ML17309A663

Forwards Copy of NPDES Permit Notification Request Sent to EPA on 911016,per Section 3.2.4 of Environ Protection Plan

ML17309A663
Person / Time
Site:	Saint Lucie
Issue date:	11/01/1991
From:	Sager D FLORIDA POWER & LIGHT CO.
To:	NRC OFFICE OF INFORMATION RESOURCES MANAGEMENT (IRM)
Shared Package
ML17223B307	List: ML17223B306 ML17223B308 ML17223B309 ML17223B310 ML17223B311 ML17309A663
References
L-91-299, NUDOCS 9111140217
Download: ML17309A663 (182)

Text

ACCELERATED DI UTIO DEMONST WTION SYSTEM W J REGULATORY INFORMATION DISTRIBUTION SYSTEM (RIDS)

ACCESSION NBR:9111140217 DOC.DATE: 91/11/01 NOTARIZED: NO DOCKET FACIL:50-335 St. Lucie Plant, Unit 1, Florida Power & Light Co. 05000335 50-389 St. Lucie Plant, Unit 2, Florida Power & Light Co. 050 0 AUTH. NAME AUTHOR AFFILIATION SAGER,D.A. Florida Power & Light Co.

RECIP.NAME RECIPIENT AFFILIATION Document Control Branch (Document Control Desk)

SUBJECT:

Forwards copy of NPDES permit notification request sent to EPA on 911016,per Section 3.2.4 of Environ Protection Plan. D DISTRIBUTION CODE: C001D COPIES RECEIVED:LTR ENCL 'IZE:

TITLE: Licensing Submittal: Environmental Rept Amdt & Related Cor espondence NOTES:

RECIPIENT COPIES RECIPIENT COPIES ID CODE/NAME LTTR ENCL ID CODE/NAME LTTR ENCL PD2-2 LA 3 3 PD2-2 PD 1 1 D NORRIS,J 1 1 D

INTERNAL: ACRS 6 6 NRR/DET/ESGB 8D 1 1 FMB 1 0 OGC/HDS3 1 0 REG- 01 1 1 RGN2 DRSS/RPB 1 1 EXTERNAL: EG&G SIMPSON, F 2 2 NRC PDR NSIC 1 1 D

D D

NOTE TO ALL "RIDS" RECIPIENTS:

PLEASE HELP US TO REDUCE WASTE! CONTACT THE DOCUMENT CONTROL DESK, ROOM P 1-37 (EXT. 20079) TO ELIMINATEYOUR NAME FROM DISTRIBUTION LISTS FOR DOCUMENTS YOU DON'T NEED!

TOTAL NUMBER OF COPIES REQUIRED: LTTR 20 ENCL 18

P.O. Box 128, Ft. Pierce, FL 34954-0128 gOV 0 g ~gg~

L-91-299 EPP 3.2.4 U. S. Nuclear Regulatory Commission Attn: Document Control Desk Washington, D C 20555 Gentlemen:

Re: St. Lucie Units 1 and 2 Docket Nos. 50-335 and 50-389 NPDES Permit Modification Attached is an information copy of the National Pollutant Discharge Elimination System (NPDES) Permit modification request, which was sent to the U. S. Environmental Protection Agency on October 16, 1991. This document is being sent pursuant to Section 3.2.4 of the St. Lucie Units 1 and 2 Environmental Protection Plan.

Should you have any questions on this information, please contact us ~

Very truly yours, D. A. S er Vice P e ident St L Pl DAS:JJB:kw cc: Stewart D. Ebneter, Regional Administrator, Region Senior Resident Inspector, USNRC, St. Lucie Plant II, USNRC Attachment DAS/PSL 8549-91 9ilii40217 9iiiOi oo PDR ADOCK 05000335 l p PDR an FPL Group company

gh l

III

\

, Box 078768, West Palm Beach, FL 33407-0768 October 16, 1991 Mr. Ray Cunningham U.S. Environmental Protection Agency Region IV 345 Courtland St, NE Atlanta, GA 30365 RE: St. Lucie Plant NPDES Permit No. FL0002208 NotiTication of Biocide Use

Dear Mr. Cunningham:

Florida Power and Light Company's (FPL) St. Lucie Plant has continued to experience severe biofouling of the plant's cooling water systems. The growth and accumulation of a variety of both shelled and soft-bodied organisms in the forebay area immediately preceding the once-through cooling water and auxiliary equipment cooling water (intake cooling water) systems seriously impairs cooling water fiow. These organisms include, oysters, mussels, barnacles, bryozoans, and hydrozoans. This macrofouling growth also results in the transport of these organisms, both dead and alive, onto the condenser tube sheets and into the condenser and heat exchanger tubes. The resulting reduction in the supply of cooling water has two main effects:

1) Increased requirements for more expensive replacement power as the units run at reduced load to facilitate manual clearing of the once-through cooling water system and,

2) Reduced availability, reliability, and capacity of the auxiliary cooling water heat exchangers, which are principal components of a nuclear safety system.

The biofouling control option currently allowed under the NPDES permit is intermittent chlorination, which has little or no effect on macrofouling organisms.

Continuous chlorination, if approval were granted, could control macrofoulants, but would be impracticable and a signiTicant safety hazard due to the large quantities of gaseous chlorine required. In cases where continuous chlorination is applied to once-through cooling water, gaseous chlorine is typically delivered by railroad car every 10 to 14 days. At the St. Lucie Plant, this quantity would have to be trucked in over the intracoastal waterway bridge, which would necessitate daily deliveries and pose unaccepatable handling and safety-related problems. In addition, gaseous chlorine is not permitted on the plant site by Nuclear Regulatory Commission regulations and would require major plant modifications before a variance could be granted.

an FPL Group company

Mr. Ray Cunningham October 16, 1991 Page 2 The use of liquid hypochlorite for continuous application is precluded since quantities would be needed that would far exceed even that required for gaseous chlorine.

Numerous options to conventional chlorination for biofouling control have been studied in considerable detail. After all studies were completed, FPL determined that a Betz Industrial product, Clam-Trol CT-1 (CT-1), is likely to be most effective method of addressing this problem.

Condition III-C of the St. Lucie Plant NPDES permit states that the permittee shall notify the Regional Administrator at least sixty (60) days prior to use of a biocide other than chlorine in the plant's cooling water systems. FPL requests that this correspondence be considered that notification. FPL also requests a permit modification, based on the information presented in this correspondence, that would allow the use of CT-1 at the St. Lucie Plant. Upon approval, FPL will be conducting an 18-month evaluation of the product to determine both its effectiveness and any environmental impact it might have. The 18-month period represents one fuel cycle for the plant. This is the minitnum of time in which the product can be evaluated since it would guarantee that the plant would be shut down and the intake structure available for inspection during the refueling process. Following this evaluation, FPL or EPA could request further modification of the permit, as necessary, based on data collected during the evaluation period.

Condition III-C also requires that certain information be supplied to EPA prior to use of a biocide other than chlorine. This information, plus additional information that EPA indicated would be necessary to gain approval for use of an alternative biocide, is provided below.

Item 1 Name and General Com osition of Biocide or Chemical CT-1 contains 13% active ingredients of two cationic surfactants and 87~/o inert materials. The two cationic surfactants are n-alkyl dimethyl benzyl ammonium chloride (QUAT) and dodecylguanidine hydrochloride (DGH). Attachment 1, the Betz Clam-Trol CT-1 Environmental Information Package, contains information on the adsorptive characteristics, toxicity to saltwater organisms, biodegradation, environmental fate, and detoxification processes of the cationic surfactants. A considerable amount of additional aquatic toxicity information will be presented later in this submittal.

Item 2 Fre uenc of Use and Item 3 uantitites to be Used The frequency and quantity of CT-1 use at the St. Lucie Plant will be determined during an initial optimization phase of the 18-month test period. The purpose of

Mr. Ray Cunningham October 16, 1991 Page 3 optimization is to minimize the number of applications per year, the period of application and the dose that will be needed to achieve efficacy. The anticipated optimal treatment will be 5 to 6 applications per year, 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> per application and a dose level of 10 mg/I. Although additional treatment may be necessary, the maximum use of CT-1 should not exceed 12 applications per year, 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> per application, and a dose level of 10 mg/L The only possible exception that can be envisioned may be in the event of an unusual storm event that could potentially cause unusually high demand to the treatment dose of CT-1. In that case, the dose level may need to be increased to no greater than 15 mg/I, although such increased demand would preclude any corresponding increase in the discharge residual concentration.

The configuration of the St. Lucie Plant allows this chemical application program to be effective against target organisms in a precisely defined area while it niininuzes the adverse environmental impact beyond the perimeter of the treatment zone. The treatment cycle will be predicated on growth characteristics of the fouling organisms using continuous surveillance equipment, condenser and forebay inspections, and condenser performance tests. The acquired data will be reviewed and an application window established.

CT-1 will be supplied in 350 gallon portable, reusable semi-bulk containers and fed through a portable pump/header system. The handling of the CT-1 in semi-bulk containers has seveial significant advantages including no permanent storage/handling facility or piping required, and minimum potential for chemical spills. Secondary containment will be provided around the CT-1 product container.

CT-1 will be introduced into one conduit at a time. For purposes of this submittal, a conduit consists of the intake forebay area, waterbox and condenser associated with a single circulating water pump. The appropriate quantity of chemical will be brought on site, placed by the target conduit, injected within a two day window with Betz personnel assisting, and the empty semi-bulk containers removed to a holding area for return to Betz for processing. This procedure can be completed within a 3 to 5 day period per conduit.

Distribution of chemical into the cooling water is critical to achieve control of macrofoulants with a minimum of product. The addition of CT-1 through a portable header located immediately upstream of the bar screen will optimize distribution of chemical to the targeted organisms. The header will be designed to apply the chemical along the boundaries or walls of the forebay to maximize the concentration of CT-1 to the organism growth sites.

Mr. Ray Cunningham October 16, 1991 Page 4 During the Betz-assisted chemical injection of CT-1, the injection rate will be monitored and controlled using an analytical test procedure capable of determining the concentration of CT-1 present in the cooling water with a method detection limit of 0.2 mg/l of product or 0.026 mg/I of total active ingredients. The ability to test for these active ingredients allows the dosage to be optimized and confirms compliance with appropriate NPDES requirements.

This analytical procedure also will be used to measure the demand of the incoming cooling water for the active ingredients in CT-1 and then predict the effectiveness of adsorption/passive neutralization. This capacity to determine when demand is lowest during an application window, translates into reduced feedrates/quantities of chemical needed per successful application thus minhnizing environmental and economic impact.

Testing for product addition rate and active ingrediants present at the point of discharge (POD) will be provided during the entire application process to confirm compliance.

Betz personnel will be present during each addition of Clam-Trol to optimize performance, monitor and control chemical addition to assure compliance, and provide FPL with on-site expertise and assistance.

In addition to distribution and feed control, the control of dosage and contact time of CT-1 is critical to effect a high (95-100%) mortality of the targeted organisms. FPL plans the following steps as the initial chemical addition regime; Unit 1 - Conduit A and B Step a - Chlorine: Discontinue addition of sodium hypochlorite to the target conduit at least 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> preceding CT-1 addition Step b - Chlorine: Continue addition to the auxiliary cooling water heat exchangers-no change Step c - CT-1: Add CT-1 at 10 mg/I (as product) for 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> Step d Chlorine: Resume addition of sodium hypochlorite within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> following CT-1 addition as per existing procedures Unit 1 - Conduit C and D Step a Chlorine: Discontinue addition of sodium hypochlorite to the target conduit at least 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> preceding CT-1 addition Step b - Chlorine: Continue addition to the auxiliary equipment cooling water heat exchanger - no change Step c CT-1: Add CT-1 at 10 mg/1 (as product) for 18 hours2.083333e-4 days <br />0.005 hours <br />2.97619e-5 weeks <br />6.849e-6 months <br />

Mr. Ray Cunningham October. 16, 1991 Page 5 Step d - Chlorine: Resume addition of sodium hypochlorite within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> following CT-1 addition as per existing procedures Unit 2 - Control unit: No treatment except normal chlorination during Unit 1 test Should the Unit 1 Test prove highly successful, application of CT-1 to Unit 2 could begin as early as May or June 1992.

This regime is subject to modiTication in response to surveillance/monitoring data, condenser inspections, condenser performance, and conduit inspections. This information will then determine future CT-1 addition frequency, concentration, and contact time.

Item Pro osed Dischar e Concentrations The proposed discharge concentrations are based on toxicity test results using saltwater species. The complete repom including test protocols and data sheets are provided in the following attachments:

Attachment Date of Number Report Title 6-10-91 The Acute' Toxicity of Betz Clam-Trol CT lth 7-24-91 The Acute Toxicity of Betz Clam-Trol CT-1 in Menidia menidia 5-16-88 Marine Toxicity Study with Biocide ¹1001 Using the Mysid Shrimp 5-16-88 Marine Toxicity Study with Biocide ¹1001 Using the Sheepshead Minnow 4-17-91 The Chronic Toxicity of Beta Clam-Trot - ~Crinodon v~rarie ates 7-31-91 The Chronic Toxicity of Betz Clam-Trol CT-1 in

~Mido sis hahia

v st Mr. Ray Cunningham October 15, 1991 Page 6 The acute toxicity results are summarized below:

Species 96-Hour LC50 (mg/l) 1.24 Silversides (Menidia ~menidia 6.0 Mysid Shrimp (MM~ido )sis b~ahia 1s45 Sheepshead Minnow (CCCrhtodon ~varie atua 7.0 The LC 0 values are expressed as nominal concentrations. Measured concentrations taken during the two more recent acute tests (Attachments 2 fk 3), however, show very little adsorption of the test substance onto test chamber surfaces. For ~Rhe ioxOnius abronius CT-1 product was measured at Te, Tm, T> and Tvs intervals. The overall average measured concentration for 18 measurements over the five test concentrations was 105% of nominal with a standard deviation of 14.90k. The LC50 value based on nominal concentrations, therefore, provides a valid and somewhat conservative estimate of acute toxicity of CT-1 to the most sensitive saltwater test species.

Although the discharge canal at the St. Lucie Plant is not accessible for use by aquatic populations in the receiving water body (Atlantic Ocean), the protocol for CT-1 use at the plant will ensure that, as a consequence of such use, there will be no acutely lethal condition prior to the POD within the canal. Given the dilution at the multiport and diffuser ports located up to 1450 feet offshore, this also will ensure that no chronic toxicity will occur in the Atlantic Ocean due to CT-1 use.

No observed effect concentrations (NOECs) were determined for two species. The lowest NOEC was 1.25 mg/1 for the mysid stuimp, ~Mido sis bahia. However, the 96-hour LC50 for this species was determined to be 1.45 mg/I, indicating a very steep dose-response slope and low margin of safety. Therefore, rather than using the lowest measured NOEC, FPL proposes use of a more conservative approach based upon calculation of an instream waste concentration (IWC).

In accordance with EPA guidance (Peltier and Weber. Methods for Measuring the Acute Toxicity of Effluents to Freshwater and Marine Organisms, Third Edition. U. S.

Mr. Ray Cunningham October 16, 1991 Page 7 EPA Environmental Monitoring, and Support Laboratory, Cincinnati, 1985), a factor of three is applied to the LC5> of the most sensitive species to define the IWC protective against acutely toxic concentrations of an effluent constituent.

Tllus:

IWC < LCSO of most sensitive s ecies (3) or, for CT-l, IWC < ~1.2 ~ml (3)

< 0.4 mg/L CT-1 will be added to one conduit at a time thus implementing a segmented application. This strategy, combined with chemical analyses and biomonitoring at the POD, and the capability for detoxification (described below), will ensure that the concentration of CT-1 at the POD will not exceed acutely toxic concentrations or an IWC of 0.4 mg/1 CT-1 product. The initial operational reduction in effluent concentrations will be a function of two factors:

1) Passive neutralization via adsorption- The cooling water in each conduit will exert a demand upon the CT-1 active ingredients above the target organism demand as a function of total suspended solids as well as conduit surface area. These active ingredients readily adsorb onto suspended solids in addition to the micro and macro-fouled surfaces. Once adsorbed, these active ingrediants are no longer bioavailable and, therefore, do not exhibit toxicity. This passive neutralization of the active ingrediants as they pass through the cooling system signiTicantly reduces their concentration prior to discharge.

2) Segmentation of treatment application- This approach allows for the dilution and passive neutralization of the treated stream with the remaining untreated cooling water. At the St. Lucie Plant segmentation results in an eight-fold reduction of active ingrediant concentrations by the dilution mechanism only as condenser and auxiliary equipment cooling water discharge streams converge in the discharge canal en route to the POD, As an application window is defined, plant engineering and environmental personnel will be advised to arrange for the maintenance of the appropriate water flow through the plant to assure discharge permit compliance. Chemical addition will be to one conduit per application with at least 4 days between treatments.

Ray Cunningham October 16, 1991 Page 8 Dilution alone will reduce the level of CI'-1 product to 1.2 mg/I (0.2 mg/l active ingredient) at the POD. Passive neutralization in the treated conduit is expected to further reduce the CT-1 product to 0.9 mg/l. Additional passive neutralization as a function of the suspended solids load of the once-through cooling water from the seven untreated conduits, as well as from adsorptive interactions with bottom sediments in the length of the discharge canal prior to the POD compliance point, should exert at least the remaining demand of 0.5 mg/l needed to achieve the proposed IWC of 0.4 mg/1, Assurance that no acutely toxic conditions will be present at the POD, however, will not be based on the above calculations. Both chemical analyses and biomonitoring will be conducted at the POD to provide virtually immediate feedback to initiate detoxification should either the concentration of CT-1 exceed 0.4 mg/1 or acute toxicity occur. Chemical analyses will be carried out during the initial testing period at least once every two hours. A bioassay trailer will be located at the POD compliance point to conduct continuous flow-through biomonitoring with M. bahia. This biomonitoring will commence at least 96-hours prior to the first application of CT-1 to provide a background toxicity check At the same time, a definitive 96-hour flow-through bioassay of CT-1 product will be carried out with M. bahia to verify the LC z obtained earlier (see Attachment 4) with measured concentrations taken daily.

At initiation of CT-1 application to the Unit 1 conduit, a second series of flow-through tests will commence with M. bahia. Concentrations of CT-1 in the test chamber will continue to be measured daily to confirm that the actual dose is the same as measured concentrations in the effluent. If at any time during this bioassay acute toxicity is observed (or chemical analysis detects CT-1 > 0.4 mg/1), detoxification willcommence.

This will consist of injection of bentonite clay into the discharge water box directly behind the treated condenser. This will provide maximum turbulence and contact opportunity for detoxification before the treated water mixes with the untreated effluent. Detoxification studies have shown that the maximum feed rate ratio of bentonite clay to residual CT-1 in order to achieve non-detectable levels of CT-1 in solution will not exceed 2 to 1. In the total absence of any system demand, this well not exceed a concentration of 5 mg clay per liter. If detoxification becomes necessary, new flow-through biomonitoring tests will commence immediately. Ample stocks of M. bahia acclimated to ambient salinity will be maintained in the bioassay trailer to conduct all planned and contingency testing.

Mr. Ray Cunningham October 16, 1991 Page 9 It is anticipated that the on-site bioassay facilities will be needed for five days prior to the first application of CT-1 to 10 days after first application. This will allow two successive 96-hour test periods following the beginning of initial application; however, facilities for several simultaneous bioassays will be available. Following this initial demonstration period, the application of CT-1 and any required detoxification will have been standardized. All subsequent applications will include provisions for spot checking by chemical analysis.

Item 5 EPA Re 'stration Number The EPA Registration Number for CT-1 is 3876-145 Previous EPA Concerns and Res onses b Betz Toxicolo sts Uses of CT-1 already have been approved by various regulatory agencies including the U. S. EPA Region I, New York DEC, Ohio EPA, Pennsylvania DER, South Carolina DHEC, and numerous other State agencies. Nevertheless, additional concerns have been raised by the U.S. EPA Region V. Attachment 8 addresses these concerns in a letter from Ms. Joan M. Karnauskas, Chief of Permit Section, to Mr. Larry Lyons, toxicologist for Betz Laboratories, Inc. The Karnauskas letter refers primarily to findings in a paper by Cherry et al. (1990 Corbicula Control Program Environmental Fate and Effects Studies - Baseline, Spring and Fall Dosing Studies. Duquesne Light Company, Beaver Valley Power Station, 1991). Also included in Attachment 8 are letters written in response to the Karnauskas letter by Dr. Donald Cherry of Virginia Polytechnic Institute and State University and by Dr. Dwight Davis and Mr. Larry Lyons, both of Betz Laboratories, Inc. We feel that these responses adequately address the concerns expressed by Ms. Karnauskas.

It should be noted it is FPL's understanding that the remaining concerns of EPA Region V are specific to application of CT-1 in freshwater environments. SpeciTically, these are related to biodegradation under anaerobic conditions and repeating the freshwater bioassays with measured concentrations. These concerns should not affect a decision for application of CT-1 in the saltwater environment of the St. Lucie Plant.

Mr, Ray Cunningham October 16, 1991 Page 10 Your prompt attention to this matter is greatly appreciated as FPL would like to conduct the first application of CT-1 in February 1992. If you have any questions of this correspondence or need additional information, please contact Ron Hix at (407) 697-6937 or Dr. Ed Zillioux at (407) 697-6932. FPL and Betz personnel also request a meeting in Atlanta to further discuss this application at EPA's earliest convenience.

Sincerely a '. Smith, Ph..

Manager, Air & Water Permitting Programs Florida Power & Light Company cc: Charles Kaplan - EPA Tammy Moore - EPA MAS/ac/rcunningham.ltl

k ff I g

P l

• )

P 0 Box 078768, West Palm Beach, Ft 33407 07%.

CERTIFIED MAIL October 25, 1991 Air. J. Scott Benyon Southeast District State of Florida Department of Environmental Regulation 1900 S. Congress Avenue West Palm Beach, FL 33406 RE: St, Lucie Power Plant Industrial Wastewater Permit ¹10-56-118222 Proposed Defouling Operations

Dear Scott:

Enclosed, please find a copy of a letter Florida Power and Light Company (FPL) sent to Mr. Hamilton Oven of the Department regarding proposed defouling operations at the St. Lucie Plant, As you know, Unit 1 of the St. Lucie Plant has individual permits and Unit 2 is certified under the Power Plant Siting Act. Although the units have a different regulatory history and status, there are numerous physical components of the plant which are commonly shared by both units. One of these components is the ocean cooling water system. Since both units share the same cooling water system and the proposed defouling program for this system requires extensive toxicological knowledge and expertise, FPL believes that the Department's review and approval of our request may be simplified if the review was managed out of the Department's Tallahassee Office. However, if the District Office feels otherwise, FPL is amenable to handling this matter in any way you feel is'ppropriate.

Please let us know as soon as possible if our proposed handling of this matter is consistent with the District's policy and preference. Please feel free to contact Winifred Perkins at (407) 697-6936 if you have'any questions or comments.

Sincer ly, Martin Smith, Ph.D.

Manager Air and Water Permitting &, Programs Attachme 8911114021 7

,l r II l

I l

I I

I 7, l llr r

~ I I

l rl4'

il I

~l OISCHARGE PIPE

(

I

(

I I

OISCHARGE PIPE A>LANTIC OCEAN INTAKE PIPES Y

II I

I

(

I'OINT OF OI SCH ARGE UJ C7 X

O Vl O

STATE ROAO A)A g 5 l i I ~

UNIT UNIT I

+ INTAKE CANAL

.BIG MUD I CREEK kg g X ST. LUCIE POWER PLANT

4 I ~C p ~

(

~ I)l d h

P 0 Sax 078768 West Palm Seach, FL 33407:0;S-CERTIFIED MAIL October 25, 1991 Mr. Hamilton Oven Administrator of the Siting Coordination 0 ice Florida Department of Environmental Regulation 2600 Blair Stone Road Twin Towers Office Building Tallahassee, FL 32399-2400 RE: St. Lucie Power Plant Site CertiGcation SPA-7442 Proposed Defouling Operations

Dear Mr. Oven:

In accordance with Condition Number VII and General Condition Number 3 of the above-referenced Site Certification, Florida Power and Light Company, (FPL) hereby notifies the Department of proposed defouling operations at the St. Lucie Power Plant.

Based on a preliminary discussion between the Department and Bill Green of Hopping, Boyd, Green and Sams, we understand that your office will coordinate with the appropriate technical sections within the Department. Concurrently, FPL is notifying the Department's West Palm Beach District office since an Industrial Wastewater Permit (Permit No. 10-56-118222) authorizes discharges from Unit l.

fn addition, FPL has submitted a request to modify the NPDES Permit (Permit No.

FL0002208) to Region IV of EPA. The package of information contained herein is similar to the information contained in a package sent to EPA on October 16, 1991.

On October 21, 1991 representatives from FPL met with EPA to discuss the proposed program and obtain EPA's input and guidance. EPA indicated that they would work diligently toward modifying the permit within 90 days,-provided the data supported our request. The NPDES permit requires that certain information be submitted prior to using a biocide other than chlorine. Since the information prepared for EPA is so comprehensive, we elected to use the same format in presenting the information to the Department. However, if additional information is required, please let us know.

The St. Lucie Plant has continued to experience severe biofouling of the plant's cooling water systems. The growth and accumulation of a variety of both shelled and soft-bodied organisms in the forebay area immediately preceding the once-through cooling water and auxiliary equipment cooling water (intake cooling water) systems seriously impairs cooling water fiow. These organisms include, oysters, mussels, barnacles, sn FPL Gtouo company

\

$~

~8 n

r l

I S

l s dt L~ =y' 1

Vga I

Mr. Hamilton Oven October 25, 1991 Page 2 bryozoans. and hydrozoans. This macrofouling growth also results in the transport of these organisms, both dead and alive, onto the condenser tube sheets and into the condenser and heat exchanger tubes. The resulting reduction in the supply of cooling water has two significant effects:

1) Increased requirements for more expensive replacement power as the units run at reduced load to facilitate manual cleaning of the once-through cooling water system and,

2) Reduced availability, reliability, and capacity of the auxiliary cooling water heat exchangers, which are principal components of a nuclear safety system.

The biofouling control option currently, allowed under the Site Certification is intermittent chlorination, which has little or no effect on macrofouling organisms.

Continuous chlorination, if approval were granted, could control macrofoulants, but would be impracticable and a significant safety hazard due to the large quantities of gaseous chlorine required. In cases where continuous chlorination is applied to once-through cooling water, gaseous chlorine is typically delivered by railroad car every 10 to 14 days. At the St. Lucie Plant, this quantity would have to be trucked in over the Intracoastal Waterway bridge, which would necessitate daily deliveries and pose unacceptable handling and safety-related problems. In addition, gaseous chlorine is not permitted on the plant site by Nuclear Regulatory Commission regulations and would require major plant modifications before a variance could be granted.

The use of liquid hypochlorite for continuous application is precluded since the quantities that would be needed would far exceed even that required for gaseous chlorine.

Numerous options to conventional chlorination for biofouling control have been studied in considerable detail. After all studies were completed, FPL determined that a Betz Industrial product, Clam-Trol CT-1 (CT-1),'is likely to be most effective method of addressing this problem.

Upon obtaining the necessary approvals, FPL will be conducting an 18-month evaluation of CT-1 to determine both its effectiveness and environmental impact. The 18-month period represents one fuel cycle for the plant. This is the minimum of time in which the product can be evaluated since it would guarantee that the plant would be shut down and the intake structure available for inspection during the refueling process. Following this evaluation, FPL will be able to determine if CT-1 is an effective product for long-term use. If it is deemed effective, FPL will request long-term approval at that time.

j J

n

- I J

il ~ ~ I I'

Mr. Hamilton Oven October 25, 1991 Page 3 Enclosed, please find the information to support our notification:

Item 1 Name and General Com osition of Biocide or Chemical CT-1 contains 130/o active ingredients of two cationic surfactants and 87% inert materials. The two cationic surfactants are n-alkyl dimethyl benzyl ammonium chloride (QUAT) and dodecylguanidine hydrochloride (DGH), Attachment 1, the Betz Clam-Trol CT-1 Environmental Information Package, contains information on the adsorptive characteristics, toxicity to saltwater organisms, biodegradation, environmental fate, and detoxification processes of the cationic surfactants. A considerable amount of additional aquatic toxicity information will be presented later in this submittal.

