ML20024H325
| ML20024H325 | |
| Person / Time | |
|---|---|
| Site: | Limerick  |
| Issue date: | 05/21/1991 |
| From: | Beck G PECO ENERGY CO., (FORMERLY PHILADELPHIA ELECTRIC |
| To: | NRC OFFICE OF INFORMATION RESOURCES MANAGEMENT (IRM) |
| References | |
| NUDOCS 9105310197 | |
| Download: ML20024H325 (61) | |
Text
{{#Wiki_filter:. EPP 3.2 Pillt.ADEl.I'lll A El ECTRIC COMi%NY NUCLEAR GROUP HEADQUARTERS 955-65 CllESTERBROOK BLVD. WAYNE, PA 19087 5691 (215) 640-6000 NUCtfAR LNGINFLRINO & $1:RYlCl3 DEPARTMENT May 21, 1991 Docket IJos. 50-352 50-353 License !Jos. IJPF-39 IJPF-85 U.S. !Juclear Regulatory Commission Attn: Document Control Desk Washington, DC 20555
Subject:
Limerick Generating Station, Units 1 and 2 Proposed Change to the IJational Pollutant Discharge Elimination System Permit Gentlemen: The Limerick Generating Station (LGS), Units 1 and 2, Environmental Protection Plan (EPP), Section 3.2, stipulates that the !!RC shall be receive a copy of any proposed change to the LGS
!!ational Pollutant Discharge Elimination System (11PDES) peruit at the same time the proposed change is submitted to the permitting agency.
By letter dated May 1, 1991 to the Pennsylvania Department of Environmental Resources (PA DER), Philadelphia Electric Company (PECo) requested a change to the LGS liPDES Permit !!o. PA0051926 to allow for the addition of new chemical additives for use in the secondary cooling water to control Asiatic clams. The PA DER had previously authorized the use of these new chemicals at our Peach Bottom Atomic Power Station facility to inhibit Asiatic clam fouling of their secondary cooling water systems. Therefore, in accordance with the LGS EPP Section 3.2, a copy of the May 1, 1991 letter to the PA DER (including attachments) requesting the change to the LGS 11PDES permit is enclosed.
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U.S. IJuclear Regulatory Commission May 21, 1991 l Docut"2ent CoIlt_r_stl_De s h Pa g e_;!
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- If you have any questions, please do hesitate to contact ur.
I h Very truly yours, , /--
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,c G. J. 13eck Manager Licensing Section IJuclear Engineering and Services I
l Enclosure i cc: T. T. Martin, Administrator, Region I, US!JRC ( v/ enclosure) T. J. Kenny, US!JRC Senior Resident Inspector, .GS w/ enclosure) 1 i l l A
- .. . , . - ~ . . a-. l l l ENCLOSURE
PillLADELP111A ELECTRIC COMPANY G.J. BECK 2301 MARKET STREE1 UCEG3 SECM p.o. nox 8699 PillLADELPlilA, PA 19101 MY 0 61991 (215) 841-4000 NOTED: t REFERRED TO: @ W C' _ May 1, 1991 Etikeg; bOEUS193l Mr. James Newbold Chief, Permits Section E eg Bureau of Water Quality Management ' L9partment of Environmental Resources Lee Park, Suite 6010 555 horth Lane Cen6hohocken, PA 19428 E: Limerick Generating Station, NPDES Permit PA0051926 Request for Use of New Chemicals for Control of Asiatic Clams D at Mr. Newbold: 1 with Chapter 92.7 " Reporting of New or In accordance Regulations, I. creased Discharges", of the Department's Rules and Betz Clam-trol CT-1, Betz se hereby request approval to use at Limerick i Foamtrol CT and Betz DTS in the cooling water discharge systems point 001. These Bet h Generating Station (LGS), concert with each other to control in chemicals will be used Asiatic clams. clams have caused substantial water system Asiatic including Peach Bottom problems throughout the utility industry, Once they have entered into plant i Atomic Pcwer Station (PBAPS). causing severe cooling water systems, they can reproduce events and grow,have resulted in increased NRC restrictions. These This letter flow 89-13. concern, most notab2y through Generic Letter this type to develop some mechanism to preventeffect, as ,,~ requires utilities water scr'eening has little of flow blockage. Makeup small to screen, and standard chlorination larval clams are too regulation do not permit sufficient practices restricted by existed in the time. Asiatic clams have chemical contact Schuylkill River for years.poseThey a have 3.ow progressed to areas near threat to plant reliability and LGS intakes, and thus operation. plant problems, we wish to begin a blocide prevent To used successfully at other facilities. In program similar to that89-13 response to the NRC, we indicated that our Generic Letter action, provided that environmental this would be our course of resolved. We would apply Betz CT-1 towater both concerns could be safety-related service cooling towers, and directly tofrom the the spray pond. Each cooling systems ~ that take suction l l
w Mr. James Newbold Page 2 May 1, 1991 , i tower / service water system is expected to be treated 2 times per year, but more frequent applications are possible. The duration of treatment should be approximately 24 hours per system. Normal CT-1 concentrations _ should be 15 ppm; however, concentrations of 50 ppm H may be used when it is necessary to " lay up" components with treated water. Due to the number of systems involved, and chemical - holding times within those systems, CT-1 could enter the plant discharge for up to 2 weeks per application. To preclude the discharge of CT-1 to the river, we intend to feed Betz DTS, a 231 bentonite clay slurry, to the blowdown line (discharge 001) whenever Betz CT-1 residual would exist in the cooling tower blowdown. Approximately five (5) ppm of this slurry would be fed for every 1 ppm of CT-1 entering in discharge 001. Betz DTS, as well as existing solids in the water, will detoxify the active ingredients in CT-1. As a monitoring requirement, we propose that, during treatment, the level of CT-1 should be i verified to be less than 0.2 ppm at discharge point 001 once per j day. This value represents the lower limit of detection for the l CT-1 test method. Betz DTS is a non-toxic agent used to detoxify Betz CT-1. Should a total suspended solids limit be required due to this additive, a net limitation would be appropriate since the cooling tower blowdown already contains TSS from the Schuylkill River. The Steam Electric Effluent Guidelines contained in 40 CPR Part 423 indicated that a net TSS limitation of 30 mg/l and 100 mg/1, monthly average and daily maximum, respectively, may be applied. Since CT-1 does have some surfactant qual,ities, foaming in cooling tower systems could result. In preparation, we also request approval of Betz Foamtrol CT to control foaming if necessary. _This product _is essentially non-toxic, and would be applied at a 10 ppm concentration directly to the areas of foaming. Thus, when used in this fashion, we do not expect detectable levels of Foamtrol CT in the blowdown. Based on the current status of Schuylkill River clam populations, we feel that we will need to begin treatments in mid- _ , , June 1991. The application of this treatment will be controlled by written plant procedures, and oversight will be provided by Betz personnel familiar with_ the applications at other facilities. l j Furthermore, we intend to minimize chemical discharges by decreasing cooling tower blowdown as much as possible. Technical infctmation regarding the products is attached. For additional information, it would be best to contact Steve Jordon, of Betz Industrial, at 215-524-6080. Although we could conceivably pursue the use of equivalent products at some time in the future, (similar to our current intent regarding cooling tower chemicals), it is not likely due to existing U.S. patent concerns. Therefore, the permit amendment can be specific to the Betz products. l l
Mr. James Newbold Page 3 , May 1, 1991 ? If there are any questions, please call David Mobraaten at t (215) 841-5679. 3 very truly yours, ~! l k/ George M. Morley Director Lnvironmental Affairs ; l DWM/1th Attachments bec: J. M. Madara, Jr. w/o attachment G. M. Leitch J. Doering, Jr. R. W. Dubie1 w/ attachment G. J. Madsy'n w/ G. J. BeckV w/ " R. J. Scholz w/ " CCD w/ PaDER BRP Inspector w/ " z- . l
. -.. .. -. - - _ ~ - . . . ~. . - - _ . - ... -.--._.- - --- l BETZ LABORATORIES,INC. 4636 SOMERTON ROAD,TREVOSE,PA.19047 1 C C' PRODUCT: 13ETZ DTS 4/15/91 AQUATIC TOXICOLOGY - DAPHNIA MAGNA 0% MORTALITY: 435 MG/L 48 HR. SCR. FATHEAD MINNOW 0% MORTALITY: 435 MG/L 96 HR. SCR.
-4/15/91 MAMMALIAN TOXICOLOGY ORAL LD50 -NO DATA DERMAL LD50 -NO DATA SKIN 1RRITATION SCORE-NO DATA EYE IRRITATION SCORE-NO DATA INHALATION-No DATA i
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i BETZ LABORATORIES,IllC. 4636 SOMERTO!1 ROAD,TREVOSE,PA.19047 2 c- PRODUCT: FOAM-TROL CT 4/15/91 AQUATIC TOXICOLOGY _ DAPHNIA MAGliA 0% MORTALITY: 100 MG/L 48 HR. SCR. BLUEGILL SUNFISH 0% MORTALITY: 1000 MG/L 48 HR. SCR. 4/15/91 MAMMALIAN TOXICOLOGY ORAL LD50 -No DATA DERMAL LD50 -No DATA SKIN IRRITATION SCORE-NO DATA EYE IRRITATION SCORE-No DATA INHALATION-No DATA OXYGEN DEMAND (ppm) PRODUCT CONCENTRATION (ppm) BOD COD TOC 1000 249 1280 110
, = m
BETZ LABORATORIES,INC. 4636 SOMERTON ROAD, TREVOSE, PA. 19053 BETZ MATERIAL SAFETY DATA SHEET EMERGENCY TELEPHONE (!!EALTH/ ACCIDENT) 800-877-1940 (PAGE 1 OF 3) PRODUCT : CLAM-TROL CT-1 c0 EFFECTIVE DATE 02-16-91 PRINTED: 1-Mar-1991 REVISIONS TO SECTIONS: -; EDIT: APPENDIX _ PRODUCT APPLICATION : WATER-BASED MICROBIAL CONTROL AGENT.
-----SECTION 1-----------HAZARDOUS INGREDIENTS---------------
INFORMATION ON PHYSICAL HAZARDS, HEALTH HAZARDS, PEL'S AND TLV'S FOR SPECIFIC PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIONS STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF THE 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 * *
- CAS # 107-21-1 ; LIVER , KIDNEY AND BLOOD TOXIN;CNS DEPRESSANT; ANIMAL TERATOGEN (HIGH ORAL DOSES) ;PEL/TLV: 50 PPM-C.
ALKYL DIMETHYL BENZYL AMMONIUM CHLORIDE ***CAS#68424-85-1; CORROSIVE (EYES); PEL:NONE;TLV:NONE. ISOPROPYL ALCOHOL (IPA) * *
- CAS # 67-63-0 ; FLAMMABLE LIQUID; CHRONIC OVEREXPOSURE MAY CAUSE LIVER AND KIDNEY TOXICITY;PEL/TLV:400 PPM (5 00 PPM-STEL) .
DODECYLGUANIDINE HYDROCHLORIDE * * * ( DGH) ; CAS # 13 590-97-1 ; CORROSIVE ; PEL: NONE : TLV:NONE. , ETHYL ALC OHOL(ETHANOL) * *
- CA'a # 64 S ; FLAMMABLE ; EYE IRRITANT; MAY CAUSE DEFATTING DERMATITIS, DIZZINESS AND HEADACHE;PEL/TLV:1000 PPM.
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. (7 QE)OR DENSITY: 1.022 '" VAPOR PRESSURE (mmHG): 23 VAPOR DENSITY (AIR =1): >l VISC cps 70F: 23 % SOLUBILITY (WATER) : 100 EVAP. RATE: <1 ETHER =1 APPEARANCE: COLORLESS PHYSICAL STATE: LIQUID FREEZE POINT (DEG.F): <-30
-----SECTION 3-----------REACTIVITY DATA------------------------------
STABLE.MAY MACT WITH STRONG OXIDIZERS.DO NOT CONTAMINATE.BETZ TANK CLEAN-OUT CATEGORY 'B' THERMAL DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES. l l
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~ _ . .
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. POTENTIAL SKIN SENSITIZER ACUTE EYE EFFECTS *** CORROSIVE TO THE EYES ACUTE RESPIRATORY EFFECTS *** PRIMARY ROUTE OF EXPOSURE VAPORS, GASES, MISTS AND/OR AEROSOLS CAUSE IRRITATION TO UPPES RISPIRATORY TRACT C' CHRONIC EFFECTS OF OVEREXPOSURE *** PROLONGED OR REPEATED OVEREXPOSURES MAY CAUSE: TISSUE NECROSIS; BLOOD CELL - DAMAGE OR IMPAIR BLOOD CELL FUNCTION; REPRODUCTIVE SYSTEM TOXICITY; SKIN SENSITIZATION. MEDICAL CONDITIONS AGGRAVATED *** NOT KNOWN SYMPTOMS OF EXPOSURE *** INHALATICN OF VAPORS / MISTS / AEROSOLS MAY CAUSE EYE, NOSE, THROAT AND LUNG IRRITATION; SKIN CONTACT MAY CAUSE SEVERE IRRITATION OR BURNS. PRECAUTIONARY STATEMENT BASED ON TESTING RESULTS *** MAY BE TOXIC IF ORALLY INGESTED.
SECTION 5------------FIRST AID INSTRUCTIONS----------------------
SKIN CONTACT ***. REMOVE CLOTHING. WASH AREA WITH LARGE AMOUNTS OF SOAP SOLUTION OR WATER FOR 15 - MIN.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.IMMED. CONTACT PHYSICIAN. DILUTE COKrENTS OF STOMACH USING 3-4 GLASSES MILK OR WATER
SECTION 6---- '------S PILL, DIS POS AL AND FIRE INSTRUCTIONS---------
SPILL INSTRUCTIONS *** VENTILATE AREA,USE SPECIFIED PROTECTIVE EQUIPMENT.CONTAIN AND ABSORB 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 CONTAMINATED WITH THIS PRODUCT MAY BE SENT TO A SANITARY SEWER TREATMENT FACILITY,IN ACCORDANCE WITH ANY LOCAL AGREEMENT, A PERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT PRODUCT (AS IS)- DISPOSE OF IN 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, CARBON DIOXIDE, FOAM OR WATER
1 BETZ MATERIAL SAFETY DATA GHEET (PAGE 3 OF 3) PRODUCT: 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 IS LIKELY, USE A RESPIRATOR WITH ORGANIC VAPOR CARTRIDGE & DUST / MIST PREFILTER 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 LOCATICN. STORE AWAY FROM OXIDIZERS HANDLING INSTRUCTIONS *** COMBUSTIBLE. DO NOT USE AROUND SPARKS OR ILAMES. BOND CONTAINERS DURING FILLING OR DISCHARGE WHEN PERFORMED AT TEMPERATURES AT OR ABOVE THE PRODUCT FLASH POINT.
*o*oco********************************************************************
THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD ococco******************************************************************** APPENDIX: REGULATORY INFORMATION THE CONTENT OF THIS APPENDIX REPRESENTS INFORMATION FJ10WN TO BETZ ON THE EFFECTIVE DATE OF THIS MSDS. THIS INFORMATION IS BELIEVED TO BE ACCURATE. ANY CHANGES IN REGULATIONS WILL RESULT IN UPDATED VERSIONS OF THIS DOCUMENT.
...TSCA: THIS IS AN EPA REGISTERED BIOCIDE AND IS EXEMPT FROM TSCA INVENTORY REQUIREMENTS . . . FIFRA (4 0CFR) : EPA REG .NO. 3876- 145 ... REPORTABLE QUANTITY (RQ) FOR UNDILUTED PRODUCT:
NOT APPLICABLE
... RCRA: IF THIS PRODUCT IS DISCARDED AS A WASTE,THE RCRA HAZARDOUS WASTE IDENTIFICATION NUMBER IS: D001= IGNITABLE;D002= CORROSIVE (SKIN) ... DOT. HAZARD /UN#/ER GUIDE # 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) , 21.0-30.0% ; ... SARA SECTION 312 HAZARD CLASS: IMMEDIATE(ACUTE), DELAYED (CHRONIC) AND FIRE ... MICHIGAN CRITICAL MATERIALS: NONE NFPA/HMIS : HEALTH - 3 ; FIRE - 2 ; REACTIVITY - 0 ; SPECIAL - CORR ; PE - D 1
O y I
m_ BETZ LABORATORIES,INC. 4636 SOMERTON ROAD, TREVOSE, PA. 19053 BETZ MATERIAL SAFETY DATA SIIEET EMERGENCY TELEPl!ONE (HEALTH / ACCIDENT) 800-877-1940 (PAGE 1 OF 3) PRODUCT : FOAM-TROL CT EFFECTIVE DATE 02-16-91 PRINTED: 1-Mar-1991 REVISIONS TO SECTIONS: -; EDIT: APPENDIX ~ PRODUCT APPLICATION : ANTIFOAM.
-----SECTION 1-----------RAZARDOUS INGREDIENTS---------------
INFORMATION ON PHYSICAL HAZARDS, HEALTH HAZARDS, PEL'S AND TLV'S FOR SPECIFIC PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIONS STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF THE 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. MINERAL OIL (MILDLY SOLVENT-REFINED OR HYDROTREATED OILS)**- CAS#64742-30-9; POTENTIAL SKIN TUMORIGEN(BASED ON CHRONIC ANIMAL SKIN PAINTING STUDIES) ; PEL:5MG/M3;TLV:GMG/M3. 4 NONHAZARD INGREDIENTS: POLYPROPYLENE GLYCOL GLYCEROL -ETHER (25791-96-2) ; 'OCTADECANOIC ACID (57-11-4) ; POLYETHYLENE GLYCOL MONOOLEATE(61791-00-2)
-----SECTION 2-----------TYPICAL PHYSICAL DATA-------------------------
i P!I: 50% SOL- . (APPROX.) 6.8 ODOR: MILDT '=-- l FL. PT.-(DEG . F) : >200 SETA(CC) SP.GR. (70F)OR DENSITY: 0.841 j VAPOR- PRESSURE (mmHG) : <10 VAPOR DENSITY (AIR =1): >l ,VISC cps 70F: 30 % SOLUBILITY (WATER): 0 EVAP. RATE: <1- ETHER =1 APPEARANCE: OFF WHITE TO AMBER
- PHYSICAL STATE
- LIQUID FREEZE POINT (DEG.F) : ND i-----SECTION 3-----------REACTIVITY DATA------------------------------
STABLE.MAY REACT WITH STRONG OXIDIZERS.DO NOT CONTAMINATE.BETZ TANK CLEAN-OUT CATEGORY 'B' ! THERMAL DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES. L . .. __ _ _ _. _ . _ . . _ _ _ _ - . ~ . -
BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3) PRODUCT: FOAM-TROL CT
-----SECTION 4-----------HEALTH MAZARD EFFECTS------------------------
ACUTE SKIN EFFECTS *** PRIMARY ROUTE OF EXPOSURE SL3GHTLY IRRITATING TO THE SKIN.MAY CAUSE DERMATITIS. ACUTE EYE EFFECTS *** MODERATELY IRRITATING TO THE EYES ACUTE RESPIRATORY EFFECTS *** VAPORS, GASES fMISTS AND/OR AEROSOLS MAY CAUSE IRRITATION TO UPPER RESPIRATORY' TRACT CHRONIC EFFECTS OF OVEREXPOSURE *** ~ PROLONGED OR REPEATED EXPOSURES MAY CAUSE DEFATTING-TYPE DERMATITIS; LIFETIME SKIN PAINTING STUDIES IN MICE MAVE PRODUCED SKIN TUMORS. MEDICAL CONDITIONS AGGRAVATED *** NOT KNOWN SYMPTOMS OF EXPOSURE *** PROLONGED EXPOSURE MAY CAUSE D'RYING AND CRACKING OF SKIN.
