ON CHEVAL ADDITIVES KNONN EN EXPECTED TO IE RESENT IN THE DISCHAIGE Lowest WhoIe Whde anal ~ essive pro&set +QAKl OutfIN 5uiitaacem ~awP'laJWy Arrelytjcal OC Hr LCSI M Hr LC%

Ceayeae4 Impalas ENwal'Ualls {eylle IaayN) er I Lewl Qvytl) sINcles eyecies 071 Clam-Trol Betz Laboratories 750-1a125 10 < 0.2 eg/1 Rainbow Daphnia CT-1 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 UNIT 1 COOLING TOUR COOI ING TOOER CIRC. 11TER CIRC. ViTER SVSTEK SVSTEK SERV. Q1TER SERV. 11TER SVSTHf 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)

PRODUCT: CLAM-TROL CT-1 EFFECTIVE DATE 01-24-92 PRINTED: 28-Jan-1992 REVISIONS TO SECTIONS: APPENDIX PRODUCT APPLICATION : WATER-BASED MICROBIAL CONTROL AGENT.

-SECTION 1----.-------HAZARDOUS INGREDIENTS---

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.

ETHYLENE GLYCOL***CASg 1 07 2 1 1 f LIVERY KIDNEY 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) PEL: NONE TLV:NONE.

g p 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'FLAMMABLEtEYEIRR1TANT MAY CAUSE DEPATTZNG DERMATZTZS,DZZZZNESS AND HEADACHE;PEL/TLU:1000PPM.

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 FREEZE POINT(DEG.F): <-30

---SECTION PHYSICAL STATE lsIQQID 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/MISTS/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.IMMEDIATELYCONTACT 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.IMMEDIATELYCONTACT A PHYSICIAN.

INGESTION**~

DO NOT FEED ANYTHING BY MOUTH TO AN UNCONSCIOUS OR CONVULSIVE VICTIM DO NOT INDUCE VOMITING.IMMEDIATELYCONTACT 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 ON ABSORBENT MATERIAL.PLACE IN WASTE DISPOSAL CONTAINER. THE AND'BSORB 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 MAMMALIANTOXICOLOGY 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 (PAGE 1 OF 3)

PRODUCT : BETZ DTS 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(CRYSTALLINESILICA)***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;IRRITANTPOTENTIAL 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

-SECTION 3 LIQUID

---REACTIVITY DATA-FREEZE POINT(DEG.F): 32 STABLE., BETZ TANK CLEANOUT CATEGORY 'Bi THERMAL DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES'

BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3)

PRODUCT:

4---

BETZ DTS SECTION - ---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 IMPROPER 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) 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 MAMMALIANTOXICOLOGY 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 StdylligFth dill delhi Determination of Effect of Detoxified Clam-Trol CT-1, II A Long-Term 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 DWELLLINGORGANISM. 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.

AQUATIC TOX(COLOGY LA,BQRATQRIES. INC. 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 substrate. This is probably both an artifact organisms of the on the natural sterile of the glass beads and an illustration of the extent to which thenature natural sediment mediates CT-1 toxicity.

For the natural substrate using river sediment, the survival of the larvae exposed to all different from the control. test midge concentrations was not significantly 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.

Mean Chironomid Dry Weight r CT-1/L:

\ Survival (mg + SE) mg/ Clay/L A N A N 0 0 87 0 '754(0.0343) 0 '347(0.0583) 0 100 93 0 ~ 6779 (0 ~ 0478) 0 ~ 8930 (0 ~ 0512)

'10 0 30 0 ~ 0641(0 ~ 0103) + 0.6782(0.0286)*

10 10 77 0 ~ 2272 (0 ~ 0107) + 0 '069(0 '527)*

10 20 93 0.3900(0.0534)

0 '585(0.0695) 10 30 100 0 '476(0 '443) 0+8369(0.0252) 10 50 100 0 ~ 5558 (0 0108)

~ 0.7916(0.0263)

Significantly different from Control (a~0.05, Fisher's LSD)

A Artificial substrate N ~ Natural substrate

AQUATIC TOXICOLOGY LABORATORIES, INC. LABORATORY SOMERTON ROAO+TREVOSE. PA 1 9047iU.S.A. 1 TEL: 21 Si355 3300'ELEX: 1 73 1 48iF AX sr 355.2969 tcaix '.