Item 2 Fre uenc of Use and Item 3 uantitites to be Used The frequency and quantity of CT-1 use at the St. Lucie Plant will be determined during an initial optimization phase of the 18-month test period. '%e purpose of optimization is to minimize the number of applications per year, the period of application and the dose that will be needed to achieve efficacy. The anticipated optimal treatment will be 5 to 6 applications per year, 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> per application and a dose level of 10 mg/L Although additional treatment may be necessary, the maximum use of CT-1 should not exceed 12 applications per year, 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> per application, and a dose level of 10 mg/L The only possible exception that can be envisioned may be in the event of an unusual storm event that could potentially cause unusually high demand to the treatment dose of CT-1. In that case, the dose level may need to be increased to no greater than 15 mg/l, although such increased demand would preclude any corresponding increase in the discharge residual concentration.

The configuration of the St. Lucie Plant allows this chemical application program to be effective against target organisms in a precisely defined area while it niinunizes the adverse environmental impact beyond the perimeter of the treatment zone. The treatment cycle will be predicated on growth characteristics of the fouling organisms using continuous surveillance equipment, condenser and forebay inspections, and condenser performance tests. The acquired data will be reviewed and an application window established.

CT-1 will be supplied in 350 gallon portable, reusable semi-bulk containers and fed through a portable pump/header system. The handling of the CT-1 in semi-bulk containers has several significant advantages including no permanent storage/handling faci1ity or piping required, and minimum potential for chemical spills. Secondary containment will be provided around the CT-1 product container.

I I

i '

JL

Mr. Hamilton Oven October 25, 1991 Page 4 CT-1 ~41 be introduced into one conduit at a time. For purposes of this submittal, a conduit consists of the intake forebay area, waterbox and condenser associated with a single circulating water pump. The appropriate quantity of chemical will be brought on site, placed by the target conduit, injected within a two day window with Betz personnel assisting, and the empty semi-bulk containers removed to a holding area for return to Betz for processing. This procedure can be completed within a 3 to 5 day period per conduit.

Distribution of chemical into the cooling water is critical to achieve control of macrofoulants with a miriimum of product. The addition of CT-1 through a portable header located immediately upstream of the bar screen will optimize distribution of chemical to the targeted organisms. The header will be designed to apply the chemical along the boundaries or walls of the forebay to maximize the concentration of CT-1 to the organism growth sites.

During the Betz-assisted chemical injection of CT-1, the injection rate will be monitored and controlled using an analytical test procedure capable of determining the concentration of CT-1 present in the cooling water with a method detection limit of 0.2 mg/l of product or 0.026 mg/l of total active ingredients. The ability to test for these active ingredients allows the dosage to be optimized and confirms compliance with applicable State requirements.

This analytical procedure also will be used to measure the demand of the incoming cooling water for the active ingredients in CT-1 and then predict the effectiveness of adsorption/passive neutralization. This capacity to determine when demand is lowest during an application window, translates into reduced feedrates/quantities of chemical needed per successful application thus minimizing environmental and economic impact.

Testing for product addition rate and active ingrediants present at the point of discharge (POD) will be provided during the entire application process to confirm compliance.

Betz personnel will be present during each addition of Clam-Trol to optimize performance, monitor and control chemical addition to assure compliance, and provide FPL with on-site expertise and assistance.

In addition to distribution and feed control, the control of dosage and contact time of CT-1 is critical to effect a high (95-100%) mortality of the targeted organisms. FPL plans the following steps as the initial chemical addition regime;

<t Mr. Hamilton Oven October 25, 1991 Page 5 Unit 1 - Conduit A and B Step a - Chlorine: Discontinue addition of sodium hypochlorite to the target conduit at least 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> preceding CT-1 addition Step b - Chlorine: Continue addition to the auxiliary cooling water heat exchangers-no change Step c - CT-1: Add CT-1 at 10 mg/l (as product) for 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> Step d - Chlorine: Resume addition of sodium hypochlorite within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> following CT-1 addition as per existing procedures Unit 1 - Conduit C and D Step a - Chlorine: Discontinue addition of sodium hypochlorite to the target conduit at least 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> preceding CT-1 addition Step b Chlorine: Continue addition to the auxiliary equipment cooling water heat exchanger - no change Step c - CT-1: Add CT-1 at 10 mg/l (as product) for 18 hours2.083333e-4 days <br />0.005 hours <br />2.97619e-5 weeks <br />6.849e-6 months <br /> Step d - Chlorine: Resume addition of sodium hypochlorite within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> following CT-1 addition as per existing procedures Unit 2 - Control unit: No treatment except normal chlorination during Unit 1 test Should the Unit 1 Test prove to be successful, application of CT-1 to Unit 2 could begin as early as May or June 1992.

This regime is subject to modification in response to surveillance/monitoring data, condenser inspections, condenser performance, and conduit inspections. This information will then determine future CT-1 addition frequency, concentration, and contact time.

Item Pro osed Dischar e Concentrations The proposed discharge concentrations are based on toxicity test results using saltwater species. The complete reports including test protocols and data sheets are provided in the following attachments:

Mr. Hamilton Oven October 25, 1991 Page 6 Attachment Date of Number Report Title 6-10-91 The Acute Toxicity of Betz Clam-Trol CT Rhe~ox~us abronius 7-24-91 The Acute Toxicity of Betz Clam-Trol CT-1 in Menidia menidia 5-16-88 Marine Toxicity Study with Biocide ¹1001 Using the Mysid Shrimp 5-16-88 Marine Toxicity Study with Biocide ¹1001 Using the Sheepshead Minnow 4-17-91 The Chronic Toxicity of Beta Clam-Trol - ~Crinodon v~arie atua 7-31-91 The Chronic Toxicity of Betz Clam-Trol CT-1 in

~Mido sis bahia The acute toxicity results are summarized below:

Species 96-Hour LC 0 (mg/1) s I'rr~lu 'b 1.24 SBversides Q'denidia ~menidia 6.0 Mysid Shrimp ~Ms~ido rais b~ahia 1.45 Sheepshead Minnow C rinodon v~arie atua 7.0 The LC50 values are expressed as nominal concentrations. Measured concentrations taken during the two more recent acute tests (Attachments 2 & 3), however, show very little adsorption of the test substance onto test chamber surfaces. For Rhe~ox~us abronius CT-l product was measured at Te, Tm, T< and Tss intervals. The overall

Mr. Hamilton Oven October 25, 1991 Page 7 average measured concentration for 18 measurements over the five test concentrations was 105% of nominal with a standard denauon of 14.9%. The LC50 value based on nominal concentrations, therefore, provides a valid and somewhat conservative estimate of acute toxicity of CT-1 to the most sensitive saltwater test species.

Although the discharge canal at the St. Lucie Plant is not accessible for use by aquatic populations in the receiving water body (Atlantic Ocean), the protocol for CT-1 use at the plant will ensure that, as a consequence of such use, there will be no acutely lethal condition prior to the POD within the canaL Given the dilution at the multiport and diffuser ports located up to 1450 feet offshore, this also will ensure that no chronic toxicity will occur in the Atlantic Ocean due to CT-1 use.

No observed effect concentrations (NOECs) were determined for two species, The lowest NOEC was 1.25 mg/i for the mysid shrimp, ~Mido sis bahia. However, the 96-hour LC 0 for this species was determined to be lA5 mg/1, indicating a very steep dose-response slope and low margin of safety. Therefore, rather than using the lowest measured NOEC, FPL proposes use of a more conservative approach based upon calculation of an instream waste concentration (IWC).

In accordance with EPA guidance (Peltier and Weber. Methods for Measuring the Acute Toxicity of Effluents to Freshwater and Marine Organisms, Third Edition. U, S.

EPA Environmental Monitoring and Support Laboratory, Cincinnati, 1985), a factor of three is applied to the LC50 of the most sensitive species to define the IWC protective against acutely toxic concentrations of an effluent constituent.

IWC < LCSO of most sensitive ecies (3) or, for CT-1, IWC < ~1.2 ~mQ (3)

< 0.4 mg/l.

CT-1 will be added to one conduit at a time thus implementing a segmented application. This strategy, combined with chemical analyses and biomonitoring at the POD, and the capability for detoxification (described below), will ensure that the

Mr. Hamilton Oven October 25, 1991 Page 8 concentration of CT-1 at the POD will not exceed acutely toxic concentrations nor an IWC of 0.4 mg/1 CT-1 product. The initial operational reduction in effluent concentrations will be a function of two factors:

1) Passive neutralization via adsorption- The cooling water in each conduit will exert a demand upon the CT-1 active ingredients above the target organism demand as a function of total suspended solids, as well as conduit surface area. These active ingredients readily adsorb onto suspended solids in addition to the micro and macro-fouled surfaces. Once adsorbed, these active ingrediants are no longer bioavailable and, therefore, do not exhibit toxicity. This passive neutralization of the active ingrediants as they pass through the cooling system significantly reduces their concentration prior to discharge.

2) Segmentation of treatment application- This approach allows for the dilution and passive neutralization of the treated stream with the remaining untreated cooling water. At the St. Lucie Plant segmentation results in an eight-fold reduction of active ingrediant concentrations by the dilution mechanism only as condenser and auxiliary equipment cooling water discharge streams converge in the discharge canal en route to the POD. As an application window is defined, plant engineering and environmental personnel will be advised to arrange for the maintenance of the appropriate water flow through the plant to assure discharge permit compliance. Chemical addition will be to one conduit per application with at least 4 days between treatments.

Dilution alone will reduce the level of CT-1 product from 10 mg/l (1,3 mg/I active ingredient) to 1.2 mg/l (0.2 mg/l active ingredient) at the POD. Passive neutralization in the treated conduit is expected to further reduce the CT-1 product to 0.9 mg/l.

Additional passive neutralization as a function of the suspended solids load of the once-through cooling water from the seven untreated conduits, as well as from adsorptive interactions with bottom sediments in the length of the discharge canal prior to the POD compliance point, should exert at least the remaining demand of 0.5 mg/l needed to achieve the proposed IWC of OA mg/L Assurance that no acutely toxic conditions will be present at the POD, however, will not be based on the above calculations. Both chemical analyses and biomonitoring will be conducted at the POD to provide virtually immediate feedback to initiate detoxification should either the concentration of CT-1 exceed OA mg/l or acute toxicity occur. Chemical analyses will be carried out during the initial testing period at least

Mr. Hamilton Oven October 25, 1991 Page 9 once every ovo hours. A bioassay trailer ii% be located at the POD compliance point to conduct continuous flow-through biomonitoring with M. bahia. This biomonitoring will commence at least 96-hours prior to the first application of CT-1 to provide a background toxicity check At the same time, a definitive 96-hour flow-through bioassay of CT-1 product will be carried out with M. bahia to verify the LC50 obtained earlier (see Attachment 4) with measured concentrations taken daily.

At initiation of CT-1 application to the Unit 1 conduit, a second series of flow-through tests will commence with M. bahia. Concentrations of CT-1 in the test chamber will continue to be measured daily to confirm that the actual dose is the same as measured concentrations in the effluent. If. at any time during this bioassay acute toxicity is observed (or chemical analysis detects CT-1 > 0.4 mg/1), detoxification willcommence.

This will consist of injection of bentonite clay into the discharge water box directly behind the treated condenser. This will provide maximum turbulence and contact opportunity for detoxification before the treated water mixes with the untreated effluent. Detoxification studies have shown that the maximum feed rate ratio of bentonite clay to residual CT-1 in order to achieve non-detectable levels of CT-1 in solution will not exceed 2 to 1. In the total absence of any system demand, this will not exceed a concentration of 20 mg clay per liter. If detoxification becomes necessary, new flow-through biomonitoring tests will commence immediately. Ample stocks of M. bahia acclimated to ambient salinity will be maintained in the bioassay trailer to conduct all planned and contingency testing.

It is anticipated that the on-site bioassay facilities will be needed for five days prior to the first application of CT-1 to 10 days after first application. This will allow two successive 96-hour test periods following the beginnirig of initial application; however, facilities for several simultaneous bioassays will be available. Following this initial demonstration period, the application of CT-1 and any required detoxification will have been standardized. All subsequent applications will include provisions for spot checking by chemical analysis, Item 5 EPA Re 'stration Number The EPA Registration Number for CT-1 is 3876-145 Uses of CT-1 already have been approved by various regulatory agencies including the U. S. EPA Region I, New York DEC, Ohio EPA, Pennsylvania DER, South Carolina DHEC, and numerous other State agencies. Nevertheless, additional concerns have been raised by the U.S. EPA Region V. Attachment 8 addresses these concerns in a

Mr. Hamilton Oven October 25, 1991 Page 10 letter from Ms. Joan M. Karnauskas, Chief of Permit Section, to Mr. Lany Lyons.

toxicologist for Betz Laboratories, Inc. The Karnauskas letter refers primarily to findings in a paper by Cherry et al. (1990 Corbicula Control Program Environmental Fate and Effects Studies - Baseline, Spring and Fall Dosing Studies. Duquesne Light Company, Beaver Valley Power Station, 1991). Also included in Attachment 8 are letters written in response to the Karnauskas letter by Dr. Donald Cherry of Virginia Polytechnic Institute and State University and by Dr. Dwight Davis and Mr. Larry Lyons, both of Betz Laboratories, Inc. We feel that these responses adequately address the concerns expressed by Ms. Karnauskas.

It should be noted it is FPL's understanding that the remaining concerns of EPA Region V are specific to application of CT-1 in freshwater environments. Specifically, these are related to biodegradation under anaerobic conditions and repeating the freshwater bioassays with measured concentrations. These concerns should not affect a decision for application of CT-1 in the saltwater environment of the St. Lucie Plant.

Your prompt attention to this matter is greatly appreciated as FPL would like to conduct the first application of CT-1 in February 1992, If you have any questions on this correspondence or need additional information, please contact Winifred Perkins at (407) 697-6936 or Dr. Ed Zillioux at (407) 697-6932. FPL and Betz personnel are also available to meet with you if the Department has any detailed inquiries.

Sincerely, Martin A. Smith, Ph.D.

Manager, Air & Water Permitting Programs Florida Power & Light Company Attachments cc: J. Scott Benyon - DER/WPB Steve Wolf - DER/TalL Bill Green - HBG&S

0

~

~ 0 0 0 l

I ~

~ 0

~ '

l r ~ o I I.I I I I

~

p%

R R

J r

h

AQUATIC TOXICOLOGY LABORATORIES, INC. LASORATORY SOMERTON ROAOiTREVOSE, PA 1 9047eU.S.A. i'EL:81 5e355-3300e TELEX: 1 73 1 48iFAX ¹ 355-2869 EmXRONMENTAL INFO~TXON ON CLAM-TRQL CTM FOR MACROFOUQINQ "'ONTROL, '

Clam-Trol CT-1 is a patented nonow'idizi'gg~~lu'scjiid'e.~boa,yidigg e

state-of -the-art control -for my,crpgou@pcj':;caui'ed"A j'~j@~'0 'a3:ams,:-"-

4 Zebra mussels and marine foulipg organl.'qms',.",'Mlmj~q1-'~~<<4.=a4 a,"'""..,

federally registered molluscici.gp'-" for-'.~e"-. 4i Knee 'gg'?~',+%@,".=-'";,,-'.: .'" +~

• recirculating cooling systems.,)he.".hph';,!n jgdwstrs&cn '585i~M..(gal 3876-145. 's Clam-Trol CT-1 has been used since 1886 for,-.ksi'atic clam'ma'cmfo~gg ':..

control to power plants, steel -mi3.,3.s, cht'mical rdfinhrie's.an'd', +h'er..:'"

manufacturing facilities. Appendix I pre'sent's "some".case .hiitojzei "for"-.

Asiatic clam control.

The efficacy of CT-1 towards zebra'-"muasels-has been. demonstratea i.n,

, >laboratory studies and it has also'.-',b'caen utilizeR for tahe-.'eMrmin'a'pioij,"

of zebra mussels at power plants".and'ncIustriai 'Xacil'i+Les','-'The".".',." ':., .

evaluat,ions (See Appyiidi;x" 2 j -4imianstrated-'tnh~~ghqg.'.~." .. '..>."'aboratory CT-1 for exposure periods of 6 to--24: hoGW Q'.vafeP+ekpeghtWe)."p~..

50 100 150 and 200C. It has peen'~demonat~Kteh'@K%'7aOrtyl>tg'",-.;-:

are dependent upon-CT.-1+6age ="-ixpi'sixie$i F4'gK",.","@@"';;:, .=;.',. "" --

temperature. Appendix 3 presentj-';-j pase-+Xst jory".:on ~-.~it, for"eradication .of ~@bga,pusse15'-.at;:Cwo'-j)oper"pl~'QW.

-'Cg~l, ==

'esponses

'pplications located along Lake Erie in 1989..

Marine macrofouling can be caQsqd'.Qy.:a- ivarietg oi orgm>.sms., "@~b<ji;,.:: " +y",

blue mussels, oysters, barnacles, >hj5gozoans,'brjozo'Ahab.;- .tug3M'&el~,==-a . =->>.,

and others. A review on ci-1 coptroI"methods: fo'r'"hvÃ1S "mussel,g5ILij$ ;,: ';'*

(See Appendix 4) provides a referjiicer&ox"'.,4mplementf~"cqgjtWQ;:.'~."';.'.:.

programs to cooling systems. Another 'paper:-Remonstrate's Gt@-.qd&$ajry'" ..

of monthly CT-1 treatment programsL'dur'ing .a -90 'day's@sspaY~,',",,--.,

evaluation (See Appendix 5) for ma'oro'foul'gg -contdi&6'ted>4$ ..yiCkrs:,'..".

ribbed mussels, barnacles and other'~b'ioi-@@ling'-growth~"" -"

InfOrmatiOn On Clam-TrOl CT-1 tO aid'in'~a@dreSSingr,,Ã+EeS'- permiC is being presented, as followi:-""-' '-" 'equirements

.'ame of the additive Clam-Trol CT-1 contains 13<,.active'ingredients'two,'cbtiqnic.:,-'.,<---'-

surfactants) and 874 inert materials'.,'=;.. The:-,,"tVo';:catioj4c'.;.,",,',.".-"

are N-alkyl dimethylbenzyl'mmondjiim -.chleiide",:(QQat)p';: -;.'urfactants and dodecylguanidine hydrochloride -(+AH);.- -;-.The'.ner't.-materials O'.

89111140217

".ri .n~ >>( j; X Tf( QP><<'

<<fill (9>>> +.J 'I '. d, I

<<>><<IJg +@<<( t >>> ~ I' f '(1 C'P r.r.' i." ~o,"i:I =""'af. ( <<>>,

c<<>w j, >i

<-'X V '". -' c.'OU;".- ..C ."(.'TSILVSa'<<; " rig.(

>> <<>>f

~ ~ i ~ ~

~ 4>>ii<<BS&C i~i ~ P( ~ ~ ( ~

(<<<<'

(

( J1S ('i i>>v I

>~ >>.

~ r~g ( >>tC>,

v4 > g ~

(~

(1f, )\

>><<f'

(

~'QP C(. >><<<> g

<<>> I" CC hei(t ~ ~.LC r:

g (>>>>>

( (9a flan

~ ( 'qr<<

(. ~ .) . i.

v. f g fl h A(,, ~

~ <<

C>, 'V >>

'4 i ~ \

~ ~ <<i( J C

K ~ >> A( f<< '> ~ > 5 ( ~ l , IIl>><<>f

~, ~

this formulation: ethylene glycol, isopropyl alcohol and water are relatively nontoxic to aquatic organisms.

2. Concentration (mg/L) of the additive to be used:

1 Il I Clam-Trol CT-1 is usually fed at concentrations ranging, from 10 to 25 mg/L. 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 to 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> depending upon the water and the CT-1 dosage. 'emperature I

Either seasonal or bimonthly treatment 'programs ranging from 1 to 4 times/year is required for macrofouling control of either zebra mussels or Asiatic clams. Treatment programs for;the control of marine macrofouling will range from 4 to >6 times/year depending upon the kinds of marine organisms and the length of the growning season. It must be noted that the objective of,these seasonal or bimonthly applications is to provide a preventative treatment program by exterminating the juvenile stages to prevent their growth to adult fouling size and to reduce the overall accumulation of juvenile stages 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 1 to >6 times/year, will depend upon the degree of larvae and juvenile infestations and the kind of macrofouling control so the operations of the power plant or industrial facility are 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 treatment programs are designed so is always less than 1 that the concentration of Clam-Trol CT-1 mg/L in the discharge. The reduction of CT-1 from the point-of-feed to less than 1 mg/L at the outfall is achieved by one or more of the following approaches:

1) Both the intake river water and the cooling system have many kinds of naturally occurring materials silts, clays, suspended solids, humic 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 neutralization longer exhibit toxicity. Thus the passive of the CT-1 actives as they pass through the cooling

<<4 system will significantly reduce the concentration prior to discharge.

'-s",oaf:>:! '.6dzH ad =-'..>" s~,"'."'! -".fo":,.'.

IC'1 V

--'.6 ~reT (r ',',xsc~ ~c:~r ':e:s" 5".:

>J .'" 'l. ) g'; kf.',-'. 'P Ji.' tt ff Ig e '.vfV BitC3$ 1 i fi Q i QB 'ting "I ' i)g/g g ~

Vle e' f +<. 1>S "+ '>~ K <<PVt" >We-IW< >1; 3 ~ '(>'.I'J5

'i~

g gS cpm gevC~t~gg eifvggg%e jg VI

' V; e 'VD ne '> 'P'>no; a "~s 'eze y~,. ~..

'"~~>

~yaL.

r~'" ~E,,c,<>,',e:.i fe P ~ ~i't ' ee" aisle 'v <<'I Cf&eev. <<8 vi~. wed' )1e; 'O

-'Z<>."."2-6-~~5" Xai

'~'f "- eeV'$~Q f f Q>> = $ 'geegeet

'id~'QQ tl i eQ I rtgtl Mgt eggs I C

~ ( ~ tj ee V

V ggiVgee ek g g( Il ( +l Ie Ieeegy j eel fVJC jV + 'I V3d,f. J."Q ~ 7 f, "

(

'"".L.~~

-07. O<R"

VQD -'Iaaf.PVe-.,- A. '. /e ~h ~

7

'1 I

~ a I aJ Pke eC DI .II iV e f~p i~

QCX Vie.

Appendix 11: Detoxification Potential of Clam-Trol CT-1 with Clays and Other Materials to Fathead Minnows and

~Da hnia maqne Appendix 12: ( (~( ( ' y Survival and Growth Study of Detoxified Clam-Trol CT-1 with Clays Appendix 13: A Long Term Study With Fathead Minnows and ~Da hn3.a macCna on the effect of Detoxified Clam Tr-ol CT-l Appendix 14: A Comparison on the Acute Toxicity (LC5p's) of Clam-Trol CT-1 at Different Water Hardness Appendix 15: Abiotic Effects (pH and temperature) on Detoxified Clam-Trol CT-1 with Clays Appendix 16: The Effect of Ammonia Levels on Detoxified Clam-Trol CT-1 Appendix 17: Analytical Method for Clam-Trol CT-1 Appendix 18: MSDS Appendix 19: LC50 Values of Clam-Trol CT-1 (Neat Formulation):

Marine Species Appendix 20: A 7-day Sheepshead Minnow Chronic Toxicity Test with Clam-Trol CT-1 Appendix 21: A 7-day Mysid Shrimp Chronic Toxicity Test with Clam-Trol CT-1 Prepared by:

Larry A. Lyons Acpxatic Toxicologist Laboratory Manager LAL cn

C P

F.F ~

F E

F l,

~

F P gVtn ~

F f

$ FF ~

E F

F -FF F

' F P

Technical Paper 299

~~Benz kt Lz/imtÃxP AMERICAN POWER CONFERENCE ILLINOIS INSTITUTE OF TECHNOLOGY CHICAGO, ILLINOIS APRIL 18-20, 1988 EVALUATIONOF A NEW MOLLUSCICIDE FOR ALLEVIATING MACROFOULING BY ASIATIC CLAMS LARRY A. LYONS BETZ LABORATORIES, INC.

TREVOSE, PA OMAR CODINA TU ELECTRIC DALLAS, TX RAYMOND M. POST BETZ INDUSTRIAL TREVOSE, PA DAVID E. RUTLEDGE TU ELECTRIC IVIESQUITE, TX 1S88 Betz Industrtel. All Rtghts Reserved

EVALUATION OF A NEW MOLLUSCICIDE FOR ALLEVIATING MACROFOULING BY ASIATIC CLAMS Larry A. Lyons ers, increased maintenance costs for equipment, and Supervisor, Aquatic Toxicology forced plant outages. These pests must often be. physi-Betz Laboratories, Inc. cally removed from the systems they invade. EPRI has Trevose. 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 dollars per year (1).

TU Electric The threat to safety-related and service water systems is Dallas, TX another major problem. Following the Arkansas Nuclear One forced outage, the 1981 NRC bulletin to all nuclear Raymond M. Post plant licensees recommended the Implementation of a ProJect Engineer monitoring program for determining the severity of Asiatic Betz Industrial clam fouling. It also recommended the establishment of Trevose, PA preventative control measures for all safety-related com-ponents (2).

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 Mesquite, TX mechanical methods or the use of oxidizing biocides.

t ABSTRACT Macrofouling by Asiatic clams impedes the efficiency, operation, and safety of power plants by plugging con-denser tubes, threatens plant availability, jeopardizes safety-related water systems, and damages equipment.

The use of screens and strainers or physical removal measures (such as dredging and vacuuming operations) do not prevent the growth and proliferation of the clam, but only provide temporary relief from advanced fouling conditions. Oxidizing biocides, (e.g., chlorine or bro-mine) require weeks of continuous, uninterrupted appli-cations to achieve efficacy (3). When continuous chlorination Is permitted, the effect on corrosion, espe-The current state-of-the-art control technology lacks an cially of copper alloys, is a major concern. Because Asi-effective biocide for alleviating and preventing this seri- atic clams have chemoreceptors that detect low concen-ous problem. trations of oxidizing blocldes, they can avoid contact by clamming-up for extended periods.

At TU Electric's Lake Hubbard station. the clam popula-tions colonizing the Intake bays caused chronic fouling of Alternative chemical control agents are either ineffective the main condenser tubes. The new molluscicide 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 maintain control by exter- before discharge (1, 4, 5).

minating juvenile Asiatic clams that recolonize the sys-tem. Seasonal molluscicide applications from June 1986 This paper describes the successful application of a new through October 1987 were shot fed to nonoperating in- mollusclclde that is considerably more effective on the take bays. The performance of the molluscicide applica- target organisms than chlorine and which can be con-tions requiring only brief exposure periods has been veniently applied to intake bays.

evaluated with In situ biomonitoring methods.

BIOLOGY OF THE ASIATIC CLAM t

INTRODUCTION Asiatic clams, often referred to by their scientific name The cost of Asiatic clam macrofouling to the power in- "Corbicula". are bivalve mollusks that thrive in fresh dustry is associated with reduced cooling efficiency and water environments. This extremely hardy species lives plant output by plugging condenser tubes, impaired and In a wide range of freshwater habitats throughout most of damaged circulating pumps and oil and hydrogen cooi- the United States. It can even prosper in moderately pol-

luted waters. The increased ambient water temperatures actively detoxified with certain clays or other inert materi-surrounding a power plant further enhances the prolifera- als, if necessary.

tion and establishment of Asiatic clam populations.

Asiatic clams colonize In dense populations; 1000 to APPLICATION EXPERIENCE 10,000 clams per square yard are common. The clams Although TU Electric's Lake Hubbard Station is the first are filter feeders that siphon ln algae and bacteria from field application to nonoperating intake bays. the new the water. Their natural predators are fish and crayfish. A molluscicide has been used in other Asiatic clam control plant's cooling system offers an ideal clam environ-applications (7-9). Examples of other types of applica-ment it is free of predators and provides a continuous tions include a seasonal preventative treatment program supply of food.

for the service and safety-related water systems of a nu-An Asiatic clam reaches sexual maturity when it is about clear facility; a combined microorganism and Asiatic 6 months old (3'n. in size). Each adult is capable o! clam fouling control program of the molluscicide coupled self-fertilizatlon and can release many thousands of with chlorine; and plant-wide applications to a steel mill veliger larvae during the spawning seasons from Spring with a water system network containing miles of pipe-through the Fall. lines, Juvenile clams (less than ji4 in. In size) and larvae are LAKE HUBBARD STATION small enough to pass through cooling system intake screens. Once inside, they settle out primarily in low flow The Lake Hubbard station of TU Electric, a two.unit gas-areas. They attain adult size within a few months and are fired generating facility, has experienced chronic fouling then transported further Into the cooling system. It is the and forced outages resulting from the pluggage of the transport of adult sized clams further into the cooling sys- main condenser tubes by Asiatic clams.

tem that causes the chronic fouling problems that threaten the safety, operation, performance, and sys- Lake Hubbard's intake bays measure 40 x 11 ft with a tems availability of power plants. high-water depth of 40 ft (see Figure 1). Unit 1 has two intake bays (1A and 18), and Unit 2 has three intake bays (2A, 2B. and 2C).