- ---SECTION 5------------FIRST AID INSTRUCTIONS----------------------
SKIN CONTACT *** REMOVE CONTAMINATED CLOTHING. WASH EXPOSED AREA WITH A LARGE QUANTITY OF SOAP SOLUTION OR WATER FOR 15 MINUTES EYE CONTACT *** IMMEDIATELY FLU H EYES WITH WATER FOR 15 MINUTES.IMMEDIATELY CONTACT A PHYSICIAN FOR 7sDITIONAL 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 l- DO NOT INDUCE VOMITING.IMMED. 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 ABSORB ON ABSORBENT MATERIAL. PLACE IN WASTE DISPOSAL CONTAINER. THE WASTE CHARACTERISTICS OF THE ABSORBED MATERIAL,OR ANY CONTAMINATED SOIL, 1 SHOULD BE DETERMINED IN ACCORDANCE WITH RCRA REGULATIONS.
- FLUSH 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 FACILITY,IN ACCORDANCE WI-TH ANY LOCAL AGREEMENT, A = PERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT PRODUCT (AS IS)- INCINERATE OR BURY IN APPROVED LANDFILL FIRE EXTINGUISHING INSTRUCTIONS *** FIREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING APPARATUS (FULL FACE-PIECE TYPE) . PROPER FIRE EXTINGUISHING MEDIA: DRY CHEMICAL /CO2/ FOAM OR WATER. SLIPPERY CONDITION. USE SAND / GRIT 1
l BETZ MATERIAL SAFETY DATA SHEET (PAGE 3 OF 3) l PRODUCT: FOAM-TROL CT
-----SECTION 7-----------SPECIAL PROTECTIVE EQUIPMENT-----------------
USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITH 29CFR SECTION 1910.132-134. USE RESPIRATORS WITHIN USE LIMITATIONS OF 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 IS LIKELY, USE A RESPIRATOR WITH ORGANIC VAPOR CARTRIDGES. RECOMMENDED SKIN PROTECTION *** NEOPRENE GLOVES WASH OFF AFTER EACH USE. REPLACE AS NECESSARY RECOMMENDED EYE PROTECTION *** SPLASH PROOF CHEMICAL GOGGLES
-----S ECTION 8 -----------STORAGE AN D HAN DLING PRECAUTIONS-------------
STORAGE INSTRUCTIONS *** KEEP DRUMS & PAILS CLOSED WHEN NOT IN USE. STORE IN COOL VENTILATED LOCATION. STORE AWAY FROM OXIDIZERS IIANDLING INSTRUCTIONS *** NORMAL CHEMICAL HANDLING ococco***A**************************************************************** THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD
***ooo********************************************************************
APPENDIX: REGULATORY INFORMATION THE 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 IN REGULATIONS WILL RESULT IN UPDATED VERSIONS OF THIS DOCUMENT.
...TSCA: ALL COMPONEIITS 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 /UN#/ER GUIDE # IS: NOT APPLICABLE ... CALIFORNIA SAFE DRINKING WATER ACT (PROPOSITION 65) MATERI ALS :
THIS PRODUCT CONTAINS THESE CHEMICALS KNOWN TO THE STATE OF CALIFORNIA TO CAUSE CANCER OR REPRODUCTIVE TOXICITY: MINERAL OIL (64742-30-9) --
... SARA SECTION 302 CHEMICALS: NONE ... SARA SECTION 313 CHEMICALS: NONE ... SARA SECTION 312 HAZARD CLASS: DELAYED (CHRONIC) ... MICHIGAN CRITICAL MATERIALS: NONE NFPA/HMIS : HEALTH - 1 ; FIRE - 1 ; REACTIVITY - 0 ; SPECIAL - NONE ; PE - B i
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. . - .- . . - -.- - - _~. - ._..-- _ - _ .. . . - - - -- . _~
BETZ IABORATORIES,INC. 4636 SOMERTON ROAD, TREVOSE, PA. 19053 BETZ MATERIAL SAFETY DATA SHEET EMERGENCY TELEPHONE (llEALTil/ ACCIDENT) 800-877-1940 (PAGE 1 OF 3) PRODUCT : BETZ DTS EFFESTIVE DATE 02-16-91 PRLcTED: IS-Apr-1991 PRODUCT APPLICATION : A DETOXIFYING AGENT.
-----SECTION 1-----------HAZARDOUS INGREDIENTS---------------
INFORMATION ON PIIYSICAL IIAZARDS, HEALTH !!AZARDS, PEL'S AND TLV'S FOR SPECIFIC PRODUCT INGREDIENTS AS REQUIRED BY THE OSIIA IIAZARD COMMUNICATIONS STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF TIIE POTENTIAL ACUTE AND CHRONIC !!AZARDS OF THIS FORMULATION. Tl!IS PRODUCT IS SUBJECT TO THE PENNSYLVANIA AND NEW JERSEY WORKER AND COMMUNITY RIGHT TO KNOW LAW. SODIUM MONTMORILLONITE ***CAS#1302-78-9;POSSIBLE CHRONIC LUNG HAZARD; QUARTZ (PEL: 10MG/M3/ (SiO2+2) RESP;TLV: 0,1MG/M3 RESP) ; NOTE-TRIDYMITE & CRISTOBALITE(PELs&TLVs:1/2 QUARTZ VALUES) MAY BE PRESENT. i NONHAZARD INGREDIENTS: WATER (7732-18-5) ; 2-PROPENOIC ACID,
!!OMC, POLYMER (9003 4 ) ; SODIUM TRIPOLYPHOSPHATE(7758-29-4)
-----SECTION 2-----------TYPICAL PHYSICAL DATA-------------------------
PH: AS IS (APPROX.) -5.9 ODOR: SLIGIIT FL.PT.(DEG.F): >200 P-M (CC) SP.GR. (70F;)OR DENSITY: 1.142 __,,,
- VAPOR PRESSURE (mmHG): 18 .. VAPOR DENSITY (AIR =1): <1 VISC cps 70F: 2,000 % SOLUBILITY (WATER): 0 l -EVAP. RATE: ND . WATER =1 APPEARANCE: GREEN-BROWN PHYSICAL. STATE: LIQUID FREEZE POINT (DEG.F): 32
-----SECTION 3-----------REACTIVITY DATA------------------------------
I STABLE. BETZ TANK CLEAN-OUT CATEGORY 'B' THERMAL; DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES. l l
,..,~wa.~. ,w.. m ,. ~ . ~ .. . .~ , . , . , -. --.,,n,,. ,. ~~,.n. - - - , ~ ,,,-..e.- ,...n ~ ,. -- r-- ~ , -
BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3) _ PRODUCT: BETZ DTS
-----SECTION 4-----------HEALTl! HAZARD EFFECTS------------------------
ACUTE SKIN EFFECTS *** PRIMARY ROUTE OF EXPOSURE SLIGHTLY IRRITATING TO THE SKIN ACUTE EYE EFFECTS *** MODERATELY IRRITATING TO Ti!E EYES ACUTE RESPIRATORY EFFECTS *** l MISTS / AEROSOLS MAY. CAUSE IRRITATION TO UPPER RESPIRATORY TRACT l CHRONIC EFFECTS OF OVEREXPOSURE *** NO EVIDENCE OF POTENTIAL CHRONIC EFFECTS. cf MEDICAL CONDITIONS AGGRAVATED * *
- _
NOT KNOWN SYMPTOMS OF EXPOSURE *** MAY CAUSE REDNESS OR ITCHING OF SKIN.
-----SECTION 5------------FIRST iID INSTRUCTIONS----------------------
SKIN CONTACT *** REMOVE CONTAMINATED CLOTHING. WASH EXPOSED AREA WITl! A LARGE QUANTITY OF SOAP SOLUTION OR WATER FOR 15 MINUfES EYE CONTACT *** IMMEDIATELY FLUSH EYES WITli 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 *** i VENTILATE AREA,USE SPECIFIED PROTECTIVE EQUIPMENT.CONTAIN AND ABSORB ON ABSORBENT MATERIAL. PLACE IN WASTE DISPOSAL CONTAINER. THE WASTE CHARACTERISTICS OF THE ABSORBED MATERIAL,OR ANY CONTAMINATED SOIL, SHOULD BE DETERMINED IN ACCORDANCE WITl! RCRA REGULATIONS. FLUSH AREA WITH WATER. WET AREA MAY BE SLIPPERY. SPREAD l SAND / GRIT. l DISPOSAL INSTRUCTIONS *** WATER CONTAMINATED WITH THIS PRODUCT MAY BE SENT TO A SANITARY SEWER TREATMENT FACILITY,IN ACCORDANCE WITH ANY LOCAL AGREEMENT,A PERMITTED WASTE TREATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT PRODUCT (AS IS)- _.
~""
INCINERATE OR BURY IN APPROVED LANDFILL FIRE EXTINGUISHING INSTRUCTIONS *** FIREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING APPARATUS (FULL FACE-PIECE TYPE). PROPER FIRE EXTINGUISHING MEDIA: l DRY CHEMICAL, CARBON DIOXIDE, FOAM OR WATER
BETZ MATERIAL SAFETY DATA SHEET (PAGE 3 OF 3) PRODUCT: BETZ DTS
-----SECTION 7-----------SPECIAL PROTECTIVE EQUIPMENT-----------------
USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITl! 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 IS LIKELY, - USE A RESPIRATOR WITH DUST / MIST FILTERS. RECOMMENDED SKIN PROTECTION *** PJBBER 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 *** NORMAL CHEMICAL HANDLING
*************************************************************r************
THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD APPENDIX: REGULATORY INFORMATION THE 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 IN REGULATIONS WILL RESULT IN 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 kCRA HAZARDOUS WASTE IDENTIFICATION NUMBER IS: NOT APPLICABLE
... DOT HAZARD /UN#/ER GUIDE # IS: NOT APPLICABLE
... CALIFORNIA SAFE DRINKING WATER ACT (PROPOSITION 65) MATERIAIS: NONE
... SARA SECTION 302 CHEMICALS: NONE ~
. . .S ARA SECTION 313 CHEMICALS : NONE
... SARA SECTION 312 HAZARD CLASS: IMMEDIATE(ACUTE) .
... MICHIGAN CRITICAL MATERIALS: NONE n- ,,
1 NFPA/MMIS : HEALTH - 1 ; FIRE - 1 ; REACTIVITY - 0 ; SPECIAL - NONE ; PE - B
A00ATIC = LABORATORIES INC. BORA R BOMERTON ROAD.T AEVOSE.PA 19o47.U S A: / TEL:215 3SS 33co. TELEX: 1731484 AX # 3SSI 2069 ENVIRONMENTAL INFORMATION ON CLAM-TROL CT-1 - FOR 2EBRA MUSSEL AND ASIATIC CLAM FOUL %NG CONTROL Clam-Trol CT-1 is a patented nonoxidizing molluscicide providing state-of-the-art control for macrofouling caused-by Asiatic clams, Zebra mussels and marine fouling organisms. Clam-Trol Ci-1 is a federally registered molluscicide for use in once-through and : recirculating cooling systems. The EPA registration number for CT-1 is 3876-145. Clam-Trol CT-1 has been used in the past_4 years for Asiatic clam macrofouling control to power plants, steel mills, chemical refineries and other manufacturing facilities. Appendix A presents some case histories for Asiatic clam control. The efficacy of CT-1 towards cobra mussels has been demonstrated in
-laboratory studies and it has also been utilized for the exterminatien of zebra mussels at two power plants near Detroit in November / December 1989. The laboratory evaluations (See Appendix B) demonstrated the efficacy of CT-1 for exposure periods of 6 hrs to 24 hrs at water temperatures of 50, 100, 150 and 200C. It has been demonstrated that mortality responses are dependent upon CT-1 dosage, exposure period, and: temperature. 4 The performance of the CT-1 in the extermination of zebra mussels at
.the J. R. Whiting Power Plant and the Fermi II Nuclear Power Plant has-been presented at.several conferences in 1990 (See Appendix C). These 12 to 15 hour applications were monitored for zebra mussel mortalitiee using flow through side stream bioboxes. Mortality responses ranced from greater than 95% at the outlet of the condensers when eter temperatures were 140 to 170C to 25-35% at tha inlet ends with colder
. temperatures of 20 to 60C. CT-1 treaturente or 6-to 8 hr being applied -
to cooling systems _during the Summer of 1990 when water temperatures were above 20 OC achicved 80,to 100% mussel eradication. Recommendations for optimizing Clam-Trol CT-1 applications for Zebra , mussel control and meeting discharge permitting requirements are presented in this pub 1_ cation. Information-on Clam-Trol CT-1 to aid in addressing NPDES permit requirements is being presented, as tollows:
- 1. Name of the additive Clam-Trol CT-1 contains 13% active ingredients (two cationic
... . _ , _ . _ . . . _ . . _ _ _ . . _ , _ . .__m.-._ _ ._._ __ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ _ _ . _ _ _ _
Y surfactants) and 87% inert materials. The two cationic surfactants are N-alkyl dimethylbenzyl ammonium chloride (Quat) and dplecylguanidine hydrochloride (DGH). The inert materials of this' formulation - ethylene glycol, isopropyl alcohol and water - relatively nontoxic to aquatic organisms. -
- 2. Concentration (mg/1) of the additive to be used:
Clam-Trol CT-1 is usually fed at concentrations ranging from 10 mg/l to 25 mg/1. The concentration to be fed will primarily depend upon the demand of the cooling system, resulting in passive neutralization of the CT-1 actives. The length of the exposure period will vary from 6 hours to 24 hours depending upon the water temperature and the CT-1 dosage. Either seasonal or binonthly treatment programs ranging from 2 to 6 times / year is required for macrofouling control of either zebra nussels or Asiatic clams. It must be noted that the objective of these seasonal or binenthly applications is to provide a preventative treatment program by exterminating the juvenile mollusks to prevent their growth to adult fouling size and to reduce the overall accumulation of juvenile rollusks setting within cooling systems. Each cooling system will have a specific treatment program to meet the macrofouling control requirements for that facility. The frequency of the applications, ranging from 2 to 6 times / year, will depend upon the degree of larvae and juvenile mollusk infestations and the kind of nacrofouling control so the operations of the power plant or industrial facility is not impeded.
- 3. Expected concentration of the additive contained in the discharge or blowdown immediately prior to entering state surface waters:
All seasonal or bimonthly CT-1 treatr.ent programs are designed so that the concentration of Clam-Trol CT-1 is always less than 1 mg/l in the discharge. The reduction of CT-1 from the point-of- '- feed to less than 1. mg/l at the cutfall is achieved by one or more of the following approaches:
- 1) Both the intake river w.Ler and the cooling system have many kinds of naturally occurring materials - silts, clays, suspended solids, hunic acids, and the microfouled surfaces of cooling pipes - that will exert a demand upon the CT-1 actives. Both actives (Quat and DGH) will readily adsorb to these materials. Once adsorbed they no longer exhibit toxicity. Thus the passive neutralization of the CT-1 actives as they pass through the cooling (Astem will significantly reduce the concentration prior to diacharge.
EBBITaZ
- 2) Many Clam-Trol CT-1 treatment programs focus upon segmented applications where only a portion of the total cooling water is being treated at any one time. This segmented treptment approach allows for the dilution and passive neutralization of the treated water with the remaining untreated cooling water. This segmented _
treatment approach can often achieve CT-1 concentrations i of less than 1 mg/1.
- 3) If necessary, clam-Trol CT-1 applications can be actively detoxified by feeding a blend of clays prior to discharge. Clays are fed at a ratio of 1 mg/l of clay i for each 1 mg/l of CT-1 to be detoxified to achieve I discharge concentrations of less than 1 mg/1.
- 4) An analytical photometric method is available for monitoring the concentration of CT-1. This field method has a sensitivity c! 0.2 mg/1. (Appendix J)
- 4. Toxicity information regarding additive only minimal amounts of Clam-Trol CT-1 are required for short treatment periods (6 to 24 hrs) to provide macrofouling control.
The discharge of CT-1 concentrations of less than 1 mg/l would not result in an environmental impact to the receiving stream or lake. In fact, even the most sensitive aquatic organisms would not be affected in either an acute or chronic sense beyond the mixing zone of the discharge stream. In addition, detoxified CT-1 remains neutralized so that it would not impact benthic crganisms. ' Neutralized CT-1 actives would be further subject to biodegradation that would prevent any accumulation of these I actives in the environment. The following toxicity information is available: Appendix D: LC50 Values of Clam-Trol CT-1 (Neat formulation) Appendix E: Detoxification Potential of Clam-Trol CT-1 with Clays and Other Materials To Fathead Minnows and Daphnia nacna.