The term "benthic" refers to organisms that live in the bottom sediments of lakes and streams. Aquatic

~ - '

used to study the effects of materials on bottom-living insects such as the midge s

larvae were exposed for 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months to 10 mg/L of Clam-Trol cT-1 and to Clam&rol CT-1 which was detoxified by the addition of organisms.'idge 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 "

2-day exposure to ratios of Betz. Clam<rol CT-3. Zillk11llh

~ CbiDU and Betz DT-1 followed by recovery for 8 days in dechlorinated laboratory wata at ZOoC. (n~30)

Mean Chironomid mg CT-1/L mg DT-1/L Mortality (0) Dry Weight (mg+SE) 0 0 9048 (0 ~ 0121) 100 0 9789 (0 0136) 10 0 80* 0.8121 (0 0135)

10 10 10 0.8748 (0 '122) 10 30 0 0.9164 (0. 0112) 10; 50 0 '278 (0 0115) 10:. 100 0 9502 (0. 0180)

Significantly different from controls (a~0.05, Dunnett's test)

AQUATIC TOXICOLOGY LABQRATQRIES, INC. 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 0' 's 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 96 hr LC50 ~ 11.0 mg/L (Snail)

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) .

AauATIC TOXICOLOGY LABQRATC3RIES, INC. 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 0.00667 hours 3.968254e-5 weeks 9.132e-6 months 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 Mortality We m F s

~e S.D

'54 --

~

0~0 5' 0 '90 0 ~ 032 0 0.329 0.4 2' 0.296 0.029 0.261 0.333 0 ' 0 0.292 0.029 0.259 - 0.324 1.6 7' 0 '68 0.022 0.245 - 0.291 3'

6' 12 '

100 100 12.5 0.029* 0 '19 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 hours 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 0.00333 hours 1.984127e-5 weeks 4.566e-6 months 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 7-day after a 12 hour1.388889e-4 days 0.00333 hours 1.984127e-5 weeks 4.566e-6 months exposure to Clam-Trol CT-1.

CT-1 Concentration Mortality Average 0 of m e oduc 0.0 0 25 '

0.05 0 28 '

0 0

'0

'0 0 0

23 '

24 '

0 '0 0.80 10 9 0*

22 '

18 total neonates*

1.60 100

Significantly different from Control (a 0.05, Dunnatt's test)

AQUATIC TOXICOLOGY LAEIQRATQRIES, INC. LABORATORY SOMERTON AOAOiTREVOSE, PA 1 9047+U.S.A. / TEL: 21 Si355.3300'ELEX: 1 73 1 48iF AX e 355 2869 Aquatic Toxicity Report Determination of the Effect of Detoxified Clam-Trol CT 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.

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 Test Fathead minnow and Q. ]~ggL were exposed to the Type/'onditions:

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 mg clay (a CT-1 to clay ratio of 1:10).

/l of bentoniteite The two materials vere mixed with a mechanical s xrrer at t'ca rp or 30 minutes. All treatments vith ccl ayy were mixed in the same manner. Fifteen liters of solution were prepared for each treatment. replicate.

Twenty fish vere e xp o sed to each treatment two replicate an a d 10 fish per 15 liter of solution.

All treatments with .exception of th e conttinuousl aerated 25 ppm C3.am-Tro3. CT-1:250 ppm bentonite clay were renewed vith freshly prepared solutions on the followin da s test vas initiated on day one. Du r ng the reneval of test sol utions, only the supernatant was siiphonedone from each test container and the s e dimen t a tion of cia on the retained in the con a ner th e t containe test. Fresh test solution daily. Observations of mortality and vas added after siphoning and. mixed w ith th e existing umulated clay. Fish were fed commeercxa flake n behavio f food e av oz response were assessed daily.