DEVELOPMENT OF A NEW MOLLUSCICIDE The new molluscicide, called Clam-Trot CT-1 (patent Side Vihv pending). is effective against all life stages of the Asiatic clam, using short exposure periods of relatively low con- I I

I I I I

~

I I

I ~ I I I centration. Clam-Trol CT-1 is an aqueous based formula- Water Swfoce I >

I II r tion containing two cationic surfactants, alkyldimethylben- I I

~

>>>It I

I zylammonium chloride and dodecylguanidine hydrochlo- I ~ tl I I I >t>l I ride. I t

~

II I I

Frontof Bay I I I >I I I I I I I I> I I I I> ~

I

>I 40 ft Oin This new mollusciclde presents a unique advancement in I >1>> I

> I I I I the art of macrofouling control by having the capability of I >>,>I r I I I I I killing adult as well as juvenile Asiatic clams ln cooling I

I I' I I > Spa>car Ip wr I >t>t Fee> Po>ht I sytems using feasible, cost-effective treatment regi- >.ohe I ~ >> I I IIV

/

SiCh p>ant S>ae mens. When applied, the material remains substantially undetected by the clam, which siphons in a lethal dos- 40ft Oin age during an exposure period of approximately 24 to 48 TOP YiPW hr (depending on concentration and water temperature). r A delayed mortality response occurs following the brief >>I exposure period. Since the clam requires several months I I>t>f I>tt I I>

II 0 II>I B>h I I>"'

to a year to grow a shell of fouling size, periodic applica- I I> I

> I II I tions following peak spawning periods are sufficient to prevent clam fouling. Studies have shown that once the Coouta t inc Pump Stat>aha>7 Bc>eche molluscicide actives are adsorbed by substrates (includ- Trove>tino Screen Service Water Pump>

Tra>h Screen Ing sediments, suspended solids, and even the surfaces of cooling systems), they no longer exhibit toxicity to Figure 1 ~ Intake bay at TU Electric's Lake nontarget organisms (6). The molluscicide can also be Hubbard Station.

'I

Asiatic clams colonize both the plant and lake sides of Before this treatment, the only recourse for reducing the the five intake bays. Each bay is equipped with one number of clams transported to the main condensers In-travelling screen and two stationary screens. Since these volved periodic mechanical clean-outs of the intake bays screens have a mesh size 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-y4 in. in size (about 6 months old) maneuver through the ducing the number of adult clams.

screens at all water depths (see Figure 2). These infil-trating juvenile clams then colonize and grow on the plant For these reasons, Clam-Trol CT-1 was applied to exter-side of the intake bays (see Figure 3). Adult clams that minate the juvenile clams that were recolonizing the in-have attained the size of Q to P4 in. are then trans- take bays.

ported to the main condensers and auxiliary coolers and MOLLUSCICIDE APPLICATION METHODS plug the tubes. Previous clean-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-sity of the clam population residing ln the bays and their size range. In many cases, mechanical clean-outs may C

be required prior to the initiation of molluscicide treat-ments in order to prevent a massive transport of dead clams further Into the cooling system. At Lake Hubbard, the intake bays were cleaned out using divers.

The feed system was designed to maximize the disper-sion of the molluscicide at the bottom of the intake bays.

A sparge header (1-in. diameter and 10-ft long) was 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.

A 50-gal stock solution of the molluscicide was prepared 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 further diffusion of the molluscicide. Shot-fed dosages for Figure 2. Juvenile Asiatic clams maneuvering the various applications were determined based upon the through plant intake screens. dilution of the stock solution by the total volume of water In the intake bay.

+55 Following 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 analytical photometric method (10) was used for monitor-C ing the discharge.

I JUNE 1986 MOLLUSCICIDE APPLICATIONS h p Two intake bays were treated in this application.

Bay 1B. The stationary screens in the intake bays at the Lake Hubbard Station are constructed with "I" beams, creating a 4-in. deep trough for the clams to colonize.

The secondary stationary screen of bay 1B was cleared of all clams residing on the beams. Every other 3.ft beam Figure 3. Clams colonizing plant side of Intake was then reseeded with 75 clams ranging In age from 3 screens. months to 3 years, and the stationary screen was low-

TABLE 1:

STATIONARY SCREEN "I" BEAM BIOMONITORING*

Bay 1B: 48.hr Treatment Period/4 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment Depth of Bay. ft 0 1 2 3 37 88 91 93 99 100 31 0 36 63 77 81 85 25 0 23 5 88 100 19 0 0 1 5 11 15 13 0 0 0 0 0 0

'June 1986 applications.

ered back into the bay. Bay 1B received four shot feed TABLE 2:

applications of 60 ppm each during a 48-hr treatment STATIONARY SCREEN "I" BEAIVI period. The clams were examined daily for 5 days follow-BIOMONITORING*

ing the treatment (see Table 1).

Bay 2B: 24-hr Treatment Period/2 Shot Feed Bay 2B. The "i" beams of the secondary stationary Applications (60 ppm Each) screen of bay 2B were not cleared prior to the treatment No. of Alive Clams Counted/

but were allowed to retain the existing population. They Estimated Cumulative %

were also examined during the post-treatment period.. Mortality on the Following Only a qualitative examination was made, since the hun- Days After Treatment dreds of live clams residing on the ledges were not Depth of Bay, ft 2 4 counted prior to treatment. Bay 2B received two shot 37 12/>95 6/>95 feed applications 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 mortality estimations (see Table 2). "June 1986 applications.

Lake Side Monitoring. Following each treatment period, clams were collected from the lake side of each bay using a ponar dredge. The clams 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 replenished with fresh lake water two to known causes that occurred in the control tank on the three times daily during a 4-day post-treatment period. 5th day (see Table 3).

TABLE 3:

DREDGE SAIVIPLES OF CLAMS COLLECTED FROM LAKE SIDE OF BAYS" Cumulative %'ortality on the Following Days After Treatment 2 3 Control 0 0 0 2 Bay 1B (Lake Side) 74 82 82 82 Bay 2B (Lake Side) 15 41 66 (Dredge Sample. 41)

Bay 2B (Lake Side) 23 34 (Dredge Sample P2)

'June 1986 applications.

In Vitro Monitoring. Treated water was collected from the 40-ft depth locations on the east and west sides of both bays and transferred to aquaria containing clams.

The clams were collected from the intake bays prior to the treatments. Each aquarium received treated water 30 min and 3 hr following each shot feed application. Fol-lowing the exposure period, each aquarium was replen-ished two to three times a day with fresh lake water.

Dead clams were removed during the daily post-treat-ment examinations (see Table 4).

1987 SEASONAL APPLICATIONS In situ cages on the bottom of the bays were used for monitoring during the 1987 applications (see Figure 4).

At specified intervals following the treatments, the clams retained within the cages were examined for mortality (see Tables 5-7). Ambient lake water temperatures for Figure 4. Cricket cages used for in situ bio-February, June, and October were 50, 75, and 68 'F, monitoring.

respectively.

RESuLTS OF APPLICATIONS Molluscicide applications at the Lake Hubbard Station A stratification of the molluscicide at the lower depths of were assessed by biomonitoring methods. Clams were the intake bays was observed, as exemplified by mortal-recorded as dead when the bivalve shell had gaped ity responses ranging from 100% at the 37-ft depth to open, Occasionally. the viability of a clam was deter- 15% at the 19-ft depth (see Table 1). This biomonitoring mined by gently prying open the bivalve shell slightly. A of the vertical molluscicide dispersion supports localizing clam was judged to be alive if it-clammed up again. the applications to the bottom of intake bays where Asi-atic clams tend to colonize and grow. Even the clams June 1986 Applications. Mortality responses of between that were recolonizing the lake sides of the intake bays 90 and 100% were observed for both the 24-hr treatment were exterminated quite effectively (see Table 3).

with two-dose applications (bay 2B). and the 48-hr treat-ment with four dose applications (bay 1B) (see Tables 1 The lower mortality responses recorded in Tables 3 and and 2). 4 were continuing when the monitoring was terminated TABLE 4:

JUNE 1986 APPLICATIONS/AQUARIABIOMONITORING Bay 1B: 48-hr Treat'ment Period/4 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment 0 1 2 3 Control 0 0 0 0 1B-Plant Side 6 95 98 100 1B-Lake Side 12 66 100 Bay 2B: 24-hr Treatment Period/2 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment 1 2 3 2B-Plant Side 0 0 30 63 2B-Lake Side 30 88 100

because of unexplained clam mortality in the control tank June 1987 Applications. All three applications resulted 5 days after treatment. In clam mortalities of 96% to 100% for the plant sides of the intake bays (see Table 6). Clam mortalities on the February 1987 Applications. The colder water tempera-lake side of the intake bays ranged from 25% to 85%.

tures during this time of year resulted ln a slower rate of mortality response. However, increasing the application period to 72 hr caused clam kills of 98% to 100% on the October 1987 Applications. A 100% mortality response plant side of the bay (see Table 5). was achieved on the plant side of the intake bay being monitored. No clam mortalities were reported on the lake A slower kill rate was also observed ln cold water appli- side (see Table 7). Further modifications or positioning of cations at another facility (8). This may be attributed to the sparge header may be required to increase the dis-reduced metabolic and siphoning activity by the clam persion of molluscicide to the lake side of the bays if during the winter months. extermination of, the recolonizing clams is needed.

TABLE 5:

FEBRUARY 1987 APPLlCATION RESULTS Bay 1A: 72-hr Treatment Period/6 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment 0 1 2 3 18 1A-Plant Side 56 82 86 86 98 (back of bay) 1A-Plant Side 32 46 50 76 100 (middle of bay) 1A-Lake Side 6 > 6 (front of screen)

Bay 2A: 48-hr Treatment Period/4 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment 2 3 18 2A-Plant Side 24 26 30 32 46 (back of bay) 2A-Plant Side 20 32 58 72 80 96 (middle of bay) 2A-Lake Side 10 10 10 (front of screen)

Bay 1B: 24-hr Treatment Period/2 Shot Feed Applications (60 ppm Each)

Cumulative % Mortality on the Following Days After Treatment 0 1 2 3 1B-Plant Side 30 44 50 50 (back of bay) 10-Lake Side (front of screen)

TABLE 6:

JUNE 1987 APPLICATION RESULTS Bay 2A: 48-hr Treatment Period/1 Shot Feed Application (100 ppm Each)

Cumulative % Mortality on the Following Days. After Treatment 1 2 3 2A-Plant Side 77 96 96 96 2A-Lake Side 0 0 25 25 Bay 2B: 48-hr Treatment Period/2 Shot Feed Applications (50 ppm EacH)

Cumulative % Mortality on the Following Days After Treatment 1 2 3 2B-Plant Side 11 43 91 97 2B-Lake Side 59 85 85 85 Bay 2C: 48-hr Treatment Period/1 Shot Feed Application (100 ppm)

Cumulative % Mortality on the Following Days After Treatment 1 2 3 2C-Plant Side 96 100 2C-Lake Side 8 44 52 52 TABLE 7: erations. This stops the mass transport of OCTOBER 1987 APPLICATION RESULTS clams and relic shells further into the system and, consequently, prevents tube pluggage.

Bay 2C: 48-hr Treatment Period/1 Shot Feed Application (100 ppm) Step 2. Molluscicide is applied using appropriate meth-Cumulative % Mortality on the ods to assure good distribution to the areas of colonization. Vigilance to prevent the further Following Days After Treatment transport of adult clams that were not removed 1 2 3 during the cleanout operations is required.

2C-Plant Side 57 98 100 2C-Lake Side 0 0 0 Step 3. Seasonal applications (2 to 4 times per year) are scheduled to exterminate larvae and juve-nile clams that will be recolonizing the system.

CONCLUSIONS At Lake Hubbard, mortality responses of 90-100% were consistently observed for each of the four seasonal appli-The new molluscicide, Clam-Trol CT-1. is extremely ef-cations to the plant side of the intake bays. The mollus-fective against all life stages of the Asiatic clam with only cicide was conveniently shot fed and diffused to the bot-brief treatment periods of 24 to 48 hr. It can be easily tom of the intake bays with a sparge pipe. The easy-to-applied by shot feed or continuous feed (depending on Use blomonitoring methods that were used for evaluating the system to be treated) and. if necessary, detoxified treatment effectiveness can also be used for optimizing prior to discharge.

the application. If the molluscicide is fed during the winter For optimum results. the Asiatic clam control program months. a longer application period may be required to consists of three basic steps for eliminating clam popula- compensate for reduced metabolic and siphoning activity tions and preventing recolonization. in cold water. Regulatory requirements are met by modi-fying discharge procedures.

Step 1. Adult clams in the cooling system are physi-cally removed by dredging or vacuuming op- Seasonal applications of the new molluscicide at Lake

Hubbard proved to be a good economic alternative for search Institute. Palo Alto, CA, 1983.

Asiatic clam control. The treatment program was etfec-tive in exterminating juvenile and larval clams and pre- 5. Neitzel, D. A.; Johnson, K. I.: Page. T. L.: Young, venting the reinfestation ot adult clams in the intake bays. J. S.; Daling, P. M. "Bivalve Fouling ot Nuclear The most significant benefit to the Lake Hubbard Station Power Plant Service-Water Systems" U.S. Nu-

~

is the reduced tube pluggage in the main condenser and clear Regulatory Commission Bulletin, Vol. 1-3, auxiliary coolers. This not only improves cooling effi- U.S. Regulatory Commission, Washington, D.C. ~

1984.

ciency, but also minimizes microfouling and sedimenta-tion. Maintenance activities, such as blowing and rodding

6. Lyons, L. A. "Detoxification Potential of a New ot tubes, have also been greatly reduced. Vacuuming of Molluscicide for Asiatic Clam Fouling Control",

intake bays is no longer necessary. The control of Asi-Annual Meeting ot the Society of Environmental atic clam macrofouling has eliminated forced unit.out-Toxicology and Chemistry, Pensacola, FL. No-ages due to clams at the Lake Hubbard station.

vember 1987.

REFERENCES 7. Fellers, B. D. "Corrosion, Biocides and Inhibitors in Once-Through Cooling Waters, EPRI Nuclear

1. "Condenser Macrofouling Control Technologies," Plant Layup and Service Water System Mainte-EPRI Report CS-3550, Electric Power Research in- nance Seminar, Charlotte, NC. November 1987.

stitute, Palo Alto. CA, 1984.

8. Post R. M.; Lyons, L. A. Electr. Light Power, 65

2. "Flow Blockage of Cooling Water to Safety Sys- (10), 26 (1987).

tem Components by Corblcula sp. (Asiatic clam) and Mytllus sp. (Mussel)". U.S. Nuclear Regula- 9. Lyons, L. A.; Post, R. M. "Development and Ap-tory Commission Bulletin, U.S. Regulatory Com- plication of a New Material for Control of Asiatic mission, Washington, D.C., 1981. Clams". abstract submitted to International Water Conference. 1988, Betz Labortories, Inc..

3. Doherty, F. G.; Farris, J. L.: Cherry, D. S.; Cairns, Trevose, PA.

J.C. Arch. Environ. Contam. Toxlcol. 15, 532-542 (1986). 10. "Determination of Clam-Trol CT-1 by Modified, Photometric Chromate Complex Procedure", Betz

4. "Macrofouiing Control Technologies: State ot the Laboratories Analytical Method, Betz Laborato-Art". EPRI Report CS-3343, Electric Power Re- ries, Inc., Trevose, PA.

t Technical Paper 320 EPRI Service Water System I

Reliability improvement Seminar ASIATIC CLAM CONTROL EXPERIENCE AT PEACH BOTTOM ATOMIC POWER STATION Duane Mowery Philadelphia Electric Company Peach Bottom Atomic Power Station Delta, PA E. McCiellan RMC Environmental Services Drumore, PA'.

A. Lyons Betz Laboratories, Inc.

4636 Somerton Road Trevose, PA 19047 D. M. Austin and D. N. Karlovich Betz Industrial .

1 Quality Way Trevose, PA .19047 NR~~Betz Pskrm9m@H@l 1990 Betz Laboratories, Inc. All Rights Reserved.

0

'(

\

4 4

ASIATIC CLAM CONTROL EXPERIENCE AT PEACH BOTTOM ATOMIC POWER STATION Duane Mowery Philadelphia Electric Company Peach Bottom Atomic Power Station Delta, PA E. McClellan RMC Environmental Services Drumore, PA L. A. Lyons Betz Laboratories, inc.

4636 Somerton Road Trevose, PA 19047 D. M. Austin and D. N. Karlovich Betz Industrial 1 Quality Way Trevose, PA 19047 ABSTRACT A preventive treatment program effectively controlled microscopic larval and juvenile clams. Oxidizing Asiatic clams in the service water and safety related blocides (e.g;, chlorine or bromine) require weeks of t cooling systems at the Peach Bottom Atomic Power Station of Philadelphia Electric Company. The mollusclcide used, a nonoxidizlng biocide, provides 100% efficacy after a short exposure period and is more environmentally attractive than traditional oxidizing blocldes. This paper details the Asiatic clam control program at Peach Bottom and describes application experiences. The spawning characteristics of the Asiatic continuous, uninterrupted applications to achieve efficacy.2When continuous chlorination Is permitted, the effect on corrosion, especially of copper alloys, is a major concern. Because the chemoreceptors of Asiatic clams detect low concentrations of oxidizing biocides, the clams avoid contact by "clamming-up" for extended periods.s Advances in treatment technology over the past few years allow this macrofouilng problem to be clam in the plant makeup waters withrespect to time and addressed using a nonoxidizing biocide. The Asiatic temperature, as well as mollusciclde treatment levels clams do not sense the nonoxidlzlng material ln the and feed duration, are also reviewed. water and siphon ln a lethal dose during an application period.

INTRODUCTION APPLICATION EXPERIENCE AT PEACH Asiatic clam macrofoullng is estimated to cost U.S. BOTTOM industry more than.$ 1 billion annually. These costs are related to flow restrictions, reduced cooling efficiency, The Peach Bottom Atomic Power Station is a two-unit maintenance expenses, replacement of damaged boiling water reactor with once-through cooling water equipment, and forced outages.~ The vulnerability of systems. Located on the Susquehanna River In southern fire-protection systems and safety-related systems In Pennsylvania, the station found Asiatic clams in both the nuclear-fueled generation stations is of special concern. cooling water intake bays and discharge canal. Due to environmental discharge limitations, extended low-level Early attempts to control the proliferation,-and thus the continuous chlorination was not possible at Peach fouling ability, of the Asiatic clam were focused on Bottom.

physical and mechanical methods or the use of oxidizing blocldes. These control measures, however, In the Spring of 1987, the application of an t

were proven to be largely ineffective. The use of screens environmentally acceptable molluscicide that provides and strainers or physical removal measures (such as 100% mortality on adult Asiatic clams,within a 24-hour dredging and vacuuming operations) provide only exposure period was recommended to Philadelphia temporary relief from advanced fouling conditions. They Electric. The proposedbenefits of the new mollusclcide do not prevent the growth and proliferation of the were: relatively small, economical dosages were

required, the product wa's easy to apply, and It was Cold Water noncorrosive to system metallurgy.

The mollusclclde was first applied In December 1987 r

to the high-pressure service water systems. Clam The product (Betz Clam-Trol CT-1) is registered by mortality was monitored using several hundred adult the U.S. EPA for use against mollusks in once-through clams from the Susquehanna River that were graded in systems, recirculating cooling systems, influent size in a multichambered aquarium. Product systems, and auxiliary water and waste systems concentration was monitored throughout the 48-hour (including intake bays and fire-protection systems). The application using a colorimetric test procedure. The active Ingredients In the product are a quaternary amlne product was applied to the inlet of the HPSW system at a (QUAT) and dodecylguanldlne (DGH) in an aqueous concentration of 25 ppm. Free product residual at the solvent system. The product contains no heavy metals discharge of the HPSW system was 17.5 + 1.5 mg/L.

or EPA priority pollutants. Both actives are cationlcally Free product concentration to the Susquehanna River at charged surfactants that are readily adsorbed by the outfall was below detection limits (less than 1.0 naturally occurring materials, such as clay, suspended mg/L) after reaction with the solids ln the circulating solids, humic acids, and sediment. Once adsorbed, the water dilution flow. This circulating water flow provided a actives are not toxic to aquatic species.4 dilution factor well below the LC50's of the mollusciclde to aquatic organisms.

Based on the success of laboratory evaluations During the application, two sample populations of performed by RMC Environmental Services (see Figure Corblcula were placed In aquaria and exposed for 24

1) and proJected savings compared to hypochlorite and 48hr, respectively, to free product residual in treated inJectlon, permission was obtained from the water obtained from the HPSW system. This provided Pennsylvania Department of Environmental Regulations additional data on the required exposure period under (PADER) to apply the mollusclcide to the service water, low temperature conditions (5-7 'C). The aquaria were high-pressure service water (HPSW), emergency placed in an insulated blobox through which water was service water, and fire protection systems of Units 2 and circulated to maintain clams at ambient water 3 at the Peach Bottom Atomic Power Station. temperature. The treated water was replaced hourly for 100 DOSAGE LEVEL 80 R 15 ppm 25 ppm 50 ppm 60 .">Km'>,.'3.

'&'x:,2%4(':

'e6$

O 40

.st'IF'.'.;.jN('::.. Nw)ji 20 $ >:/k',;

>j". 4>94 pijj;:

0 1 2 3' Observation Time (Days)

Figure 1: Latent mortality response of Corblcula to Clam@'ol CT-1: 24-hr exposure at 20 4C.

the first 2 hr of injection and then at 4-hr intervals for the This adaptatlon to cold weather also presents a duration of the 48-hr exposure. Following the 48-hr difficult problem from a treatment standpoint. Based on exposure, the clams were moved off-site to a nearby obsewatlons of clams evaiuatedby RMC Environmental laboratory and maintained at 5-7 'C along with the Services, Corbicula exposed to water at less than 2 'C control population. Whereas the control population rarely siphon compared to those maintained at 5 to 6 'C.

continued to siphon normally, both treated populations This limited siphoning activity complicates the treatment ceased all siphoning activities after exposure. A portion program and extends the latent efficacy period, of the control group, 24-hr exposure group, and 48-hr probably beyond that seen in Figure 2 at 5-7 'C.

exposure group was sacrificed at 1, 11, 16, 23, 27, 30, and 37 days following the initial exposure, and the gill Warm Water tissues were examined under a microscope for cillia beating. The results (Figure 2) show that 100% mortality Based on these findings, further treatments to the was achieved in both the 24-hr and 48-hr exposure PBAPS service water systems were postponed until the summer of 1988. In August of 1988, molluscicide was groups, while 0% mortality was observed in the control population. The retardation of the latent mortality applied for a 24-hr period to the Unit 2 HPSW system.

Twenty-five parts per million of the molluscicide was fed response under cold water (5 'C) conditions was at ambient water temperatures ranging from 24 to 29.5 considered particularly significant. Another significant C. Mean mollusciclde concentration throughout the finding of Philadelphia Electric's clam control program ls that clams in the Susquehanna River spawn from treated systems during the exposure period was 19.8 +

1.4 ppm. Monitoring was conducted as described earlier mid-May through late fall and that during the winter utilizing the biobox, and Corblcula were exposed for 12 months, juvenile and adult Asiatic clams survive for and 24 hr. At the end of the exposure periods, test clams weeks In harsh winter water temperature (0-1 'C). were again transported to holding facilities at a nearby Brooding larvae were found ln adults in December 1987 laboratory and monitored for latent mortality. Water at ambient water temperatures approaching 5 'C (see temperatures in the holding facilities ranged from 23 to Figure 3). This finding is troublesome for the industry, 24 'C throughout the mortality obsenratlon period.

since It suggests that the species Is beginning to adapt to colder climates once thought to be a barrier to survival The latent mortality of control and test clams exposed In the northern United States. to the Clam-Trol CT-1 molluscicide for 12 and 24 hr at

'1 00 EXPOSURE PERIOD 80 ~ 24hr ~48hr

>o 60 6$

40 20 1 10 15 23 30 37 Obsetvation Time (Days)

Figure 2: Latent mortality response of Corblcula: PBAPS (Dec 8-10, 1987), HPSW loop 3B, water temper-ature 5-7 'C.

80

% of Adults Brooding 60 40 Water temp

('C) 20 3/1 4/12 7/5 8/16 9/27 11/8 12/20 1/31 Date Figure 3: Spawning activity of Corblcula (percent of adults with only larvae on gills), March 1987-January 1988.

24-29.5 'C is shown in Figure 4. Test clams ln both the conducted ln the same manner as described above. The 12 and 24 hr tests experienced 100% mortality within 76 Unit 2 General Service Water (GSW) system was treated and 88 hr, respectively. The control clams experienced when water temperatures were approximately 18 'C,.

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 and monitoring techniques were between 15 and 16 'C. As shown in Figures 5 and 6, the 100 EXPOSURE PERIOD 80 ~ 12 hr HZ'4 hr

~p 60 C5 40 20 24 48, 64 72 88 Observation Time (hr)

Figure 4: Latent mortality response of Corblcula: PBAPS (Aug 19-20, 1988), HPSW loops 2A/28, water

'emperature 24-29.5 'C.

100 EXPOSURE PERIOD 12 hr 80 IZg 14 hr oo 60 C5 O

ao 20 0

1 2 3 4 5 6 7 8 9 Obsewatlon Time (Days)

Figure 5: Latent mortality response of Corblcula: PBAPS (Oct 6-7), Unit 2, GSW system, flow rate 25,800 gpm, water temperature 18 'C.

100 EXPOSURE PERIOD 80 ~12hr ~24hr g 60 C5 ao 20 0

1 2 3 4 5 6 7 8 9 Observation Time (Days)

Figure 6: Latent mortality response of Corblcula: PBAPS (Oct 13-14), ESW system, flow rate 3,300 gpm, water temperature 15-16 'C.

time to achieve 100% mortality Increased with lowering ~

'components can be tested and returned to operation temperature, as expected based on earlier sooner).

obseNations. Figure 7 summarizes the time to achieve Future plans are to evaluate the Installation of a 100% mortality as a function of water temperature. The increased time to achieve mortality Is directly related to permanent feed system for the molluscicide at Peach the decreased siphoning activity of the Asiatic clam Bottom Atomic Power Station. This will allow for short while In a cold water environment. periodic InJectlons of the product on an intermittent basis throughout the year to control the station Asiatic clam The resident fish population was monitored during the population.

cold and warm water inJectlons. No visible effect was noted on the fish population. REFERENCES CONCLUSIONS (1) Applebome, P. "Small Clam Is Big Trouble for Water Systems", New York Times, May 4,1987.

The application of a nonoxldlzlng biocide at Peach.

Bottomresulted in100% mortality In Asiatic clams with a Doherty, Fl. G.; Farris, J. L.; Cherry, D. S.; Cairns, (2) 24-hr exposure period at temperatures as low as 5 4C. J. C. Arch. Environ. Cotam. 7oxlcol. 15, 532-542 Latent mortality of the clams increased with lower (1986).

ambient water temperatures.

When water temperatures were greater than 15 'C, (3) Post, R. M.; Lyons, L. A. Electr. Vght Power, 65, both 12 and 24 hr applications of mollusclclde at similar 26 (1987)..

concentrations were equally effective in killing clams.

Further testing is being conducted to confirm these (4) Lyons, L. A.; "Detoxification Potential of a New results and could lead to shorter injection periods during Molluscicide For Asiatic Clam Fouling Control",

the summer months. The advantages of a shorter SETAC Poster Session, Nov. 9-12, 1987, lnJectlon period are both economical (reduced chemical Pensacola, FL.

and feeding costs) and operational (system 25 t

0 20 CL

~Q) 15 1009o I Mortality 10 70'ortality '0 10 '15 20 25 30 35 Mortality Observation Time (Days)

Following CT-1 Exposure Period Figure 7: TIme (days) for test Corblcula to achieve 70 and 100% mortality following exposure (12 to 48 hr) to Clam4 ol CT-1 concentrations > 15 mg/L during product applications at various water temperatures (5-24 'C) at PBAPS, December 1987 - October 1988.