'~
Appendix F: A 7-day Fathead Minn v Chronic Toxicity Test on the ! effect of Detoxified Clam-Trol CT-1 With Clays Appendix G: Effect of Detoxified Clam-Trol CT-1 to a Benthic Organism: Chironomus, a midge larva. Appendix H:. A Long Term Study Using Fathead Minnows and Daphnia magna on the effect of Detoxified Clam-Trol CT-1
EBETE Appendix I: Clam-Trol CT-1/Environnental Package Appendix J: Analytical Field Method for Cla,*.ETrol CT-1 Appendix K: MSDS -. Prepared by:
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Larry A. Lyons Aquatic Toxicologist Laboratory Manager LAL cn 1 l l l l l
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Technical Paper 299 (~ n Batz Duh%9620 AMERICAN POWER CONFERENCE _ ILLINOIS INSTITUTE OF TECHNOLOGY CHICAGO, ILLINOIS APRIL 18-20,1988 EVALUATION OF A NEW MOLLUSCICIDE FOR ALLEVIATING MACROFOULING BY ASIATIC CLAMS ( LARRY A. LYONS s BETZ LABORATORIES, INC. TREVOSE, PA OMAR CODINA TU ELECTRIC DALLASrTX _ RAYMOND M. POST BETZ INDUSTRIAL TREVOSE, PA DAVID E. RUTLEDGE L TU ELECTRIC MESQUITE, TX C1988 Betz induS'Jial. M Rights Reserved
EVALUATION OF A NEW MOLLUSCICIDE FOR ALLEVIATING MACROFOUltNG BY ASIATIC CLAMS Larry A. Lyons ers, increased maintenance costs for equ!pment, and Supervisor Aquatic Toxicology forced plant outages. These pests must often be physi. Bet: Laboratories, Inc. ca!!y removed from the systems they invade. EPRI has Trevese. PA estimated that the loss of plant availability could cost
$500.000! day for a typical 600-MW coal unit, and the -
Omar Codina loss of 1% efficiency of a typical 600-MW coal unit ex-Chemical Coordinator ceeds 1 million do!!ars per year (1). TU Electric The threat to safety.related and service water systems is DMas. TX another major problem. Following the Arkansas Nuclear One forced outage, the 1901 NRC bulletin to all nuclear Raymond M. Post plant licensees recommended the implementation of a Project Engineer mon ltoring program for determining the severity of Asiatic Bet: Industrial clam fouting, it also recommended the establishment of Trevose. PA preventative control measures for att safety related com-ponents (4 David E. Rutledge Senior Technician Attempts to control the proliferation, and thus the fouling TU Electric ability, of the Asiatic clam have focused on physical and MesquHe TX mechanical methods or the use of oxidizing biocides. The use of screens and strainers or physical removal measures (such as dredging and vacuuming operations) ABSTRACT do not prevent the growth and proliferat:on of the clam, but only provide temporary relief from advanced fou!ing Macrofouling by Asiati0 clams impedes the efficiency, cond:tions. Oxidizing biocides. (e.g., chlorine or bro-Operation, and safety of power plants by plugging con' mine) require weeks of continuous, uninterrupted appfi-denser tubes, threatens plant availability Jeopardizes cations to achieve efficacy (3). When cont;nuous safety related water systems, and damaDes equipment. chlorination is permitted, the effect on corrosion, espe. The Current state of the art control technology lacks an cially of copper Blicys, is a major concern. Because Asi. effective biocide for a!!cviating and preventing this scri- atic clams have chemoreceptors that detect low concen-s problem. trations of oxidizing biocides, they can avoid contact by clamming up for extended periods, At TV Electric's Lake Hubbard station, the clam popula-tions colon!:ing the intake bays caused chronic fouling of Alternative chemical control agents are either ineffective the main condenser tubes. The new mofluscicide treat- In short application periods, present an unacceptably ment program allowed the station to gain control of the high environmental risk, or cannot easily be detoxified macrofouling problem and then mainta!n control by exter- before discharge (1. 4,5), minat;ng juveaile Asiatic clams that recolonize the sys- _ tem. Seasonal motiuscicide applications from June 1986 This paper describes the successful application of a new through October 1987 were shot fed to nonoperating in- molluscicide that is considerably more effective on the take bays. The performance of the molluscicide applica- target organisms than ch!crine and which can be corn tions requiring only brief exposure periods has been veniently applied to intake bays. eva!uated with in situ biomonitoring rnethods. BIOLOGY OF THE ASIATIC CLAM IN'TRODUCTION Asiatic clams, often referred to by their scientific name The cost of Asiatic clam macrofouling to the power in. "Corbicula", are bivalve mo!!usks it.,a thrive in fresh dustry is associated with reduced cooling efficiency and water environments. This extremely hardy species lives plant output by plugging condenser tubes. Impa! red and in a wide range of freshwater habitats throughout most of - damaged circu!ating pumps and oil and hydrogen cool- the United States. It can even prosper in moderately pot-1
luted waters. The Increased ambient water temperatures actively detox;fied with certain clays or other inert materi-surrounding a power plant further enhances the prohfera. als, if necessary, tion and estabhshment of Asiatic clam populations. APPL 10ATION EXPERIENCE Aslatic clams colonbo in dense popu!ations: 1000 to 10.000 clams per square yard are common. The clams Although TU Electric's Lake Hubbard Station is the first are fi!ter feeders that siphon in a!gae and bacteria from fie!d apph;ation to ncnoperating intake bays, the new the water. Their natural p*:dators are (;sh and crayt:sh. A
~
molluscicide has been used in other Asiatic clam control plant's cooling system offers an ideal ctam environ- appheatens (7-9). Exampics of other types of apph a-ment-It is free of predators and provides a continuous lions include a seasonal preventabve treatment program - suppty of food- for the service and safety-retated water systems of a nu-clear facih!y; a combined microorganism and Asiat;; An Aslatic clam reaches sexual maturity when it is about clam fouhng control program of the mo!!usct:Ide coup!cd 6 months old (14 In. In s! e). Each adu!! is capable of with chlorine; and plant wide apphcal:ons to a s!cel m!! se:f fert;lbation and can re! case many thousands of wsh a water system network containing m/es of pte. veliger larvas during the spawning se: sons from Spring MCL through the Fa!!. Juven"e clams (less than 14 in. In size) and la vae are LAKE HUBBARD STATION small enough to pass throuDh cochng system intake screens. Once inside, they settle out primarily in low f;ow The Lake Hubbard staton of TU Electric. a loo-unit gas-areas. They attain adult s!:c within a few months and are fired generat.ng facdity, has experienced chronic fou!ng then transported further into the cochng system. It is the and forced outages resu!!ing from the pluggage of the transport of adu!! sbed clams further into the cochng sys- main condenser tubes by Asiatic clams. tem that causes the chronl0 fouting problems that Lake Hubbarfs intake bays measure 40 x 11 ft w!!h a threaten the safety, operation, performan0c. and sys. high water depth of 40 ft (see Figure 1). Un:t 1 has two tsms availabihty of power plants. M!ake bays (1 A and 1B), and Un:t 2 has three intake DEVELOPfAENT OF A NEW fAOLLUSClOIDE g The new manuscicide, ca!!ed Clam-Tro! CT 1 (patent s e, m
i pending), is effective against all1.fo stages of the Asiatic i;
'i '. '; ;
clam. using short exposure penods of relatively low con-
" " ' " lL lD '
centration. Clam-Trol CT 1 is an anucous based formu!a-tion contalning two cationic surfcetants, alkyldtmethyten- f;U! ! {; ; zy! ammonium ch!0 ride and dodecylguanid;ne hydrochlo- l (({!! !y fid0- ,,....., ! lllll j ll 40"0* l ll ' This new mo!!usticido presents a unique advanament in l ll{ll { l; l
; l the art of macrofou!ing control by having the capability of l 'h;;l { ll kining adu!! as well as juvenile Asiatic clams in cochng ! ll s.m. L- J sytems using feasible, cost effective treatment regi- _
pll ! f ((!)~'[,'[ mens. When apphed, the materia! remains substantially lF "*" f ,= undetected by the c!am, which s?hons in a lethal DOS-age during an exposure period of approximate!y 24 to 4B ru r,,, 7 hr (depending on concentraton and water temperature). .. A de:ayed mortaay response occurs fcl lowing the brief { {h. ,, O I exposure period. Since the clam requires several months l l ', \ O to a year to grow a she!! of foutng size, period;c app!;ca. l
' 't**
I tions fo3cw!ng peak spawning periods are sufficient to _ N m 'a prevent c!am f0u!!ng. Studies have shown that once the ,
. . . ~ .
mo!usticide actives are adsorbed by substrates (in !ud- u. ms Ing sed;ments, suspended solids. and even the surfaces cf coo!!ng systems), they no Icnger exhibit toxicity to nontarget organisms (6). The mo!!uscicido can a!so be Figure 1. Intake bay at TU Electric's Lake Hubbard Station. h) l 2 l l
Aslatic clams colonize both the plant and lake sides of Defore this treatment, the only recourse for reducing the the five intake bays. Each bay is equlpped with one number of clams transported to the maln condensers in-travelling screen and two stationary screens, Since these volved periodic mechanical clean-outs of tha intake bays screens have a mesh st:0 of 0.25 in., they do not restrict with the aid of scuba divers. These physical control the infiltration of larval and juvenile clams. Even clams of measures only reduced the degree of pluggage by re. M in. In stze (about 6 months old) maneuver through the ducing the number of adult clams. I- screens at all water depths (see Figure 2), These infil. s ForLese reasons, Clam-Trol CT 1 was applied to exter-trating juvenile clams then colonize and grow on the plant minate the juvenile clams that were recolonizing the in-side of the intake bays (see Figure 3). Adult clams that - take boys. have attained the sl e of M to M in are then trans-ported to the main condensers and auxiliary coolers and gottg3eieing ,pptie47;og pg7ggn3 plug the tubes. Previous cican-outs of the water boxes at the condensers have removed enough clams to fill two Lake Hubbard's intake bays were inspected with the aid 55-gal drums, of a ponar dredge sampling device to estimate the den-s!!y of the clam popu!ation residing in the bays and their size range. In many cases, mechanical clean outs may e, .** 'y .g- em* , c_ be required prict to the initiation of molluscicide treat-monts in order to prevent a massive transport of dead g %s4C %(* c!ams further into the cooling system. At Lake Hubbard.
.e , p- - g ' M the intake bays were cleaned out using divers, gj. .
j' @b The food system was designed to maximi:e the disper. f . ~gM- . slon of the molluscicide at the bottom of the intake bays. d@. b .' '. ' A sparge header (1 in. diameter and 10-ft tong) was (
'Q""p.M [' -
- used that had a tee in the middle of the pipe for connect.
,' , ([. [ ing a hose. The header was positioned at the bottom of the plant side of the secondary stationary screen.
g ' gO pg A 50 gal stock solution of the molluscicide was prepared h' E yf y,.f with lake water in a drum. The contents of this drum were then pumped to the header. Another 30 gal of lake , water was also directed to the sparge header to assist in ([ ~
, y g./
further diffusion of the molluscicide. Shot-led dosages for Figure 2. Juvenile Aslatic clams maneuvering the various applications were determined based upon the through plant intake screens, dilution cf the stock solution by the total volume of water in the intake bay. kt Fo!!owing each treatment, the water from each intake bay was pumped with either the main circulating pump or service water pumps at a rate adjusted to assure suffi-
] cient dilution of the biocide at the discharge point. An m
analytical photometric method (10) was used for moniter- , Ing the d!scharge. p, . JUNE 1986 MOLLusCICloE APPLICATIONS Two intake bays were treated in this application. 3 . . .. , Bay 18. The stationary screens in the intake bays at the c- ,M,C ' .WN..;t3lg, %.g C. ,",
' b. '
Lake Hubbard Station are constructed with *1' beams. I.- fK. *g I i,;', j -
*J 7( creNing a 4.in. deep trough for the clams to colonize.
hk,Z[P.#.
- 2. !.
,4 ~,2 gk Q;,, p.g,, NJ The secondary stationary screen of bay 1B was cleared g of all c!ams residing on the beams. Every other 3 ft beam O r'avre a- ciems =='omiz'"2 ai="t s'ee or imi>*e screens,
*e> '"c" reseeoce *ttn 7s c' ems <a"o'"o io ece ' rom o months to 3 years and the stationary screen was low-3
. _. . -~_- - M-
TABLE 1: STATIONARY SCREEN "1" BEAM BIOMONITORING* Bay 18: 48-hr Treatment Period /4 Shot Feed Applications (60 ppm Each) h) Cumulativo % Mortality on the Foilowing Days After Treatment Depth of Bay. ft 0 1 2 3 4 ,c 5
'~
37 88 91 93 99 100 - 31 0 36 63 77 81 85 _ 25 0 23 5 83 100 - 19 0 0 ' 5 11 15 13 0 0 0 0 0 0
' June 1996 applications.
cred back into the bay. Bay 1B roccived four shot feed TABLE 2: appucations of 60 ppm each during a 43-hr treatment STATIONARY SCREEN "l" BEAM period. The clams woro examined dally for 5 days follow- glg gggj79gggg. Ing the treatment (see Table 1). Bay 29: 24.hr Treatment Period!2 Shot Food Bay 28. The 11" beams of the secondary stationary App!! cations (60 ppm Each) screen of bay 2B wpre not c! cared prior to the treatment No. of Alive Clams Counted! but were al lowed to retain the existing population. They Estimated Cumu! alive % 0 Y h were also examined during the post treatment period. s her Tre k*' 9 Only a qual;tative examination was made since the hun-Depth of Bay, ft 2 4 dreds of live clams residing on the ledges were not counted prior to treatment. Bay 2B received two shot 37 12/>95 6'>95 - feed apphcations of 60 ppm each during a 24.hr treat. 33 24!>90 15!>95 ment. During these examinations, dead clams were dis. 28 280/30 115!>50 carded and the remaining live clams were counted to 21 400/<5 220/>25 provide percent mortahty est:mations (see Table 2). ' June 1986 applications. Lako Sido Monitoring. Fo!!owing each treatment period, clams were collected from the lake side of each bay using a ponar dredge. The c!ams were transferred to These dredge samples were not monitored beyond 4 aquaria for monitoring the mortality responses. The days, because of a significant clam mortality from un-aquaria were replen!shed with fresh take water two to known causes that occurred in the control tank on the three t;mes da!!y during a 4 day post treatment period. 5th day (see Table 3). TABLE 1: = l DREDGE SAMPLES OF CLAMS COLLECTED FROM LAKE SIDE OF BAYS
- Cumulativo % Mortahty on the Following Days After Treatment 1 2 3 4
- Control 0 0 0 2 l Bay 1B (Lake Side) 74 82 82 82 1 Bay 2B (Lake Side) - 15 41 66 l (Dredge Samplo #1) i Bay 2B (Lake Side) -
9 23 34 (Dredge Sample #2)
' June 1986 apphcabans.
g 4
_ - - - - ~ . - - . - _ . _ _ . ~ . ~ . - . . . . - . . - - - - - - b d I in Vitro Monitoring. Treated water was co!!ected from , the 40 ft depth locations on the east and west sides of , both bays and transferred to aquaria containing clams. .- O The ciems were coiiected irom ihe i,take eex, n,ior to the treatments. Each aquarium received treated water 30 min and 3 hr fo!!owing each shot feed apphcaton. For- , , I lowing the cyposure period, each aquarium was repien- -{ ' ished two to three times a day w!!h fresh take water. A, y \'
~
Dead clams were removed dunng the da;ly post treat- . ment exam! nations (see Table 4). .- g' , g e i e
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g
- 1987 SEASONAL APPLICATIONS .. . . 7 s
In situ cys on the bottom of the bays were used fcr a; L,1,, y _ _ .i ) l i monitoring d,Jring the 1987 applicat.ons (see Figure 4). '.' . , At specihed it"crvals lo!owing the treatments, the clams . . .., ~-;.. a retained within the cages were examined for mortahty 3 (see Tab!es 5-7). Ambie".! lake water temperatures for F gute 4. Cric';et cages used for in situ bio-February, June and October were 50, 75, and OB 'F. monitoring. l l respectively, HEsVLTS OF APPLICATIONS Mo!!uscicide appkcations at the Lake Hubbard Stat:en A strotscat.on of the mctluscicide at the lov.er depths cf l were assessed by biomonitoring methods. Clams were tne intake bays was observed, as exemph!.ed b/ mortal-recorded as dead when the bivalve sho!! had gaped it/ responses rang:ng from 100% at the 37.tt depth to open. Occasionally, the viabihty of a c!am was deter. 1E% at the 19.ft depth (see Tab!c 1). Th:s biomonitonng mhed by gent!y prying open the bivalve she!! shght!y. A of the vert; cal me!!uscicide d:spersion supports locah::ng l clam was judged to be ahvo if it clammed up aga:n. the apphcations to the bottom cf intake bays where Asi-at.c c ams tend to cotenite and grow. Even the c!ams June 1986 Applications. MortaEty responses of between tnat were reco!cni:ing the lake sides of the intake bays 90 and 100% were cbserved for both the 24-hr treatment were exterminated quite effechvely (see Tabte 3). with two dose apphcatons (bay 2B), and the 48 hr treat-ment with four dose apphcations (bay 18) (see Tab!es 1 The lower mortanty responses recorded in Tables 3 and and 2).
, 4 were cont.nuing when the mon.tonng was terminated TABLE 4:
JUNE 1986 APPLICATIONS /AOUARIA BIOMONITORING Day 1D: 48.hr Treatment Period!4 Shot Feed Applications (60 ppm Each) Cumulative % Mc Sht/ on the Following Days After Treatment 0 1 n 2 3 4 , , Control 0 0 0 0 3 1B-Plant Side 6 95 93 100 - 1ELLake Side 12 06 100 - - Bay 20: 24-hr Treatment Period /2 Shot Feed Applications (60 ppm Each) Cumu!at:ve % Mortaht/ on the Fol:okng Days After Treatment 1 2 3 4 23-Piant Side C 0 30 63 g 30 06 100 v PB-Lake Sido 5 l l _ , _ _ _ ,
because of unexplained clam mortal.ty in the control tank June 1987 App!ications. All three applications resu!!ed 5 days after treatment. in clam morta!, ties of 95% to 100% tor the piant sides of the intake bays (see Table 6) Clam mortal dies on the February 1987 Applications. The colder water tempera-take side of the intake bays ranged from 25% to E5%. tures during this time of year resulted in a stower rate of modahty response. However, increasing the application period to 72 hr caused clam kills of 98% to 100% on tne October 1987 Applications. A 100% mortahty response plant side of the bay (see Table 5). was achieved on the plant side of the intake bay be;ng monitored, tJo clam mortahties were reported on the lake A slower ki!! rate was a!so observed in cold water app!i- side (see Tab!c 7) Further mod:fical;ons or pcs:tioning of _ cations at ancther fac!!ay (B). This may be altributed to the sparge header may be reauired to increase the dts-reduced metabo:ic and siphoning activity by the c!am persion of mo:uscicide to the lake side of the bays if during the winter months. exterminal;on of the recolon!2ing clams is needed TABLE 5: FEBRUARY 1987 APPLICATION RESULTS Bay 1 A: 72-hr Treatment Period!6 Shot Feed Applications (60 ppm Each) Cumulat!ve % Mortahty on the Following Days After Treatment 0 1 2 3 18 1 A-Plant Side 56 82 06 86 93 (back of bay) 1 A-Plant Side (mid$e of bay) 32 46 50 76 10's h 1 A-Lake Side 2 6 6 6 6 (front of screen) Bay 2A: 48 hr Treatment Period!4 Shot Feed Applications (60 ppm Each) Cumulative % Mortality on the Following Days Aher Treatment 0 1 2 3 4 18 2A-Plant Side 0 24 26 30 32 46 (back of bay) 2A-Plant Side 20 32 58 72 80 96 (middle of bay) .. 2A-Lake Side 0 4 4 10 10 10 (front of screen) Bay 18: 24 hr Treatment Period!2 Shot Feed Applications (60 ppm Each) Cumulat;ve % Morta!.ty on the Fo!!owing Days After Treatment 0 1 2 3 18 IB-Plant Side 6 30 44 50 50
~
(ba::k of bay) 10-Lake Side 0 0 4 4 4 (front of screen) 6
TABLE 6: JUNE 1987 APPLICATION RESULTS Day 2A: 48-hr Treatment Period /1 Shot Feed Application (100 ppm Each)
) '
Cumulative % Mortality on the Fotlowirig Days After Treatme it 1 2 3 5 2A-Piant Side 77 96 96 96 2A-Lake Side 0 0 25 25 Bay 28: 4B hr Treatment Period /2 Shot Feed Applications (50 ppm Each) Cumu!atrve % Morta!,ty on the Fo towing Days After Treatment 1 2 3 5 11 43 91 97 2B-Plant Side 23-Lake Side 59 ES E5 65 Bay 2C: 45-hr Treatment Period!1 Shot Feed Application (100 ppm) Cumulative % Mortakty on the Fo! lowing Days After Treatmen' 1 2 3 5 2C-P: ant Side 96 100 2C-Lake Side 8 44 52 52 erat:cns. This stops the mass transport cf h TABLE 7: OCTOEIR 1987 APPLICATION RESULTS c:ams and rehc she!!s further into the system Bay 20: 4S-hr Treatment Period!1 Shrt Feed Application (100 ppm) Step 2. Mcl!uscicide is appled using appicpriate meth-
' ds to assure good distribution to the areas of Cumulative % Mortahty en the ,
colonizahen Vigilance to prevent the further Fo!! awing Days After Treatment transport of adu!! clams that were not removed 1 2 3 dunng the cleanout operat.ons is required. 2C-Flant Side 57 98 100 2C-Lake Side 0 0 0 Step 3. Seasonal apphcations (2 to 4 times per year) are scheduled to exterminate larvae and juve. nite clams that will te reccion!:ing the system. CONCLUSIONS At_ Lake Hutbard, mortahty respenses of 90-100% were ssWy cmd b ead cf N low seasonal ap The new me!!uscicide. Clam-Trci CT 1, is extreme!y ef-cahons to Wie plan sde of me stake bayL h mh fechve against alllife stages of the Asia!!c clom with cnly cicide was conveniently shot fed and datused to tne bet-brief treatment perieds of 24 to 48 hr. !! can be easa tom of the intake bays with a sparge pipe. The easy to-applied by shot feed or cont:nuous feed (depend.ng on use biomonitoring methods that were used for evaluahng the system to be trCad) and. if necessary, detoxif,ed treatment eMectess can abo M used for optm:mg prior to discharge. the apphcation. If the mol!uscicide is led dunng the winter For ept: mum results, the Asiatic clam contrci program months, a longer apphcation period may be repuired to censists of three basic i,teps for chminabng ciam popula- compensate fcr reduced metabolic and siphoning actreity tiens and prevent ng recolonization. in cold water. Regu!atory requirements are met by med,- e . lying d:scharge procedures.
!] Step 7. Aduft c!ams in the cco!.ng system are physi-ca!/ removed by dredging or vacuum:ng op- Seasonal applicaticns of the new molluscicide at Lake 7
I 1
Hubbard proved to tie a good economic a!!ctnative for search hstitute. Pato A!!o, CA.1903.