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 t 24, 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months .

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 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months periods to renewed or aged detoxified Clam-Trol CT-1 solutions.

0 0

AQUATIC TOXICOLOGY

~BQRATQRIES, INC. 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.

after DT-1.

a y

7-day exposure to

~

ratios of Betz Clam-Trol

(~ CT-1 and Betz I

Mean Fathead mg CT-1/L mg DT-1/L Mortality (4) Dry Weight (mg+sE) 0 0 0 ~ 3101 (0 0157) 0 100 0 2855 (0.0015) 10 0 100+ mmmmmmmmmmmm~mm*

10 10 13 0~ 1881 (0 ~ 0242)

10 30 7 0 '032 (0 '158) 10 50 18 0.3355 (0.0046) 10 100 10 0.2811 (0 0112)~

Significantly different from control.s (a~0.05, Dunnett's test)

APPENDIX C J4 Analytical Data

~ Clam-Trol CT-1, Hollusk Control Agent, Hethyl Orange Hethod

CLAM-TROL CT-1 Mollusk Control Agent METHYL ORANGE METHOD APPARATUS REQUIRED CT-1 Buffer Reagent i591 Beaker, glass, 50 mL (2 required) Code Methanol (reagent grade or equivalent) 322 Cylinder, graduated, 25 mL 2622 Drying Reagent. with a plastic dipper I27t Funnel Rack, separatory 936

SUMMARY

OF METHOD Funnel, separatory, with a Teflon stopcock, 250 mL In thIs procedure the dye in the CT1 Buffer Reagent com-(2 required) plexes with the active ingredients in Clam-Trol CT- 1 >is Glass Rod complex is extracted into 1, 2 - dlchloroethane. The cr-Optical Cell, (2 required) ganlc layer containing the complex is separated from:r:e aqueous layer and drtedwlth a drying reagent containing Safety Bulb, rubber 1575 anhydrous sodltxn sulfate. The color intensity of the I. 2 Spectrophotometer dichloroethane layer ls then measured in a spectropho-tometer at 415 rxn.

GENERAl APPARATUS ~

This methodmust be customizecf to each specific aocii-Cylinder, graduated, 100 mL Code 121 cation. Vary the voitxnes of sample, CT-1 Buffer Reagent.

Cylinder, graduated. 250 mL 917 and 1, 2- dichloroethane according to the test range (see Tttbte 1). Ifa higher absorbance is needed, increase Rask, volumetric, 1 L, glass (4 required) 935 the vokane of sample or decrease the volume of t. 2-Pipet, glass, graduated, 1 mL 140 dichloroelhane. When increasing the sample volume it volumetric, mt. 888 may be necessary to Increase the volixne of CT-1 Buffer Pipet, glass, 1 Reagent used. For samples <150mluse 10ml of CT- I Plpet, glass, voltanetric, 3 mL Buffer Reagent; for samples between 150 and 300 mL pipet. glass, volunehc, 5 ml 124 use 15 mL of CT-1 Buffer Reagent. Make sure that enough 1, 2 - dlchloroethane Is used to leave a smail Pipet, glass, volianetk, 10 ml 123 Plug Of SOIVent In the SeParatOry funnel When the OOItcm Pipet, glass, volwatlc, 15 mL 861 layer of solvent ls removed and to fill the optical celt properly~

Pipet, glass, vollneirlc, 20 mL 1278

'ipet, glass, voltxnetric, 25 mL 117 GENERALPROCEDURE Pipet, glass, volumetric, 30 mL Use a weI-ventmated or hooded area to run the test.

The general apparatus required for the test Is deter- Always use a safety bulb when pipetting liquids.

mined by the specific test procedtxe used.