Reprint Number 048 Electric Light 8 Power ovember 1987 Molluscicide controls Asiatic clam problems R.M. Post Betz Industrial and L.A. Lyons Betz Laboratories A new cost-effective chemical treat- interrupted applications are required bleach alleviates the safety concern, ment that can be used at both fossil- over several weeks. But Asiatic but costs several times more than fueled and nuclear power plants ap- clams have chemoreceptors that can gaseous chlorine. Utilities also are pears to offer an exciting new weapon detect very low concentrations of oxi- under increasing environmental pres-for use in the battle against the Asiat- dizing biocides. When they sense the sures to reduced their discharge of to-ic clam. presence of these materials, the clam tal residual chlorine. Continuous Asiatic clam fouling is estimated to avoids contact by "clamming up," chlorination/dechlorination would en-cost U.S. industry more than $ 1 bil- closing its shell and remaining that able complaince, but again at in-lion annually. These costs are related way for extended periods. Thus it is creased expense.

to power outages or plant shutdowns, believed that oxidizing biocides cause Recent developments reduced operating efficiencies, main- clam mortality by asphyxiation, rath-tenance expense, replacement of er than by direct toxicity. The ideal chemical control agent quipment and other costs associated Since clams will resume siphoning would provide effective extermina-with controlling this pest. The vul- as soon as the chlorine residual disap- tion of Asicatic clams with short ap-nerability of safety-related systems, pears, any interruption in chemical plication periods within the plant and including fire sprinkler equipment, feed for maintenance or repair of the could be rendered non-toxic before its also is a major concern to industrial chlorination system will result in in- discharge. Betz Laboratories recent-managenents. effectual control of the clam popula- ly has introduced a molluscicide that Mechanical/ Physical Control tion. In addition, continuous chlorina- closely matches these requirements.

tion requires large inventories of The new molluscicide exterminates Screens and strainers cannot pre- chlorine gas, which not only is expen- all life stages of the Asiatic clam with vent microscopic larval and juvenile sive, but also is the subject of grow- a single short application of 12 to 48 clams from infesting cooling systems. ing insurance and safety concern. hours, depending on concentration Other mechanical methods, such as Use of liquid sodium hypochlorite and temperature. Treatment pro-wire mesh across the face of tube sheets or plastic strainers in tube in-lets, still require the physical remov-al of accumulated clams, shells and entrapped debris.

Physical control measures consist primarily of dredging and vacuuming adult clams from accessible low-ve-locity areas, where clams are prone to colonize. This operation often re-quires the use of divers. Outages or reduced load operations are required 1 r to allow water boxes, service water heat exchangers and piping to be cleaned out.

Moreover, mechanical or physical F control methods do not prevent fouling. They merely provide a means of dealing with advanced fouling onditions.

Chemical control In order to reduce the severity of clam infestations with chlorine or oth-er oxidizing biocides, such as bromine Microscopic Asiatic clam larvae pass through power plant intake screens and grow to a fouling and chlorine dioxide, continuous, un- size downstream. These fresh water clams demonstrate the futility of screening devices.

grams employing the new mollusci- containers, using standard metering that once the organic active materials cide range from simple extermination pumps. Since the containers are re- are adsorbed, the molluscicide no applications at intake structures and turned when empty, costly on-site longer exhibits toxicity with regar<

other in-plant colonization areas all storage and handling facilities are to fish.

the way to large-scale plant-wide ap- not required. Molluscicide applications are tai-plications involving multiple reser- Environmental,considerations lored to make the best use of these voirsandmilesofpipe. Thefrequency - "

passive absorptive properties. I f of application is based on the In contrast to chlorine or other oxi- required, the detoxification process spawning activities and the'.. dizing biocides, the new molluscicide can be accelerated by the addition of clams'easonal vulnerability of the system to clam involves short application periods specific detoxification agents. An an-infestation. and small product requirements. alytical method using prepackaged After the initial application and re- These result in only minimal chemical reagents and a photometer also is moval of large shells, periodic appli- additions to the environment. More- available for monitoring product cations are made to exterminate lar- over, the chemical is rapidly neutral- concentrations.

vae and juvenile (less than '/8-in. dia.) ized or detoxified. The active constit- The material has been registered clams. This prevents shell growth to a uents are short-lived because they with the EPA by Betz Laboratories fouling-size, which would occur in can be adsorbed onto a variety of sub- for use against Asiatic clams in once-just a few months. strates, including suspended solids, through and recirculating cooling The liquid molluscicide is dispensed sediments, and even the surfaces of systems, influent systems and fire-easily from portable 300-gal. bulk cooling systems. Studies have shown protection systems.

AQUATIC TOXICOLOGY LABORATORY SOMERTON RQAOiTREVQSE, PA 1 9047iUSA. / TEL: 21 5>355-3300iTELEX: 1 73 1 48iPAX 4355.2669 Society of Environmental Toxicology and Chemistry (SETAC)

Presented at Toronto, Canada Meeting October 28 - November 2, 1989 FOULING CONTROL POTENTIAL FOR ZEBRA MUSSELS WITH CLAM-TROL CT-1, A MOLLUSCICIDE. L. A.

Lyons, D. P. Davis, Z. C. Petrille, M. W.

Werner, Betz Laboratories, Inc., Trevose, PA; William Kovalak, Detroit Edison, Detroit, MI.

European mollusk that has invaded the Great Lakes within the past few years. This new pest is becoming well adapted and already imposing ma j or foui ing concerns by attaching to the bottoms of boats, growing within potable water supply intake conduits, and threatening the operations of gower plants. An estimation of 2000 mussels/m~ within the intake bays of a cooling system have been reported at a power plant near Detroit,. Chlorination practices for controlling this mollusk. infestation to cooling systems cannot be accomplished without continuous application for several weeks.

A new molluscicide, Clam-Trol CT-1, that is providing state-of-the-art control for Asiatic clam fouling to power plants and industrial facilities, has also demonstrated its effectiveness toward the Zebra mussel in laboratory studies. Efficacy determinations for Clam-Trol CT-1 concentrations from 5 mg/1 to 15 mg/1 for exposure periods of 6 hrs. to 24 hrs. have been evaluated at 10o, 15 , and 20oC.

Mortality responses were shown to be dependent upon dosage, exposure period and temperature.

Update: A recent inspection (Sept. 1989) at a Detroit Edison power plant estimated 600,000 mussel/m2 were attached to all surface areas within the intake bays of the cooling system.

Note: ~ Clam-trol CT-1 is a formulation containing 134 active ingredients.

~ ~

~ Effective feed concentrations of 5 mg/1 to 15 mg/1 as

~

Clam-trol CT-1 would represent total active concentrations of 0.65 mg/1 to 1.95 mg/l.

~ ~

0:

Produced bg SAI fox BETZ 69B5-Bi wdRS Clam-Trol C T-1:

A Molluscicide That Controls Fouling Afussels by'ebra and Asiatic Clams Note: Clam-Trol CT-1 is a formulation containing 13% active ingredients. I: f fective feed concentrations of 5 mg/I to 15 mg/1 as Clam-'I'rol O'I'-I would represent total active concentrations of 0.65 mg/l to 1.95 mg/l.

I Produced bg SAI for BETZ 6985-85 ard28 Clam-Trol CT-1 Efficacy To Zebra Nussels

'/o Mortality: 12 hr. Exposure at 11 C 100 90 80 70 60 50 40 30 20 10 0

24 hr. 48 hr. 72 hr. 120 hr.

II 5 mg/1 II 10 mg/1 II 15 mg/1

Px oduced bg SAI fox BETZ 6985-82 wd28 .. CI Clam-Trol CT-1 Efficacy To Zebra Mussels

% Mortality: 6 hr. Exposure at 15 C 60 46 40 35 30 25 20 15 10 5

0 24 hr. 48 hr. 72 hr. 120 hr.

8 5 mg/1 8 10 mg/1 hIl 16 mg/1

Pr oduceck bg SA I foz BETZ 6985-83 aa828 CI Clam-Trol CT-1 Efficacy To Zebra Mussels

% Mortality: 14 hr. Exposure at 15 C 100 80 60 40 20 0

24 hr. 48 hr. 72 hr. 120 hr.

8 5 mg/1 5 10 mg/1 IIl 15 mg/1

Produced bg SA I for BETZ 6985-94 wd28 Clam-Trol CT-1 Efficacy To Zebra Nuaseia

'/o Mortality: 24 hr. Exposure at 15 C 100 90 80 70 60 50 40 30 20 10 0

24 hr. 48 hr. 72 hr. 120 hr.

8 5 mg/1 5 10 mg/1 8 15 mg/1

0'r oduced bg SAI for BETZ 6985-97 wd28 Clam-Trol CT-1 Efficacy To Zebra Nussels

'L Mortality: 6 hr. Exposure at 20 C 100 80 60 40 20 0

24 hr. 48 hr. 72 hr. 120 hr.

8 5 mg/1 8 10 mg/1 fII 15 mg/1

0'x

~

Cl oduced bg SAI For BETZ 6985-88 wd38 Clam-Trol CT-f Efficacy To Zebra Mussels

'L Mortality: 14 hr. Exposure at 20 C 100 90 80 70 60 60 40 30 20 10 0

24 hr. 48 hr. 72 hr. 120 hr.

8 6 mg/0 5 10 mg/1 ill 16 mg/1

Technical Paper 325 American Power Conference Illinois Institute of Technology April 1, 1990 New Treatment Employing a Molluscicide for Macrofouling Control of Zebra Mussels in Cooling Systems L. A. Lyons and J. C. Petrilte Betz Laboratories, inc.

Trevose, PA S. P. Donner and R. L. Fobes Consumers Power Company Jackson, Ml F. Lehmann Detroit Edison Company Detroit, Ml P. W. Althouse, L. T. Walt, R. M. Post, and W. F. Buerger Betz industrial Trevose, PA

~ -e~z RPz@mCAx0 O1990, Betz Industrial. All Rights Reserved.

NEW TREATMENT EMPLOYING A MOLLUSCICIDE FOR MACROFOULING CONTROL OF ZEBRA MUSSELS IN COOLING SYSTEMS L. A. LYONS and J. C. PETRILLE Two power plants near Detroit, Michigan received the Betz Laboratories, Inc. Trevose, PA first CT-1 applications during the fall/winter of 1989. The J. R. Whiting Power Plant, a 3-unit (350 MW) coal-fired facility, received 124r applications to each main circu-S. P. DONNER and R. L. FOBES lating and service water system. The Enrico Fermi II Consumers Power Company Nuclear Power Plant, a 1-unit (1100 MW) facility, Jackson, Ml received a 15-hr CT-1 application to the service water system. The performance of these applications was blo-F. LEHMANN monitored using flow-through bloboxes. Mortality Detroit Edison Company responses were correlated with dosage and water tem-Detroit, Ml perature. Recommendatlons for optimizing treatment programs basedupon seasonal ambient water tempera-tures and the degree of mussel Infestation are provided.

P. W. ALTHOUSE and L. T. WALL Betz Industrial Granger, IN INTRODUCTION Zebra mussels are estimated to cost the Great Lakes R. M. POST and W. F. BUERGER region 5 billion dollars between1990 and 2000 (1). Zebra Betz Industrial musseis will adversely impact commercial fisheries, Trevose, PA recreational activities, potable water suppliers, and industry. They willalso significantly alter the ecosystems of these lakes. Zebra mussels are expected to spread throughout the Great Lakes and to many rivers and lakes ABSTRACT of North America within the next 5 to 10 years.

The Zebra m ussel is a European mollusk that has Juvenile mussels or vellger larvae were probably trans-Infested the Great Lakes within the past few years. This ported to the Great Lakes in 1986 via the ballast water ln new pest is extremely prolific and aggressively attaches a ship originating from a European freshwater port.

to all types of surfaces. Power plants situated around Zebra mussels were first found In Lake St. Clair in 1988.

Lake Erie and Lake St. Clair are experlenclng extensive Presently, Zebra mussels are found throughout Lake mussel macrofouling. Incidences of macrofoullng Erie; the most extensive populations are in the Western include colonies of more than 500,000 mussels per Basin. Scattered populations of Zebra mussels have square meter; these mussels completely cover all sur- been reported in Lake Ontario and a few mussels have face areas of intake bays, plug chiller units and main also been found ln Lake Michigan's Green Bay.

condenser tubes, and grow within service-related cool- The prolNc and rapid growth of Zebra mussel popula-Ing pipes. There Is an obvious danger of forced outages tions attest to the need for a monitoring program at raw if preventative measures are not taken. water lntakes. These monitoring programs provide sur-veillance for mussel Infestation and determine the A nonoxidizing molluscicide, Clam-Trol CT-1, which Is degree of colonization and fouling within a cooling sys-providing state-of-the-art control for Asiatic clam fouling tem. This rapid colonizatlon has been exemplified at the in power plants, has also demonstrated effectiveness in Detroit Edison Company's Monroe Power Plant located controlling Zebra mussels. The results of efficacy deter- on the Western Basin of Lake Erie. The densities of Zebra minations from laboratory studies for ClamTrol CT-1 at mussels found in the intake canal at the Monroe station concentrations from 5 mg/L to 15 mg/L, for exposure have increased exponentially from 50mussels/m2 in the periods of 6 to 24 hr, and at water temperatures of 11 'C, fall of 1988 to greater than 700,000 mussels/m2 in the fall 15 C,and20 Careprovided. TheoptlmumCT-1 appli-of 1989 (2).

cation for mussel fouling control willbe dependent upon dosage, exposure period, and water temperature. It Is This macrofouling pest aggressively attaches to all anticipated that many systems will require seasonal types of hard substrates, including cement walls, applications (2to 4 times/year) basedupon growthrate, screens and trash racks, pump housings, pipes of spawning season, and extent of setting by mussel lar- assorted metallurgy, plastic, rubber, and so forth. They vae. tend to form large clusters by attaching to each other

(see Figure 1). The formation of clusters of mussels near rate sexes) andmature sexually within one year. Fertiliza-or within the Intake structure of cooling systems threat- tion is external and females can release approximately ens circulation pump operation and Increases the poten- 30,000 to 40,000 eggs per year. The fertilized eggs tial of a forced outage. In addition, in the veliger larval develop to a planktonic vellger larval stage; the laNal stage, this mussel will pass through all intake screens stage ls microscopic (0.1 to 0.3 mm). The planktonic and ln-line basket screens and will settle within the cool- vellger stage lasts for 8 to 15 days during which they are ing system. The juvenile mussels can encrust the entire dispersed by the water currents of lakes and rivers. In surface areas of pipes. Encrustation can Impede or com- Lake Erie during 1989, veligers numbered from 40,000 pletely restrict the flow of water through these pipes. The veligers/m~ In early summer to 500,000 vellgers/m3 ln smaller diameter pipes within service water and safety late summer (3).

related systems are particularly vulnerable.

The planktonic veligers develop to a post-vellger or Juve-nile mussel stage to begin the sedentary life. They Biology of the Zebra Mussel secrete byssal threads for attaching to hard surfaces.

The reproductive capacity and life history characteristics Attachment by the byssal threads is quite tenacious and of the Zebra mussel, Dreissena polymorpha, explain the able to withstand water velocities of 3 to 5 ft/sec. Zebra successful invasion and rapid colonlzatlon to aquatic mussels tend to be quite gregarious; they colonize ln environments. Reproduction of the Zebra mussels is massive clusters and mats.

highly prolific with a spawning season extending from the spring, when water temperatures rise above 12 'C to 15 'C, to October. Zebra mussels are dloecious (sepa-Control Methods: European Experience Controlmeasures employed in Europe for fouling control of Zebra mussels has involved mechanical/physical methods (4,7,9) and the use of oxidizing chemicals lf (4,5,6,8).

The various physical/mechanical control methods.

)r Include: clea~uts, piping replacement, screening and straining, thermal backflushlng, ultrasonic vibration, and electrical shock. Clean-outs for the removal of mussels and the replacement of piping requires scheduled plant outages. Although screens and strainers do not prevent the entrainment of juvenile or larval vellgers into the cool-ing systems, they are necessary to prevent the transport of adult mussels or clusters of mussels further into a cooling system, Thermal backflushlng of heated con-denser water can provide fouling control for selected ar-eas of a cooling system, usually intake bays. For those facilities having thermal treatment capabilities, a15-60 min application at 40 'C will effectively control mussel Infestations. Ultrasonic vibration and electrical shock have also been attempted in Europe with varying degrees of success.

Chlorination is the most common chemical control for Zebra mussel fouling. Continuous chlorination for 2-3

, weeks is required to achieve efficacy. Intermittent chlori-nation programs, that feed a few hours each day are inef-fective. The application of other oxidizing chemicals (e.g., bromine, ozone, hydrogen peroxide, and potas-Figure 1: Cluster of Zebra Mussels Attached to a sium permagenate) is restricted because they arecostly, Native Mollusk Shell environmentally prohibitive, or impractical to distribute throughout a cooling system.

CLAM-THOLCT NONOXIDIZING neutralized by either passive or active processes. Both MOLLUSC!CI DE CT-1 actlves (Quat and DGH) are short-lived because they are readily adsorbed by naturally occurring sub-Clam-Trol CT-1, patented for use as a nonoxidizing mol- strates including silts, clays, suspended solids, humlc lusclcide, Is a water miscible formulation containing two acids, and even the microfouled surfaces of cooling sys-cationic surfactants: alkyldlmethylbenzylammonlum tems. Studies (10) have shown that once the actives are chloride (Quat) and dodecylguanldine hydrochloride adsorbed, they no longer exhibit toxicity. If required, (DGH). Clam-Trol CT-1 is USEPA registered for use as a CT-1 applications can be actively detoxified byapplying mollusclclde for once-through and recirculating cooling a blend of clays (Betz DT-1) to the treated water (11).

systems. This molluscicide presents two significant fea-tures: the ability to eradicate mollusks, like Zebra mus- Clam-Trol CT-1 treatment programs are designed to sels, when applied for only 6 to 24hr and the ability to be maximize the passive neutralization of the actives within neutralized prior to discharge. the cooling system. For example, a segmented treat-ment approach is often used to focus applications to specific areas or system components. Mollusclcide CT-1 Applications: Zebra Mussel Fouling requirements are further minimized by reducing flow Control rates or using static treatments where possible.

This mollusclclde presents an unique advancement ln To obtain discharge permitting approval from a state reg-the art of macrofoullng control; Clam-Trol CT-1 eradi- ulatory authority, an application package would Include:

cates adult and juvenile Zebra mussels in cooling sys- a description of the macrofoullng problem to the power tems using feasible, cost effective, treatment reglmens. plant and the need for control, CT-1 product description When applied, CT-1 remains substantially undetected (constituents, MSDS, and aquatic toxicity data), CT-1 by the mussel, which siphons in a lethal dose during an application procedures and expected discharge con-application period of 6 to 24 hr (depending on dosage centrations, a description of the monitoring program dur-and water temperature). A delayed mortality response ing treatments, and a description of the detoxification occurs following the brief exposure period. program (if needed).

Periodic applications during the spawning and mussel setting period from May to September will provide effec- Application Experience: Asiatic Clam Ma-tive control of Zebra mussel fouling. Treatment applica- crofouling tions willfocus upon the eradication of juvenile mussels Since 1986, Clam-Trol CT-1 treatment programs have to prevent their growth to adult size and to prevent the been providing stat~f-the-art macrofouling control for accumulation of mussel encrustatlons within the cooling fouling caused by Asiatic clams ln freshwater cooling system. Once the juvenile mussels expire, they will systems (12). Seasonal applications (2 to 4 times/year) detach and pass through the cooling system. The fre-provide a preventative treatment program by focusing quency of applications (2 to 4 times/year) will be site upon the eradication of juvenile clams and preventing specific for each cooling system since the degree of their growth to adult fouling size. The eradication of juve-mussel infestatlon will vary from one system to another. nile clams that colonize intake bays has eliminated the A monitoring program to determine the extent and need for annual cleanouts of adult populations and pre-degree of mussel infestatlons can be established by vents the threat of forced outages due to macrofouling at using monitoring devices (l.e., Betz 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 infestatlon, rate of mussel growth, nuclear power plants are also providing a better control and the the effectiveness of mollusciclde applications alternative than continuous chlorination to assure the un-can be monitored with these surveillance devices. obstructed operation of these systems (14). In addition, industrial facilities 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 ln contrast to continuous chlorination, Clam-Trol CT-1 experiences for Asiatic clam macrofoullng 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 fouling control programs.

LABORATORY EFFICACY STUDIES:

ZEBRA MUSSELS Methods f 70

> 0780 Zebra mussels, 10 to 20 mm in size, were collected from the intake canal of a power plant in Lake Erie in 1989 when ambient water temperatures were 5 to 7 C. The mussels were shipped ln these cold water conditions to Betz'quatic Toxicology Laboratory fn Trevose, Penn- 10 sylvania. The mussels were fed twice a day with algae 0 and gradually acclimated over several weeks In recircu- 6 12 24 6 12 24 6 12 24 Application 10 mg/L 15 mg/L lating culture chambers to three temperature regimes: 11 Period (0 65) (1 3) (1.95)

'C, 15 'C, and 20 'C. (Hours)

Spring, 1989 CT-1 Concentration (Active mg/L Conc.)

For the efficacy evaluations 20 to 25mussels were trans-ferred to 5-L glass aquaria and given a 24-hr acclimation Figure 2: Clam-Trol CT-1 Efficacy to Zebra Mus-period. Mussels that did not reattach within the test sels at 20 'C aquaria and were not actively siphoning were removed.

Static renewal bloassays were Initiated by replacing the culture water with different concentrations of Clam-Trol CT-1 test solutions: 0 mg/L (Control), 5 mg/L, 10 mg/L, and15 mg/L. Following exposure periods from 6 to 24hr for each test concentration, randomly selected test aquaria were renewed with fresh culture water. Delayed f 70 mortality responses were monitored for several days fol- 5o lowing each exposure. Mortality determinations were re-corded when the bivalve shells were gaped open and 00 did not respond to gentle prodding. In many cases evi-dence of tissue putrefaction was noticed. Mussels that 10 were alive in the control and treatment tests were usually 0 6 14 24 6 14 24 6 14 24 actively siphoning. Applicathn 5 mg/L 10 mg/L 15 mg/L Period (0.65) (1 3) (1.95)

(Hours)

ResuIts Spring, 1989 CT-1 Concentration (Active mg/L Conc.)

The mortality responses of these laboratory efficacy evaluations correlated with GT-1 dosage, exposure peri- Figure 3: Clam 1l'ol CT-1 Efficacy to Zebra Mus-od, and water temperature. Figures 2, 3, and 4 present sels at 15 'C the cumulative mortality responses 4 days after the CT-1 applications, Note that Clam-Trol GT-1 contains 13% to-tal active concentration. Thus, Clam-Trol CT-1 concen-trations of15mg/L,10mg/L, and 5mg/Lcontalntotal ac-tive concentrations of1.95mg/L, 1.3 mg/L, and 0.65mg/

L, respectively. 70 At 20 'C (see Figure 2) mortality responses of 70% and 90% were achieved at10 mg/L as CT-1 for exposures of 6hr and12hr, respectively. A Mr application of15mg/L ~~~ 3O as CT-1 caused a 100% kill at 20 4C. At 15 'C a 20 Q

at 15mg/L GT-1 caused 50% mortality and a6'pplication 10 14-hr, application at 15 mg/L GT-1 achieved 100% mor- 0 tality (see Figure 3). The 10 mg/L GT-1 applications for Application 12 24 12 24 Period 10 mg/L 10 mg/L

&hr, 14-hr, and 244r caused 20%, 70%, and100% mor- (Hours) (1.3) (1.3) tality responses respectively, at15 'C. Then, at11 'C ef- CT-1 Concentration (Acthe mg/L Conc.)

Spring, 1989 ficacy data becomes more variable, but 12- and 24-hr applications of CT-1 at 15 mg/L achieved 80% to 95% Figure 4: Clam@'ol CT-1 Efficacy to Zebra Mus-mortalities (see Figure 4). sels at 11 'C

FIRST ZEBRA MUSSEL TREATMENTS Two innovative treatment programs employing CT-1 applications for Zebra mussel fouling control were con-ducted at Detroit Edison Company's Enrico Fermi II

< Nuclear Power Plant and Consumers Power Company's J. R. Whiting Power Plant. Both power plants are located near Detroit, use Lake Erie water in their cooling sys-tems, and were experiencing Zebra mussel Infestations necessitating preventative fouling control measures.

These first Clam-Trol CT-1 applications were conducted In November/December of 1989 during a period when ambient lake water temperatures declined to below 5 C. These severe temperature conditions were expected to hamper optimal treatment programs. Blo-monitoring of treatment effectiveness was conducted at both power plants. The effectiveness was corelated with CT-1 dosage and water temperature.

CONSUMERS POWER COMPANY J. R.

WHITING STATION FIgure5: Zebra Mussel Fouling of a Cooling Loop, J. R. Whiting Station

Background

mussels and meet environmental discharge require-The J. R. Whiting station, a 3-unit (350 MW), coal-fired ments. This program was implemented In December of generating power plant, first reported Zebra mussels 1989.

within plant water systems in July 1989. The mussels were Initiallynoticed uniformly attached to the concrete Molluscicide Application Procedures walls of the plant's oil-water (API) separator at a density Treatment of the Whiting station consisted of several pro-of 1 mussel per 4 In2. A rapid Infestation occurred during cedures Including segmented treatment approach, flow the following4-6 weeks. The fish deterrent nets situated rate reduction of treated systems, detoxification, and across the intake canal became so Infested with attached mussels that the weight of the mussels caused recirculation of heated cooling water to the intake to raise the ambient water temperature, These procedures the nets to be pulled fromthe bottom due to the restricted flow through the nets. During one week, the nets had to helped minimize the amount of mollusclclde required and meet the discharge permit requirements. They also be changed twice.

Increased the efficacy of CT-1 applications.

In September an accumulation of mussels ln Unit 1 con- As part of the segmented treatment approach, separate tributed to a shutdown for cleanout and repair of equip- mollusclclde applications were fed to each of the three ment. Approximately 4 fts to 6 ft~ 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 also found in the house service water system. The water application. Flgwe 6, a schematic of the Whiting cooling flow to the boiler feed pumps had been restricted by systems, shows three separate Intake bays each con-mussel clogging. These blockages required that feed sisting of two main circulatory pumps and two service pumps be switched and cleanouts be scheduled during water pumps. Since all six service water pumps feed to a the weekends when load was reduced, Figure 5 shows commonheader, only a single feed point was required to extensive fouling and Impingement of mussels at the apply Clam-Trol CT-1 to the service water system, inlet side of a cooling loop. It also shows many of the tubes plugged with mussels on the outlet side. For each of the main circulating systems," CT-1 was applied directly with a sparge header, which was posi-This mussel infestation created extensive macrofoullng tioned ln front of the intake bays, upstream of the travel-condltlons that threatened equipment operation and ling screens. To minimize the amount of CT-1 fed, only jeopardized plant availability. A molluscicide treatment one of two main circulating pumps was operated; this control program was designed to eradicate the Zebra reduced the flow rates to the unit being treated. Table 1

Detoxification of the service water system application was not required because treated water was rerouted Inj~

n k

[J Oo ~ CT-1 Unit1 Main Condenser

~ and diluted within the plants'sh ponds. Residual CT-1 was measured using an analytical photometric method (15) with a detection limit of 0.1 mg/L as Clamltol CT-1 (or 0.013 mg/L as total active concentration). All outfall Intake Unit 2 Main samples collected during each 12+r application were

~I~ ~

Forebay Condenser nondetectable (<0.1 mg/L).

Unit3Maln To increase the ambient Intake water temperature, a por-P Condenser tion of the heated discharge water was recirculated to House Servhe Water Pumps Grcutatlng Water Pumps the Intake canal during mollusclclde application peri-take Erie Travilllng Screens ods. Increasing the siphoning and metabolic activity of Outfall 001 the Zebra mussels by elevating the intake water temper-Figure 6: J. R. Whiting Plant, Consumers Power ature would aid ln increasing the mortality responses.

Company The ambient intake water temperatures were between 0 'C and 2 'C, The recirculated water provided a 4 T between 2 'C to 6 'C.

Table 1: J. R. Whiting Station, December 1989 Results of J. R. Whiting Applications System Reduced Cor-Trot CT-1 is Fhw Flow Rate Applhathn Min. Max. Avg. Outfall Each of the mollusciclde applications at the J.R. Whiting Rates Treatedi perhd (mg/L) (mg/L) (mg/L) (mg/L) station was assessed with blomonitorlng procedures.

(GPM) (GPM) (hr) Flow-through bloboxes were positioned at the Inlet and outlet ends of the treated cooling systems (see Figure7).