/sstatic clam controt. The t calment program was offer- l tive in caterminahng Juvenue and tarval ctams and pre. 6. tJeittet. D. A.; Johnson, F , .Nge T. L: YounD.
von 9ng the reinfestehon of adatt c!ams in the intake bays. I Sa Dahng. P. M.
- Watec Fouhng of Nxtcar Power hant Service Water Systems". U S. tJJ.
g The most sign.tcant beneht to the Late Hubbard Stabon clear Regulatory Commission Bu!!chn, Vol.1-3, j 15 the reduced tube plu[jage in the main condenser and U S. Regu atory Comm:tsion. Washington. D C., auxil.ary coplcts. This not on!y improves cootng oth. 19N' ciency, but a'so mininjs microfoubng and tedimenta. tion, f.bntenante attdes such as ttwing and r0dding 6 Lyons, L / *Detoxitett4on Potental cf a New of tubes. have a'so been grea!!y reduced Vacuuming of f/o!!us cde for Asieb Clam f ouhng Control *.
~
toteke bays is tso longer necessary. 'The control of Asl. /snnual fAcetng of the Stiety of Environmental l et;c c!am macrofoub; has ehminated forced un.t out' Toucotopy and Chcmittry, Pensato:a' F L, f;o. ages du9 to clams st the Lake Hutbard stt00n
- 7. Fetiers, D. D. ' Corrosion, Dio: ides and inh;b, tors REFERENCES in Once.Thtcugh Cochng Waters, EPRI ttx! car
- 1. *Condenscr PAacrulou!.na Contrci Te:Snologies
- Plant Leyup and Servi:o Water System t,'ain'a.
EFRI Report CS.35?D. Electric Power Research in. nance Seminar. Charlotte, t,'C. November 1987. st,tute. Pa!o Alto, CA,1084.
- 6. Post R. M.; Lyons. L. A. fle:lt. Light Power, 65
- 2.
- Flow Blockago of Cochng Water to Safety Sys- (10), 26 (1557).
tem Components by Corbecula sp. (Asiatic chm) and Mylilas sp. (Musse!)*, U.S. Nv:! car Regula. 9 Lyons. L A.; Post. R. f3
- Development nd Ap.
tory Comm:tsior, Bul!ctin. U.S. Regulatory Com, ptical:on of a New Matcriai for Contrc; of A5! abo \ missich. Washington. D C.,1EB1. Clams", aostract subm!!!cd to Intemahona: Water Conference, 1928. Betz Labortches, Inc.,
- 3. Doherty. F. O.; Fartis. J. L: Cherry. D. S.; Cairns. Trevese. PA.
JC Arch. Emiron. Contam. Tcu:01 15, 532-ba2 (1966). 10 *Determinat<0n of Clam Trol CT 1 by Modified Photomeinc ChromCe Complex Procedure", Bet:
- 4. *Matrefou!:ng Control Techn !og es; State of the Laboratories Analyt:cl Method. Ec!2 Laborato.
Art *, EFR1 Report CS-3343. Electri: Power Re. ties. in, , Trevose, PA. 3 , i i O l B
- - _ _ - . _ . - - . ~ . _ - . . . . . - _ - _ _ . _. - _... - ,_.- . - -.. . - ___ .-
Technical Poper 320 EPRI Service Water System . I Rollability improvement Seminar l
..O ASIATIC CLAM CONTROL EXPERIENCE AT PEACH BOTTOM ATOMIC POWER STATION v
O l Duano Mowery Philadelphia Electric Company Peach Bottorn Atomic Power Station ., Do!!a,PA ., E. McClellan RMC Erwironmental Sorvices Drumore, PA L A.Lyons DeV utocratories, Inc, 4636 Somerton Road ;. - - Trevoce, PA 19047 D. M, Austin and D. N. Karlovich Ect2 inciestrial i 1 Quality Way Trevoso, PA 19047 Betz YNXh'NE$J$$
#1990 Betz Laboratories, Inc. All Rights Reserved.
4
ASIATIC CLAM CONTROL EXPERIENCE AT
.q PEACH BOTTOM ATOMIC POWER STATION 'J Duane Mowery Philadelphia Electric Company Peach Dottom Atomic Power Station Delta, PA ,f E. McClellan HMC Environmental Services --
Drumore, PA L.A.Lyons Dotz Laboratories, Inc. 4G36 Somerton Road Trevose, PA 19047 D. M. Austin and D. fJ. Karlovich Detz industrial 1 Quality Way Trevoso, PA 19047 ABSTRACT A preventive treatment program effectively contiolled mictoscopic larval and juvenlio clams. Oxidtzing Aslatic clams in the service water and safety related blocides (e.g., chlorine or bromlnc) require weeks of cooling systems at the Peach Dottom Atomic Power continuous, uninterrupted applications to achieve Statlon of Philadelphia Electic Company. The efficacy 3 When continuous chlorination is perm!tted, the
~
molluscicide used, a nonoxidizing blocido, provides effect on corrosion, especlatly of copper alloys, is a 100% efficacy after a chart exposure period and is more major concem. Because the chemoreceptors of Asiatic environmentally attractive than traditional oxid! zing clams detect low concentrations of oxidizing biocides, blocides. This paper detalls the Asiatic clam control the clams avoid contact by *clammingop* for extended program at Peach Bottom and describes application periods.3 Advances in treatment technology over the orperiences.The spawning characteristics of the Aslatic past few years allow this macrofouling problem to be clam ln the plant makeup waters with respeci to time and addressed using a nonorldizing blocide. The Asiatic temperature, as well as molluscicide treatment levels clams do not sense the nonoxidizing material in the and feed duration, are also reviewed. water and ciphon in a lethal dose during an app!! cation it1TRODUCTIOtt l APPLICATIOt1 EXPERIEtiCE AT PEACli Aslailc clam macrofou!!ng is estimated to cost U S' Industry more than $1 bl!! ion annually. These costs are BOTTOM related to flow restrictions, reduced cooling efficiency, The Peach Dottom Atomic Power Station is a two unit I maintenance exper,ses, replacement of damaged bolling water reactor with once ttvough cooling % s equipment, and forcod outages.1 The vulnerability of systems. Located on the Susquehanna River in sc .rtaem fire-protection systems and safety related systems In Pennsylvania, the stallon found Asiatic clams in both the nuclear fueled generation stations is of special concem. Cooling water Intake bays and %scharge canal. Due to
# # " 'U * '
Early attempts to controf the proliferation, and thus the us chlorination was not possible at Peach l fouling ability, of the Asiatic clam were focused on D physical and mechanical methods or the use of oxidizing blocides. These control measures, however, in the Spring of 1987, the application of an were proven to be lar00ly ineff e clive, The use of screens environmentally acceptable molluscicide that provides and stralners or physical removal measures (such as 100% mortality on adult Asiatic clams within a 24-hour p dredging and vacuuming operations) provide only exposure period was recommended to Philadelphia V temporaryrelief from achancedfouling conditions They Electric. The proposed benefits of the new molluscicide do not prevent the growth and proliferation of the were: selatively small, economical dosages were i 1 tequired, the product was easy to apply, and it was Cold Water noncorrosivo 10 syt. tem metallurDY. . The molluccicide was firt.! applied in December 1987 g i to the high pressure service water systems. Clam W l The product (8012' Clam Trol' CT 1) is registered by mortality was mon!!ored using t.everal hundred adult ! the U.S. EPA for use againt.t mollusks in oncc-through clams from the Susquehanna Piver that were graded in . systems, recirculating cooling systems, influent stro in a multicharnbered aquarium. Product ] systems, and audliary water and waste systems concentration was monitored throughout the 48 hout j (including intake bays and fitcoprotection systems). The application using a colonmetric ter,t procedoro.1ho l activo ingredients la the product are a quaternary amino product was applied to the inlet of the HPSW system at a ~ j (OVAT) and dodecylguanidino (DGH) in an aqueous concentration of 25 ppm Free product residual at the solvent system. The product contains no heavy metals d:schargo of the HPSW system was 17.5 & 1.5 ma'L. i or EPA priority pollutants. Both actives are cationically Free product concentration to the Susquehanna River 61 4 charged surfactants that are readily adsorbed by the outfa!! was below detection limits (less than 1.0 ) naturally occurring materials, tuch as clay, surpended mg1) after reaction with the sollds in the circulating so! ids, humic acids, and sediment. Once adsort ed. the water d;1u11on flow. This circulating water flow provided a actives are not toxic to aquatic species 4 d,lution f actor well below the LC5rf s of the mollusticido to aquatic organit.ms. Based on the success of laboratory evaluations During the app!ication, two sample populations of perictmed by RMC ErMronmental SoMces (see Figaro Corbicula were placed in aquaria and exposed for 24 l 1) and projected savings compared to hypochlorito and 48 hr, respectively, to tree product residual lo treated j injection, permission was obtained from the water obtained from the HPSW system. This provided i Pennsylvania Department of Environmental Regulations additional data on the required orposure period under l (PADER) to appt/ the motiuscicide to the service water, low temperature conditions (5-7 *C). The equarta were j high pressure service water (HPSW), emergency placed in an insulated blobox through wfiich water was I t,ervice water, and fire protection systems of Un;ts,2 and circulated to maintain clams at ambient water ! 3 at the Peach Dottom /stomic Power Station. temperature. The treated water was replaced hourly for l 100 DOSAGE LEVEL e 80 - 15 ppm
@ 25 ppm f 1 I 50 ppm /
@ CD -
x - iiO / r
/
n 40 - n / ,= 20 - ~
/ ;
4 /A / A' 0 i 'l" i- i 1 2 3 4 i Observation Time (Days) figuro 1: Latent mortality response of Corbicula to Clam-Trol CT-1: 24 hr e posure at 20 'C. ;
i i
- the first 2 hr of injection and then at 4-hr Intervals for the This adaptation to cold wlcather also presents a duration of the 48-br exposure. Following the 484g difficult problem from a' treatment standpoint. Dased on
] exposure, the clams were moved off-rlte to a nearby observations of clams evaluated by RMC Environmental !' laboratory and maintained at fr7 'C along with the Services, Corbicula emosed to watet at less than 2 'O j control population. Whorcas the control population rarely siphon compared to thoso maintained at $ to 6 'C. )- continued to siphon normally, both treated populations This limitod siphonin0 activity compilcates the treatment j ceased all siphoning activities after crposure. A portion pro 0 ram and ex1 ends the latent officacy period, ! of tP9 control group 24-hr exposure group 6d 48 hr probably beyond that seen in Fi0uro 2 at 5-7 *C. j exposure group was sacrificed at 1,11,16,23,27,30, I and 37 days following the Initial exposure, and the gill Warn 1 Water _
, tissues were examined under a microscopo for clllla j beating. The results (Figuro 2) show that 100% mortality Dased on theso findings, further treatments to the I was achieved in both tho 24-hr and 48 fu crposure pDAPS service water systems were postponed until tho l groups, wtllo 0% mortality was observed in tha control summer of 1988. In August of 1988, motiuscicide was population. The retardation of the latent I ortality apptled f r a 244v period to the Unit 2 HPSW system.
!' Twenty-five parts per million of tho molluscicide was ted response under cold water (S 'C) conditions was ! considered particularly significant. Another significant f t ambient water temperatures ranging frorn 24 to 29.5 C. Wan moHuscicide concentrabon througnout the f!nding of philadelphia Electric's clam controlprogram is treated systems during the exposure period was 19.8 i that clams in the Susquehanna River spawn from 1.4 ppm. Monitoring wa s conducted as described earlier mid-May throu9h lato fall and that during the winter utilizing the blobox, and Corbicula were exposed for 12 months, lWenile and adult Atlatic clams survive for and 24 hr. At the end of the erposure periods, test clams weeks in harsh winter water temperature (0-1 *C). were agaln transported to holdin0 facilities at a nearby j Drooding larvae were found in adults in December 1987 laboratory and monitored for latent mortality. Water j at ambient water temperatures approaching 5 'C (see temperatures in the holding facilities ranged trom 23 to Figure 3). This findin0 is troublesome for the industry. 21 *C ttvoughout the mortality observation period. sinco it suggests that the species is beginning to adapt to colder climates once thought to be a battler to survival The latent mortal:ty of control and test clams expoted in the northem United States. to the Clam-Trol CT1 molluscicido for 12 and 24 hr at i 100 EXPOSURE PERIOD ' j - M 24 hr (M 48 hr 00 - ... . ... ... . 4 I ( GO - - . - - -- -- - .. - ... . ! b Y t: i 8 40 - - - -. -- -- - ... -.. ...
... ,a ,
i i 20 .. ....... .. . . ... ... ... ... . 0- 5, ! i . /- g 1 10 15 23 26 _0 37 j Observation Time (Days) 1 Figure 2: Latent mortality response of Cotblcular PDAPS (Dec 8-10,1987), HPSW loop 10, water temper. ature 5-7 'C. l l j 4 _- - - -.a
l l i 60
% of Adults 3 l Brooding N / (
W
......s...4...............................
N
~
l
..... ... . . . . . . .h . . . \.g .c. . .
43 Water temp h
-l
('C) 4-H-+#g]ik". - - - - - - -- l p > . + A '+- 20
+%
- i a~%
\N Nh7 l -A +/Y ' 4 !' ' ' ' ' ' ' ""''''''*% i-- ' Q ';' ,
0 " -' 4 1 12/20 1/31 3/1 4/12 5/24 7/5 8/16 9/27 11/8
- Date j Figure 3: Spawning activlty of Corbicula (percent of adutts with onty larvao on g!!!s), March 1987-
! January 1988. , 24-29.5 'C ls shown in Figure 4. Test clams in both the conducted in the same manner as de scribed above.The ! 12 and 24 hr tests crperienced 100% mortality within 70 Un!! 2 Generat Service Water (GSW) system was treated : and BB hr. respectively. The control clams experienced when water temperatures were approximhtely 18 *C, f no mortality, while the Emergency Service Water (ESW) system was Two additional applications took place in October of treated a week later with ambient water temperatures 1988. Treatment anc monitoring techniques wer9 between 15 and 10 'C. As chown in Figures 5 and 6.the h) 100 EXPOSURE PERIOD 80 - - M 12 hr M 24 hr - -- --- T co - ... . .. . . { . ....... . . 3 40 - - ---- - - - - -- - - .
. t 20 - -
l i 0 i i 24 43 64 72 18 Observation Time (hr) l Figure 4: Latent mortality response of Corbicula: PB APS (Aug 19-20,1988), HPSW loops 2A/20, water temperature 24-29.5 'C.
. 4-1 e+-e9 -abme 4 W -e+wru-*-e-*4+t-9-w e h MP E ge= ^+1e w Nge 4he 9- It wi -*+W -+4 =-sw- - ~ v - 6 . e+s-ww&q,sw wg-,-wwen-e,-m-ee-m%m-W-wA+t*+th 4-9"Mt' . M *ew'ru WkV 7"'T
l 5 j 100 EXPOSURE PEnlOD 12 hr .. 80 . I
@ 14 hr d
i y en . ... ... ...... . . .. .. ... .... . . b i 5 1 5 ao. ...... ....... . ... . . . .. .. .... ... . l l 20 - - - - - - - - - 0
"@ I t i ! i e i 1 2 3 4 ;
e 7 8 9 i ObseNation Time (Days) l Figure 5: Latent mortality response of Corbicula: PDAPS (Oct 6-7), Unit 2, GSW system, flow rate 25,800 i spm, water temperature 18 'C. 10 0 -- -- - l EXPOStlRE PERIOD ,' 80 - - M 12 hr - 24 hr . ... . . . .. l 60- - - f - - e - - - - - - { 40 - -- - -- - - - -- - 20 - -
- -- l.l/r r
/ _ ,
i 0- i i. , . _ . 4 i ' 1 2 3 4 5 6 7 8 9 Observation Time (Days) l ;; Figure 6: Latent morta!!!y response of Corbicula: PBAPS (Oct 13-14), ESW system, flow rate 3,300 gpm, water temperature 15-16 *C. i I *
,.,...--.--,,.,-.~,..--.-.-,.,,.._,.,_._---....,_,.,,,-_.--.,,_.,_,,.,,,_,,,,,,,,.,.,._,,,-,v,,.,w,_,..,. - ,,.-e,.,,, n...,,,,,nw,,,,,__.,,4,,
timo to achieve 100% mortality increased with lowering components can be losted and retumed to operation temperature, as expected based on cartier sooner). observations. Figure 7 summarizes the time to achieve uro plans are to evaluate the installation of a 100% mortality as a function of water temperature. The pemianent feed system for the mo!!usclcide at Pcath increased time to achieve mortality is directly related to Bottom Atomic Power Station. This will allow for short the decreased siphoning act!vity of the Asiatic clam periodic injections of the product on an intermittent basis while in a cold water environment. throughout the year to control the station Asiatic clam The resident fish population was monitored during the population. cold and warm water injections. fJo visible effect was noted on the fish population. REFERENCES l
~1 CONCLUSIONS (1) Appiebome, P. *Small Ciam is alg Trouble for j Water Systems", ? Jew York Times, May 4,1937.
The appilcation of a nonoxidizing blocide at Peach Bottom tesulted in 1C0% mortalityln Asiatic clams with a Dohorty, Fl. G.; Farris, J. L.; Chorty, D. S.; Caims (2) 24 hr exposure period at temperatures as low as 5 'C. J. C. Arch. Environ. Cotam. Toxicol. 15,$32-542 Latent mortality of the clams increased with lower (1986), ambient water temperatures. . When water temperatures were greater than 15 'C, (3) Post, it. M.; Lyons, L. A. Electr. Light Power, 6 5, I both 12 and 24 hr applications of molluscicide at similat 26 (1987). concentrations were equally effective in killing clams. Lyons L. A.;
- Detoxification Potential of a tJew (4)
Further testing 16 being conducted to confirm these Molluscicide For Asiatic Clam Fouhng Cont c1', tesults and could lead 'o shorter Injection periods during SETAC Poster Session, tJov. 9-12, 1937, es of a shorter Pensacola, FL. the summer months. The a hantag'reducedchemical; injection period are both economical ( and feeding costs) and operational (system O, 25-
- 9
\
6 s 20 - 's
$! ' \ $ N -
a E 15-. ~,~~- % 100 % Mortahty
!2 G 10- ~s 70 % '~~ @ Mortality 'e A 5- n
- 0 4 4 i i i I 3 0 5 10 15 20 25 30 35 Mortality Observation Time (Days)
Following CT-1 Exposure Period Figure 7: Time (days) for test Corbicula to' achieve 70 and 100% morta!!ty f ollow!nD exposure (12 to 48 hr) to Clam-TrolCT 1 concentrations > 15 mg/Lduring product applications atvariouswater temperatures (5-24 'C) at PBAPS, December 1987 - October 1988.