'~ Apparatus not available through Betz Lab Supply 1,2 - Dlchioroethane (also known as Ethylene Dichlo-ride) Is a pretty pollutant and a specifically-Iisted should be obtained through a local supplier. RCR&regutatedmaterial SubjeCt tO SPeCifiC diSpOSal re-strictions andlor prohibitions. For this reason, aII used CHEMICALS REQUIRED 1,2- dichloroethane should be segregated from other 1, 2- Dlchloroethane (reagent Code 1668 waste streams. Dispose of waste 1,2- dichloroelhane in grade or equivalent) an approved manner (e.g., labpacking or incinerationi AP 35S 9000 ~ 1QO BETZ LASORATOAIES. INC. ALL AIGHTS RESERVED. oage i

1. Refer to Table 1 for the appropriate range and vol- CALIBRATIONCURVE PREPARATION umes to use in this procedure. Transfer an aliquot of 1. Prepare a 1000 mg/L CT-1 stock soluticn by ac=-

the water sample to a separatory funnel (the sam- rately Weighing 1.00 g Of CT-1 intO 1 L Of aiStiaea,=r ple). Transfer the same volume of distilled (or deion- deionized) water.

ized) water to a second separatory funnel (the blank). Run the blank once for each set of samples 2. pipet designated volumes of the stock solution ir:o tested(see Notes1,2, and 3). 1-L volumetnc flasks. These are the stancar" s=" ~

tions used in preparing a calibration curie Lee

2. Add CT-1 Buffer Reagent to both the sample and the Table 2 to make appropriate dilutions cf:ne s',c=k blank. solution for each specific application,

3. Using a pipet; add 1, 2- dichloroethane to both se- 3. Follow the General Procedure using the spec ..c s-paratory funnels. Iution volumes ',hat have been determinea!cr;.".e

4. Insert the stoppers in each of the separatoiy funnels. application ano prepare a calibration c ive Deter-invert and briefly open the stopcock to vent the fun- mine the absorbance of a blank solution using ".s.

nels (see Notes 4 and 5). When venting the funnels, tilled (or deionized) water. This blank can ce suc-point the tip of the funnel away from yourself and tracted from the sample absorbance cr csea:c others. zero the spectrophotometer so that the calibra.: r, Shake the funnels moderately for 30 sec, vent the curve goes through the origin. The caiibra:icn 5.

curve should be linear over the incica!="

funnels, then allow them to stand for 10 min (but no ranges.

longer than 15 min).

6. Collect the lower layer (1, 2 - dlchloroethane) from Table 2. DI!utions for Calibration Curve Prepara-each funnel in 50mL beakers leaving about 1-2 mL. tion Based on a Final Solution Volume in the funnel. This will prevent significant removal of of1L.

water. Concentration CT-1 Stock Sciu-

7. Using the plastic dipper, add 2 scoops of Drying Re- CT-1 Desired tion Added to Make agent to eachbeaker and stir with a glass rod for 15 (mg/L) 1 L (mL) sec (but no longer than 30 sec).

8. Wait approximately 1 to 2 min (but not more than 5 0.2 02 min). Then carefully decant the extract offof the dry- 0.4 04 ing reagent Into an optical cell. 0.6 06 0.8 08 1,2-dlchloroethane. Measure and record the absor-bance of the blank and the sample (see Note 6). 1.0 1.0

10. The sample absorbance minus the blank absor- 5.0 5.0 bance is used to determine the concentration of 10.0 10.0 CT-1 ln the sample. From a prepared calibration 15.0 15.0 cuve, determine the CT-1 concentration In the sam-ple (see Calibration Curve Preparation). 20.0 20.0

11. Clean the cells alter each meaarement 25.0 25.0 (see Note 7).

Table 1. Suggee&d Voturttee for Verfous Ranges of CT-1 .

Range Voltatto Volume Volume Optical CT-1 (mg/L) CT-1 Buffer Dlchloroethane Sample Cell Size (mL) (mL) (mL) 0.2- 3.0 10 t 0crn

~~

1.0- 25.0 10 5 cm 0.2- 1.0 15 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 7. It Is imperative that the sample cells are kept clean during the nmnlng of the test. It is recommended ttiat

1. For maximln ocaracy the calibration cthe should the cells are cleaned after each measurement using be checked by every operator using this test and the following procedure:

shouldbe verNed a mlnimmn of twice per monthus-ing a freshly prepared CT-1 standard. a) Rinse the cell three times with distilled (cr

2. A blank meastsement (the blank should be a sam- deionized) water.

ple of the system water prior to CT-I treatment) must be recorded for each set of samples. The blank b) Rinse the cell three times with methanol.

reading may vary slightly; however, the absolute dif-ference between the sample and the blank remains C) RinSe the Cell three timeS With I, 2 - diChlarO.

relatively constant. ethane to remove methanol from the cell.