Unit 1 66,000 33,000 12 4.3 13.9 6.9 NDs Approximately 40- 80 Zebra mussels measuring 4-20 Unit 2 66.000 33,000 12 12.6 17.0 14.6 ND mm were placed in each blobox. Constant water flow Unit 3 90,000 45,000 12 11.6 16.5 14.3 ND was malntalned through the bloboxes during each of the 124r applications and for several weeks following each SWSo 3 400 3 400 12 NDe 36.0 14.3 ND application to monitor delayed mortality responses.

~ Flow rate was reduced by operating only one of two circulNng Mussels were dead when the bivalve shells gaped open pumps. This minimized the cooling water being treated. and did not close when gently prodded. The control

> ND Nondectable (c0.1 mg/Las Clam-Trol CT-1 or <0.02mg/L mussels had cumulative mortality responses of 0 to 2%

total active concentration). for the duration of the monitoring period.

a SWS . Sewhe Water System

~ The feed pump to the servhe water system was Inoperable for short duration.

presents the fiow rates of each unit, the reduced flow rates of the treated cooling water during the 124r appli-cation period, and CT-1 concentrations measured within the system being treated and at the outfall to receiving waters.

All the cooling water from each system converges at the Inlet end of the 1/4 mite discharge canal. The mixing of the treated water with the untreated cooling water helped reduce the residual CT-1. Detoxification of the remaining CT-1 residual was achieved by feeding Betz DT-1 (a blend of bentonite clays) directly to the discharge canal.

The clays were fed using a powder screw feeder at an approximate feedrate of 1 mg/Lof clays for each 1 mg/L of residual CT-1 to be detoxified. The average clay con-centrations fed during the treatments of Units 1, 2, and 3 Figure 7: Flow Through Bloboxes for Monitoring were 5.9 mg/L, 6.7 mg/L, and 8.8 mg/L respectively. the Efficacy of Appllcatlons

The mortality responses, which were monitored at the North inlets and outlets of the units treated with 12-hr CT-1 Tower applications, correlated with water temperatures (see Figure 8). Mortalities of greater than 95% were achieved at the outlets of units where water temperatures ranged Main from 14.5 C to 19 'C. At the Inlets of the service water Decant system and at Unit 1, mortality responses of 5% or less resulted when the water temperatures never exceeded South Tower 4 'C or 5 'C. Units 2 and 3 had inlet water temperatures Main Pumphouse of 6 'C and 8 'C; their mortality responses were 43 and Lake Erie 26%. Main Condenser DETROIT EDISON COMPANY ENRICO FERMI II NUCLEAR POWER PLANT General Senitce GSW Water System Pump Background Ptt House The Enrico Fermi II Nuclear Power Plant Is a single-unit (1100 MW) facility with a recirculating cooling system Figure 9: Enrico Fermi II Nuclear Power Plant, (see Figure 9). The main circulating cooling water flows Detroit Edison from the cooling pond through the main condensers to the hyperbolic cooling towers, thenreturns to the cooling exchangers, and main turbine lube oil coolers. AIIZebra pond. The makeup water to the cooling pond originates mussels were Juveniles from 3 to 5 mm In size.

in the once-through service water system, which uses raw water from Lake Erie. The decant or blowdown pipe of the cooling pond is the point of discharge to Lake Erie.

Molluscicide Application Procedure Clam-Trol CT-1 was applied at the service water pump Zebra mussels were first found colonizing the concrete intake for 15 hr. This application was initiated when the walls of the seNice water intake stmcture ln late August, Intake water temperature was 4 'C. The Intermittent chlo-1989. Diver inspection of the intake structure revealed rination treatment for the service water system wasterml-uniform populations of 20,000 mussels/m2. Subsequent nated 24 hr prior to feeding Clam-Trol CT-1. This proce-inspections of the service water components during 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 setvlce water pump wouldnot be actively siphoning during the CT-1 applica-casings, reactor building closed cooling water heat tion.

100 To prevent any release of residual CT-1 to Lake Erie, the 90 X inlet cooling pond blowdown was terminated and the service 80 water pump suction was switched from Lake Erie to the Cl Outlet cooling pond. CT-1 was applied directly into the setvlce 70 14.5 'C 18.0 'C 19.0 'C

~ 60 water pump suction pit via a sparge header. The entire service water flow enters the cooling pond and provides 50 a significant dilution of the CT-1 treatedwater. To provide further neutralization, the service water pump suction g 40 remained In recirculation mode (suction from cooling 30 60C pond) for 10 hr after CT-1 application. To complete the 20 neutralization process, dry clays (Betz DT-1) were fed to 10 40C 5'C 8'C the cooling pond.

0 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 CT-1 service water was fed to the fire protection system Figure 8: J. R. Whiting Power Plant/December upon analytical verification of a targeted 20 mg/L CT-1 1989 Zebra Mussel Mortality concentration ln the service water. The fire protection Responses: 12-hr Clam-Trot CT-1 system was closed once the CT-1 application was Appllcatlons injected into the system.

Results of Fermi II Applications 100 90 Application Period: 15 hr Two flow-through bloboxes were positioned within the 80 CT-1 Concentration: 21.5 mg/L service water system to monitor the efficacy of the 154r Temperature: 4 'C t= 70 application. Each biobox contained approximately 60-100 mussels and received service water continuously

> 6o during the application and for 42 days following the

~ 5o application to monitor the delayed mortality response.

Clam-Trol CT-1 was analytically determined each hour I~ 30 during the application (See Table 2). The average CT-1 concentration was 21.5 mg/L o 20 10 Figure 10 presents the delayed mortality responses fol-final 0

lowing the molluscicide application. The 4 'C water tem- Bloboxes 1 2 1 2 1 2 1 2 14 21 28 42 perature causes a slow mortality response. On day 27 the delayed mortality responses were 39 and 42%. the Obsetvatlon TIme (Days) mortalitie of 62 and 73% were achieved on day42.

The higher mortality responses for the Fermi II applica- Figure 10: Enrico Fermi II/Service Water System:

tion compared to the inlet responses at the Whiting Sta- Zebra Mussel Mortality Responses tion can be correlated with a higher CT-1 dosage (21.5 mg/L at Fermi II Instead of approximately 15 mg/L dos-ages at the Whiting Station) and a longer application CONCLUSIONS period (1 &hr at Fermi II instead of 124r at the Whiting Station). The objectives of a Clam-Trol CT-1 treatment program for Zebra mussel fouling control is to eradicate the juvenile mussels and to prevent the accumulation of mussels within the cooling system. The frequency of applications Table 2: Fermi II Nuclear Power Plant GT-1 Analy- (2to 4 times/year) required to achieve propermacrofoul-sis of The Service Water System Ing control will be site specific for each cooling system.

Certain systems and specific components may require Sampling Time more frequent applications. A mussel surveillance pro-During Treatment gram to monitor the occurrence and extent of mussel (in hr) CT-1 (in mg/L) infestation and their growth within a cooling system Is recommended as an integral part of the overall proce-0.0 dure for a Zebra mussel fouling control program.

0.5 14.1 If Zebra mussels are known to be colonizing a particular 1.0 15.2 area within the general geographic region of a power 2.0 17.7 plant, the following steps are recommended:

3.0 18.3 4.0 27.7 Step 1: Establish a mussel surveillance program at the 5.0 21.0 cooling water lntakes and within the cooling 6.0 27,8 system, particularly, at the safety-related and 7,0 26.3 service water systems.

8.0 18.6 9.0 21.8 Step 2: Develop a treatment strategy for applying the mollusclclde to provide fouling control 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 15.0 237 Step 3: Maintain a vigilance of the fouling. Zebra mus-sel fouling can abruptly develop into advanced Treatment Stopped Average = 21.5 mg/L fouling that may require a cleanout of the system before protective treatment program initiation.

Step 4: Apply Clam-Trol CT-1 treatments based upon responses of >>9596 achieved at the condenser outlets the extent of mussel infestation. Optimize the of the J.R. Whiting station (see Figure 8) when watertem-CT-1 applications (6 to 12 hr) when water tem- peratures ranged from14.5 'C to 19 'C and from the lab-peratures are ~15 'C. oratory efficacy studies conducted at 15 'C and 20 'C (see Figures 2 and 3). Even CT-1 applications as brief as At Fermi II a preventative treatment program was 6 hr when water temperatures are 20 'C should provide implemented to eliminate any impediment to water flow effective treatments in July and August.

of the once-through service water system. Preventing macrofouling within this service water system Is essen- When Clam-Trol CT-1 must be applied during the colder tial for the operation of this nuclear facility. The initial months of the year, longer treatment periods of24to 72hr 1989 CT-1 application provided mortality responses of will be required or intake temperature should be ele-62% to 73% when the water temperatures were 4 'C. vated to 215 'C by recirculating the heated cooling wa-Applications willberesumed in the spring of 1990based ter.

upon a mussel surveillance program. The threat posed by the Zebra mussel has been well-Atthe J.R. Whiting station Zebra mussels are well estab- documented. In this paper we have described a very lished within the vicinity of this power plant and will practical and cost effectiv treatment program that has require a regimentedmollusclcide treatment program to been successfully applied at two power plants. The protect equipment and maintain plant availabilitgj. CT-1 effect of water temperature on the treatment is important was fed In segmented applications (12hr or less) and the and Is also thoroughly reviewedhere. Successful Zebra amount of mollusclclde was mlnimizedby reducing fiow mussel control in power plants is achievable.

rates. This provided an effective means of controlling the chronic infestation at this facility. In addition, the detoxifi-REFERENCES cation potential of this molluscicide provided a means of eliminating toxicity at the discharge. 1. Mallory, M., "The Tiny Mussels Choking the Great

'the monthly Lake Erie water temperatures measured at Lakes", Busfness Mfeek, February 19, 1990.

the Intake of the J. R. Whiting Station from May through 2. Griffiths, R. W.; Kovalak, W P.; Schloesser, D. L.,

September were 15 C or greater (see Figure 11). It Is "The Zebra Mussel, Drelssena polymorpha, in during this period that spawning actlvityand Infiltrationof North America: Impact on Raw Water Users", EPRI Juvenile mussels or vellgers into cooling systems Service Water System Problems Affecting Safety-occurs. Therefore, most treatments should be applied Related Equipment Seminar, Charlotte, North Car-between May and September for optimal fouling control. olina, 1989.

Optimizing preventative treatment programs byapplying Clam-Trol CT-1 for 12 hr or less can be successfully 3. Garton, D.; Haag, W., "Reproduction and Recruit-accomplished when water temperatures ared5 C or ment of Dreissena During the First Invasion Year ln greater. This has been demonstrated by mortality Western Lake Erie", Conference on the Zebra Mus-seis: The Great Lakes Experience, University of Guelph, Ontario, 1990.

4. Mackle, G. L.; Gibbons, W, N.; Mancaster, B. W.;

200 Gray, I. M., "The Zebra Mussel, Drelssena po/y-morpha: A Synthesis of European Experiences and A Preview For North America", Environment

~ 15' Ontario, Water Resources Branch, Report, July 1989.

~10

5. Jenner, H, A., "Chlorine MinimlzatloninMacrofoul-Ing Control In the Netherlands", Water Chlorlnatlon Vol. 5: Chemistry, Environmental Impact and Health Effects, R. E. Jolly et.al. Eds., 1984.

00 2 3 4 5 6  ? 8 9 10 11 12 6. Jenner, H. A., "Control of Mussel Fouling ln the Month of the Year Netherlands: Experimental and Existing Methods",

Macrofoullng Control Technologies: Staff-the-Figure 11: Lake Erie inlet Temperature: J.R. Whiting Art, EPRI Report CS-3343, Electric Power Power Plant Research Institute, Palo Alto, CA, 1983.

7. Whltehouse, J.W.; Khalanski, M.; Sarogola, M.G.; Clam-Trol CT-1, a New Mollusclclde", Betz Labo-Jenner, H. A. "The Control of Blofouling in Marine ratories, Trevose, PA, 1987.

and Estuarine Power Stations: A Collaborative Research Working Group Report for Use by Station 12. Post, R. M.; Lyons, L A., "Mollusclclde Controls Designers and Station Managers", Central Elec- Asiatic Clam Problems", Electr. Vght Power, 65 tricity Research Laboratories, Surrey, England, (1 0), 26 (1987).

1985.

13. Lyons, L A.; Codlna, O.; Post, R.M.; Rutledge, D.

8. Clarke, K. B., "The Infestatlon of Waterworks by E., "Evaluation of a New Mollusclclde for Alleviat-Drelssena poQmorpha a Freshwater Mussel", J.

ing Macrofouling by Asiatic Clams", Proceedings

/nst. Water. Engrs. 6: 370-378. 1952. of the American Power Conference, Vol. 50, 1988.

9. Klrplchenko, M. YAMikheev, V. P.; Stern, E. P.

"Battling Overgrowth of Drelssena at Hydroelectric 14. Mowery, D.; McClellan, E.; Lyons, L A.; Austin, D.

Power Plants", Elektr. Stn. 5:30-32, 1962. M.; Karlovich, D. N., "Asiatic Clam Control Experi-ence at Peach Bottom Atomic Power Station",

10. Lyons, L A., "Detoxification Potential of a New EPRI Service Water System Reliability Improve-Mollusclclde For Asiatic Clam Fouling Control", ment Seminar, Charlotte, North Carolina, Novem-Presented at the Annual Meeting of the Society of ber, 1989.

Environmental Toxicology and Chemistry, Pensa-cola, Rorlda, 1987. 15. "Determination of Clam-Trol CT-1 by Modified Photometric Methyl Orange Complexatlon Proce-

11. Lyons, LA., Detoxification of the Effluent From an dure", Betz Laboratories Analytical Method, Betz industrial Cooling Water System Treated with Laboratories, Inc., Trevose, PA, 1989.

Technical Paper 327 EPRI Condenser Technology Conference September 18-20, 1990 Proposed Blue Mussel Fouling Control Technology Using a Nonoxidizing Molluscicide I

~N L. A. Lyons Manager, Aquatic Toxicology Laboratory D. P. Davis Assistant Vice President, Regulatory Affairs J. C. Petrille Aquatic Biologist M. W. Werner Bioassay Research Specialist L. J. Briggs Aquatic Biologist J. R. Burkle Field Engineer Betz Laboratories, Inc.

Trevose, PA 19053

~"Benz RPudimeHz0 O1990, Betz Laboratories, Inc. All Rights Reserved.

5*

PROPOSED BLUE MUSSEL FOULING CONTROL TECHNOLOGY USING A NONOXIDIZINGMOLLUSCICIDE ABSTRACT Blue mussels are mollusks that cause chronic macro-fouling problems in seawater cooling systems world-wide. Control technology for alleviating blue mussel macrofoullng has been primarily limited to thermal back-washing or continuous chlorination.

A nonoxldizing mollusclcide, referred to as Clam-Trol CT-1, is providing state-of-the-art macrofoullng control for Asiatic clams and Zebra mussels. New treatment technology for blue mussel fouling control employing Clam-Trol CT-1 is being proposed. The capability of this mollusclcide to be effective with short application peri-ods (6 to 24hr) would eliminate the accumulation of juve-nile blue mussels within the cooling system. As with ther-mal backwashlng, CT-1 applications would be initiated every 4 to 8 weeks during the peak spawning and growth season to provide fouling control of juvenile mussels. Figure 1: Cluster of blue mussels ranging In size The expired mussels following these treatments would from ~/s to ~/z In, ln length detach and pass through the cooling system without hin-Macrofouling caused by blue mussels is a major threat drance of plant operations. The frequency of applica-to the operations of power plants that use brackish and/

tions to a cooling system will be basedupon the degree or seawater cooling systems. Blue mussels colonize ln of mussel infestatlon and growth, which shouldbe deter-massive clusters within the intake structure and condults mined by surveillance programs.

of cooling systems. They will aggressively attach and This paper presents the results of sldestream accumulate upon every available hard surface encrust-flow-through studies of the efficacy of Clam-Trol CT-1 lng the walls, pump housing, trash racks, and screens.

applications on blue musseis at different temperature Blue mussels often reduce the inside diameters of main reglmens (11 'C, 15 C, and 20 'C). The Implementa- conduits. The smaller diameter pipes of service water tion of environmentally acceptable treatment strategies systems are particularly vulnerable to partial and com-using Clam-Trol CT-1 are discussed. In addition, the re- plete pluggage of water flow, which can cause the dis-search efforts planned for 1990 and 1991 are presented. ruption of plant operations and damage equipment. Blue These research efforts include the evaluation and opti- mussel fouling also Jeopardizes the integrity of safety-mization of CT-1 treatment programs to selected cooling related cooling systems. Blue mussel macrofoullng systems for control of blue mussel fouling. costs the power Industry tens of millions of dollars per year because of reduced cooling efficiency, scheduled shutdowns for mussel cieanouts, and forced outages.

INTRODUCTION Extent of Macrofouling Biology of the Blue Mussel The blue mussel reaches sexual maturity within one year.

The blue mussel, Mytilus edulis, also commonly referred The fertilization of eggs and sperm is external to the to as the black or bay mussel, belongs to the mollusk organism. Planktonic stages undergo several metamor-family of Mytllidae. This group of mussels is found world-phoses to the pediveliger larval stage. Once a pedivelig-wide off Australia, New Zealand, india, Japan, as well er settles on a suitable substrate, it develops into a plan-as along the coasts of Europe, North America, and South tigrade (the post larval stage) and secretes a byssal America. Along North America, the blue mussel ranges thread for attachment. Plantigrades are about 0.3 mm in from Nova Scotia to North Carolina on the Atlantic coast size (see Figure 2).

and from Alaska to Baja California on the Pacific coast. > The blue mussel attaches to all types of hard The reproductive cycle varies in different geographical surfaces using its byssal threads. Blue mussels are often areas. Generally, spawning activity occurs when water found as the dominant organism in an area colonizing in temperatures rise above 10 - 15 'C and decline below extensive mats and clusters (see Figure 1). 20 'C. The spawning season can last from several

Chlorination/Bromination

('<<

Chlorine programs used in macrofouling control have been studied at various power plants. Essentially, it has been concluded that intermittent chlorination for a few

<<. <<g.g$ Q.<< hours per day is ineffective in controlling blue mussel fouling. Both juvenile and adult blue mussels sense the presence of oxidizing biocldes (e.g., chlorine, bromine, and ozone) and avoid contact by closing their bivalve e shells. Investigators noted that the mussels close their bivalve shells during intermittent chlorine applications and resume siphoning activity when the treatment termi-Jg, nates. Chlorine minimization studies have demonstrated

~l fj Iwr, that a continuous chlorination program must last for sev-eral weeks to effectively eradicate juvenile and adult

'I = ,<<

blue mussels. s 4 ~ s Often chlorine treatment programs Figure 2: Microscopic view of post-larval stages are applied through the entire reproductive seasons to of the blue mussel. Larvae are 0.1 - 0.3 provide effective control. In addition, environmental dis-mm In size. charge restrictions for chlorine (0.2 mg/L for 2 hr/day) to power plants presents significant limitations on macro-fouling control for blue mussels.

weeks to more than 6 months. Within a particular area, spawning can vary from one habitat to another, and with-In a particular habitat, spawning cycles can vary from

-one year to the next. Thermal Backflushing Growth rates of blue mussels also vary depending upon nutrition, temperature, season, and habitat. Blue mus- Thermal treatment or backwashlng ls a macrofouling sels can grow from 1 2mm (1/qs in.) each year to >50 control methodusedby a few power plants that have the mm (2 in.) each year. The life span of a blue mussel can capability to redivert heated condenser water to the main reach 20 yr. >.2 intake conduits and intake bays to eradicate Juvenile mussels. The typical thermal treatment employed by Because of the extensive variability ln spawning activity several plants ~ employs a 4 hr exposure at 40.5 'C and growth, an ongoing monitoring program for any (105 'F), but a shorter exposure period of 30 60 min-cooling system that is exposed to blue mussel macro- utes have also proven to be effective. These thermal fouling is necessary. The monitoring program should de- treatments are scheduled every 4- 6 weeks during the termine the degree of larvae infestatlon, the recruitment peak spawning and growth season. Thermal treatments of Juvenile mussels into the system, and the seasonal eradicate the juvenile blue mussel before attaining foul-growth rates of the mussels. This monitoring program ing size (e.g., 10mmin length). Thermal treatments elim-will help determine when fouling control measures inate the need for physical cleanouts since the expired should be implemented. juvenile mussels detach from the surfaces of the intake bay and pass through the cooling system. s 78 The limitations of thermal backwashing include:

CONTROL METHODS

~ only a few power plants have the capability of Methods for blue mussel macrofouling control are lim- reversing the flow of the heated condenser water.

ited to either physical means (cleanouts and hydraulic

~ thermal backwashing usually cannot be used in ser-flushing), mechanical methods (screens and strainers), vice or safety-related cooling systems.

or eradication procedures that use thermal backwashing or chlorination. Physical and mechanical methods pro- ~ the power plant output must be reduced during vide a means of dealing with advanced fouling condi- thermal treatments.

tions, but do not provide preventative macrofouling con-trol. The performance and limitations of chlorination o special procedures andnonstandard operations are practices and thermal backwashlng are summarizedbe- required to reverse flow rates of main circulating low. cooling water.

CLAM-THOLCT-1: NONOXIDIZING The proposed CT-1 technology is appropriate for blue MOLLUSCICIDE mussel control within intake bays andmaln cooling sys-tem conduits and service and safety-related cooling sys-The proposed blue mussel fouling control technology tems. A surveillance program, whichmonitors the setting employing ClamTrol CT-1 applications Is supportedby of mussel larvae infesting the cooling system and the the side-stream studies being reported in this paper and seasonal growth rate of juvenile musseis, ls recom-the application experiences employing CT-1 for macro- mended to optimize treatment programs.

fouling control of freshwater mollusks. The initial CT-1 application experiences for the control of blue mussel fouling at two Industrial cooling systems in Europe pro- Environmental Considerations vides further confirmation for this proposed macrofoul-ing technology.* In contrast to continuous chlorination, Clam-Trol CT-1 treatment reglmens have short application periods, Clam-Trol CT-1 is a water miscible formulation containing small product volume requirements, and can be readily two cationic surfactants: alkyldimethylbenzylammo-neutralized by either passive or active processes. Both nlum chloride (Quat) and dodecylguanidine hydrochlo-CT-1 actlves (Quat and DGH) are short-lived because ride (DGH). Clam-Trol CT-1 is patented for use as a non-they are readily adsorbed by naturally occurring sub-oxldlzlng molluscicide andis EPA registered foruse as a strates including silts, clays, suspended solids, humlc mollusclcide for once-through and recirculating cooling acids, and even the mlcrofouled surfaces of cooling sys-systems that use freshwater or seawater.

tems. Studies have shown that once the actives are This molluscicide has two significant features: adsorbed, they no longer exhibit toxicity. 9 If required, CT-1 applications can be actively detoxified by applying o it can provide fouling control of mollusks, such as blue mussels, when applied for only 6- 24 hr a blend of clays (Betz DT-1) to the treated water.

o it can be neutralized prior to discharge Clam Trol CT-1 treatment programs are designed to max-imize the passive neutralization of the actives within the CT-1 Applications: Blue Mussel Fouling cooling system. For example, a segmented treatment Control approach is often used to focus applications in specific areas or system components. Mollusclcide concentra-The capability of CT-1 applications to control blue mus- tions are further minimized by reducing flow rates or sel fouling with short applications of 6- 24 hr presents a using static treatments where possible.

feature that is analogous to thermal backwashlng tech-nology. Like thermal treatments, CT-1 applications elimi- When obtaining discharge permitting approval from a nate juvenile musseis before they attain fouling size and state regulatory authority, an application package before the Juvenile mussels accumulate to intolerable should include:

encrustations.

o a description of the macrofouling problem in the To provide appropriate macrofouling control, this moi- power plant and the need for control lusclclde should be applied every 4 to 8 weeks. The exact scheduling willbe dependent upon several condi-

~ CT-1 product description (constituents, MSDS, and aquatic toxicity data) tions:

o the degree of larvae infestation and recruitment of ~ CT-1 application procedures and expected dls-Juvenile mussels entrained into the cooling system char'ge concentrations o growth rate of the mussels a description of the monitoring program during treat-o the size of piping within the cooling system to allow ments passage of expired mussels following CT-1 applica- o a description of the detoxification program (if tions needed)

• A petroleum refinery and'a manufacturing plant imple-mented CT-1 applications for blue mussel macrofouiing controi. Each application achieved 80-100/o blue mussel mortality responses.

Application Experience: Asiatic Clams/ Two types of flow-through systems were designed. One Zebra Mussels system was constructed of 4-PVC (4 in. diameter) tubes (see Figure 3). Each tube was 3 ft long and contains Since 1986, Clam-Trol CT-1 treatment programs have plates for the settlement of macrofoullng organisms.

been providing state-of-the-art macrofouling control for Flow rates of 10 gal/min were regulated through these fouling caused by Asiatic clams, Corbfcula flumfnea, in tubes. This system was developed to permit the settle-freshwater cooling systems. >o Seasonal applications ment and accumulation of Juvenile blue mussels and (2-4 times/yr) provide a preventative programby signifi- other fouling organisms. The specific tests conducted cantly eradicating juvenile clams, which prevents their with this particular flow-through system were scheduled growth to adult fouling size. The elimination of juvenile at the time of preparation of this presentation (see R8 D clams that colonize intake bays eliminates the need for objectives for 1990/1991). The results willbe made avail-annual cleanouts of adult populations and prevents the able in a later publication.

threat of forced outages due to macrofouling at power plants. >> Seasonal CT-1 applications for 12 to 24 hr to In the other flow-through system (see Figure 4) a series of the safety-related and service water systems of nuclear open troughs were used to assess the optimal CT-1 con-power plants are providing a better control method than centration and exposure period for the eradication of continuous chlorination In assuring the unobstructed op- blue mussels. Water to each trough was regulated with a eration of these systems. >> In addition, industrial facili-gate valve at a flow rate of 2 gal/min. Stock solutions of ties are employing Clam-Trol CT-1 treatment programs CT-1 were delivered by peristaltic pumps to Z-shaped for the control of Asiatic clams in their entire process sys-pipes, which facilitated proper mixing of the CT-1 stock tems. solutions before delivery to the test troughs. Each trough The Zebra mussel, Dre/ssena polymorpha, is an Euro- contained 6 U-shaped, PVC inserts.

pean freshwater mollusk that invaded the Great Lakes in 1985 and has already caused extensive fouling prob-lems in Lake Erie power plants. >s ~4 Like the blue mus-sel, the Zebra mussel Is quite prolific and has a plank-tonic larval stage that is entrained into cooling systems.

Like the blue mussel, the Zebra mussel causes similar fouling conditions in cooling systems by aggressively attaching to all system components and accumulating in mats and clusters. In 1989, CT-1 treatment programs were initiated for Zebra mussel control at two power plants near Detroit. >> Like the proposed blue mussel control program, Zebra mussel fouling control programs focus on the spawning season, growth rate, and the accumulation of Juvenile mussels within a cooling sys-tem.

SIDESTREAM EFFICACY STUDlES ON BLUE MUSSELS Methods and Equipment A mobile bioassay trailer was outfitted with flow-through testing systems at the Betz Aquatic Toxicology Labora- t tory in Trevose, Pennsylvania and moved to Salem Har-bor, Massachusetts. Testing was conducted in August and September 1989 and resumed in May 1990.

Seawater from Salem Harbor Bay was pumped into two ~i@

60-gal polyethylene tanks with submersible pumps.

Each tank had an overflow standpipe that maintained a constant head pressure to each flow-through trough. Figure 3: Flow-through fouling tube system to Two recovery tanks were also maintained: they received monitor the detachment rate of Juvenile a continuous supply of fresh seawater. mussels following CT-1 treatments

end of the test because of the stress on the mussels.

wi Explredmussels exhibited discolored and often putrified tissue. The maJority of the mussels were dead based I

upon the gaping bivalve shells.

CT-1 concentrations in each treatment trough were ana-lyticallymonitored at various intervals with a photometric method. >~ Dissolved oxygen, pH, salinity, and temper-ature were also monitored.