Reprint Number 018 Dcctric light !, Puer thember 195' Molluscicide controls Asiatic clam problems R.M. Post Bett Industrial and L A Lyons Betz Laboratonet A new cost effective chemical treat. interrupte<i appiieation- are reindr ed bleach alleviate
- the safet:. cancern ment that can be used at both fossil- over ces e rai w eekx lhit .b ia t n but costs several times mere t h a t.
fueled and nuclear power plants ap- elams have enemoreceptors that v.m gaseous chlortne. Utihtie. also ,i r e detect u:ry low concentrations of ou- under increasmg envirnnmentai cre* pears to offer an excitmg new weapon for use in the battle against the Asiat- diring biochies When they sens the sures to reduced their disenaree of to. le clam. presence of these materials, the clam tal residual chlorine. Continuous Asiatic clam fouling is estimated to avoiris contact by " clamming up. chlormation dechlorination w oulu n-cost U.S. industry more than $1 bil- closing its shell and remainine that alde complamce, but acam at m. lion annually. There costs are related way for extenned periods. Thur it t- creaded expense. to power nutaces or plant shutdowns. believed that osidizine bmeide- cauw Recent clevelopments reduced operating efficiencies, main- clam mortality by asphysiation. t at n-tenance expense. replacement of er than by direct toucity. '% e ideal chemical ont rm aca a equipment and other costs asse:iated Since clams will resume siphonme w on ni prm nie effectn e w. e r m m m with controlling this pest. The vul- as soon as the chlorine residual ciuao- tion of A3icatic clam w ith 3r. ort an. nerability of safety related systems. pears, any interruption in chemical pbcation pernuls within the niant arm including fire sprinkler equiptnent. fe ed for maintenance or repair of the coubt he retulered non tour wfort :t - also is a major concern to industrial chlarmation y tem will result m m. disenarge. Het: Laboratorie- retem managenents. effectual cont red of the clam popul.e ir har introduced a nu,llu.c :d. :%t tian. In adthtion. continuou chiorm.e cyclv matche- there requir-ment, Mechanical / Physical Conttr, tion require- !arce m ven t one, on t he new mollusen ule .mternanat. chlorine gas, w ha h not only is e spen- all hte 3 tace., of the A siatic t:am a it a Screens and strainers c . t pre-vent microscopic larval ar 'e r.iie sive, but also is the subject of grow - a single short appheation of 12 to 4-clarns from infestmg cooling ,, .en.8. ing insurance and safety concern. hours, dependine on conuntratom Other mechanical incthods, such aa Use of liquul sodium hypochlorite and temperature. Treatment pro wire mesh across the face of tube , , , . , , , sheets or plastic strainers in tube in- ,,, ,3,..
.j . , . , , ,
lets, still require the physical remov. '"*i.
, . p' %,.,' 'il l q -
.-?'.,,*,,,
al or accumulated clams, shells and .'. 6 .'. C, . entrapped debris. '. c
- f ' ' " ' ' *g r. ' Q \ ' -. 33] 5 L'rM' *G ." 5$
Physical control measures consist Jo.Q'p,Q{37,
;q 4 . : J '8' Q V ,j.; --
@ ',' 1 --
.dQ primarily of dredging and vacuuming '
adult clams from accessible low ve-
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in order to reduce the severity of *h b. " - D clam infestations wit h chlorine or uth-er oxidizing biocides, such as bromine .meroscopic A siauc clam larvae pass througn power piani entpe screens and g<ow to a toAng and chlorine dioxide, continuous, un. see downsneam inese tresn water ciams cemonsoate me iuanty of screering cevices N . _ _ - _ - - - _ . _ _ - __ _ _ _ _ _ _ _ _ _ _ _ ____ _ _
I l grams employing the new mollusci- containers, using standard metering that once the organic active material > cide range from simple estermination pumps. Since the containe'.s are re- are adsorbed, the ino!!uscicide no applications at intake structure.s and turned when empty, costly on site longer eshibits tosicity with regard other in plant colonization areas all storage and handhrig facilities are to fish, the way to large-scale plant wide ap. not required. Molluscicide applications are tai-plications involving multiple reser. Environmental considerations 1 red to make the best use of these voirs and ndles of pipe. The frequency passive absorptive properties. If of application it ba>ed on the clams' In contrast to chlorine or other oti- required, the detosification proccu 8easonal spawning activitie, 'a nd the dizing tuocides, the new mollu>cicide can be accelerated by the addition of vulnerahihty of the system to clam involves short appheation permda sperine detoxification acents An an-mfestation, and small product requirements. alytical method using preparkaved . After the initial application and re- These result in only minimal chemical tragents and a photorneter also te moval of large shells, periodic appli- additions to the environment. More- available for monitoring product cations . ire made to esterniinate lar- over, the chernical n rapidly neutral- concentrations. vae and juvenile llen than L-in. dia.) ired or detou0ed. The active constit- The rnaterial has been registered clam.<. This prever.ts shell growth to a uents are short lived because they with the 1:l'A by liett 1,aboratorit 8 fouling 8 ire, which would occur in can be adsorbed onto a variety of sub- for use against Asiatic clams in once. Ju> t a few rnont h3. strates. includmg suspended solnis,. through and recirculating couhne The liquhl molluscicide i3 thspented sediments, and even the surfaces of systems, influent systems and fire-easily frorn portable 300-gal. bulk cooling systems. Studie8 have show n protection systems. I 1 i
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n-- T0XICOLOGY MD i"El5_[ LABORATORIES. INC. LABORATORY % soventoN noco.mtvese r=a mo.:v.u e a m r 3 e.aee mco.1cm 17a 4.w.ra e :me r m ec -_4e t "; cd 7..".'..._.e."...'._' "'c _ . . . d. c a l c c. v. and C.w.e 4 s m . ,f ( .c. z. . . .m. , Presented at rcren:c, Canada Meeting Oc cher 28 - Ncvember 2, 1989 _ t en. v a.m.1G C-u.<a:w. u f- ,. r .o r-.. n-.'
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ebra mussel in
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i i 4 P ro cita c e st lig SGI for DETZ 6905-05 w.12 8 no, 7b l Clam-Trol C7~1 Efficacy To Zebra Mussels t 1 1 j % Mortality: 12 hr. Exposure at 1' C ) 100 - 90 -
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I P ro el t e c J 19 SAI for TIETZ 6905-03 w.12 8 gg, , i Clam-Trol C7~1 Efficacy To Zebra Mussels l % Mortality: 14 hr. Exposure at 15'C 100 - y gy , mf I; h E f l 60 - fff pt < A ^ 60 20 - l j O :,, 24 hr. 48 hr. 72 hr. 120 hr. E 5 mg/1 M 10 mg/1 0 15 mg/1 t i
i ! l P r o et ti c e .1 I,9 SGI f o n- IlET2 6905-04 w.1211 no, I i Clam-Trol CT-1 Efficacy To Zebra Mussels i \ l % Mortality: 24. hr. Exposure at 15'C l 100 - v- , l" f 90 -
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- O '*llilacis en- ro- co-ence lastitute of Toctviology * ~ . t y April 1,1990 .
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- i 1 New Treatment Employing a Molluscicide for Macrofouling Control of Zebra Mussels in Cooling Systems L. A. Lyons and J. C. Petrille O Betz 'aboratories inc.
Trevose, PA S. P. Donner and R. L. Fobes Consumers Power Company Jackson, MI [ . >
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- Detroit Edison Company Detroit, Ml
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P. W. Althouse, L. T. Wall, R. M. Post, and W. F. DucrDer Betz Industrial Trevoso, PA l l O 'TBetz DWdhn9%s10 c1090, Detz Industrial. All Rights Reserved.
tJEW TREATMEtJT EMPLOYltJG A MOLLUSCICIDE FOR - MACROFOULitJG COi1 TROL OF ZEBRA MUSSELS !!J COOLitJG SYSTEMS l
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L. A. LYONS and J. C. PETRILLE Two power plants near Detroit, idichigan received the Detz Laboratories, Inc. Trevose, PA first CT 1 applications durinD the fall / winter of 1989.The J. R. %hlting Power Plant, a 3-unit (350 fd#, coat fired f acility, received 12.hr applications to esp main circo-G. P. DONNER and R. L. FODES lating and service water system. The(nrico Icrmt 11 Consumers Power Company Nuclear Power Plant, a 1 unit (1100 idW) facility, Jackson,foi received a 1Ehr CT 1 application to the service water syr, tem.1ho perf orrinnce of these applications was bio- i monitored using flow through bloboxes. Mortality l F. LEHMANN responses were cmrelated with dosage and water tem- l Detroit Edison Company perature. Recommendations for optimizing treattner.1 Detroit, Mi proorams based upon seasonal ambient water tempera-tures and the degree of mussellnfestation are provided. P. W. ALTHOUSE and L. T. WALL Detz Industrial Granger, IN If1TRODUCTIO!J Zebra mussels are estimated to cost the Great Lakes region 5 billion dolturs between 1000 and 2000 (1). 2 ebra R M. POST and W. F. DUERGER mussets will adversely impact commercial fir.herles, Betz Industrial Trevoso, PA recreational activities, potable water suppilers, end industry. They will also significantly . tor the ecosystems of these lakes. Zebra mussels are expected to spread throughout the Greal lakos and to many rivers and tak es of Norin America within the next 5 to to years. ABSTRACT O Tne zeera messei is a cutoPeaa moi'ecx taai na-infested the Great Lakes within the past few years. This ported to the Great Lakes in 1900 via the ballast water in a s@ ogndng kom a hropean tmshwaw pm new post is extremely prolific and aggressively attaches a mussds wem ksmud Mau R Cak h M to all types of surfaces. Power plants situated around Presently, Zebra mussels are found throughout Lake Lake Erie and Lake St. Clair are experiencing extensive Die; the most extensive populations are In the Westem mussel macrofouling, incidences of macrofouting Basin. Scattered populations of Zebra mussets have include colonies of more than 500,000 mussels per been reported in Lake Ontarlo and a few mussels have square meter; these mussels completely cover all sur- also been found in Lake Mgan's Gmen Bay face areas of Intake bays, plug ch!Iler units and main condenser tubes, and grow within service related cool- The prolific and rapid growth of Zebra mussel popula-Ing pipes.There is an obvious danger of forced outages tions atlett to the nood for a monitoring program at raw if preventative measures are not taken- water intakes.These monitoring programs provide tur-veillance for mussel infestation and determine the A nonoxidizing mollusticide, Clam-Tr018 CT 1, which is degree of colonization and fouling within a cooling t,ys- providing state of the-art contr01for Aslatic clamfouhng iem.This rapid colonization has been exemplified atthe in power plants, has also demonstrated effectiveness in Detrolt Edison Company's Monroe Power Plant located controlling Zebra mussels.The results of efficacy deter
- On tneWestern Basin of Lake Erio.The densities of Zebta minations from laboratory studies for ClamTrol CT 1 at mussels f ound in the intake canal at the Monroe station concentrations from 5 mg/L to 15 mg/L, for exposure have increased exponentially from 50 mussets/m2 in the periods of G to 24 hr, and at water temperatures of 11 'C- f all of 1988 to greater than 700,000 mussels /m2 in the fall 15 *C, and 20 'C are provided.The optimum CT 1 appil- og3ggg(p),
cation f or mussel fouting control will be dependent upon dosage, exposure period, and water temperature. It is Th!s macrofouting pest aggressively attaches to all anticipated that many systems will require seasonal types of hard substrates, including cement walls, t.creens and trash racks, pump housings, pipes of applications (2 to 4 times / year) based upon growth rate, assorted metallurgy, plastic, rubber, and so forth. They spawning season, and extent of setting by mussellar-ieoo io 'orm iarce c'es'er= ov at'a "'ao io eaca otner l O vee-1
l (see figure 1).The formation of clusters of mustelt near rate Lexer.) and mata'e i nually within one year i u1:h7D. or within the intake Ltmcture of cochng systems thf eat- tion is ex1ernal and females can relente tpproximately ens circulation pump eperation and lncreates the pcten- 30.033 to 40,033 ( ggs per year.1he ferlihted ( ggs 1.at cf a forced outaDe. In add. bon, in the vehger larval t,tage, this muttel will pass through all Intnke tcreens develop to a planktonic vehger larval ttage; the larol stage is microttepic (0.1 to 0 3 mm). The planktonic g and in line backt t t creens end will Lettle within the cool- vehger stage lasts 1or B to 15 days daing v.hlch they are l Ing syt, tem. The ja/enlle mustels can encrust the entire surtate areas of pipes. Encructation can impedo or com-ditperced by the water currents of lakcs and rivers. In Lake Eric dur!ng 1M9, vehgers numbered from 40fo3 l pletely restrict the flow of water through there ppes The vehgers/m3 in earl / Eummer to 500.003 vehgert/m 3 h ,
, cma!!er d;ameter pipes within service water and refety late summer (3).
related syt.! ems are particularly vulnerable. _ n:le mussel tta10 to begin the todontary Ife. lhey Biology of the Zebra f.1ussel teen te mcalitem for exhg to we um The reprodJctive capacity and hf e history charactirittics Attrhment by the Dyttal tha ads is qude tenacious and able to withstand wattt velociUes of 3 to 5 f;/tec. Zebra of the Zebra mussel, Dreissena poymorpha, explain the t.uccessful invasion and rapid colon! abon to aquaUc mustels tend to te qu:te gregarious; they colon::e h environments. ReprodJction of the 2ebra muSLf!s Is rDasLlve Clutters End m3tS. highly prohfic with a tpawning season ex1end;ng from the tpring,when water temperatures flse above 12 *C t Controf f.icthods: European Experience 15 *C, to October. Zebra mut,sels are dioecious (tepa. I Contr01 measun s employed in Europe f or f ouhng cont:ol
' ,5. - 5,'.1 2 N5 h Nelacs of Zebra mutrels has involved mechanical / physical g . - _. a x'.L: q.a.pa.pQ,i'gA4~.% methods (4,7,9) and the ut.e of oxid: ling chemica!s v.s y .wpp m v ..w w ( n ,U p ;
(4,5,6,c), ., y . . -> . c . m e4. . , + s . . - .t ~ - . < M ;.[.. ., ry .. ij The varlous physical / mechanical control methods L.SM@g'p ' Ma include: clenn-outs, piping replacement, tcreening and ttraining,thermalbackfluthing UltraLonic v;btatich, and I, p -$ M I',p,;. t
' Ele:'
p electrical thctk. Clean outs f or the removal of mu:tels ~ and the replacement of piping requires cchedJ ted ptant W., /A [. t outages. Although screens and straincro do nct prevent [ " the entrainment of juvenite or larvalvehgert into the coS ing syr tems, thej are necessary to preyc nt the trantpo1
' of adu!! mu;Lt!s or clusters of mustels funher into a cochng system. Thermal backflushing of heated con-M _~
denser water can provide fouhng control for telected ar.
,J eas of a coohng tystem, usuauy intake bays. For thole
~~*
r f acihtles having thermal treatment capabibbe s, a 15 - 63
.grM jM min application at 40 *C will effectively control muttel Infestations. Ultrasonic vibration and electrical thock
,,fMt.@ have also been attcmpted in Europe with varying
.... N C d degrees of CUCCets.
y 7"* b i 4$'h[D Mt C. .C.19 y. J 8 Chlorination is the most common chemical control for Zebra mussel fouhng. Conhnuous chlorinahon f or 2 - 3 P 4
- w. m f. r ,@4wpH week s is required to achieve efficacy. Interm;ttent chlori.
Fh . fp p .g (u sq v ,1a ' j nation programs, thal f eod a tew hourt e ach day are intf-hk ,_ # C;;3t]l.c'E U. C d fective. The application of other oxidizing chemicals (e 0., bromine, olone, hydrogen peroxide, and pctas. t,tum permagenatt) lc restricted because they ar e co;Uy, FIDure 1: Cluster of Zebra Mussels Attached to a Native Mollutk Shell envimnmentaHy prohbuve, or impractical to d:stribute tnroughout a cooling Lystem. 2
CLAM TROL CT-1: f40NOXID12lt1G neutralized by either passive or cetive processes. Both MOLLUSCICIDE *, CT 1 actives (Qual and DGH) aro t.hort lived becauso they are readily adsorbed by naturally occurring sub-O clamnroict 4 nateatedior use a= a aoooxio> iao moi-lusclcido, is a water miscible formulation containing two st'aie ia=iveiao $iiis. ciav=. =ueneaeee soiies. no mio acids, and even the microfouted surf aces of cooling sys-cationic surfactant 5: alkyldlmethylbenzylammonlum tems. Studies (10) have f.hown that once the actives ero chlorido (Quat) and dodecylguanidino hydrochlorido adsorbed, they no longer exhibit toxicity. If required. (DGH). Clam-Trel CT 11s USEPA registered for use as a CT 1 applications can be actively detoxified by applylng mottuscleide for onco-through and recirculating cooling a blend of clays (Detz DT 1) to the treated water (11). systems. This motluscicide presents two significant fea. Clam Trol CT 1 treatment programs are designed to - tures: the ability to eradicato mollusks,like Zebra mus-sels,when applied for only 6 to 24 hr and the ability to be neutralized prior to dischargo. eWg@m6 mAauOMMw ment approach is often used to focus applications to specific creas or system components. Molluscicldo CT 1 Applications: Zebra Mussel Fouling requirements are further mlnlmized by reducing flow Control rates or using static treatments whero possibto. This molluscicldo presents an unique advancement in To obtaln discharge permitting approval from a state reg-the art of macrofoullag contrul; Clam-Trol CT-1 eradi. utatory au'hority, an application package would include: cates adult and Juvenllo Zebra mussels in cooling sys. a description of the macrofouling problem to the power tems using feasible, cost effective, treatment regimens, plant and the need for control, CT 1 product description When applied, CT 1 remains substantia!!y undetected (constituents, MSDS, and aquatic toxicity data), CT-1 by the mussel, which siphons in a lethal doso during an app!lcation procedures and expected discharge con-application period of 6 to 24 hr (depending on dosage centrations, a description ot the monitoring program dur-and water temperature). A delayed mortality response inD treatments, and a description of the detoxification occurs following the brief exposure period. program (if needed). I Periodic applications during the spawning and mussel Application Experience: Aslatic Clam Ma-setting period from May to September will provide eff ec-crofouling O i've cooiroi o' zeora mvseei'o iioo.T<eatmeot anni >==- tions will focus upon the eradication of juvenile mussels Since 1986, Clam-Trol CT 1 trealment programs have to prevent their growth to adutt size and to prevent the been providing state of the-art macrofouling control for accumulation of mussel encrustations within the ccoling fouling caused by Asiatic clams in freshwater cooling system. Once the juvenile mussels expire, they will systems (12). Seasona! applications (2 to 4 times / year) detach and pass through the cooling system. Tla fr'" provide a preventative treatment program by focusing quency of app!! cations (2 to 4 times / year) will bt r,te upon the eradication of juvenlic clams and preventing specific for each cooling system since the degree of their growth to adult fouling size. The eradication of juve-mussel infestation will vary ftom one system to another. nile clams that colonize intake bays has eliminated the A monitoring program to determine tno extent and need for annual cleanouts of adult populations and pre. degree of musset infestations can be ostablished by vents the threat of forced outages due to macrofouling at using monitoring devices (i.e., Detz Macrotracker) and power plants (13). Seasonal CT-1 applications of 12 to suspending substrates located near cooling system 24 hr to the safety related and service water systems of Intakes.The degree of infestation, rate of mussel growth. nuclear power plants are also providing a better control and the the effectiveness of molluscicide applications aiiernative than continuous chtorination to assure the un-can be monitored with these surveillance devices. obstructed operation of these systems (14). In addition, industrial f acilities are employing Clam Trol CT 1 treat-Environmental Considerations ment programs for the eradication and control of Asiatic clams for their entire process systems. The application , la contrast to continuous chlorination, Clam-Trol CT 1 experiences for Asiatic clam macrofouling control treat-treatment regimens have short application periods, ment programs are directly applicable to the developing small product volume requirements, and can be readily Zebra mussel fouting control programs. O 3 ,
i I 'M - ,c' LABORATORY EFFICACY STUDIES: ' [ Q ZEBRA f.iUSSELS , ,
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2ebra mussels 10 to 20 mmin size,were coliccted trom #9so . the intake canal of a power plant in Lake Erie in 1999 ) 43
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- 33 .
" m when'omblent water temperatures were 5 to 7 'C The k h f p
mucfels were r, hyped in these cold water conditions to ;o . Octz' Aquatic Toxicology Laboratory in Trevose, Penrw 3o . p _ o sylvania.The mussels were fed twice a day with algae 24 6 12 24 6 12 24 and gradually ace'tated over teveral weeks in recircu- nne,,, 6 ,12 59 Ned (o eq (i 3; (i pf; lating culture chartiers to three temper ature regime s: 11
'C,15 'C, and 20 'C. ["])9e9 CT 1 concentraton petr . mat cone) f For the efficacy evaluations 20 to 25 mussets were trans-F10ure 2: Clam Trol CT 1 Efficacy to Zebra f,ius-f erred to S L gtats aquaria and givon a 24-hr acclimation sels at 20 *C period. fAussets that did not reattach within the test aquaria and were not actively siphoning were removed.