3. Chlorine causes a negative interference in the test. 8. Itxbidlty can i.iterfere with this test prcceaure This can be eliminated by adding 0.1 N Sodium Ibrbldity may:

Thiosulfate (Code 235) to the water sample before running the test. The amount added is based on the ~ Create an emulSiOn in the 1.2, - diCRICrO-concentration of chlorine in the system. For a ethane layer that does not separate atter 100mL water sample containing 0.3 mg/L chlorine, standing for 10 min when the funnel is add 10 drops of 0.1 N Sodium Thiosulfate to remove shaken.

the interference. ~ create a positive interference. ( A yellow color is extracted into the 1,2 - dichloro-

4. A slight emulsionmay form whenuslng natural water ethane layer. )

samples. When this happens, vary step 5 of the procedure. Shake the funnel for 30 sec, vent it, then These probloms can be removed by centrifuging II;e allow It to stand for 5 min. Gently invert the funnel sample (10mkt at 3500rpm or 30min at 2500 rpm) betore once then allow the funnel to stand for 5 min. performing step 1 of the procedure.

5. It Is Impotant to vent the separatly funnel both be- 9. Ifyouneedto change test conditions(l.e., use differ-fore and after shaking it. Otherwise, a pret+we will ent volumes than those in Table 1), contact the Ana-build up in the funnel that can cause the stopper to lytical Testing and Development Group in Trevcse be forced out of the top of the funnel. for assistance

6. Use caution when Inserting or removing the sample cell In the photometer. The 1,2- dlchloroethane can

10. This method is adapted from Wang, L K.: Lai.aiy. 3 F. Ind. Eng. Chem., Prod. Res. Dev., 1975. 14, 3 damage the cell compartment. 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

AQUATIC TOXICOLOGY LABORATORIES, INC. LABORATORY SPMERTPN) PAPaTPEVPSE.PA19047>USA./ TE{-.215~355.33OO~TSI ~ 'f E X; 1 73 945aFAX 4355-cBS BETZ CLAM-TROLCT-1 ENVIRONMENTALINFORMATION 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 NH I II n-C14H29 N+ CH2 Cl n-C1zH25-NH-C-NH2HCI I

CH3 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 st<<

toxic proPer '

a The membrane proteins are essential f with membrane P various sPecific ion transport channels. The alkyl mechanisms 'ncl"dingtives becomes imbedded in these membranes. In effqcg od biocidal performers but the cationic surfacta" >s neutralized upon adsorption to varvarious ous surfaces.

their positive charge ruat hav xtremely strong affinities for many kinds of suspended OGH and tes. A series of laboratory and field studies conducted material the ~r -

and su electrostatically Cy ""d ComPany evaluated the degree and rate that OGH is boun to suspended matter and other substrates b

I one stud In t d weighed portions of sludge containing 5.2% solids obtained from a t lant were inoculated with 10 ppm and 20 ppm of OGH (Ip~

active) and thoroughly mixed. to seParate After 1 hour1.157407e-5 days 2.777778e-4 hours 1.653439e-6 weeks 3.805e-7 months and 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , duplicate samples of the mixtures were centrifuged the solids. OGH was analyzed in the The results in the table below show that less than 2 PPm of OCH supernatant.

remained in the supernatant Contact OGH F ound OGH added Time in Supernatant 10 1 1.2 10 1 1.6 10 24 1.0 10 24 1.2 10 (Control; water only) 11.0 20 1 1.1 20 1 1.7 20 24 1.6 20 24 1.3 20 (Control; water only) 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:

Residual OGH OGH added (ppm) in n n 350 19 95 350 17 95 700 24 97 700 31 96 1750 52 97 1750 85 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 1 28 6 16 24 12 1750 1 82 6 61 24 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.