F;g j~' P> RESULTS I

Table 1 presents the cumulative mortality responses at three temperature regimens (11 'C, 15 'C, 20 'C) for fi ~,

CT-1 dosages ranging from 5mg/Lto 25mg/L and appli-1 cation periods ranging from 6 hr to 24 hr. Mortality re-sponses of > 70% were achieved for 30 of the 52 differ-Figure 4: Flow-through test troughs with blue ent treatment applications evaluated. Of these 30 treat-mussels In U-shaped PVC Inserts. Mesh ment applications, 21 had mortality responses ranging was used to prevent mussels from mov- from 80% to 100%. Note that Clam-Trol CT-1 contains Ing between inserts. 13% total active concentration. Clam-Trol CT-1 concen-trations of 5 mg/L, 10 mg/L, 15 mg/L, 20 mg/L, and 25 mg/L contain total active concentrations of 0.65 mg/L, 1.3 mg/L, 1.95 mg/L, 2.6 mg/L, and 3.25 mg/L, respec-Blue mussels used in these efficacy studies were col- tively.

lected from the Jetties around Salem Harbor within the Clam-Trol CT-1 applications cause a delayed mortality mean low tide zone. Mussels 8 30 mm in size were response that Is usually Initiated 2-4 days following the carefully separated from their byssal attachment and treatment. Figures 5, 6, and 7 show the delayedmortality randomly placed into the inserts. Each Insert contained responses resulting from 18-hr CT-1 applications at 20 individual mussels (or 120 mussels per trough). Each 11 'C, 15 'C, and 20 'C, respectively.

insert was separated with a mesh to prevent the move-ment of mussels between inserts. Within less than one hour, the mussels reattached to the inserts. The mussels were acclimatized for 24 hr in the troughs before receiv-g 10 mg/L CT-1 Q 15 mg/L CT-1 g] 20 mg/L CT-1 ing CT-1 treatments.

100 CT-1 treatment levels of 0 mg/L(control) to 25 mg/L were randomly assigned to each trough. Certain CT-1 concen- 90 trations (e.g., 15 mg/L) were run in replicate (2 troughs). 80 g 70 Each set of inserts within each trough were randomly as-signed CT-1 exposures 3 - 24 hr. Following each expo- ~o 0

80 sure period, individual inserts were removed from the 50 treatment troughs and placed In a recovery tank. After the longest treatment period (24 hr), all inserts were 40 0

returned to their designated trough for observation and 30 received only seawater (no CT-1). Delayed mortality re- 20 sponses and behavioral obsetvations were recorded at 24-hr intervals for several days following the treatments. 10 Musseis were considered dead when the bivalve shell I- 4days -I I 6days -I I-13days I gaped and the valves didnot close when gentlyprodded Observation Days with a blunt probe. For those mussels with their bivalve shells tightly closed, mortality was determinedby gently prying open the bivalve shell and checking for an adduc- Figure 5: Delayed Mortality Responses at 11 'C.

tor muscle response to close the shell. This particular Blue Mussels Were SubJected to 18- Hr method of assessing mortality was only performed at the CT-1 Applications of Varying Doses.

Table 1: Cumulative Percent Mortality of Blue Mussels Total Active Clam-Trol CT-1 Concentration Application Temperature (mg/L) (mg/L) Period (hr) 11 OC 15 oc 20 'C 0.65 6 0 5 0.65 12 5 30 0.65 18 30 '0 0.65 24 30 10 1.3 6 0 25 35 10 1.3 12 35 40 75 10 1.3 18 50 35 70 10 1.3 24 80 70 70 15 1.95 6 17.5 46.5 62.5 15 1.95 12 62.5 75 85 15 1.95 18 85 81 87.5 15 1.95 24 100 87.5 90 20 2.6 6 50 60 80 20 2.6 12 70 85 60 20 2.6 18 100 80 80 20 2.6 24 100 85 100 25 3.25 6 74 70 25 3,25 12 80 77.5 3.25 18 91 95 25 3.25 24 95 95 EI 5 mg/L CT-1 II 10 mg/L CT-1 Q 15 mg/L CT-1 H 5 mg/L CT-1 g 10 mg/L CT-1 Q 15 mg/L CT-1 g] 20 mg/L CT-1 Pg 25 mg/L CT-1 Ij 20 mg/L CT-1 g 25 mg/L CT-1 100 90 90 g

80 70 I 7O o 60 60 I) 50 ) 50 40 I 40 30 ~ 3O 20 20 10 10 0

I4days I I7da ySM 14da ys I I I 2days I I6days I I10days I Observation Days Observation Days Figure 6: Delayed Mortality Responses at 15 'C. Figure 7: Delayed Mortality Responses at 20 'C.

Blue Mussels Were SubJected to 18- Hr Blue Mussels Were SubJected to 18- Hr CT-1 Applications of Varying Doses. CT-1 Applications of Varying Doses.

Several behavioral responses were exhibitedby the blue mussels exposed to CT-1 treatments. Mussels partially H 11'C Q'154C O20'C retracted their siphon sensory tentacles and sensor 90 papillae along the mantle edge. However, all mussels ~ .80 remained siphoning during the initial hours of exposure. 70 As the treatment duration increased, mussels began to close their valves. In the 12-hr, 18-hr, and 24-hr treat- 60

~O ments, more than 50% of the mussels still had their 0 50 valves open and slphons extended. Within 24 hr follow- ) 40 ing initiation of CT-1 treatments the blue mussels were sluggish to gentle prodding. All control mussels be- Ã 30 haved normally and no mortality occurred. O 20 l,l'everal 10 individual mussels within each treatment group were severely stressed. Stressed Individuals exhibited an abnormal gaping response of the bivalve shells the I- 6hr -I I- 12hr+ I-18hr-I I-24hr-I edge of the mantle tissue was retracted and the visceral Length of Application tissue was entirely exposed. In addition, the bivalve shells were abnormally gaped open more than ninety Figure 9: Efficacy of 10 mg/L CT-1 Applications to degrees. All gaping mussels responded to prodding by Blue Mussels for Different Appllcatlon closing their bivalve shells, but within minutes afterward Periods and Temperatures they actively resumed gaping. All severely stressed mussels (with the extended, gaped valves) eventually expired. All 24-hr CT-1 applications (10 mg/L) achieved between 70% to 80% mortalities at each temperature (see Fig-For the 5 mg/L CT-1 applications (see Figure 8), mortality ure 9).

responses correlated with temperature higher mortal-ity occurred at 20 'C than at 15 'C. In comparison to the The 15 mg/L (1.95 mg/L total active) CT-1 applications 5 mg/L CT-1 applications, the 10 mg/L (1.3 mg/L total obtained 81 -100% mortality responses for all 18-hr and 24-hr applications at the three temperatures (see Figure active) applications (see Figure 9) demonstratedhigher mortality responses in all CT-1 applications evaluated. 10). In comparison, the 6-hr and 12-hr applications of 15 At 20 'C mortality responses of 70-75% were achieved mg/L appeared to correlate with temperature in-at each 10mg/L CT-1 application (12 hr, 18 hr, and 24 hr). creased mortality was found at higher ambient water temperatures.

60 El 15'C mj 20'C Q 11 'C ~ 15 'C mj 20 'C 100 y, 50 90 80 40 70

~O

>oo 60

) 30 g 50 4Q~

E 20 O 30 10 20 10

>0 I- 6hr -I I- 12hr I I-18hr I I- 24hr I I- 6hr w I-12hrw I-18hr~ I-24hr-I Length of Application Length of Application Figure 8: Efficac of 5 mg/L CT-1 Applications to Figure 10: Efficacy of 15 mg/L CT-1 Appllcatlons Blue Mussels for Different Application to Blue Mussels for Differen Applica-Periods and Temperatures tion Periods and Temperatures

The 18-hr and 24-hr, 20 mg/L (2.6 mg/L total active) CT-1 CON CLUSlONS applications achieved 80 90% mortality responses (see Figure11). The 6-hr and12-hr,20mg/LCT1 applica- Sldestream evaluations have demonstrated that tions had mortality responses that correlated with Clam-Trol CT-1 applications (6 - 24 hr) can significantly temperature, with the exception of one anomaly (the eradicate blue mussels. The proposed CT-1 treatment 12-hr CT-1 application at 20'C). technology presents an alternative method to traditional continuous chlorination and thermal backwashlng tech-All 18-hr and 24-hr, 25 mg/L (3.25 mg/L total active) CT-1 nology for the control of blue mussel fouling.

applications achieved 91 95% mortality responses (see Figure 12). Even the 6-hr CT-1 applications at Unlike CT-1 applications, chlorine requires continuous 25 mg/L achieved mortality responses of 70 - 74%. application for several weeks to eradicate Juvenile mus-sels. In addition, distributing and maintaining a chlorine residual continually throughout the cooling system is B 11oC 815oC HI20oC often not practical. Furthermore, discharge permit 100 requirements can restrict proper fouling control with 90 chlorine. Although thermal backwashlng Is effective in eradicating Juvenile mussels in intake bays and main 80 cooling system conduits, only a few power plants have Q 70 . this capability. These thermal treatments are not applica-O 60 ble for fouling control of service water and safety-related 50 cooling systems.

40 The proposed CT-1 treatment technology would entail 30 E intermittent applications every 4 8 weeks during the 20 reproductive and growth seasons of the blue mussel.

10 The objective of the proposed treatment program is to 0 eradicate the Juvenile mussels and to prevent the accu-I- 6hr-I I-12hr-I I-18hr I I-24hr-I mulation of mussels within the cooling system. This pro-Length of Application posed treatment technology is applicable for all types of cooling systems and components.

Figure 11: Efficacy of 20 mg/L CT-1 Applications to Blue Mussels for Different Application CT-1 treatment programs should be optimized with a Periods and Temperatures mussel surveillance program. In a surveillance program, sidestream monitoring devices piped within the cooling system and substrates suspended within intake bays shouldbe used to monitor the occurrence and degree of mussel fouling and the mussel growth rate. The devices 100 0 15'C Hl 20'C used in the surveillance program can determine when CT-1 applications are required and can assess the treat-90 ment performance.

g'O.

g 70

~ 6o R&D Objectives for 1990/1991 I

~O 50 The proposed CT-1 treatment program will be further m 40 evaluated for the control of blue mussel fouling ln 1990 I 3O and 1991. These evaluations will include treatments to the cooling systems of power plants and also at the 8 2O industrial facilities already initiated in Europe. Other 10 research activities will include:

0 I- 6hr -I I- 12hrd I-18hrd I-24hr-I ~ Evaluate multiple, short-term CT-1 applications Length of Application under various conditions.

~ Access the detachment rate of expired mussels fol-Figure 12: Efficacyof 25mg/LCT-1 Appllcatlonsto lowing CT-1 applications. The flow-through system Blue Mussels for Different Application (see Figure 3) willbe used for some of these access-Periods and Temperatures ments.

~ Evaluate different surveillance devices and Control at Millstone Nuclear Power Station, Water-approaches that determine the rate of fouling within ford, Connecticut". Symposium on Condenser a cooling system and that determine Juvenile mus-sel growlh. Macrofoullng Control Technologies: The

~ Evaluate the contribution of other organisms, such State-of-the-Art, CS-334319 Palo Alto, California:

as hydrozoans, bryozoans, barnacles, and other Electric Power Research Institute, December mollusks that may contribute to macrofouling within 1983, pp. 25 cooling systems. Determine the efficacy of CT-1 applications on these organisms. L.A. Lyons. "Detoxification Potential of a New Mol-lusclcide for Asiatic Clam - Fouling Control." Ab-stract. Society of Environmental Toxicology and ACKNOWLEDGEMENTS Chemistry, 1987.

Betz Laboratories would like to thank the New England 10. R.M. Post and L.A. Lyons. "Molluscicide Controls Power Company for their cooperation In this study. Asiatic Clam Problems." Electric Light Power, October, 1987, p. 26 REFERENCES L. A. Lyons, O. Codina, R. M. Post and D. E. Rut-ledge. "Evaluation of a New Molluscicide for Alle-

1. B. L. Bayne. Marine Mussels: Their Ecology and viating Macrofoullng by Asiatic Clams." Proceed-Physiology. London: Cambridge University Press, ings of the American Power Conference, vol. 50, 1976, 506 p. 1988.

2. U.S. Nuclear Regulatory Commission. 1984 Bi- 12. D. Mowery, E. McClellan, L.A. Lyons, D. M. Austin valve Fouling of Nuclear Power Plant Service and D. N. Karlovich. "Asiatic Clam Control Experi-Water System. NUREG/CR-4070 Vol. 1 - 3. Wash- ence at Peach Bottom Atomic Power Station."

ington, D.C. EPRI Service Water Supply Reliability Improve-ment Seminar, Charlotte, North Carolina: Electri-

3. L.N. Scotton, W.J. Armstrong, J.F. Garey and D.J. cal Power Research institute, November 1989.

McDonald. "Development and Future Trends of the Mussel Control Program at Pilgrim Nuclear Power 13. R.W. Griffiths, W. P. Kovalak and D. L. Schloesser.

Station." Symposium on Condenser Macrofouling "The Zebra Mussel, Drelssera polymorpha, in Control Technologies: The State-of-the-Art. CS- North America: Impact on Raw Water Users." EPRI 3343. Palo Alto, California: Electric Power Re- Service Water System Problem Affecting Safety-search institute, December 1983, pp. 24 Related Equipment Seminar, Charlotte, North Car-olina: Electrical Power Research Institute, 1989.

4. Condenser Macrofouling Control Technologies.

CS-3550. Palo Alto, California: Electric Power 14. G.L. Mackle, W. N. Gibbons, B.W. Mancaster and Research Institute, June 1984. I. M. Gray. "The Zebra Mussel, Dreissera polymor-pha: A Synthesis of European Experiences and A

5. Biofouling Control Investigation: 18-Month Sum- Preview for North America." Environment Ontario, mary Reports. EPRI EA-1082. Palo Alto, California: Queen's Printer for Ontario, July, 1989.

Electric Power Research Institute, Interim Report, May 1979. 15. L.A. Lyons, J. C. Petrille, S.P. Donner, R. L. Fobes, F. Lehmann, P. W. Althouse, L. T. Wall, R. M. Post

6. M. Khalanskl and F. Bordet. "Effects of Chlorina- and W. F. Buerger. "New Treatment Employing a tion on Marine Mussels". Water Chlorination vol.3. Molluscicide for Macrofoullng Control for Zebra 1980, pp. 557 567. Mussels ln Cooling System." Proceedings of the American Power Conference, vol. 52, 1990.

7. Pilgrim Nuclear Power Station: "Chlorination and Biofouling Monitoring Program". Annual Report, 16. "Determination of Clam-Trol CT-1 by ModifiedPho-1988. Boston Edison Company, 41 p. tometrlc Methyl Orange Complexation Proce-dure". Betz Laboratories Analytical Method, AP

8. G. Johnson, J. Joerth, M. Keser, and B. Johnson. 368, Betz Laboratories, Inc., Trevose, Pennsylva-

"Thermal Backwash as a Method of Macrofouling nia, 1990.

~ rr

@8'Pz@me@Hx0

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SOMERTQN RQAOiTREVOSE, PA 1 9047iU.S.A. f'EL:21 5i355-3300iTELEX: 1 73 1 48iFAX 4 355.2869 A Comparative Marine Macrofouling Control Study Between Chlorine and a Nonoxidizing Molluscicide II L A. Lyons Manager, Aquatic Toxicology Laboratory Betz Laboratories, Inc, Research and Development Department Trevose, PA 19053 J. C. Petriiie Aquatic Biologist Betz Laboratories, inc, T. E. Thompson Senior Biological Specialist Carolina Power & Light Company Brunswick Biological Laboratory Southport, NC M. W. Wemer Bioassay Research Specialist Betz Laboratories, Inc.

ABSTRACT This study evaluated treatment programs to control the potential macrofouling caused by oysters, bar-nacles, ribbed mussels, and hydrozoans at the Brunswick Plant. An on-site bioassay traHer was outfitted; with 12 pressurized sidestream loops. Each loop was equipped with an automatic chemical feed system and a continuous computer tracking system to monitor flow rates. This computerized sidestream unit had an alarm system to alert personnel ln case of malfunction. This 90-day study was conducted during the peak fouling season.

This study compared a daily chlorination program (4 hr/day) with an alternative control technology using a nonoxidizing mollusclcide, being referred to as DGH/QUAT. DGH and QUAT are the two active constitu-ents of the patented molluscicide Clam-Trol CT-1. Two treatment protocol evaluated monthly applications of DGH/QUAT (12 hr/month fed at two concentrations). Selected combinations of chlorine and DGH/

QUAT were also evaluated to determine if macrofouling control improved when a chlorination program was complemented with monthly DGH/QUAT applications and when chlorine usage was'minimized.

The effectiveness of each treatment was determined by the degree of settling, growth, and accumulation of dominant macrofouling organisms within each sidestream loop. Further studies were also performed to evaluate the mortality responses of juvenile organisms (oysters. ribbed mussels, and barnacles) ex-posed to these treatment programs. All treatments were run in duplicate and compared to untreated con-trol loops.

Test results with the chlorine treatments alone (4 hr/day) showed no or limited mortality to oysters or ribbed mussels. The chlorine treatments showed limited mortality and no reduction of growth by oysters com-pared to the control. In contrast, significant eradication and growth reduction of oysters, ribbed mussels and barnacles occurred in all DGH/QUAT alone treatments and all combined treatment programs with chlorine and DGH/QUAT. Final study results on the effectiveness of each macrofouling control treatment protocol are presented.

INTRODUCTION SITE DESCRIPTION The Brunswick Plant (BP) is a 2-unit facility (designed 1630 MMI) owned and operated by Carolina Power and Light Company. Each unit receives once-through main circulating cooling water from the mouth of Cape Fear River. This estuarine water is divertedthrough a1-mile intake canal to the plant's intake pumps.

At the intake, each unit pumps water through the travelling screens to four 586-ft conduits that lead to a c.'ebris filter prior to passing through the main condensers. All cooling water is discharged to a 7-mile dis-charge canal.

The current chlorination program for fouling control in the main circulating cooling systems injects approxi-mately 4000 lb of gaseous chlorine for 4 hr/day. Total residual concentrations of < 0.1 to 0.7 mg/L are de-tected at the condensers.

Macrofouling in the main circulating cooling systems is an accumulation of the American oyster (Crassos-trea virginica), ribbed mussel (Geukens/a dern/ssa). barnacles (Be/anus sp.), hydrozoans, andbryozoans.

Previous inspections during the 1989 and 1990 outages revealed that 6096 to 80% of the biomass con-sisted ofmollusks primarily oysters and ribbedmussels. Although barnacles were abundant, they made up only a small percentage of the total biomass. The remainder of the encrusting macrofouling growth included hydrozoans, bryozoans, and various adventitious organisms. Macrofouling growth encrusted the entire surface areas of the main conduits. ln addition. both the debris filters and the tube sheets were also impinged by macrofouling organisms that had been growing within the cooling system.

Sidestream studies addressed two primary objectives. One objective was to simulate the existing chlorina-tion program (4 br/day) and evaluate its effectiveness. The other objective was to evaluate alternative treat-ment programs, which employed anon-oxidizing molluscicide with and without chlorinetreatments during the peak fouling season.

NONOXIDIZINGMOLLUSCICIDE The nonoxidizing molluscicide, Clam-Trol CT-1, fs a proprietary water miscible formulation containing two cationic surfactants: alkyldimethylbenzylammonium chloride (QVAT) and dodecyl guanidine hydrochlo-ride (DGH). Clam-Trol CT-1 ls EPA registered for use as a moliusctcfde for once-through and recirculating cooling systems that use freshwater, estuarine, or seawater. DGH/QUATcontrolled macrofoullng caused by freshwater mollusks like the Asiatic clam (Corblcuia /iuminea) (3,4) and the Zebra mussel (Dreissena poiymorpha) (2). tn addition, DGH/QVAThas also been used to control blue mussels fouling (Mytilus edu-iis) in the cooling systems of power plants and industrial facilities (1).

In 1989, laboratory flow-through studies were conducted prior to this sidestream study at Brunswick's Bio-logical Station for evaluating the effectiveness of 6-24 hr DGH/QUAT applications ln eradicating oysters, ribbed mussels, and barnacles. The capability of DGH/QUAT to control fouling organisms with periodic applications could potentially eliminate the accumulation of juvenile fouling organisms within the cooling system at the Brunswick facility. The frequency of DGH/QUAT applications during the fouling seasons must be o ptimizedbaseduponthe rate of infestation and growth of the dominant fouling organisms. These applications must be frequent enough to eradicate the juvenile organisms so that their growth and accu-mulation is prevented. This sidestream study further assisted In optimizing and evaluating the potential of monthly OGH/QUAT applications for marine macrofouling control.

SIDESTREAM STUDY This sidestream study evaluated five rnacrofouling control treatment programs and a control (see Table 1).

Table 1 Macrofouling Treatment Programs Treatment Programs Chlorine OGH/QVAT

1. Control

2. Chlorine only Daily, 4 hr 0.5 mg/L TRC

3. DGH/QUAT Monthly, 12 hr 1.3 mg/L

4. OGH/QUAT Monthly, 12 hr 1.95 mg/L

5. DGH/QUAT + Daily, 4 hr Monthly, 12 hr Daily Chlorine 0.5 mg/L TRC 1.95 mg/L

6. DGH/QUAT + 3 times/week, 4 hr Monthly, 12 hr Reduced Chlorine 0.5 mg/L TRC 1.95 mg/L Tests were run for 90 days. The performance of these fivetreatment programs was assessedby their ability to inhibit the accumulation of macrofouling growth on substrates, which were exposed to cooling water through the peak fouling season, and to inhibit the growth and eradicate the dominant fouling organisms.

A detailed description on the procedures, test facility, and results are provided.

MATERIALAND METHODS SIDESTREAM TEST FACILITY A computerized, mobile test facility (see Figure 1) with 12 sidestream fouling chambers and tanks was designed to permit continuous flow of cooling estuarine water. This design is a modification of previous investigators'acilities (5.6). The facility was positioned near the intake structure at the Brunswick Plant.

Estuarine water was contin'uously piped from the unchlorinated travelling screen spray wash system to a 4-in. PVC manifold within the mobile laboratory. Water flow and pressure was maintained with a ball valve and pressure regulator installed on the 4-in. PVC 12-part manifold.

Water was distributed from the manifold into 12 '/.-in. PYC pipes one for each of the 12 vertically-ori-ented fouling chambers (4-in. in diameter by 28-in. long) (see Figure 2). Water flowto each fouling cham-ber was regulated at 10 gal/min with a ball valve and continuously monitored with a Signet paddle wheel flow sensor. The flow sensor was wired to a computer for data acquisition and to an alarm system.

The alarm system had modem call-out features. In the event of reduced or elevated flows to fouling cham-ber, an alarm would alert Carolina Power 8 Light personnel. If the alarm system is activated, the power supply to the sodium hypochlorite and DGH/QUAT metering pump is deactivated to eliminate inadvertent delivery of dilute or concentrated chemical solutions.

5

'T

~~

Figure 1. Flow Through Sidestream Testing Unit.

Monftor

~ Water Row

~ Temperature

~ ConductMy O. 4tarm System

~ Control I chemical I 1eed pumps I 12-Port I ~ Phone out Thermistor I Manifold capabilities I I I I I I I I Fouling I I Chamcer I L a L

I I

I I

I I

I I I I I I I I I I I I I Common Drain L

Ffgure 2. Schematic Diagram of Computerized Flow-Through Unit.

Within each fouling chamber, a concrete test panel measuring 3.6-in. wide x 12-in. !ong x 0.75-in. thick was used as the substrate to permit settling and growth of fouling organism. A spacer (a 6-in. long concrete panel) was installedbelow the test panel to aid even distribution of the incoming flow. After passing through the fouling chamber, a portion of the water was diverted to 10-gal polypropylene tanks. These tanks were used to expose juveniie oysters and ribbed mussels to further efficacy evaluatfons. Ail water from each fouling chamber and exposure tank was discharged to a common 6-in. diameter pipe.

CHEMlCALtNJECTlON Chemical applications were fed into the%-fn.feed lines of each fouling chamber. Alltreatments were ran-domly assigned a fouling chamber. For chlorine treatments, stock solutions of sodium hypochlorite were prepared and fed at a rate that achfeved a total residual chlorine (TRC) concentration of 0 5mg/L (see Fig-ure 3). Chlorine levels (TRC) were measured every weekday at the outlet of the fouling chambers using a DPD colorimetric method (7). Chlorine metering pumps were adjusted as needed to achieve the target concentration.

DGH/QUATtreatment applications were applied once a month for a12-hr period. During monthly DGH/

QUAT appficatfons, dilute stock solutions were prepared fn distilled water and metered to deliver 1.3 mg/L and 1.95 mg/L active concentrations. DGH/QUAT concentrations were measured at the outlet of foulirlg chambers using a colorimetric method (8).

0.75

~ ~ ~~

~ oo cb E ~ ~o ~ ~ ~o

~ ~ ~ ~ ~

c= 0.50 ~ ~ ~ h ~ ~

~ ~

~ ~

O ~~ N oo ~ ON

~

I o ~

0.25 0.00 0 10 30 40 50 70 90 Time (in Days)

Figure 3. Total Residual Chlorine (TRC) Monitored Daily.

ln the two chambers treated with both DGH/QUATand chlorine, chlorine was not administered during the days when monthly DGH/QUAT treatments were applied. Mollusks can detect trace chlorine levels and willavoid contact by closing their bivalve shells. Simultaneous treatment thus could potentially reduce the biocidal effectiveness of DGH/QUAT. Each of the five treatments evaluated was replicated by randomly assigning two fouling chambers for each treatment. Prior to evaluation, concrete test panels were precon-ditioned; they were suspended in the intake canal and allowed to foul for several days.

The panels were then scraped clean before the study was initiated. The concrete test panels were inserted on June 16, 1990 in the fouling chambers and lett undisturbed for 90 days. Chlorination was initiated on June 17. Table 2 lists the events of the 90-day study.

MEASURING TREATMENT EFFECTIVENESS The effectiveness of the five different treatment programs was evaluated by a series of assays conducted using the fouling chambers and the treatment tanks. These procedures include measuring biofouling on test panels, oyster growth and mortality, and ribbed mussel growth and mortality, recruitment of oysters and barnacles on test panels. and barnacle mortality.

lin At the end of the 90-day study, each concrete test panel was removed and photographed. On each test panel attached fouling organisms were identified, enumerated, and measured. The accumulation of foul-ing growth on test panels was scraped into preweighed dishes. Each side of the test panel was scraped into a separate dish. The scraped material was dried at 85 'C for 48 hr then cooled and weighed.

Table 2 90-Day Sidestream Study - Schedule of Events Day Date 6/15 - Juvenile oysters placed into exposure tanks 6/15 - Concrete test panels inserted into fouling chambers 0 6/17 90-day study started with the daily chlorination 23 7/10 - Oyster growth study initiated. Weighed juvenile oysters inserted on 6/15.

First ribbed mussel efficacy study initiated.

24 7/11 - First DGH/QUAT treatment-12-hr application 53 8/9 - Terminated first ribbed mussel efficacy study Weighed juvenile oysters Second ribbed mussel efficacy study initiated Oyster fouled plates suspended into exposure tanks 54 8/10 - Second DGH/QUAT treatment-12-hr application 79 9/4 - Weighed juvenile oysters and oyster fouled plates 80 9/5 - Third DGH/QUAT treatment-12-hr application 89 9/14 - Terminatedjuvenileoystergrowthtest,oysterfouledplategrowth study, and second ribbed mussel efficacy study Terminated chlorination programs 90 9/15 - Terminated90-daymacrofoulinggrowthstudy,retrievedandprocessed fouled test panels.

The effectiveness of each treatment program was determined by comparing the weight of accumulated fouling growth between all treatment programs and the control. The relative effectiveness was calculated with this equation:

Relative Effectiveness 1 -wt wc x 100

Where, wt = the mean dry weight of fouling growth on test panels from a given treatment program.

wc mean dry weight of fouling growth on untreated control test panels.

0 ster rowth T t1 Recently settled oysters, which were 5-10 mm in size and attached to relic oyster shells, were collected from the BP intake canal. All oyster clusters were randomly placed into each flow-through exposure tank on June 15. They were initiallyweighed after the first DGH/QUATapplication on July 11. Following subse-quent monthly DGH/QUAT applications in August and September, the oysters were reweighed after 66 days to determine their growth. The growth of all treatments and the control were compared.

ster Mortali d e t The second oyster efficacy study used 4-in. x 4-ln. plexiglass fouling plates that had been suspended in the intertidal zone of the Brunswick's intake canal and were covered with oysters. The settled oysters on these plates were 70 days old or younger. Three oyster fouled plates were randomly suspended in each exposure tank and exposed for the last 36 days of the 90-day study. Each plate was weighed before and after exposure. Mortality responses of oysters on each plate were also recorded.