Static renewal bloa ssays were initiated by replacing the 100 I culture water with different concentrations of Clarr> Trol M ' CT 1 test solutions: 0 mg/L (Controf),5 mg/L,10 ma'L, 80
- and 15 mat. Following exposure periods from 0 to 24 hr i
for each test concentration, randomly selected test (hqM '
~
aquaria were renewed with fresh cuttpro water. Delayed )$ M
- g' M ,,,,
mortality responses were monitored for several days f ol-lowing e ach exposure. fAortality determinations were re. e { 40 30 j ,,, e corded v,tien the b! valve shells were gaped open and " M ~ 9 did not respond to gentle prodding. In many cases evi-dence of tissue putrefaction was noticed fAussels that to 0 g Q Q were ative 10 the control and trealment tests were usuatly 6 14 24 0 14 24 6 14 24 Appheaton 6mn 10 mot % mg1 actively s) phoning. (% R3) ( ou ) Results conna. ms cT.1 concentratm ew. mos cone) The mortality responses of these laboratory officacy Figure 3: Clam Trof CT 1 Efficacy to Zebra fdus-evaluations correlated with CT 1 dosage, exposure peri- sels at 15 'C od, and water temperature, figures 2,3, and 4 present the cumulative mortality responses 4 days after the CT 1 applications Note that Clam-Trof CT-1 contains 13% to-
- tal active concentration. Thus, Clam-Trol CT-1 concerv 80 ~
trations of 15 ma'L,10 mg/L, and 5 mnfL contain total ac-
# 80 ~
tive concenttallons of 1.95 mat,1.3 mg/L, and 0.65 mg/ L, respectively. $M t 3 e. 00
~
At 20 *C (see Figure 2) mortality responses of 70% and / S so - 90% were achleved at 10 mg/L as CT 1 f or crposures of I) 4o - 6 hr and 12 hr, respectively. A G-hr application of 15 mat f
- ao as CT 1 caused a 100% kill at 20 *C. At 15 *C a Shr 3 co -
application at 15 mg/L CT 1 caused 50% mortality and a to - 14-ht, application at 15 mg/L CT 1 achieved 100% mor- o 12 4 4 tality (see Figure 3) The 10 mat CT-1 applications for AP,ngi m 39 1,2 9 Ehr,14-hr, and 24-hr caused 20%,70%, and 100% mor- Moun) (1.3) (1.3) ! talityresponsesrespectively,at15 *C.Then,at 11 *Cet* spnng.1989 cT 1 concentraton getra mot cone) ficacy data becomes more variable, but 12- and 24-hr Figure 4: Clam Trol CT 1 Efficacy to Zebra FAus-apphcations of CT 1 at 15 mat achieved 80% to 95% mortalities (see Figure 4). seis at 11 *C h 4
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I ! I i ! l FIRST 2EDRA f.iUSSEL TREATf.iEllTS - A p " % g,. ,@ M Two innovative treatment programs employing CT 1 O [' - applications for Zebra mussel fouling control were cord
.I [ , @ ,, f ,.; ,
D' ducted at Detro!! Edison Compar.y's Enrico Fermi 11 -
- p. 3 . , , .,
p i tJuclear Power Plant and Consumers Power Company's 2, ; , N J. R. %h; ting Power Plant. Both power plants are lccated .g p .. Q M( ) ,' 4 C3 near Detto;t, use Lake Erie water in thel {cochng sys- - ] . y{,, . . ; . '; ,, , ( %, j i tems, and were experiencing 2etira mosselinfestations %.S (. r . y.,s...N',,[4 i necessita!:ng preventaUve fouhng control measures. .{e .- *" k4 l
-l .' I.'h ~, -'yl[. ':. ,J l These first Clam-Tr01 CT.1 applications were conducted q.9.. 4 % .
in iJovember/ December of 1989 during a period when {- : ,J. m ,. . .g ; . 3
'*;'3 ^ .'r ambient icke water temperatures dechned to below $ '.[ 0 , ,
f I ! ' C. These severe temperature cond;tions were erpected to hamper ophmal treatment programs. Bio- (g .
',. , [, .
l l mon;toring cf treatment effectiveness was conducied at .
\ g N- '
both power pinnts. The erectiveness was cctre!ated j with CT 1 dosage and water temperature. [. A . -d .1 - 7, j
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l COllSUf.1ERS POWER COf. IPA 11Y J, R. WHITitlG STATIOlj rtgure N 2ebra Mussel routing of a Coeling i Loop, J. R. Whiting Station
Background
mussels and meet env!ronmental discharge require-The J. R. Whiting station, a 3. unit (350 MW), coal. fired ments. This program was implemented in December cf generating power plant, first reported Zebra mustels 1959 ! within plant water systems in Ju!y 1989. The mussels
- A* were Initia!!y noticed uniformly attached to the cenerete f.iolluccicido Application Procedures ,
walls of the plant's oH-water (API) separator at a dentity Treatment cf the Whiting station consisted of severalpro-of 1 mussel per 4 in. A rapid infestation occurred during cedures includ ng segmented treatment approach, taow - tne f allowing 4 - 0 weeks. The fish deterrent nets situated rate teduction of treated syttems, detoxnticahon, and across the intake canal became to Infested w!!h recirculation of heated cooling water to the intake to attached mussets that the weight of the mussels caused f also the ambient water temperature. These procedures tho nets to be pulled from the bottom duc to the restricted helped minim!ze the amount of motiusticide required flow through the nets. During one week, the nets had to and mect the d,scharDe permit requirements. They ak.o i be changed twke, increased the efficacy of CT-1 applicahons. ( in September an accumulation of mutsels in Unit 1 corF As part of the segmented treatment approach, separate I tt!buted to a shutdown for cleanout and repair of equ!p- rnolluscicide applications were fed to each of the three j ment. Approrlmately 4 ft 3to 6 ft3 of Zebra mussels were main condenser circulating water systems and the ser-water blasted out of the condenser. Zebra mussels were vice water system. Each system received a 12 hr CT-1 ' c!so found in the house service water system. The water opfhcahon. Figure 6, a r,chematic of the Whiting cochng 1;ow to the bolter feed pumps had been restricted by systems, shows three separate lntake bays - each con mussel clogging. These blockades required that feed sisting of two main circulatory pumps and two service pumps be switched and cleanouts be scheduled durin9 water pumps. Since all six service water pumps feed to a ! the weekends w+1en load was reduced. Figure 5 shows common header, only a single feed point was requ! red to ertensive touting and impingement of mur.sels at the apply Clam Trol CT-1 to the service water system. Inlet side of a cooling loop. ft also shows many of the ! tubes plugged with mussels on the ouuct side. For each of the main circulating systems, CT-1 was t apphed directly with a sparge header, which was posi-This mussel infestation created extensive macrofouling tiened in front of the intake bays, upstream of the travel-conditions that threatened equ!pment operation and I.ng screens. To minimize the amoun1 of CT 1 fed, cnly ' Jeopard zed plant avalabitty. A mo!!uscicide treatment one of two main circulating pumps was operated this ! h control program was designed to eradicate the Zecta reduced the flow rates to the unit being treated. Tabte 1 l _____._m___.____ _ _ _ . _ . _ _ . _ .
, - . - - ~ - - l t l 1 Detoxification of the serdce water system cpplication l 4- -- Dischange canal f was not required because treated water was rerouted
' k w Na a p s. S UM M 2r vt M .y cnha dd " # % n x t was measured using an analytical photometric method h j 5 2 _g$ c
$ $ ~) (15) with a detection limit of 0.1 ma'L as ClamTrol CT-1 (or 0 013 ma'L as total acilve concentration). All out'all J
i h*a o Oe y unn 2 Mwn _ samples collected during each 12-hr oppticahon were condens" I rmt#y Je nocte99 W W ' g """> $,En'*C ""* * / 10 incteat e the amblent intake w ater temperat.re, a por-j V tion of the heated discharge water was retircu!ated to _ ' . - y[cstn c
- vj @ P' the intake canat during mollusticide appl;catlon peri-ods Increasing the t,iphoning and metabolic activit/ cf
, we tne Tra e n] So eons OeWlC01 the Zebra mussels by c:evating the intake water temper-ature would aid in increasing the mo:1aht/ responses. ! Figure C: J. R Whl ting Plant, Consumers Power The ambient intake water temperatures were between , ( Company 0 'C and 2 'C. The rec!rculated water provided a A T : j ' bet,veen 2 'C to 0 'C. 1 Table 1: J. R. Whiting Station, December 1989 ' Results of J. R. W, hit,ing Applicat, ions Each of the mo!!usticide app!! cations at the J. R. Whiting r a e Arpacaten t. . A an station was assessed with blomon!!oring procedures. i nres Treatec* penad (mg u (mg M (mg M (mg u (GrM) (GrM) (hr) Flow through bloboxes were positioned at the Intet and l i outlet ends of the treated cooling systems (see Figure 7). Un!! 1 CE CO3 33DCO 12 43 13 9 e9 NDS Approximately 40 - 80 Zebra mussels measuring 4 - 20 Un:t 2 faoao 33to3 12 12 6 17 0 14 8 ND mm were placed in each blobox. Constant water flow was maintained through the bloboxes during each of the Unit 3 90.oco 4'. co) 12 11 5 1s 5 14.3 No 12-hr applications and f or sevual weeks following each sws' 3 400 3 400 12 No8 at 0 14 3 No epp!! cation to mon: tor delayed mortat.ty retponses. f/.ussets were dead when the bivalve shells gaped cpen
- new ra's was redated by envatng on'y one of tuo circutatng l pumps This mimmited the coahng waW txeng t'ented and did not Close when gently prodded. The Control rnuscels had CumulatNe mortaldy retponses of 0 to 2%
I
- ND = Nons.cWe (< 01 mg1 as Ciam-Tror CT-1 u < 0 00 mg t for the duration of the monitoring period.
l taw a:tve conematon). !
- SwS - Ecwe Woor sy-tem 8 The it+d pump to t 1e seWe wa:er system aas ino;crabe for r.hort
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l presents the flow rates of each unit, the reduced flow
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rates of the treated cochng water during the 12-hr appil- - -~ - ~> cation period, and CT-1 concentrations measured wdhin
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k .Y . the system being treated and at the ov' fall to receiving . a.
. .,s J' .lL waters. '. %%* ' '.** . * -= ,*.-
.= ,;,
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s 4 All the cooling water from each system converges at the E' inlet end of the 1/4 miie d.scharge canat The m!xing of ". .
the tre ated water with the untreated coc'.ng water helped a ' f 3, I reduce t'ie residual CT-1. Detoxification of tne remaining , y.. - , CT 1 residual was achieved by feeding Bet: DT-1 (a ,e. . . 4
=3,,,%.-?
blend of benton!!e clays) direct;y to the discharge canal. ? + ~, The clays werd fed using a powdct screw feeder at an I . Kf[@< approximate feed rate of 1 m3/L of clays for each 1 mg'L 0' -
- *M +*
l ' of residual CT 1 to be detoxified The average clay cord centrations fed dJrlng the treatments of Units 1,2, and 3 Figure 7: Flow Through Bloboxes for FAonttoring were 5.9 mg'L, 6.7 mg/L, and 8.8 mg'L respectivel/. the Efficacy of Applications h 6 l -
The mortality responses, which were monitored at the N *th inlets and outlets of the units treated with 12 hr CT 1 *'*] I applications, correlated with water temperatures (see Figure 8). Mortalltles of greater than 95% were achieved f st the outlets of units where water temperatures ranged N Mam from 14.5 'C to 19 'C. At the inlets of the service water Dwant system and at Unit 1, mortality responses of 5% or less . resutted when the water temperatures never exceeded $$l yy dh,
+-
4 *C or 5 *C. Units 2 and 3 had inlet water temperatures of 6 *C and 8 *C; their mortality respenses were 43 and j j g tr.s - 26E g,,, er ras < DETROIT EDISOt1 COMPAt1Y EllRICO , @-_@ ,j FERMI 11 IJUCLEAR POWER PLAT 1T o,n.,, s,nx, csw weer system p pQ _ g Background gMem,w3 m., The Enrico Fermi Il Nuclear Power Plant is a sin 0 o-unit t (1100 MW) facility witi; a recirculating cooling system FIDure 9: Enrico Fermt ll Nuc! car Power Plant' Detrott Edison (see Figure 9). The main circulating cooling water flows from the c Dng pond through the main condensors to the hyperb ic coollag towers, then retums to the cooling exchangers, and main turbine tube oll coolerr. All Zebra pond. The Tiakeup water to the cooling pond orl0inates mussels were juveniles from 3 to 5 mm in s!ze. In the once-throu0h service water system, which uses raw water from Lake Erle. The decant or blowdown pipe Molluscicide Application Procedure of the cooling pond is the point of discharge to Lake Erle. Clam-Trol CT-1 was appfled at the service water pump Zebra mussels were first found colonizing the concrete intake for 15 hr. This app!! cation was initiated v. ten the walls of the service water Intake structure in late August. Intak e water temperatur e wa s 4
- C. The intermittent chlo-r 1989. Diver Inspection of the intake structure reveeled rination treatment for the service water system was termi.
\
uniform populations of 20.000 mussels /m2. Subsequent nated 24 hr prior to feeding Clam Ttol CT 1. This proce-inspections of the service water components durlog the dure was necessary because Zebra mussels will close refueling outage (September - November, 1989) their bivalve shells in the presence of chlorine and thus revealed mussels attached to the service water pump would not be actively ciphoning during the CT 1 applica-casings, reack' building closed cooling water heat tion. 100 _ To prevent any release of residual CT 1 to Lake Erie, the 90 - c@ ling pond blowdown was terminated and the servic> EInlet
, water pump suction was switched from Lake Erle to the 80 O Outlet cooling pond. CT-1 was applied directly into the service 70 - 14.5 *C 18.0
- C 10.0 'C water pump suction pit via a sparge header. The entire d go -
service water flow enters the cooling pond and provides j SO . a significant dilution of the CT 1 treated water. To provide
;g . ~
furtber neutralization, the service water pump suction == g 40 remained in recirculation mode (suction from cooling ! 30 - 6'C pond) for 10 hr after CT 1 application. To complete the 20 . neutralization process, dry clays (Betz DT 1) were fed to i
, 4.C 5'C i
- g. E umumunni The fire protection system was statically treated during HSWS Unit 1 Unit 2 Unit 3 this service water application.The fire protection pumps Location take a suction from the service water pump pit. Treated l CT-1 service water was fed to the fire protection system j Figure 8: J. R. Whiting Power Plant / December upon analytical verification of a targeted 20 mg/L CT 1
- 1989 Zebra Mussel Mortality concentration in the service water. The fire protection Responses
- 12-hr Clam Trol CT 1 system was closed once the CT 16pplicatlon was App!!catlons injected into the system.
7
1 I Results of Fermill Applications 100 I DO - Applicatlon Period: 15 hr l ! Two flow-through bloboxes were positioned within the d 80 , CT 1 Concentration: 21.5 ma'L : service water system to monitor the efficacy of the 15-hr 5 - application Each blobox contained approximately 60 - 370 00 100 mussels and re9lved service water continuously , during the application and for 42 days following the j'50 - app!! cation to monitor the delayed mcrtality response. [S 40 - Clam-Trol CT 1 was analytically determined each hout - during the 8tpplication (Son Table 2). The average CT-1 O h30 , concentration was 21.5 mg/L. g 10
" g Figure 10 presents the delayed mortality responses fol- 0 lowing the molluscicide appilcation. The 4 ;C water tem.
Bloboxes 1 2 1 2 1 2 1 2 perature causes a slow mortality response. On day 27 the delayed mortaFty responses were 39 and 42R The (Days) final mortaDtics of 62 and 73% were achieved on day 42. The higher mortality responses for the Fermi 11 applica- Figure 10: Enrico Fermi il/Servlee Water System: tion compared to the Ir:!et responses at the Wh!!Ing S'.a- Zebra Mussel Mortality Responses tion can be correlated with a higher CT 1 dosage (21.5 mg/L at Ferml11instead of approximately 15 mg/L dos-ages at the Whiting Station) and a longer application CONCLUSIONS perbd (15-hr at Fermi ll Instead of 12-hr at the Whiting Station). The objectives of a Clam-Trof CT-1 treatment program for Zebra mossel fouling controlis to eradicate the juvenile mussels and to prevent the accumulation of mussels withinthe cooling system.Thefrequencyof applications (2 to 4 times /ye ar) required to achieve proper macrotout. Table 2: Fer.nlli Nuclear Power Plant CT.1 Analy- , Ing control will be site specific f or each cooling system. sls of The Service Water System Certain systems and specific components may require more frequent applications. A mussel surveillance pro-Sampling Time gram to monitor the occurrence and extent of mussel During Treatment CT 1 (in mg/L) Infestation end their growth within a cooling system is , l (in hr) recommended as bn integral part of the overall proco- . l dure for a Zebra mussel fouling control program. l i 0.0 0.5 14.1 if Zebra mussels are known to be colonizing a particular 1.0 15.2 area w!!hin the general geographic region of a power l. l 2.0 17.7 plant, the following steps are recommended: , 30 18.3 . 4.0 27.7 Step 1: Establish a mussel surveillance program at tne l 5.0 21.0 cooling water intakes and within the cooling l system, particularly, at the safety-related and 6.0 27.8 . 7.0 26.3 - ;. service water r.ystems. y 8.0 i Step 2: Develop a treatment strategy for applying the 9.0 . molluscleide to provide touting contr01 and also 10.0 21.0 to meet discharge permit requirements, imple- : ! 11.0 21.6 ment procedures to obtain approval with the ' 12.0 22.0 regulatory authorities. Note that approval can 13.0 23.2 often take several weeks. 14.0 24.3 15.0 23.7 Step 3: Maintain a vig!!ance of the foul!ng. Zebra mus-sol fouling can abruptly develop into advanced Trbatment Stopped Average = 21.5 mg/L fou'hg that may require a cleanout of it's system before protective treatment program initiation. h 8
Step 4: Apply Clam-Trol CT 1 treatments based upon responses of > 95% achleved at the condenser outlets the extent of mussel infestation. Optimize the of the J. R. Whiting station (see Figure B)wtion wahr tem-CT 1 applications (6 to 12 hr) when water tem- peratures ranged from 14.5 'C to 19 'C and from the iab-oratory efficacy studies conducted at 15 *C and 20 'O f) peratures are 215 'C. V (see Figures 2 and 3). Even CT 1 applications as brief as At Fermi 11 a preventative treatment pro 0 ram was 6 hr when water temperatures are 20 'O should provide implemented to climinate any impediment to water finw effective treatments in July and August. of the once-through service water system. Preventing J Woen Clam-Trol CT 1 must be applied during the colder macrofouling within this service water system is essen-months of the year longertreatment periods of 24 to 72hr lla! for the operation of this nuclear facility. The initial ~~ will be required or intake temperature should be efe-1989 CT 1 epplication provided mortality responses of 62% to 73% when tha water ternperatures were 4 'C. vated to 215 *C by recircutating the heated cooling wa-ter, Applications will be resumed in the spring of 1990 based upon a musset surveillance program. The threat posed by the Zebra mussel has been well-documented in this paper we have described a very At the J. R.Wh! ting station Zebra mussels are well estab-lished within the vicinity of this power plant and will practical and cost effective treatment program that has been successfully applied at tyco power plants. The requ!re a regimented molluscleide treatment program to effect of water temperature on the treatment is important protect equipment and maintain plant availability. CT . and is also thoroughly reviewed here. Successful Zebra was f ed in segmented applications (12 hr or less) and the amount of molluscleide was minimized by reducing flow mussel control in power plants is achievable, rates.This provided an eff ective means of controlling the chronic infestation at this f acility. In addition, the detoxifi- REFERENCES cation potential of this molluscicide provided a means of eliminating toxicity at the discliarge. 1. Mallory, M., 'The Tiny Mussels Choking the Great s", Business M, hary 4, un The monthly Lake Erie water temperatures medsured at the intake of the J. R. Whiting Station from May through 2. Griffiths, R. W,; Kovetak, W. P.; Schloesser, D. L, September were 15 *C or greater (see Figure 11), it is .The Zebra Mussel. Dreissena polymorpha, in during this period that spawning activity and inflttration of North America: Impact on RawWater Users *, EPRI Q Juvenile mussels or vellgers into cooling systems occurs. Theiefore, most treatments should be applied Service Water System Problems Affecting Satety-Related Equipment Seminar, Charlotte, North Car-between May and September for optimal foullng control. oilna,1989. Optim!:ing preventative treatment programs by applying Clam-Trol CT 1 for 12 hr or less can be successfully 3. Ganon, D.; Haag, W.,
- Reproduction and Recruit-accomplished when water temperatures are 15 'C or ment of Dreissena During the First inv'eslon Year in greater. This has been demonstrated by mortality Westem Lake Erle*, Conference on the Zebra Mus-sels: The Great Lakes Experience, University of e , Ontarlo, M 25*
- 4. Mackle, G. L.; Gibbons, W. N.; Mancaster, B. W.;
20' . Gray, L M , "The Zebra Mussel Drelssena poly-morpha: A Synthesis of European Experiences
~~ ==
15' - - ---- - - - ----- -
- Ontario, Watcr Resources Branch,' Report, July g
D - 1989.