OGH Content Oil and Grease in Effluent Sam Tim Addition of OGH 8:15 am 158 0 (16-17 ppm) 9:30 am 1300 0 10.15 am 700 0.4 12:00 pm 1500 0.9 makeup Mater 14 0 added 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.

Suspended Organ) c OGH Content Solids Carbon in Effluent m l Before addition 1:30 pm 17 OGH addition 13 ppm After addition 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)

Contact 1e Adsorbent Time (hr) Ini ti al Final Adsorbed River Silt 1/60 0.070 0.006 91 Aquatic Plant (Azol'la Caroliniana) 24 0.056 0.008 86 Alum Floca 1/2 0.094 . 0 100 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 Oose 1 Oose 2 Oose 3 Oosing (hrs) (60 ppm) (30 ppm) (30 ppm) 1 60.0 26.8 31.6 2.5 52.2 21.1 21.0 5 44.8 14.8 14.2 8 26.5 10.6 9.9 72 5.18 0.25 0.041 120 2.50 0.011 NOR 168 1.16 0.008 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 follows:

for Clam-Trol CT-1 with ingredients is provided as 13K'ctive

~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).

formulation is exposed to adsorbent material (i.e., bentonite d~,

However, when the 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 Trol CT-1 which has been exposed to various concentrations of either f'lam 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 ~N Incubation Period 24 hr/48 hr 24 hr/48 hr 24 hr/48 hr 24 hr/48hr Percent Oegraded 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 a~ unde-graded active removed from the closed system and the presentsupernatant 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.

i n Pr Day DOC mg/L % Degradation 0 34 1 39 0 4 26 33 7 26 33 14 17 56 18 16 59 22 26 18 13 10

'754 74 29 31 9 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 0.00667 hours 3.968254e-5 weeks 9.132e-6 months 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 Oetoxification of Clam-Trol with Bentonite Clay 1'able 1: CT-1 Fathead Minnow - Cumulative

% Mortality Clam-Trol CT-1 Active Clay Clay:

4hr h 4 h Control 0 0 0 10 mg/L 100 100 100 100 mg/L 0 0. 0 10 mg/L 10 mg/L 0 0 0 10 mg/L 20 mg/L 0 0 0 10 mg/L 30 mg/L 0 0 0 10 mg/L 50 mg/L 0 0 0 10 mg/L 100 mg/L 0 0 0 TABLE 2 Table 2: Oetoxification of Clam-Trol CT-1 with Bentonite Clay Oaphnia magna - Cumulative

% Mortality Clam-Trol CT-1 Active Clay Cl ay:

1 h 4 hr 48 hr Control 0 0 0 10 mg/L 100 100 100 100 mg/L 0 0 0 10 mg/L 10 mg/L 1:1 35 100 100 10 mg/L 20 mg/L 2:1 0 85 100 10 mg/L 30 mg/L 3:1 0 30 30 10 mg/L 50 mg/L 5:1 0 0 0 10 mg/L 100 mg/L 10:1

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

% Hortality Clam-Trol CT-1 Activated Carbon Carbon:

W 4 h Control 0 0 0 12.5 mg/L 0 0 0 25 mg/L 0 0. 0 10 mg/L 100 100 100 10 mg/L 12.5 mg/L 1.25:1 0 0. 0 25 mg/L 2.5 :1 0 0 0 10 25 mg/L mg/L 12.5 mg/L 25, 1:2 1:1 0 0

0 0

25 mg/L mg/L TABLE 4 Table 4: Oetoxification of Clam-Trol CT-1 with Activated Carbon Oaphnia magna - Cumulative

% Mortality Clam-Trol CT-1 Activated Carbon Carbon:

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

0

ML18026A418

Text

Dear Hr. Swerdon:

SUMMARY

Navigation menu

Search