Ribbed Mussel Mort li T st Two short-term studies were conducted on ribbed mussels to compare the effectiveness of the treatment programs. In the first study, twenty ribbed mussels. 10-20 mm in size, were placed in each flow-through exposure tank. The mussels were acclimatized for 24 hr before receiving only one DGH/QUAT12-hr appli-cation on July 11. The test was terminated 29 days later, after receiving the daily and 3 times per week chlorine treatments. Mortality responses of the ribbed mussels and the total weight of the twenty mussels were recorded.

i b Mu s I Mortali T t For the second short-term test, ribbed mussels were also collected from the power plant vicinity and ex-posed to the treatment programs. The length of each mussel was recorded. Twenty mussels were placed into nylonmesh bags, weighed, and suspendedinto each treatment tank on August 9. Mussels were accli-mated for 24 hr before exposure to the treatment programs for the remaining 36 days of the 90-day study.

These mussels received two monthly DGH/QUAT applications during this study. At the conclusion of tl. e test, the mortality response, the length of each mussel, and total weight of the twenty mussels in each ex-posure tank were recorded.

RESULTS FOULING ON TEST PANELS The effectiveness of the five selected treatment programs was evaluated by comparing the fouling growth of the test panels of untreated control and of the perspective treatments at the end of 90 days. The recruit-ment of oysters and barnacles and the total accumulation of macrofouling biomass were compared. Fig-ure 4 shows a comparison of the test panels for each treatment program. Both the control panels and the chlorine only panels had the greatest number of oysters setting and growing on the panels. The daily 4-hr chlorination treatment program of 0.5 mg/L was the least effective treatment program. The four treatment programs that received monthly 12-hr DGH/QUAT applications had significantly less oysters present and the majority of them were expired.

Although the daily 4-hr chlorination program did not Inhibit either the recruitment or survival of the oysters (See Table 3), it did significantly reduce the settlement of barnacles compared to the control panels. All oysters exposed to daily chlorine treatments survived. A total of 48 oysters set on the chlorine only panels compared to 57 oysters on the control panels. The total number of barnacles on the control panels was 92 compared to 36 for the chlorine only treatment. However, the chlorine only treatment showed only a Ii g4

~ I 5 I 6 Figure 4; Test Panels after 90-Day Exposure. Panels shown from left to right:1) Intermittent Chlorination 3limes/III/k Plus Monthly DGH/QVAT; 2) Daily Chlorination 4 Hr/Day Plus Monthly DGH/

QUA7; 3) Daily Chlorination 4 Hr/Day; 4) Control; 5) 1.95 mg/L DGH/QUAT 12 Hr/Month; 6) 1.3 mg/L DGH/QUAT 12 Hr/Month.

Table 3 Total Number of Oysters and Barnacles Settling on Test Panels and Cumulative % Mortalities Total Oyster Total Barnacle Number Mortality Number of Mortality Treatment Program Replicate of Oysters (%) Barnacles (%)

1. Control 26 44 31 48

2. 0.5 mg/LTRC-4 hr/day 26 16 6 22 20 10

3. 1.3 mg/L DGH/QUAT 12 hr/month 8 87 6 33 6 83 27 59

4. 1.95 mg/L DGH/QUAT 12 hr/month 9 89 18 72 8 75 10 40

5. 0.5 mg/LTRC-4 hr/day 13 61 25 6 50 22 1.95 mg/L DGH/QUAT 12hr/month

6. 0.5 mg/L TRC -4 hr/3 times/wk 14 93 13 61 14 64 18 28 1.95 mg/I DGH/QUAT 12hr/month 8% cumulative mortality for those 36 barnacles present. The four treatment programs with DGH/QUAT had mortality responses ranging from 22% to 72%.

The most effective programs in inhibiting setting and growth of fouling organisms were those with monthly DGH/QUAT applications. Three 12-hr monthly applications were administered during the study. The first treatment was applied 24 days after the initiation of the study. The second and third DGH/QUAT applica-tions were administered on days 54 and 80. respectively. The effectiveness of the monthly DGH/QUAT applications at both 1.3 mg/L and 1.95 mg/Lwere effective as DGH/QUATtreatments combined with either the daily 4-hr chlorine applications or the 3 times per week chlorine treatment. The recruitment of oysters to test panels receiving DGH/QUAT applications was significantly reduced compared to the control and the chlorine only treatment. Furthermore, the mortality responses for those oysters receiving DGH/QUAT applications ranged from 50% to 93%. (See Table 3).

The average cumulative biomass (total dry weight) of fouling growth for the two untreated test panels was 17.3 g. The average biomass for all of the treatment programs receiving DGH/QUATapplications was 2.0 g (See Table 4). One panel, treated with 0.5 mg/L daily chlorine and 1.95 mg/L DGH/QUAT had a weight of 6.01 g, and therefore, varied from other DGH/QUAT results.

Relative effectiveness for both the 1.3 mg/L and 1.95 mg/L monthly DGH/QUAT applications was 88%

to 95% using the previously described equation. The relative effectiveness for the dally chlorine treatments was 51% to 68% and the average biomass was 6.7 g.

Table 4 Total Biomass af Fouling Growth on Test Panels Range of Effectiveness Relative to Control Panels Total Average Biomass Biomass per Range of Treatment Program Replicate gm/Panel Treatment Effectiveness*

1. Control 15.61 17.3 18.99

2. 0.5 mg/L TRC - 4hr/day 7.39 6.7 51-68 6.04

3. 1.3 mg/L DGH/QUAT -12hr/month 1.0 1.05 93-95 1.11

4. 1.95 mg/L DGH/QUAT -12hr/month 1.05 1.46 88-94 1.88

5. 0.5mg/LTRC -4hr/day 6.01 3.9 61-90 1.95 mg/L DGH/QUAT-12 hr/month 1.82

6. 0.5 mg/L TRC -4hr/3 times/wk 0.99 1.67 85-95 1.95 mg/L DGH/QUAT-12hr/month 2,35

• Range of Effectiveness is Relative to Control ster Growth Test 1 The growth of juvenile oysters was monitored for 66 days of the 90-day exposure. The initial weight of the oyster clusters in each exposure tank was first recorded 24 days after the study began. The final weight measurements of the oyster clusters were made after 66 days. at the end of the study.

Figure 5 shows the effectiveness of each treatment program as determined by the average weight of the oyster clusters. The daily 4-hr chlorination treatment did not inhibit the growth of oysters compared to un-treated oysters. The average weight gain of oysters exposed to daily chlorination was 216 grams. This is a 431% growth increase compared to a 335% growth increase for the control oysters (see Table 5).

The weight gain of oyster clusters in DGH/QUATprograms was slgniTicantly inhibited. The average weight gain was 5.2 g (10% growth) in the 15 mg/L DGH/QUAT12-hr monthly treatment and was -1.1 g (6% re- .

duction) in the daily chlorination and DGH/QUATtreatment. There was no difference in DGH/QUATtreat-ment programs with or without chlorination treatments.

Figure 6 shows the size of an oyster cluster after 90 days of exposure to the daily chlorination program.

Figure 7 shows the size of an oyster duster with no increase in biomass. All of these oysters expired from the DGH/QVATtreatments.

399 250 241 g

m 150 31

-22 -11 -16 Control DGH/QUAT DGH/QUAT CLp (7X) + CL2 (3X) + CLp 4 Mr/Day 1.3 mg/L 1.95 mg/L DGH/QUAT DGH/QUAT Treatment Application Figure 5. Percent Growth of Oyster Clusters in 66 Days.

0 ster Mortali nd Growth Test 2 Prefouled oyster plates were exposed to each of the treatment programs for 37 days (See Figure 8 and Table 6). In this evaluation, daily chlorination treatment showed an average weight gain of 74 g or a 62%

growth increase. The control oyster plates had a weight gain of 97.6 g or a 82% weight increase. In con-trast, the growth of oysters in all DGH/QUAT treatment programs was significantly reduced. During this evaluation, the oyster plates received only two 12-hr DGH/QUAT applications. Average weight gains ranged from 13.4 g of growth to a 6.6 g reduction, which resulted from the decomposition of body tissue from expired clams.

This study also assessed the mortality responses of the oysters present on the prefouled plates. All DGH/

QUAT treatment programs demonstrated mortality responses > 84%. In contrast, the daily chlorination treatment and the control had mortality responses of 13% and 16%, respectively.

Efficac to Ribb dMvssels The mortality responses of ribbed mussels was determined from two assays (see Figure 9). In the first study,40 ribbed mussels were exposed for 29 days. In the DGH/QUATtreatment programs only one 12-hr application was administered. In the second test. ribbed mussels were exposed for 36 days and thedesig-nated exposure tanks received two DGH/QUAT treatments.

Table 6 Average Weight Change and Percent Growth of juvenile Oysters Exposed 89 Days to Five Selected Treatment Programs. Monitoring Began On Day 24.

Total Average Initial Weight Weight  % Growth Treatment Program Replicate Weight(g) Change(g) Change(g) Change

1. Control 1 29.0 124.5 127 429 2 53.4 128.8 241

2. 0.5 mg/LTRC -4hr/day 1 36.6 169.2 216 462 2 65.7 262.6 399

3. 1.3 mg/L DGH/QVAT - 12hr/month 58.6 -10.6 -3.9 73.9 2.9

4. 1.95 mg/L DGH/QUAT - 12hr/month 24.7 -2.8 5.2 -11 41.9 13.2 31

5. 0.5 mg/LTRC - hr/day 1 22.4 -3.5 -16 2 34.1 1.3 4 1.95 mg/L DGH/QUAT -12hr/month

6. 0.5 mg/L TRC - 4hr/3 times/wk 1.1 0.9 3 117.8 0.7 1 1.95 mg/L DGH/QUAT 12hr/month

~ ~

~ f ~ ~

lg

~ '

'iP'l

' ~

~

~ ~ ~

r.

I gjllf e 1

~ '~ v;+~+gt k

~ ot p ~ ~ ~ I ~

~t a ." llljli;: i I I I'I'I'l'I',+I I ~I 1 o~'t tlelt 2 3 4' )

ft Figure 6. Growth of Oyster Cluster After a 89-Day Exposure to a Daily Chlorination of 4 Hr/Day.

Mortality responses of 77.5% to 98.5% were achieved, in all treatment programs receiving the monthly QVAT/DGH applications. In contrast, the daily 4-hr chlorination program of 0.5 mg/LTRC was Ineffective; mortality responses were 2.5% in both evaluations.

Q ~

.~

., p P'$

~. ~

~ ~

~ ~ \

'CQ ~.g t

'rt

~ ~ r

~ 4'pt~

g';

~ ~

I IIIIII'I I i I j

I f'i It '.r'et 1I

~

J s'i tlql/5'l Figure 7. Growth of Oyster Clusters After a 89-Day Exposure to Monthly 12-hr Exposure of 1.95 mg g/ DGH/QUAT.

97.4 C 80 74 C

15 t9 60 dl O) tO 5 40 13.4 7.8 8.8

-6.6 Control DGH/QUAT DGH/QUAT CL2 (7X) + CL2 (3X) + CL2 4 Hr/Day 1 3 mg/L 1 95 mg/L DGH/QUAT DGH/QUAT Treatment Application Average of Six Plates/Treatment Figure 8. Average Weight Gain of Prefouled Oyster Plates* in 37 Days.

Table 6 Average Weight Change, Percent Growth Change and Cumulative Mortality of Prefouled Oyster Plates Exposed for 37 Days.

Average Weight  % Growth Total ¹ 96 Treatment Program N Change (g) Change of Oysters Mortality

1. Control 97.6 82 442 16

2. 0.5 mg/LTRC -4hr/day 74 61.7 533 13

3. 1.3 mg/L DGH/QUAT - 12hr/month 13.4 11.0 400 86

4. 1.95 mg/L DGH/QUAT - 12hr/month 7.8 7.2 382

5. 0.5 mg/LTRC -4hr/day -6.6 W.9 383 89 1.95 rng/L DGH/QUAT -12hr/month

6. 0.5 mg/L TRC - 4hr/3 times/wk 8.8 369 1.95 mg/L DGH/QUAT - 12hr/month 98.5 95 95 95 93 77.5 75 2.5 2.5 0 0

'GH/QUAT DGH/QUAT CL2 PX) + CL2 (3X) + CLp 4 Hr/Day 1.3 mg/L 1.95 mg/L DGH/QVAT DGH/QUAT

'vestment Application Rgure 9. Cumulative % Mortality of Ribbed Mussels.

CONCLUSIONS Sidestream studies as described in this paper can compare the effectiveness of different treatment pro-grams and can also be used as a tool for minimizing the treatments required to provide adequate macro-fouling control. Since sidestream evaluations cannot simulate all the conditions of a particular cooling sys-tem, any treatment programs being revised should be closely monitored to determine its performance.

Inspections of cooling systems to determine the kind of macrofouling organisms and the extent of their growth within the cooling systems needs to be conducted to effectively design sidestream studies and alter treatment programs. Furthermore. the degree of macrofouling control required for any particular cooling system needs to be established to ensure power plant operations are not impeded, the equipment is protected, cooling efficiency is maximized, and the facility is amply protected from any forced outages.

The macrofouling control required for either a service water or safety related cooling system often will have different requirements as compared to a main circulating cooling system. These requirements will also change on a seasonal basis.

Appropriate macrofouling control can often be achievedby targeting treatment programs to the dominant macrofouling organisms during peak fouling seasons. Evaluation of additional studies willdetermine ifvar-ious control agents (i.e. chlorine and DGH/QUAT) could complement each other in achieving better ma-crofouling and microfouling control. Furthermore, these treatment programs must be designed to meet discharge permitting requirements.

This sidestream study, pinpointed the ineffectiveness of the daily chlorine treatment program of 4-hr/day at 0.5 mg/L TRC. The daily chlorine treatment essentially had a limited or no effect on the growth of the oysters or on the recruitment of oysters setting on the test panels. In addition, the effectiveness of the daily chlorine treatment for eradicating both the juvenile oysters and ribbed mussels was quite limited with mor-tality responses of only 13% and 2.5%, respectively. However, the daily chlorine treatment did demon-strate some effect on the recruitment of barnacles attaching to the test panels. It also inhibited the total accumulation of biomass by 60% on the test panels compared to the control.

Other investigators have also reported on the ineflectiveness of chlorine (6,9). Morris, et. al. (1983) found that the recruitment of oysters onto test panels exposed to chlorination for periods of less than 18-hr/day at 0.1 rng/LTRO was not providing macrofouling control. Enhanced settling of oysters and barnacles also occurred at high chlorine dosages of 10 mg/L fed for 10 minutes twice/day.

For this study, the monthly DGH/QUATapplications by themselves at1.3 mg/Land1.95mg/Lwere equally as effective as the DGH/QUAT combined with chlorine treatments. All of these treatments demonstrated an inhibition of total biomass accumulation ranging from 61 to 95% compared to the control and they ef-fectively reduced the recruitment of barnacles by 50% or more. Mortality responses to barnacles for all treatments receiving DGH/QUAT appffcations ranged from 22% to 72%.

In addition, all of the treatment programs employing the monthly DGH/QUAT applications for the 12-hr/

month demonstrated significant effectiveness on both oysters and ribbed mussels, the dominant macro-fouling organisms found during the inspections of the mafn circulating cooling systems at the Brunswick I t. A ed ctlon of 49 to 75% on the recruitment of oysters setting on the test panels resulted with all treatments receiving DGH/QUAT applications. In addition, oysters and oyster clusters that were exposed to the DGH/QUATtreatments showed negligible growth. Mortality responses of oysters from all GH/QUAT Il tlons ranged from 84 to 89% for test one and 50 to 9396 for test two. The mortality re-sponses to the ribbed mussels ranged from 77.5 to 98.596 for all treatment programs employing mon thly DGH/QUAT appffcatfons.

REFERENCES

1. L.A. Lyons, D.P. Davis, J.C. Petrille, M.W. Wemer. L J. Briggs, J.R. Burkte. "Proposed Blue Mussel Fouling Control Technology Using a Nonoxidizing Molluscicide." EPRI Condenser Techno ogy Conference, September 1990.

2. L.A. Lyons, J.C. Petrifle, S. P. Donner, R.L. Fobes, F. Lehmann, P.W. Afthouse, LT. Wall, R.M. Post and W. F. Buerger. "New Treatment Employing a Molluscfcide for Macrofouling Control for Zebra Mussels in Cooling System." Proceedings of the American Power Conference, vol. 52, 1990.

3. D. Mowery, E. McClellan, L. A, Lyons, D.M.Austin and D. N. Karfovich. "Asiatic Clam ControlExperi-ence at Peach Bottom Atomic Power Station." EPRI Service Water Supply Reliability Improvement, Charlotte. North Carolina: Efectrical Power Research Institute. November 1989.

4. L.A. Lyons, O. Codina, R.M. Post and D.E. Rutledge. "Evaluation of a New Mollusclcide for Alleviat-ing Macrofouling by Asiatic Clams." Proceedings of the American Power Conference, vol. 50, 1988.

L.N. Scotton, W.J. Armstrong, J.F. Garey and D.J. McDonafd. "Development and Future Trends of the Mussel Control Program at Pilgrim Nuclear Power Station." Symposium on Condenser Macro-fouling Control Technologies: The Statezf-the-Art. CS-3343. Palo Alto, California: Electric Power Research Institute, December 1983, pp. 24.

6. D.W. Morris, J.H. Tackett, J.F. Garey, J.W. Egan. Minfmfzing Chlorine Application Consistent with Effectfve Macrofoufing Control: A Pilot Study of Continuous, Low Level Chlorination." Symposium on Condenser Macrofouling Control Technologies: The State-of-the-Art. CS-3343. Palo Alto, Cali-fronia: Electric Power Research Institute. December 1983, pp. 28.

7. Standard Methods for the Examination of Water and Wastewater. 17th ed. Washfngton, D.C.: Ameri-can Public Health'Association, American Water Works Association, Water Pollution Control Federa-tion, 1989.

8. "Determination of Clam-Trol CT-1 by Modified Photometric Methyl Orange Complexation Proce-dure". Betz Laboratories, Inc., Trevose, Pennsylvania1990.

9. L. B. Richardson, D. T. Burton, A. M. Stavala. "A Comparison of Ozone and Chlorine Toxicity to Three Ufe Stages of the American Oyster Crassostrea Virg/n/ca". Marine Environmental Research, vol. 6, 1982, pp.99-113.

AQUATIC TOXICOLOGY LAEIQRATQRIES, INC. LABORATORY SQMERTON RQAOiTREVOSE. PA 1 9047iU S A. j'EL: 21 5i355-3300'ELEX: 1 73 1 48iFAX 4S 355.2869 BETZ CLAM-TROLCT-1 ENVIRONMENTALINFORMATION PACKAGE Clam-Trol CT-1 is an effective molluscicide for controlling Asiatic clam macrofouling problems in both once-through and recirculating cooling systems. The unique molluscicide applications can be used for exterminating adult Asiatic clams which cause advanced stage fouling conditions in cooling systems and can also be used as part of a preventative program for eliminating larvae and juvenile clams before they attain the adult fouling size which can cause advanced fouling conditions. Clam-Trol CT-1 can also be used as a broad spectrum microbiocide for the control of bacterial, fungal and algal slimes. f Clam-Trol CT-1 contains 13% active ingredients of two cationic surfactants and 87% inert materials. The two cationic surfactants are n-alkyl dimethyl benzyl ammonium chloride (Quat) and dodecylguanidine hydrochloride (DGH).

CH3 NH I II n-C14H29 N+ CHz Cl n-C<>H>5-NH-C-NH2HCI I

CH3 Quat DGH Both straight chain hydrocarbon containing molecules are referred to as surface active agents and have a hydrophobic tail and positively charged moiety that readily attaches to membranes to induce biocidal activity. The inert materials of this formulation - ethylene glycol, isopropyl alcohol, and water - are relatively non-toxic to aquatic organisms.

Several studies on the adsorptive characteristics, aquatic toxicity, biodegradation, environmental fate and detoxification processes have been conducted for these cationic surfactants. The results of these studies are summarized herein.

Adsor tion: Biocidal mechanism and Adsor tion Rates The toxic properties of cationic surfactants result from a strong interaction with membrane proteins. membrane proteins are essential for many transport mechanisms including various specific ion transport channels. The alkyl portion of these actives becomes imbedded in these membranes. In effect, these cationic surfactants are good biocidal performers but they are short-lived once their positive charge is neutralized upon adsorption to various surfaces.

DGH and ruat have extremely strong affinities for many kinds of suspended material and substrates. A series of laboratory and field studies conducted by the American Cyanamid Company evaluated the degree and rate that DGH is electrostatically bound to suspended matter and other substrates.

In one study, weighed portions of sludge containing 5.2% solids obtained from a sewage treatment plant were inoculated with 10 ppm and 20 ppm of DGH (100%

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

Contact DGH Found DGH added Time in Supernatant m hours 10 1 1.2 10 1 1.6 10 24 1.0 10 24 1.2 10 (Control; water only) 11.0 20 1 1.1 20 1 1.7 20 24 1.6 20 24 1.3 20 (Control; water only) 23.5

Other laboratory studies utilizing cooling tower water samples from Utah Power and Light demonstrated a loss of 95% DGH in 1/2 hour or less contact time after initial DGH concentrations of 350 ppm, 700 ppm, and 1,750 ppm were added to the samples. The residual DGH (ppm) in the supernatant after precipitates were filtered out and the % loss are provided in the table below:

Residual DGH DGH added (ppm) in Su ernatant Loss 350 19 95 350 17 95 700 24 97 700 31 96 1750 52 97 1750 85 95 The rate of adsorption (loss of DGH to the cooling tower solids) was also determined from the above sample. Results are presented below:

DGH added Contact time Residual DGH (ppm) m hours in Su ernatant 350 1 28 6 16 24 12 1750 1 82 6 61 24 42

Field studies have also demonstrated that DGH is rapidly removed from cooling water systems. The two tables below show the concentration of DGH detected in the cooling tower effluents on two different occasions.

DGH Content Oil and Grease in Effluent Sam le Ti Ale m Addition of DGH 8:15 am 158 0 (16-17 ppm) 9:30 am 1300 0 10 15 am 700 0.4 12:00 pm 1500 0.9 Makeup Water 14 0 added Samples from cooling tower operation submitted by Chevron Oil, Salt Lake City, Utah, on December 20, 1972.

Tower'as contained volume of 350,000 gallons and a blowdown of 400 gpm.

Suspended Organic DGH Content Solids Carbon in Effluent Sam le Ti Ale m m Before addition 1:30 pm 17 DGH addition

= 13 ppm After addition 3:00 pm 280 16 (233 organic) (filtered) 4:00 pm 16 5:00 pm 15

Radioactive labelled ruat solutions at concentrations of .Ol to . 1 ppm were used for studies conducted by Rohm and Haas Company (Krezeminski, SF, et.al.,

1977) to adsorptive characteristics to different types of material.

In these )determine C studies, adsorption was measured by the loss of radioactivity from the labelled solutions exposed to three different types of adsorbent material - river silt, and aquatic plant, and alum floe. Results are reported below:

Adsorptive characteristics of Hyamine 3500 (50% Active ruat)

Concentration in Water (ppm)

Contact 0/

Adsorbent Time (hr) Initial Final Adsorbed River Silt 1/60 0.070 0.006 91 Aquatic Plant (Azolla Caroliniana) 24 0.056 0.008 86 Alum Floca 1/2 0.094 0 100 a) 400 ppm - turbidity 30 ppm - alum concentration

As with the DGH studies, field studies conducted by Rohm and Haas have determined the residual ruat concentrations in cooling tower blowdown water at various intervals following biocide application. The adsorptive nature of the active to the surfaces of the cooling system and to particulate material caused a substantial loss.

Hyamine 3500 (50% Active ruat) in Cooling Tower Blowdown Water as a Function of Time After Dosinga Concentration of Hyamine 3500 (ppm)

Time After Dose 1 Dose 2 Dose 3 Dosing (hrs) (60 ppm) (30 ppm) (30 ppm) 1 60.0 26.8 31.6 2.5 52.2 21.1 21.0 5 44.8 14.8 14.2 8 26.5 10.6 9.9 72 5.18 0.25 0.041 120 2.50 0.011 NDR 168 1.16 0.008 NDR a) Three consecutive dosings (60, 30, 30 ppm) at one-week intervals b) NOR = no detectable residue; less than 0.005 ppm Cooling tower capacity = 40,000 gallons Blowdown rate - 30 gpm

A uatic Toxicit  : Adsorbed vs. Free Actives Acute toxicity tests determining LC50 active ingredients is provided as values follows:

for Clam-Trol CT-1 with 13%

~Da hnia ~ma na: 48 hn LCDD = 0.41 mg/1 (.37 - .49 T.L.)

Fathead minnow: 96 hr LC50 = 2.9 mg/1 (2.5 - 3.3 T.L.)

Bluegill Sunfish: 96 hr LC50 = 4.3 mg/1 (4.2 - 6.6 T.L.)

Rainbow trout: 96 hr LC50 = 14.7 mg/1 (10 - 15.5 T.L.)

The above LC~n values represent toxicity levels for the neat formulation when 100% of the Free" actives are available to the aquatic organism (that is, no suspended solids for adsorption of the actives).

However, when the formulation is exposed to adsorbent material (i.e., bentonite clay or activated carbon), acute toxicity is greatly reduced due to the delhi lh adsorption properties of the active ingredients. Tables 1 to 4 provide tl t tlltl t ftl 1,

d d 1 Clam-Trol CT-1 which has been exposed to various concentrations of either

~dh t ff d h ff1 tl bentonite clay or activated carbon. Even the most sensitive test species, adsorb the free actives. A ppm ratio of 1 to 1 of clay to Clam-Trol CT-1 and 2

• ll hl t to 1 of activated carbon to Clam-Trol CT-1 resulted in the reduction of acute toxicity to fathead minnows to the point that the water becomes essentially non-toxic.

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

Biode r adation The rate of biodegradation of the ruat active was evaluated in both acclimated and unacclimated microbial cultures (Gawel, L.J. 2 Huddlestown, R.L.,

Continental Oil Company, 1972). The microorganisms used for the biodegradation tests were derived from both soil and raw city sewage, and which grew on a defined medium. Rates of biodegradation were determined analytically using an extraction procedure to remove all unde-graded quat. The results reported below present biodegradation data from cultures acclimated for different time intervals to the ruat (100% active).

EFFECT OF CULTURE ACCLIMATION ON UAT BIODEGRADATION Acclimation None H II 0 Incubation Period 24 hr/48 hr 24 hr/48 hr 24 hr/48 hr 24 hr/48hr Percent Degraded 37 95 60 97 60 97 15 50 The reduced rate of biodegradation at 9 days was attributed to the additional transfers of ruat causing an increased biocidal effect upon the cultures.

The Rohm and Haas investigation, previously cited, reported biodegradation studies of ruat conducted by exposing the C labelled active to activated sludge. Fresh synthetic sewage (nutrients) and labelled ruat were renewed daily except weekends to a closed culture system durI~g a 24 day study period.

Biological activity was determined by measuring the C02 that was generated from the labelled ruat. In order to allow for acclimation and any toxic effect, dosing of the labelled active started at 1 ppm and increased gradually over period of days to 10 ppm. Figure 1 presents the results as the percent "C detected in the a~ unde-graded active removed from the closed system and the presentsupernatant C as C02 converted during biological degradation of the ruat.

During the first j~o weeks, 80% of all labelled guet added to the culture unit was converted to C02. This activity increased to a 92% conversion after a two week accumulation period. It was concluded from this study that biodegradation of the ruat was, after a short period of microbial acclimation, quite rapid and complete.

Biodegradation of DGH was examined in 1989 using the OECD Screening 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.

Biode radation of DGH OECD Protocol Day DOC mg/L  % 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, H.C., et.al., 1969), dodecylguanidine acetate (DGA), an agricultural fungicide, was investigated to evaluate the biodegradation potential by microorganisms originating from soil and river muds. Two species of soil bacteria, one an aerobe and another an anaerobe that were isolated on agar plates and then transferred to dodine (DGA) salt media, grew profusely after a 7 day lag period. When these bacterial species were transferred back to dodine-free medium, growth of the organisms was poor. This study provided a demonstration that certain organisms were quite capable of utilizing DGA as the sole source of carbon.

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

~Summar:

The biocidal activity of Clam-Trol CT-I results from the two cationic surface active agents (DGH and ruat) in this formulation. The product's efficacy is based on its ability to alter or disrupt various membrane systems of the biofouling organisms. These same inherent properties of these agents which provide biocidal efficacy are rapidly neutralized 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-I will minimize its environmental impact following its application to cooling systems. These include:

Adsorption rates of both actives are rapid and thus biocidal activity is short-lived. Both actives readily adsorb to suspend material, sediments, and the surfaces within a cooling system.