$ 10* -
Jenner, H. A.,
- Chlorine Minimization in Mactofcul-5.
~
ing Control in the Netherlands", Water Chlor / nation 5* - Vol. 5: Chemistry, Environmental Impact and Health Effects. R. E. Jolly et.al. Eds.,1984. g
- 6. Jenner, H. A., " Control of Mussel Fouling in the 1 2 3 4 5 6 7 8 9 10 11 12 Netherlarids: Experimental and Existing Methods *,
Month of the Year Macrofouling Control Technologies: State-of the-Figure 1L Lake ErleinletTemperature:J.R. Whiting Art, EPRI Report CS-3343, Electric Power Research institute, Palo Alto, CA,1983. Power Plant i l 9 ! 2
?
I i t _ - - . e
- 7. Whitehouse, J.W.; Khalanski, M.; Saro00ta, M. G.; Clam-Trol CT 1, a New Molluscicide", Det: Labo-Jennor, H A. 'The Control of Blofouling in Marino rotories, Trevoso, PA,1987.
and Estuartne Power Stations: A Coltatiorative ResearchWorking Group Report for Uso by Etation Designers and Station Managers *, Central Elec-
- 12. Post, R. M.; Lyons, L. A., *Molluscicido Controls Astatic Clam Problems", Doctr. Light Power, 65 h
tricity Research Laboratories, Surrey, England, (10),26 (1987). 1985,
- 13. Lyons, L. A.; Codina, O.; Post, Rutledge,R. D. MS,g
- 8. Clarke, K. D., "The infestation of Waterworks by E.,
- Evaluation of a New Molluscleide for Alleviat-Dreissena polymorpha a Freshwater Mussel", J. Ing Macrofouling by Aslatic Clams', Proceedings Inst. Wafer. Enges. 6:370-378.1952. of the American Power Conference, Vol. 50,1988.
- 9. Kirplchenko, M. YA.; Mikheev, V. P.; Stem, E. P.
- 14. Mowery, D.; McClellan, E.; Lyons, L. A.; Austin, D.
" Battling Overgrowth of Dreissona at Hydroelectric M.; Karlovich, D. N.,
- Asiatic Clam Control E.rperi-Power Plants *, Sektr. Stn. 5:30-32,1962.
ence at Peach Bottom Atomic Power Station *, EPR! Service Water System Rollability improve-
- 10. Lyons, L. A., " Detoxification Potential of a New ment Seminar, Charlotto, North Carr - . Novem-Molluscleide For Aslatic Clam Fouling Control *,
Presented at the An iual Meetin0 of the Socloty of ber,1989. Environmental Toxicology and Chemistry, Pensa-
- 15.
- Determination of Clam-Trol CT 1 b3 ,.+ . led cola, Florida,1987, Photometric Methyl Orange Cemplexatlon Proce-
- 11. Lyons, L. A.,"Detoxlfication of the Effluent From an date*, Dett Laboratories Anai- r Mctriod D- -
Industrial Cooling Water System Trer'ad with Laboratories, Inc., Trevose, PA.1. Y O
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. Aquatic Toxicity Report _
s Clam-Trol CT-1 Rainbow Trout : 96 hr LC50 " 14.7 E9/1 Bluegill Sunfish : 96 hr LC50 = 4.3 mg/l Fathead Minnow : 96 hr LC50 = 2 . 9 rc.g / l Dachnia macna : 48 hr LC50 = 0.4 ng/l Note: The above LC50-values represent tcxicity' levels for Clam-Trol CT-1 when 100%-of the " free" actives are available to the aquatic organism.(that is, no suspended solids for adsorption of the actives). When Clam-Trol CT-1 is exposed'to adsorbent material (i.e. "- clays, silts, suspended solids, humic acids, etc.), acute toxicity as well as chronic toxicity is-eliminated or greatly reduced due to the adsorption properties-of the active ingredients. l e 4
l l l A0UATIC ! _ai T0XICOLOGY MD E. i t. i _ LABORATORIES. INC. LABORATORY SOME ATON ACAD.T AEVOS E. P A 190<27.u S A / TEL:215 355 33OO. TELEX 1731 16.F Ax a 355 2869 (*e BETZ LABORATORIES,IliC. 4636 SOMERTOli ROAD,TREVOSE,PA.19047 PRODUCT: CLAM-TROL CT-1 8/22/90 AQUATIC TOXICOLOGY SHEEPSHEAD MIlillOW 96 HR. LC50: 7.0 MG/L MYSID SHRIMP 96 HR. LC50: 1.45 MG/L n =
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, LABORATORIES, INC. LABORATORY SOME ATON ROAD T AeVOSE. P A 19047.U S A / 7 EL 215 355-33OO. TELE x 17314G.r Ax a 35S D6e9 cR Society of Environmental Toxicology and Chemistry (SETAC)
Presented November 9-12, 1987 at Pensacola, Florida Meeting DETOXIFICATION POTENTIAL OF A ND1 MC!iUSCICIDE FOR ASIATIC CLAM FOULING CONTROL. L. A. Lyons, Bet: Labcratories, Inc. Trevoce, P1s . A new molluscicide to control Asiatic clan biofouling in cooling and service water systecs has several environmentally desirable features. Seasonal applications, requiring short treatment periods of only 24 hcurs, provide effective clan fouling control as opposed to continuous chlorination treatments. Another feature is the detoxificaticn or neutralization potential of the colluscicide by adsorption. The actives in the molluccicide are short-lived because they are + readily adsorbed by a variety of materials and substrates. Once these actives are adsorbed, they no longer exhibit acute toxicity. Thus, passive adsorption of the actives within the system can detoxify the treated water, or the treated water may be detoxified prior to the point of discharge. - The LC50's of the new nolluscicide to Dauhnia paana, fathead minnowc and rainbow trout are 0.4 ng/1, 3.0 mg/1, and 14.7 ng/1, respectively. Molluccicide concentrations ranging frcn 10.0 mg/l to 50.0 mg/l were treated with several kinds of potential sorptive detoxification media. A series of bicassays with Danhnia pacna and fathead minnows were conducted inmediately following these detoxification treatments. Determinations of the rate of survival from these detoxification treatments are provided. e
Methods: Clam-Trol CT-1 solutions were mixed for_5 minutes with potential detoxification media in glass aquaria. Aliquots (200 mL) of the mixture were removed from the aquaria for daphnid testing. Fathead minnows were placed in the aquaria. The detoxification potential was determined from the resultant mortality response.
",9 Detoxification of Clam-Trol CT-1 with Bentonite Clay 7si e winnow . cumuutw % oseans magru . Cumu sten haaty g neo,isory
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7 f i .l_ [j i LABORATORIES. INC. LABORATORY sOBAE ATON ACAD.T AEVOSE. PA 19c4 7.U S A / TEL E
- 5 255 3Occ. TELE % 173 t 4 8.F A X : 2SS-EdGO c-F cutONTC EFTE C OF DETOXTFTED C*-1 ON SE MTRVTVAL WD Gnom The chronic effect of Clam-Trcl C-1 danc::ified with Set: DT-1 was studied ucing the standard 7-day chronic fathead =innew survivability and growth rate test. The data presented in Table 6 show that 10 mg/L cf C-1 resulted in 1001 =crtality of the cinnows. The addition of Bet: DT-1 at a 1:1 ratic with C-1 cc=pletely eliminated chronic =crtality eff ects on f athead tinnows ,
but allowed sc=e growth rate i= pair:ent. Ratics of DT-1 to C-1 et 3:1 cr greater ec=pletely eliminated any effect of C-1 en b:th
=innew survivability and growth.
Mer ality and growth of the fathead ninnew (Pimerhales err mlas) after a 7-day exposure to ratics of Ecto Cla=-Trol C-1 and Set: DT-1. 1 1 i 1 r Mean Fathead l cg C-1/L mg DT-1/L Mcr ality (%) Drf Weight (tg:SE) 0 0 5 0.3101 (0.0157) 0 100 0 0.2855 (0.0015) l 10 0 100* ---------------, 1 10 10 13 0.1SF1 (0.0242)* l 10 30 _7 C.3032 (0.0158) ,, l 10 50 13 C.3355 (0.0046) 10 100 10 0.2811 (0.0112)
*Significantly different frc controls (a=0.05, Dunnett's test)
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AQUATIC
% _n T0XICOLOGY MD S: 'N
[_ LABORATORY LAEORATORIEE. INC. eCME ATON ACAD ~ AEVOSE. P A 19CC=u 5 t / TEL E ' S *35 5 33CO*T E 3 5 " 3 * .2 0.F A x # 3 5 5 2 56 9 EFrer OF C"'-1 ON BFNTRTC ORGANTSM";P s The term " benthic" refers to crcanisms that live in the ber:c= - sediments cf lakes and strea=s. Aquatic insects sucn as the midce larva (Chi cnemus rinnrius, a 2-winged fly cr cnat) , are cc==cn1*t ' used tc study the effects of caterials en better-living crganis=b. Midge larvae were expcsed for 48 hcurs to 10 :.g/L cf Clac-Trel C"' - l and t Clam-Trol C"'-l which was dencxified by :ne addi:icn of Set: DT-1, a blend of highly adscreent clays. The results, shcwn in Table 5, indicate that the Cla=-Trcl C"'-1 by itself pr duced an 80%
=cr:ality without dercxificatien. Treatment wi.h Ben: CT-1 in ratics of 1:1 tc 1:10, successfully eliminated any effects cf CT-1 cn the =c: 0211ty and gr wth rate cf the ridge larvae.
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= =. C"'-1/L = =. DT-1/L Mcr ality (%) Dr./ Weic.ht ( c..SI) 0 0 0 0.9048 (0.0121) 0 100 0 0.9739 (0.0126)
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AQUATIC 1 T0XICOLOGY MD t-
- NN hio t < v[' ,, LABORATORIES, INC. LABORATORY SOME ATON ACAD.TAEVOSE.PA 19od7.U S A / TEL 215 =355 33OO. TELE x 1731 3 0.F A X :: 3552069 Aquatic Toxicity Report Determination of the Effect of Detoxified Clam-Trol CT A Long Tern Study Using Fathead Minnows and Dat3hnia macna
. Study Conducted By:
Aquatic Toxicology Laboratory Bet: Laboratories, Inc. Trevose, PA i j r. ' m l l I
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objective: The purpose of t' 's study was to determine if any acute toxicity wculd be exhibited frem icng tern exposures of Clam-Trol CT-1 detoxified with bentonite clay' to f athead minnows and Danhnia macna and te ~ determine any evidence of desorption of the actives to a toxic form under these test conditiens. - The detoxification of the biocidal activity of Clam- ~ Trol CT-1 is.,readily achieved by adsorption with a variety of materials and substratas. Once the tuc cationic actives present in Clam-Tr:1 CT-1 are adsorbed, they no longer exhibit toxicity. The inthnt of this study was to detexify tcxic levels of Clam-Trol CT-1 and expose aquatic organisms for an extended period to evaluate any acute toxic effects of the detexified solutions and-if any pctential descrpt;:n of the actives resulted te cause tcxicity. Test Organisms: Fathead minnow (Pinerhales cromelas)
- Scurce: SP Engineering, MA
- Total length (mean): 3.5 : 0.34 cm
- Wet weignt (mean) : 0.42 : 0.19 g Dachnia macna Source: Stock culture Age: 1: 1 12 hr. old necnatec Test Type / Fathead minnow and D. macna were exposed to the COnditiens: following five treatments and test conditicns fer 20 days.
Static Penewal Treatmenen
- control 0 mg/l Clan-Trol CT-1
- 25 mg/l Clam-Trol CT-1
- 25 mg/l Clam-Trol /250 mg/l bentonite clay
- 250 mg/l bentonite clay only ,-
Static Treatment
- Continucusly aerated 25 mg/l Clam-Trel CT-1/
250 mg/l bentenite clay. . _ . - - - - , _ . _ . , ,, _ , . ~ - - - . . . Q
1 l i b Method: *n-dav Fish Tent c"A De cxified Clam-Trol CT-1 solutions were prepared by mixing 25 mg/l Clam-Trol CT-1 solution with 250 mg/l of bentonite clay (a CT-1 to clay ratio of 1:10) . _ The two materials were mixed with a mechanical stirrer a 1100 rpm for 30 minutes. All treatments with clay were mixed in the same manner. Fifteen liters of sclutien were prepared for each treatment replicate. Twenty fish were expcsed to each treatment--twc replica:a and 10 fish per 15 liter of solution. All treatments with exception of the centinuously aera ad 25 ppm Clam-Trol CT-1:250 ppm bentenite clay were renewed with freshly prepared solutiens on the following days
'thrcugh the 30-day test: 1, 4, 8, 11, 15, 22, and 25. The test was initiated or Ty one. During the renewal ci tas:
solutions, only the upernatant was siphoned from each tes: centainer and the sedimentation of clay on the bet:cm was retained in the container the test. Fresh tas soluti:n was added after siphoning and mixed with the existing accumulated clay. Fish were fed ccmmercial flake feed daily. Observations of mortality and behavier respensc were assessed daily. 48-h Darhnia maana Test .
. Standard 48 hr acute Daehnia maena bicassay tests were initiated only on days that sclution renewals were made in the fish test. Daphniids were exposed to subsamplec of test solution taken from the fish res containers. Durinc each renewal period, toxicity tests were performed with :.E.e freshly made test solutions and with the aged solutiens taken frcm each test container.
Twenty R2 maana were exposed to each treatment, 10 individuals per replicate. Mortality was assessed at 1-2, 24, 48 hours. t
7 i v} Sammary of Results Detoxified Clam-Trol CT-1 solutions were prepared by mixing 25 mg/l Clam-Trol CT-1 solutions with 250 mg/l of bentonite clay (a CT-1 to clay ratic of 1:10) . No mortality or stress was exhibited to fathead minnows that were continuously exposed fer 30 days to detoxified Clam-Trol CT-1 solutions. No mortality was exhibited to Danhnia maana that were exposed fer 43 hour perieds to renewed or aged detoxified Clam-Trol CT-1 solutiens. a l l
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*dyacine 2500 (50% Active Cua:) in Cccling Tcwer Elevdevn Water as a P.:nction of Time Af ter Desing" Concentration of Eyamine 3500 (pp )
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conversion after a two week acclimation period. It was concluded from this study that biodegradation of the Quat was, after a short period of microbial acclimation, quite rapid and complete. BiodegradationofDGHwasexaminedin1989usingthecbCDScreening Test according to EC Directive 79/831. For the OECD study, a DGH solution was diluted with nutritive salt solutions and mud from the - biological part of a clarification plant to nearly 40 mg/l DOC in water. The system was shaken at 24 C in the dark for 28 days. Dissolved Organic-Carbon (DOC) determinations were used to monitor biodegradability of the DGH compound. Test results are presented in the table below. Biodectradation of DGH (OECD Protocol) Day DOC mg/l i Degradation 0 34 1 39 0 4 26 33 7 26 33 14 17 56 18 16 59 22 18 54 26 13 67 29 10 74 31 9 77 . The DGH exhibited a DOC 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 acrobe 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 a dodine-free medium, growth of the organisms was poor. This study provided a demonstration that certain organisms were quite capable of utilitzing DGA as the sole source of carbon. I i
/
1
?iene-u-uh-fen Ricaccu=ulati:n studies (P.ch: and Haas study) with bluegill sunfish -
detc m ined the steady state interval, which is the ti=e when absery-tien eraals eli=inatica using 'c labelled cuat. The s:cady state insur-/a1 cerurred in the fish af cr 2 weeks of centinucus expesure at sublethal icvels at which ti.=e the carbon 14 residues incfthe The cencentration thecar: biccide ass and the viscera reached a plateau. in the carcass of the fish at the s:cady state was 42 times that cf
~t was also found that the biological the concentratien cf water.
half-lite. cf the ac=u=ulated residues was sher:, about 7 days, which was deter =ined by the eliminati:n af the carben 14 residues when the fish vere placed in a bic=ide-free araa.riu=. t e. em 4 #
- , . . - - - . , , -.,,.,-.,-...,,.-....,,-n. ,-n..., . , - - , , . . , - , , , - , .e... c..,., .n , - - , ,,,-w,-. , - . - , ,,. - , - , - -- - + . ,
l > Summ1n: , W The biocidal activity of Clam-T.ol CT-1 results from the two cationic surface active agents (DGH and Quat) in this formulation. The product's efficacy is based on its ability to alter or disrupt various membrano systems of the biofouling organisms. These same r inherent properties of these agents which provide blocidal efficacy are rapidly neutrali:cd upon adsorption to many types of naturally occurring materials thus reducing or eliminating acute toxicity to non target organisms. Several Key characteristics of clam-Trol CT-1 will minimize its ; environmental impact following its application to cooling systems. These inclucc: r
- Adsorption rates of both actives Both are rapid actives and thus readily adsorb blacidal to activity is short-lived.
suspended material, sediments, and the surfaces within a 2 cooling system.
- Both of the active compenents in the formulation are readily blodegradabic. Solutions of Quat have been shown to biodegrade by more than 904 in 2 days while solutions of CGH cxhibited 70', ;
biodegration in 28 days.
- Clam-Trol CT-1 provides an alternative to chlorine or a nur.ber of halogenated organic cr metal containing biocides that are considerably icos environmentally desirabic.
- Bicaccumulation of the Quat active has been deter =ined by as continuous exposure of low levels of free actives to fish, reaching a steady state after 2 weeks. The half-life of this accunulated material is short once exposure ceases.
- An analytical field method is available for determiningThe the presence of the actives in a treated cooling system.
method is also useful f cr monitoring discharges. -. Biofouling treatment programs to cooling systems need to employ innovative technology that will direct the applications in a most effective _ manner to the target organisms. Applications of Clam-Trol CT-1 can serve to_ protect cooling systems from both macrofouling and-microfouling problems using state-of-the-art technology. No other-treatment program exists that can protect a system from infestation-by adult mollusks and larvae by employing seasonal applications. hcur Effective control and protection can be accomplished within a 24 application.
~
In addition, Clan-Trol CT-1 applications can provide nicrofouling protection to safety-related cooling systems due to its unique fact-acting properties and its ability to perneate cline formations. These are applications that will not cause the corronive problems that develop fron continuous chlorinntion nor require extensive treatncnt periods for control. n- ,
i 1 l MI tMW CLAM-TROLe CT-1 METHYL ORANGE METHOD APPARAT 1)S REQUIRED CT-1 Duffer Reagent it91
" Methanol (reagent grade or equivalent) 322 Deaker, glass,50 mL (2 required) Code Cylinder, graduated,25 mL 2C22 Drying Reagent, with a plastic d pper 1071 Funnel Rack, separatory 936
SUMMARY
OF METH".)D Funnel, separatory, with a Teflon stopcock,250 mL ** (2 requited) In this procedure the dye in the CT 1 Buffer Reagent cond 114 pieres with the active ingredients in Clam-Trol CT 1. This Glass Rod corrplex in euracted into 1,2 dichloroethane. The or-Optical Coll, (2 required) ganic layer containing the complex is separated from the
.. aqueous layer and dr ed with a drying teagent containing Spectrophctometer anhydrous sodium sulfate.The color Intensity of the 1,2 dichlorocthane layer is then measured in a spectropho-GENERAL APPARATUS * ,
tometer at 415 nm. Cylinder, graduated,103 mL Code 121 This method must be customged to each specific appli-Cylinder, graduated,250 mL 917 cation. Vary the votume c of sample, CT 1 Buff er Rea gent, and 1,2 - dichloroethane according to the test range Flask, volumetoc,1 L, glass (4 required) 935 (see Table 1). lf a higher absorbance is needed, increase Pipet, glass, graduated,1 mL 140 the volume of sample or decrease the volume of 1,2 - dichloroethane. Wuen increasing the sample volume it Pipet, glass' volumetric,1 mL ESS may be necessary to increase the volume of CT 1 Duffer
" Reagent used For samples < 150mLuse 10 m'.of CT 1 Pipet, glass, volumetric,3 mL Cu+fer Reagent; for samples between 150 and 300 mL Pipet, glass, volumetric, 5 mL 124 use 15 mL of CT 1 Buffer Reagent. Make sure that
~""
Pipet, glats, volumetric,10 mL 123 enbugh 1,2 - dientorcethane is used to leave a small plug of solvent in the separatory funnelwhen the bottom Pipet, glass, volumetric,15 mL E61 layer of solvent is removed and to fill the optical cell
" PfDPUllY-Pipet, glass, volumetric, 20 mL Pipet, glars volumetric,25 mL 117 GENERALPROCEDURE Pipet, glass, volumetric,30 mL Use a well ventitated or hooded area to run the test.
- The general apparatus required for the test is deter- Atways use a saf ety bulb when pipetting liquids.
mined by the specific test procedure used. 1,2 Dichloroethane (also known as Ethylene Dichio-
" Apparatus not available through Betz Lab Supply rice) 15 a phority poHutant and a specifiCally listed should be cbtained through a local supplier.
RCRA regulated material subject in specific disposal to-stnctions and/or prohibitions. For this reason, all used CHEMICALS REQUIRED 1,2 dichloroethane should be tegregated from other 1,2 - Dich!oroethane (reagent) Code 1660 waste streams. Ditpose of waste 1,2 dichloroethane in grade or equivalent) an approved manner (e g., labpacking or incineration). AP 34 9003 *1730 EETZ LABORATORIES. INO ALL HIGHTS RESERVED hwe1
Table 1. Suggested Volumes for Various Ranges of CT 1 Range Volume Volume Volume Optical Cl-1 (rna'L) CT 1 Dutter Dichloreethane Samplo Cell Site (mL) (mt) (mL) 0.2 - 3.0 15 10 c.0 250 1.0 cm
- 1.0 250 10 30 LO 2 5 ca n " _
0.2 1.0 15 20 200 5 0 cm " *
- Thel.O cm cell (Code 1312) can be used with Hach spectrcphotometers using a 1-cm cell adapter (Code 2T/0C).
' The 2.5 cm cell is the standard Hach 1-in. Cell (Det? Code 2001). "* five centimeter cells are not available for ute with the Hath photorneters. Many laboratory spectrophotometers requite on adapter to accommodate b-cm cells. Check with the instrument rnanufacturer.
- 1. Transfer an ahquot of the water temple to a separa- CAllDRATION CURVE PREPAR ATION fory funnel (the sample). Transfer the same volume of distilled (or deiontred) water to a second separa- 1. Prt pare a 100) mg'L CT-1 stock solution by accul tory funnel (the blank). Run the blank once for each rately weighing 1.00 g of CT 1 into 1 L of distilled (or I,et of enmples tected (t.ee Notes 1,2, and 3). deionized) water.
- 2. /sdd CT 1 Du'for Reagent to both the sample and the 2. Pipet designated volumes of the stock so!ution into blank. 1 L volumetric flasks. These are the standard schF 3 Using a pipet add 1* 2 dichloroethane to both 50- S usM h ppMng a caWen m We T W 2 to m9e appropdom ddutens of the stou paratory funnels' tolution for each specific app'acaton,
- 4. Insert the stoppert in each of the separato y funnels.
Inver1 and briefly open the stopcock to vent the fun- 3. Follow the Gcneral procedure using the specite so-nets (see Notes 4 and $). When venting the funnels, krtion volumes that have been determined for the point the tip of the funnel away from yourself and application and prepare a calibration curve. Deter-others. mine the absorbance of a blank sclution using dis-
!!lled (or delonized) water. Th's blank can be t,ub-
- 5. Shake the funnels moderately for 30 sec, vent the tracted from the sample absorbance or used to zero funnels, then allow them to stand for 10 min (but no the spectrophotometer so that the calibration curve longer than 15 min), goes t'vough the origin. The cahbration curve
- 6. Collect the lower layer (1,2 dichloroethano) from should be linear over the Indicated ranges.
each funnel in 50 mL beakers leaving about 12 mL in the funnel. This will prevent significant removal of water. NOTES
- 7. Using the plastic dipper, add 2 scoops of Drying Rt*
agent to each beaker and stir with a glass rod for 15 15 f or maximum accuracy the calibration curve should sec (but no longer than 30 sec), be checked by every oporator usin0 this 105t and 8 Wait approximately 1 to 2 m:n (but not more than S *
- 8* " * # " W * * ""
rnin).Then carefully decant the extract off of the dry. N a WW ppaM G4 mMn Ing reagent into an optical cell 2. A blank measurement must be recorded for each t.et
- 9. Set the spectrophotometer at 415 nm and zero with of samples. The blank reading may vary slightly; however, the absolute difference between the sam-1,2 dichloroethane. Measure and record the absor-bance of the blank and the cample (see Note 6), pie and the blank remains relatively constant.
10 The sample absortance minus the blank absor. 3. Chlorine causes a negative interference in the test. bance is used to determine the concentration of This can be chminated by adding 0.1 N Sodium CT 1 in the cample. From a nrepared cahbration Thiosultate (Code 235) to the water sample before curve, determine the CT 1 concentration in the sam. runmng the test. The amount added be is based on ple (see Calibration Curve Preparation), the concentration of chlorine in the system. For a 100 mL water sample containinq 0.3 mWL chlorine,
- 11. Clean the cetts after each measurement add 10 drops of 0.1 N SodiumTfliot,ulf ate to remove (see Note 7). the laterference.
ea08 2 A P yA 9n3
_ . - _ _ . _ - _ . -_.- _.. _ _.- - -._. - - . . _ _ _ _ _ - . ..m._. ___m i Table 2. Ollutions for Callbratton Curve Propers. procedure. Shake the funnel for 30 sec, vent 11, then tion Dased on a Final Solution Volume allow it to stand for 5 min. Gently invert the funnel l of 1 L. once then allow the funnel to stand for 5 min, j Concentration CT 1 Stock Solo- 5. It is important to vent the separatory funnel both be- l CT.1 Desired tion Added to Make fore and after shaking it. Otherwise, a pressure will (mg/L) 1 L (mL) ~ build up in the funnel that can cause the stopper to be forced out of the top of the tunnel, [ 0.2 0.2 6. Use caution wtien Inserting or removing the sample - . cell in the photometer. The 1,2 - dichlorcethane can 0.4 0.4 damage the cell compartment. 0.6 0.6 7. It is imperative that the sample cells are kept clean 0.8 0.8 dunng the running of the lest. It is recommendea that the cells are cleaned after each measurement using 1.0 1.0 the following procedure: 5.0 5.0 a) Rinse the cell three times with dtstilled (or , J 10.0 10.0 deionized) water. l 15.0 15.0 b) Rinse the cell three times with methanol. i 20.0 20.0 c) Rinse the cell three times with 1,2 dichicro-25.0 25.0 ethane to remove methanol from the cell.
- 8. This method is based upon Wang, L. K.; Langly. D. F.
4, A slight emulsion may form when using natural water ind. Eng Chem., Prod. Aes. Dev., 1975, 14, 3. semples. When thic happens, vary step 5 of the 210 212. i t t y. I 4 8174 BETZ UDOMIORIES.INC, ALL RIGHTS AESLhvlo Page5 AP 368 9003
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BETZ LABORATORIES,Dic. 4636 SOMERT0!! ROAD, TREVOSE, PA. 19047 BET MATERIAL SAFETY DATA SHIET 24 HOUR EMERGENCY TELEPl!ONE (HEALTl! OR ACCIDENT) 215/355-3300 (PAGE 1 OF 3) PRODUCT : CLAM-TROL CT-1 EFFECTIVE DATE 05-18-69 PRINTED: 3-Sep-1989 - REV:SEC.3 PRODUCT APPLICATION : WATER-BASED HICROBIAL CONTROL AGENT.
-----S E CTI ON 1-----------HA" ARDOUS INGREDIDTTS ---------------
INFORMATION ON PHYSICAL HAZARDS, HEALTH HAZARDS, PEL'S AND TLV'S FOR SPECITIC PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIO!!S STANDARD IS LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF Tl!E POTENTIAL ACUTE AND CHRONIC HA"ARDS OF THIS FORMULATION. l ETHYLEllE GLYCOL ***CAS#107-21-1; LIVER, KID!TEY AND BLOOD T0XIN!CNS DEPRESSANT; ANIMAL TERATOGEN (HIGli ORAL DOSES) ;PEL/TLV;SOPPH-C. ALKYL DIMETHYL BDIZYL AMMO!!IUM CHLORIDE ***CAS $68424-85-1;CORROSIVI(EYES) ; PEL:NONE;TLV:NONE. i ISOPROPYL ALCOHOL * * * (IPA) ; CAS # 67-63-0 ; FLAMMABLE LIQUID ; CHRONIC OVEREXPOSURE MAY CAUSE LIVER AND KIDNEY TOXICITY; PEL/TLV: 4 00 PPM ( 500 PPM-STEL) . DODECYLGUANIDI!TE HYDROCl!I4 RIDE * * * (DGH) ; CAS # 13 S 90-97-1 ; CORROSIVE : PEL: NONE : TLV:NONE. ! ETHYL ALCOHOL * * * (ETHANOL) ;CAS # 64-17-5 ; rLAMMABLE: HAY CAUSE DETATTING DERMATITIS , DIZZINESS AND HEADAC1!E;PEL:1000 PPM;TLV:1000PPH. I 6
-----SECTION 2-----------TYPICAL PHYSICAL DATA-------------------------
PH: AS IS (APPROX.) 5.3 ODOR:rMILD ,.= TL.PT.(DEG.F): 116 SETA(CC) SP.GR. (70F) OR DDISITY: 1.022 VAPOR PRESSURE (r=HG) : 23 VAPOR DDISITY ( AIR =1) : >l VISC cps 70F: 23 % SOLUBILITY (WATER) : 100 l EVAP. RATE: <1 ETHER =1 APPEARANCE: COIARLESS PHYSICAL STATE: LIQUID FREEZE POINT (DEG.F): <-30
-----SECTION 3-----------REACTIVITY DATA------------------------------
STABLE.!GY REACT WITH STRONG OXIDIZERS.DO NOT CONTAH.LNATE.BETZ TANK CLEAN-OUT CATEGORY 'B' THERMAL DECOMPOSITION (DESTRUCTIVE FIRES) YIELDS ELEMENTAL OXIDES. l t
I i BETI MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3) PRODUCT: CLAM-TROL CT-1 EFFECTIVE DATE 05-18-8t
----- S E CTI ON 4 -----------IIEALTl! IIAI ARD ETTE CTS ------------------------
ACUTE SKIN EFFECTS *** PRIMARY ROUTE OT EXPOSURE j CORROSIVE TO SKIN.POTEllTIAL SKIN SENSITIIER ACUTE EYE EFFECTS *** CORROSIVE TO THE EYES ACUTE RESPIRATORY EFFECTS *** PRIMARY ROUTE OF EXPOSURE VAPORS, GASES, MISTS AND/OR AEROSOLS CAUSE IRRITATION TO UPPER RESPIRATORY TRACT CHRONIC LFFECTS OF OVEPIXPOSURE * *
- PROLONGED OR REPEATED OVEREXPOSURES MAY CAUSE: TISSUE NECROSIS ; BLOOD CELL DAMAGE OR IMPAIR BILOD CELL PUNCTION; REPRODUCTIVE SYSTEM TOXICITY; SK!!! -
SE!!SITIIATION. MEDICAL CONDITIONS AGGRAVATED *** NOT KNOWN SYMPTOMS OF IXPOSURE *** INHALATION OF VAPORS / MISTS / AEROSOLS MAY CAUSE EYE, NOSE,TIIROAT AND LUNG IRRITATION; SKIN CONTACT MAY CAUSE SEVERI IRRITATION OR BUFdtS. PPICAUTIONARY STATEMENT BASED ON TESTING RESULTS * *
- MAY BE TOXIC IT ORALLY INGESTED.
----- S E CTI ON 5 ------------ FI RS T AI D INS TRU CTI ON S --------- .------------ -
SKIN CONTACT *** REMOVE CLOTHING. WASH AREA WITH LARGE AMOUNTS OF SOAP SOLUTION WATER FOR 15 MIN.IMMEDIATELY CONTACT PHYSICIAN EYE CONTACT *** IMMIDIATELY FLUSH EYES WITH WATER FOR 15 MINUTES.IMMEDIATT'.Y CONTACT A PHYSICIAN FOR ADDITIONAL TPIATMEllT INH 1sLATION EXPOSURI*** REMOVE VICTIM TROM CONTAMINATED AREA. APPLY NECESSARY FIRST AID TPIATMENT. IMMEDIATELY CONTACT A PHYSICIAN. INGESTION *** DO NOT TEED ANYTHING BY MOUTH TO AN UNCO!!SCICUS OR CONVULSIVE VICTIM DO NOT INDUCE VOMITING.IMMED. CONTACT PHYSICIAN. DILUTE CONTE!!TS OF STOMACH USING 3-4 GLASSES MILK OR WATER
-----S ECTION 6-----------S PILL, DIS POS AL AND FIPI INSTRUCTI ONS ---------
SFILL INSTRUCTIONS *** VENTILATE AREA,USE SPECITIED PROTECTIVE EQUIPMENT.CONTAIN AND ABSORB ON ADSORBENT MATERIAL, PLACE IN WASTE DISPOSAL CONTAINER.THE CONTAMINATED ABSORBENT SHOULD BE CONSIDEPID A PESTICIDE AND DISPOSED OF IN AN APPROVED PESTICIDE LANDFILL.SEE PRODUCT LADEL STORAGE AND DISPOSAL INSTRUCTIONS. REMOVE IGNITION SOURCES. FLUSH APIA WITH WATER.SPPIAD SAND / GRIT. 7 " DISPOSAL INSTRUCTIONS *** WATER CONTAMINATED WITH THIS PRODUCT MAY BE SENT TO A SANITARY SEWER TPIATHENT FACILITY,IN ACCORDANCE WITH ANY IECAL AGPIEMEN7, A l PERMITTED WASTE TPIATMENT FACILITY OR DISCHARGED UNDER A NPDES PERMIT l PRODUCT (AS IS)- DISPOSE OF IN APPROVED PESTICIDE FACILITY OR ACCORDING TO LABEL INSTRUCTIONS FIRE EXTINGUISHING INSTRUCTIONS *** l FIREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING 1 APPARATUS (FULL FACE-PIECE TYPE). DRY CHEMICAL, CARBON DIOXIDE, FOAM OR WATER
i BET MATERIAL SAFETY DATA SIIEET (PAGE 3 OF 3) PRODUCT 8 CLAM-TROL CT-1 . EFFECTIVE DATE 03-18-8
-----S ECTION 7 -----------S PECIAL PROTECTIVE EQUIPMENT-----------------
USE PROTECTIVE EQUIPMENT IN ACCORDANCE WITl! 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 SIGliIFICANT PRODUCT EXPOSURE IS LI}TLY, USE A RESPIRATOR WIT 11 ORGLHIC VAPOR CARTRIDGE & DUST / MIST PRETILTER RECOMMENDED SKIN PROTECTIONa** GAUNTLET-TYPE RUBBER GI4VES, CHEMICAL RESISTANT APRON - WASH OFF AFTER EACl! USE. REPLACE AS ITECESSARY RECOMMENDED EYE PROTECTION *** SPLASH PROOF CllEMICAL GOGGLES. FACE S!!IELD
-----SECTION 8-----------STORAGE AND llANDLING PRECAUTIONS-------------
STORAGE INSTRUCTIONS *.*
}2EP DRUMS & PAILS CLOSED WHEN NOT IN USE.
STORE IN COOL VENTILATED LOCATION. STORE AWAY FROM OXIDIZERS
'IANDLING INSTRUCTIONS * *
- GENERAL-IMMEDIATELY REMOVE CONTAMINATED CLOTHING, WASH BEFORE REUSE SPECIFIC- COMBUSTIBLE. DO NOT USE AROUND SPARKS OR FLAMES. BOND CONTAINERS DURING FILLING OR DISC 11ARGE WHEN PERFORMED AT TEMPERATURES AT OR
- ABOVE THE PRODUCT FLASH POINT.
THIS MSDS COMPLIES WITH THE OSHA }IAZARD COMMUNICATION STANDARD HAROLD M. HERSH (ENVIR0!THENTAL INFORMATION COORDINATOR) APPENDIX: REGULATORY INFORMATION THE CONTENT OT: THIS APPENDIX REPRESENTS INFORMATION IOloWN TO BETI ON THE EFFECTIVE DATE OF THIS MSDS. Ti!IS INFORMATION IS BELIEVED TO BE ACCURATE. ANY CHANGES IN REGULATIONS WILL RESULT IN UPDATED VERSIONS OF THIS DOCUMENT. v
...TSCA: ALL COMPONENTS OF THIS PRODUCT ARE LISTED IN THE TSCA INVENTORY '
. . . FIFRA ( 4 0CFR) EPA REG.No. 3 87 6- 145 i
~
. . . REPORTABLE QUANTITY (RQ) FOR UNDILUTED PRODUCT:
NOT APPLICABLE
... RCRA: IF THIS PRODUCT IS DISCARDED AS A WASTE,THE RCRA IIAZARDOUS WASTE IDENTIFICATION NUMBER IS: D001= IGNITABLE D002= CORROSIVE
... DOT HAZARD CLASSIFICATION: CORROSIVE TO SKIN.COMBU3TIBLE
... DOT SHIPPING DESIGNATION IS: UN1760 CORROSIVE LIQUID, N.O.S.
. . .THIS - PRODUCT CONTAINS THESE CHEMICALS 10iOWN TO THE STATE OF CALIFORNIA TO CAUSE CANCER OR REPRODUCTIVE T0XICITY: NONE PRESENT 7H SIGNIFICANT AMOUNTS
.... SARA SECTION 302 CHEMICALS: NONE 1) RESENT IN SIGNIFICANT AMOUNTS ,.
... SARA SECTION 313 CHEMICALS: ETHYLENE GLYCOL (107-21 .1) , 21.0-30.0% ;
. . . SARA SECTION 312 HAZARD CLASS: IMMEDIATE ( ACUTE) , DEI. AYED ( CHRONIC) AND FIRE
... MICHIGAN CRITICAL MATERIALS: NONE PRESENT IN SIGNIFICANT AMOUNTS NTPA/HMIS : HEALTH - 3 ; FIRE - 2 ; REACTIVITY - 0 ; SPECIAL - CORR ; PE - D
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