Both of the active components in the formulation are readily biodegradable. Solutions of ruat have been show to biodegrade by more than 90% in 2 days while solutions of DGH exhibited 70% biodegration in 28 days.

Clam-Trol CT-I provides an alternative to chlorine or a number of halogenated organic or metal containing biocides that are considerably less environmentally desirable.

Bioaccumulation of the quat active has been determined by continuous exposure of low levels of free actives to fish, as reaching a steady state after 2 weeks. The half-life of this accumulated material is short once exposure ceases.

An analytical field method is available for determining the presence of the actives in a treated cooling system. The method is also useful For monitoring discharges.

Biofouling treatment programs to cooling systems need to employ innovative technology that will direct applications in a most effective manner to the target organisms. Applications of Clam-Trol CT-I can serve to protect cooling systems from both macrofouling and microfouling problems using state-of-the-art technology. No other treatment program exists that can protect a system from infestation by adult mollusks and larvae by employing seasonal applications.

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

In addition, Clam-Trol CT-I applications can provide microfouling protection to safety-related cooling systems due to its unique fast-acting properties and its ability to permeate slime formations. These are applications that will not cause the corrosive problems that develop from continuous chlorination nor require extensive treatment periods for control.

TABLE 1 Table 1: Detoxification of Clam-Trol CT-1 with Bentonite Clay Fathead Hinnow - Cumulative

1. Hortality Clam-Trol CT-1 Active Clay Cl ay:

m L m L Clam-Trol 4 hr 24 hr 48 hr Control 0 0 0 10 mg/L 100 100 100 100 mg/L 0 0 0 10 mg/L 10 mg/L 1:1 0 0 0 10 mg/L 20 mg/L 2:1 0 0 0 10 mg/L 30 mg/L 3:1 0 0 0 10 mg/L 50 mg/L 5:1 0 0 0 10 mg/L 100 mg/L 10:1 0 0 0 TABLE 2 Table 2: Detoxification of Clam-Trol CT-1 with Bentonite Clay Daphnia magna - Cumulative

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

m L m L Clam-Trol 6 hr 24 hr 48 hr Control 0 0 0 10 mg/L 100 100 100 100 mg/L 0 0 0 10 mg/L 10 mg/L 1:1 35 100 100 10 mg/L 20 mg/L 2:1 0 85 100 10 mg/L 30 mg/L 3:1 0 30 30 10 mg/L 50 mg/L 5:1 0 0 0 10 mg/L 100 mg/L 10 1

TABLE 3 Table 3: Detoxification of Clam-Trol CT-1 with Activated Carbon Fathead Hinnow - Cumulative

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

m L m L Clam-Trol 4 hr 24 hr 96 hr Control 0 0 0 12.5 mg/L 0 0 0 25 mg/L 0 0 0 10 mg/L 100 100 100 10 mg/L 12.5 mg/L 1.25:1 0 0 0 10 mg/L 25 mg/L 2.5 :1 0 0 0 25 25 mg/L mg/L 12.5 mg/L 25 mg/L 1:2 1:1 0 0

0 0

0 0

TABLE 4 Table 4: Detoxification of Clam-Trol CT-1 with Activated Carbon Daphnia magna - Cumulative

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

m L m L Clam-Trol 4 br 24hr 48hr Control 0 0 0 12.5 mg/L 0 5 5 25 mg/L 0 0 10 10 mg/L 100 100 100 10 mg/L 12.5 mg/L 1.25:1 0 100 100 10 mg/L 25 mg/L 2.5 :1 0 0 20 25 25 mg/L 12.5 mg/L 25 1:2 1:1 90 100 100 100 100 100 mg/L mg/L

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SQMERTON RQAOaTREVQSE. PA 1 9047a U.S.A. j'EL:21 Sa355-3300a TELEX: 1 73 1 48aFAX 4 355-2869 Acute Toxicity (LC5p~s)

Clam-Trol CT-1 Freshwater Or anisms Rainbow Trout 96 hr LC50 = 14 ' mg/L Bluegill Sunfish 96 hr LC5p = 4a3 mg/L Fathead Minnow 96 hr LC50 = 2.9 mg/L

~Da hnia ~acana 48 hr LC5p = 0~4 mg/L Cerioda hnia dubia: 48 hr LC50 = 0.45 mg/L Chironomus riparius: 48 hr LC5p = 6.5 mg/L (Midge Larvae)

Goniobasis sp 96 hr LC5p = 11.0 mg/L (Snail)

Note: The above LC5p values represent toxicity levels for Clam-Trol CT-1 when 1004 of the "free" actives are available to the aquatic organism (that is, no suspended solids for adsorption of the actives).

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SQMERTON ROAOiTREVQSE, PA 1 9047iU.S.A. / TEL:81 5i355-3300iTELEX: 1 73 1 48iFAX 4t 355-2869 Chronic Toxicit of Clam-Trol CT-1 to Fathead Minnow A 7-day static toxicity test was conducted to estimate the chronic toxicity of Clam-Trol CT-1 to the Fathead Minnow, using larvae less than 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> old. The endpoints of this toxicity test are based on adverse effects on survival and growth. This toxicity test was conducted following EPA protocol as described in "Short-Term Methods For Estimating the Chronic Toxicity of Effluents and Receiving to Freshwater Organisms, EPA/600/4-89/001."

For Clam-Trol CT-1, growth was the most sensitive endpoint producing a lowest observed effect concentration (LOEC) of 3.2 mg/L and a no observed effect concentration (NOEC) of 1.6 mg/L. The chronic value, the estimated "safe" or "no effect" concentration, for Clam-Trol CT-1 is 1.3'g/L. Dividing the chronic value generated during this study (1.3 mg/L) into the acute value (2.9 mg/L) results in an acute/chronic ratio of 2.2.

Mortality and Growth of the Fathead Minnow after a 7-day chronic exposure to Clam-Trol CT-l.

CT-1 Concentration Mortality Wei ht m Fish m L Mean, S. D.

0 ' 5~0 0.290 0 '32 0.254

- 0.329 0.4 2 ' 0.296 0.029 0.261 0.333 0' 0 0 '92 0 '29 0.259 - 0.324 1~6 7.5 0 '68 0.022 0.245 - 0.291 3.2 12 ' 0.029* 0 '19 0.186 - 0.225 6.4 100.0*

12.8 100.0*

• Significantly different from Control (a = 0.05, Dunnett's test)

AQUATIC

~OXICO~OGY CD CD LAEIQRATQRIES, INC. LABORATORY SQMERTQN RQAD~TREVQSE, PA 1 9047~U.S.A. / TEL:21 5~355-33OO~TELEX: 1 73 148~FAX 4355-2869 ON C OF D OX D - ON S V A GRO The chronic effect of Clam-Trol CT-1 detoxified with Betz DT-1 was studied using the standard 7-day chronic fathead minnow survivability and growth rate test. The data presented in Table 6 show that 10 mg/L of CT-1 resulted in 100 mortality of the minnows. The addition of Betz DT-1 at a 1:1 ratio with CT-1 completely eliminated chronic mortality effects on fathead minnows, but allowed some growth rate impairment. Ratios of DT-1 to CT-1 of 3:1 or greater completely eliminated any effect of CT-1 on both minnow survivability and growth.

th" after a 7-day exposure to ratios of Betz Clam-Trol CT-1 and Betz DT-1.

Mean Fathead mg CT-1/L mg DT-1/L Mortality (4) Dry Height (mg+SK) 0 3101 (0 0157) 0 100 0 2855 (0. 0015) 10 100*

10 10 13 0. 1881 (0. 0242)

• 10 30 7 0 3032 (0 0158)

~

10 50 18 0 '355 (0.0046) 10 100 10 0 '811 (0 0112)

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

AQUATIC TOXICOLOGY LABORATORIES, INC. LABORATORY SQMERTQN RQADiTREVQSE. PA 1 9047IU S A. j'EL:21 Si355-3300iTELEX: 1 73 1 48+FAX 4S 355-2869 Chronic Toxicit of Clam-Trol CT-1 to Cerioda hnia A 7-day static renewal toxicity test was conducted to estimate the chronic toxicity of a 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> Clam-Trol CT-1 exposure to Cerioda hnia dubia, using neonates less than 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> old. The endpoints of this toxicity test are based on adverse effects on survival and reproduction. This toxicity test was conducted following EPA protocol as described in "Short-Term Methods For Estimating the Chronic Toxicity of Effluent and Receiving Waters to Freshwater Organisms.

The lowest observed effect concentration (LOEC) for a 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> exposure to Clam-Trol CT-1 for both survival and reproduction was 0.80 mg/L.

The no observed effect concentration (NOEC) for survival and reproduction was 0.40 mg/L Clam-Trol CT-1. The chronic value,. the estimated "safe" or "no effect" concentration for Clam-Trol CT-1 is 0.56 mg/L.

Mortality and Growth of the Cerioda hnia dubia 7-day after a 12 hour exposure to Clam-Trol CT-1.

CT-1 Concentration Mortality Average 4 of m L Neonates Produced 0~0 25.5 0

0

'5

'0 0

0 0

28 23 0

0

'0

'0 10 0 24'6 22 '

0 '0 1 ~ 60 9 0*

100 18 total neonates*

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

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SQMERTQN ROAOiTREVOSE, PA 1 9047iU.S.A. /'EL: 81 5i355-33QQi TELEX: 1 73 1 48iFAX ¹ 355-8869 Society of Environmental Toxicology and Chemistry (SETAC)

Presented November 9-12, 1987 at Pensacola, Florida Meeting DETOXIFICATION POTENTIAL OF A NEW MOLLUSCICIDE FOR ASIATIC CLAM FOULING CONTROL.

L. A. Lyons, Betz Laboratories, Inc.

Trevose, PA.

A new molluscicide to control Asiatic clam biofouling in cooling and service water systems has several environmentally desirable features.

Seasonal applications, requiring short treatment periods of only 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />, provide effective clam fouling control as opposed to continuous chlorination treatments. Another feature is the detoxification or neutralization potential of the molluscicide by adsorption. The actives in the molluscicide 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 LC5ii's of the new molluscicide to ~Da hnia ~arena, fathead minnows and rainbow trout are 0.4 mg/1, 3.0 mg/1, and 14.7 mg/I, respectively.

Molluscicide concentrations ranging from 10.0 mg/I to 50.0 mg/I were treated with several kinds of potential sorptive detoxification media. A series of bioassays with ~Da hnia ~acana and fathead minnows were conducted immediately following these detoxification treatments.

Determinations of the rate of survival from these detoxification treatments are provided.

Methods:

Clam-Trol CT-1 solutions were mixed for 5 minutes with potential detoxification media in glass aquaria. Aliquots (200 mLj 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.

Detoxification of Clam-Troi CT-1 with Bentonite Cfay Fathead Minnow - Cumulative tt Oaphnla madna - Cumulative Mortality 4 Mortality Clam Tml Active Clay Clay:

CT I (

ahr 24 hr 44 hr 4 br 44 hr I) ( I) Can Tml 10 100 10 10 10 10 5:t.

'IO Detoxification of Clam-Troi CT-1 with Humic Acid Fathead Nnnmr ~ CumWatlve %

Mortality Cam-Trot CTt( )

1hr 24 hr 44 hr 10 10 IO 10 10:I 10 15 10 Detoxification of Clam-Trol CT-1 with Activated Carbon Fathead IQnnotr Cumulative%

Can.Tmi CT 1 24 hr 4hr 24 hr 10 10 125:t 10 2.5:I Detoxification of Clam-Trol CT-1 with Magnesium Silicate (Synthetic)

Oephlda mayne - Cumulative Cam Tlel CT I( )

M0 SINoete

( )

24 hr 44 hr 24 hr 10 10 10 10 100 10

'10 10

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SOMERTON ROAOiTREVOSE. PA 19047iUSA. / TEL: 215i355-3300'ELEX: 1 ¹ 73 148iFAX 355-2869 Effects of Detoxified Clam-Trol CT-1 on Chironomus Survival and Growth The effect of a 10-day exposure to Clam-Trol detoxified with Betz DT-1, a blend of highly adsorptive clays, on the survival and growth of "II exposed to various ratios of Clam-Trol CT-1 and Betz DT-1 on both an artificial substrate of glass beads and natural substrate collected from the bottom of a stream. The midge larvae were exposed for 10 days to daily renewal of test solutions.

For the artificial substrate using glass beads, a significant grovth impairment resulted from exposures to CT-1 only and the CT-1:DT-1 ratio of 1:1 and 1:2. This. growth impairment was mediated at the 1:3 ratio. Zt should be noted that the Midge larvae, on the artificial substrate exhibited lower growth compared to organisms on the natural substrate. This is probably both an artifact of the sterile of the glass beads and an illustration of the extent to which thenature natural sediment mediates CT-1 toxicity, For the natural substrate using river sediment, the survival of the midge larvae exposed to all test concentrations not significantly

,different from the control. Zn addition, growth was was only slightly Impaired at the CT-1 only and the 1:1 ratio of CT-1:DT-1. Grovth was

--iot impaired at the 1:2 ratio.

Mean Chironomid Dry Weight 4 Survival (mg + SE) z CT-1/L: mg/ Clay/L A N A N 0 87 90 0. 5754 (0. 0343) 0.8347(0.0583) 0 100 93 97 0.6779(0 '478) 0.8930(0.0512) 10 30 90 0.0641(0 '103)* 0.6782(0 '286)*

10 10 77 100 0 '272(0 0.7069(0 '527)*

10 20 93 100 '107)%'.3900(0.0534)*

0.7585(0 '695) 10 30 100 90 0.5476(0 '443) 0 '369(0 '252) 10 50 100 100 0.5558(0 0108)

~ 0.7916(0 '263)

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

-~Artificial substrate N = Natural substrate

ABSTRACT SUBMITTED FOR PRESENTATION AT THE SOCIETY OF ENVIRONMENTAL TOXICOLOGY 5 CHEMISTRY MEETING, NOVEMBER 1991 SHORT-TERM RATE OF A SURFACTANT BASED MOLLUSCICIDE AND ITS EFFECTS UPON A SEDIMENT DWELLLING ORGANISM. J.R. Bidwell, D.S. Chery, J.L. Farris, and L.A. Lyons. Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, and BENZ Laboratories, Trevose, PA 19047.

The short-term fate of the cationic surfactant based molluscicide CT-1, and its effects on larvae of the midge, Chironomus ~ri arius, were examined in laboratory and field studies. Levels of free CT-1 dropped sharply when solutions of the molluscicide were mixed with bentonite clay or placed over natural sediments, and were inversely related to the amount of suspended solids in raw river water. In sub-chronic (1 0-d) bioassays with C. ~rt arius, the impact of CT-t upon the survival and growth of the organisms was reduced or eliminated in the presence of clay or natural sediment. These results were validated by field studies conducted during the spring and fall of 1990 when midge larvae were exposed to effluent containing CT-1 and clay in ratios between 1:1 and 1:3 during a 24 hr on-site application at a power plant. Larvae were also tested in river sediments which were collected during dosing and up to 21 days after dosing from selected stations above and below the plant discharge. No significant effects on survival or growth of the larvae were associated with exposure to the CT-1 and clay in either the effluent or river sediments. These data further indicate that the adsorptive nature of the cationic surfactants in the molluscicide can serve to mediate its toxicity to non-target organisms such as the midge.

AQUATIC TOXICOLOGY LABQRATQRIEB, INC. LABORATORY

/

SQMERTON ROAQ~TREVQSE, PA 1 9047~V S A. TEL: 21 5i355-3300iTELEX: 1 73 1 46~FAX 40355-2969 E F OF - ON BENTH C ORC SMS to organisms that live in the bottom 1

used The term "benthic" refers lAlii to study

'M',

sediments of lakes and streams.

the effects of materials

'd Acpxatic insects such as the midge ClY on 9 ),

bottom>>living organisms.'idge 1Y larvae were exposed for 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> to 10 mg/L of Clam-Trol cT-1 and to Clam-Trol CT-1 which was detoxified by the addition of Betz DT-1, a blend of highly adsorbent clays. The results, shown in Table 5, indicate that the Clam-Trol CT-1 by itself produced an 804 mortality without detoxification. Treatment with Betz DT-1 in

~

ratios of 1:1 to 1:10, successfully eliminated any effects of CT-3.

on the mortality and growth rate of the midge larvae.

1kl'

• 1 ~ DJ!

2-day exposure to ratios of Betz Clam-Trol CT-1 and Betz DT-1

" followed by recovery for 8 days in dechlorinated laboratory water at 20 C (n~30)

Mean Chironomid mg CT-1/L mg DT-1/L Mortality (4) Dry Weight (mg+SE) 0 9048 (0. 0121) 100 0.9789 (0. 0136) 10 80* 0.8121 (0. 0135)'*

10 10 10 0.8748 (0.0122) 10 30 0 9164 (0.0112) 10 50 0 9278 (0 '115) 10 100 0 9502 (0.0180)

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

AQUATIC TOXICOLOGY LABORATORY SOMERTON ROAOeTREVOSE, PA 1 9047eUS A. /'EL:21 5e355-3300eTELEX: 1 73 1 48eFAX ¹355-2869 Aquatic Toxicity Report Determination of the Effect of Detoxified Clam-Trol CT-1 A Long Term Study Using Fathead Minnows and ~Da hnia macana Study Conducted By:

Aquatic Toxicology Laboratory Betz Laboratories, Inc.

Trevose, PA

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

The detoxification of the biocidal activity of Clam-Trol CT-1 is readily achieved by adsorption with a variety of materials and substrates. Once the two cationic actives present in Clam-Trol CT-1 are adsorbed, they no longer exhibit toxicity. The intent of this study was to detoxify toxic levels of Clam-Trol CT-1 and expose acmatic organisms for an extended period to evaluate any acute toxic effects of the detoxified solutions and if any potential desorption

- Source:

(

SP

(

Engineering, MA Total length (mean):

I!

of the actives resulted to cause toxicity.

' "' ")

3.5 + 0.34 cm Wet weight (mean) : 0.42 + 0.19 g

~Da hnia macCna Source: Stock culture Age: 12 + 12 hr. old neonates Test Type/ Fathead minnow and D. macCna were exposed to the Conditions: following five treatments and test conditions for 30 days.

Static Renewal Treatments control 0 mg/1 Clam-Trol CT-1

- 25 mg/1 Clam-Trol CT-1 25 mg/1 Clam-Trol/250 mg/1 bentonite clay 250 mg/1 bentonite clay only Static Treatment Continuously aerated 25 mg/1 Clam-Trol CT-1/

250 mg/l bentonite clay.

30-da Fish Test Detoxified 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 at 1100 rpm for 30 minutes. All treatments with clay were mixed in the same manner. Fifteen liters of solution were prepared for each treatment replicate.

Twenty fish were exposed to each treatment two replicate and 10 fish per 15 liter of solution.

All treatments with exception of the continuously aerated 25 ppm Clam-Trol CT-1:250 ppm bentonite clay were renewed with freshly prepared solutions on the following days through the 30-day test: 1, 4 8 11 15( 22 and 25 'he test was initiated on day one. During the renewal of test solutions, only the supernatant was siphoned from each test container and the sedimentation of clay on the bottom was retained in the container the test. Fresh test solution was added after siphoning and mixed with the existing accumulated clay. Fish were fed commercial flake food daily. Observations of mortality and behavior response were assessed daily-48-h Da hnia macana Test Standard 48 hr acute ~Da hnia ma<~n hioassay tests were initiated only on days that solution renewals were made in the fish test. Daphniids were exposed to subsamples of test solution taken from the fish test containers. During each renewal period, toxicity tests were performed with the freshly made test solutions and with the aged solutions taken from each test container.

Twenty D. macana Were expoSed to each treatment, 10 individuals per replicate. Mortality was assessed at 1-2, 24, 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br />.

Summary 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 ratio of 1:10).

No mortality or stress was exhibited to fathead minnows that were continuously exposed for 30 days to detoxified Clam-Trol CT-1 solutions.

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

AQUATIC TOXlCOLOGY LAEIQRATQRIES, INC. LABORATORY SOMERTON ROAOiTREVOSE, PA 1 SQ47iU.S.A. J'EL: 21 5i355-33QQiTELEX: 1 73 1 48ii=AX4t 355-2869 A Companson on the Acute Toxicity (LC~p's) of Clam-Trol CT-1 at different water hardness to Deohnia ~ma na Methods The effects of moderate hard water (100 mg/L as CaCOa) and very hard water (500 m@L as CaCO>) on acute toxicity of Clam-Trol CT-1 to fathead minnow was evaluated in 48-hour static tests.

Hard water was Prepared by the addition of various salts as prescribed in EpA publication 600/4-85/013. The hard water was aerated for 2 days prior to use for acclimating daphnids and toxicity testing. No daphnids expired during the 2 to 3 week acclimation period.

The toxicity tests were conducted following ASTM protocol Standard Guide for

~, Conducting Acute Toxicity Test with Fishes/ Macroinvertebrate and

--~ E-729-88a, 1989.

Amphibians," ASTM Test Results Daohnia ~acana Moderately Hard Water (100 mg/L as CaCO3) 24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> LCM 0.46 mg/L 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> LC~p ~ 0.39 mg/L Very Hard Water (600 mg/L as CaCO>)

24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> LCM = 0.89 mg/L 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> LC~p 0,49 mg/L

AQUATIC TOXICOLOGY LABORATORY LABORATORIES, INC.

SQMERTQN ROAOiTREVQSE, PA 1 9047iU.S.A. 1 TEL: 21 Si355-3300+TELEX: 1 ¹ 73 1 48iFAX 355-2869 A Comparison on the Acute Toxicity (LC50's) of Clam-Trol CT-1 at different water hardness to the Fathead Minnow.

Methods The effects of moderate hard water (100 mg/L as CaC03) and very hard water (500 mg/1 as CaC03) on acute toxicity of Clam-Trol CT-1 to fathead minnow was evaluated in 96-hour static tests.

Hard water was prepared by the addition of various salts as prescribed in EPA publication 600/4-85/013. The hard water was aerated for 2 days prior to use for acclimating fish and toxicity testing. Fathead minnows were acclimated to the hard water in two stages; first they were transferred from lab water to water of 350 mg/L hardness and held for two days and finally placed into hard water for 2 days before testing. No fish died during the acclimation period.

Fhe toxicity tests were conducted following ASTM protocol "Standard

~ ~

Guide for Conducting Acute Toxicity Test with Fishes,

~

Macroinvertebrate and Amphibians," ASTM E 729-88a, 1989.

~

Test Results The LC50's values of Clam-Trol CT-1 increased with increased water hardness.

Fathead Minnow Moderately Hard, Water (100 mg/L as CaC03) 96 hr LC50 ~ 2 ~ 9 mg/L Very Hard Water (500 mg/L as CaCO3) 96 hr LC50 ~ 4.4 mg/L

AQUATIG TOX1GOLOGY, mEIORATQRIES, INt". LABORATORY SOMERTON ROAO~TREVOSE. PA 1 9047~V.S.A. r'EL:21 5~355-33DO~TELEX: 1 73 1 48~FAX 4t 355.2869 Effects of Temperature and pH on Detoxification of Clam-Trol CT-1 A study was conducted to examine if abrupt changes in temperature and pH could have any input on releasing or exchanging Clam-Trol CT-1 residuals adsorbed onto clays.

A stock solution of Clam-Trol CT-1 and Betz DT-1, a blend of highly adsorptive clays, in a ratio of 10:30 mglL was prepared in deionized water. Samples of this CT-1:DT-1 stock solutions were then subjected to abrupt pH changes of 7.5 to 6.0, 7.5 to 9.0, 9.0 to 6.0, and 6.0 to 9.0. The pH was manipulated through addition of either lN HCL or lN NaOH. The stock solution had an initial p H of 7 .5. Analyst.s for the presence of free CT-1 was measured at 1 I in'a 8, 24, and 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> after the initial pH adjustments.

The effects of abrupt temperature change on releasing CT-1 was tested by either heating a 10:30 mg/L solution of CT-1 and clay from 20 C to 35 C and chilling from 35 C to 10 C. Samples were analyzed for the presence of Free CT-1 after heating and chilling the stock solution.

Conclusions Under the conditions of this study, the results show that abrupt temperature and pH changes had no effect on the release of Clam-Trol CT-1 residuals adsorbed onto clays.

AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SQMERTQN RQAQiTREVQSE, PA 1 9047iU.S.A. / TEL; 21 5i355-3300'ELEX: 1 73 1 49aFAX 4S 355-2959 pH Effect Residual Clam-Trol CT-1 Samnle Time Blank Sample 'orrected CT-1

~hr Absorbance Absorbance Ahsorbance ~MG/L 10 mg/L CT-1/L 0 0.010 0.161 0.151 11.3 CT-1:DT-1 10 mg/L 30 mg/L 0 0.015 0.021 0.006 ND+

pH 7.5-6.0 0.015 0.017 0.002 ND 7.5-9.0 0.015 0.017 0.002 ND 9.0-6.0 0.015 0.013 ND x 6. 0-9. 0 0.015 0.022 0.007 ND 7.5-6. 0 8 0.017 0.020 0.003 ND 7.5-9.0 8 0.017 0.020 0.003 ND 9.0-6.0 8 0.017 0.021 0.004 ND 6.0-9.0 8 0.017 0.021 0.004 ND 7.5-6.0 24 0.010 0.017 0.007 ND 7.5-9.0 24 9.010 0.020 0.010 ND 9.0-6.0 24 0.010 0.019 0.009 ND 6.0-9.0 24 0.010 0.019 0.009 ND 7.5-6.0 48 0.013 0.018 0.005 ND 7.5-9.0 48 0.013 0.021 0.008 ND 9.0-6.0 48 0.013 0.021 0.008 ND 6.0-9.0 48 0.013 0.018 0.005 ND

• ND Not detectable, less than 0.2 mg/L

AQUATIC TOXICOLOGY .KC LABORATORIES, INC. LABORATORY SQMERTQN RQAQeTREVQSE. PA 1 9047eU S A. /'EL: 21 5e355-3300e TELEX: 1 73 1 48eFAX 4355-2869 Temperature Effect Residual Clam-Trol CT-1 Temp. Blank Sample Corrected CT-1 Same le CT-1:DT-1 20 0.010 0.014 0.004 ND*

10 mg/L:30 mg/L 20 C to 35 C 35 0.010 0.017 0.004 ND 35 to 7.5 y) C C 7.5 0.010 0.008 ND

• ND Not detectable, less than 0.2 mg/L

EFFECTS OF AMMONIAON DETOXIFICATIONOF CLAMTROL CT-1 PURPOSE OF RESEARCH:

A study was conducted to examine if ammonia could have any impact on releasing or exchanging Clam-Trol CT-1 residuals adsorbed onto clays. A tier approach evaluating several variables - pH, ammonia and hardness levels - was conducted.

CONCLUSIONS:

Under the conditions of this study, the results show that ammonia levels of 1-2 mg/L as NH3 have no effect on the detoxification of the Clam Trol CT-1 in a sample. No effect was seen from any of the varied parameters. Hardness levels and pH (in the range of 6.4-8.1) did not have any measurable effect on the detoxification.

EXPERIMENTAL RESULTS:

The experiments run are summarized in a flow chart-type format in Tables 1A and 18.

The test procedure used to measure for Clam Trol CT-1 residuals is attached for reference. All of the ammonia measurements were completed by using the salicylate method for ammonia detection (AP 337). A copy of the test procedure is attached for reference. All of the samples were diluted 1:5 prior to testing for ammonia so that ammonia levels would be within the range of the test (-0.05 to 0.61 mg/L as NH3). The experimental data for both the Clam Trol CT-1 and ammonia testing is given in Tables 2A and 28. Calibration curves for both the high and low range Clam Trol CT-1 testing are attached for reference.

TESTING INFORMATION:

Preparation Of Test Solutions:

All solutions were prepared using laboratory tap water (hardness level of 78 mg/L as CaCO>) unless specifically noted otherwise. The high hardness solution was prepared by spiking tap water with a solution containing -1200 mg/L Ca as CaCO3 and -600 mg/L Mg as CaCO3 so that the final hardness level of the solution was -500 mg/L as CaCO3 (480 mg/L as CaCO3).

All solutions were buffered with a weak buffer (100 mL of 0.1 M KH2PO4 per 2 liters of solution. The pH was adjusted by addition of 0.1 M NaOH to each solution.

The test solutions were spiked with 30 mL of a 1000 mg/L Clam Trol CT-1 standard solution per 2 liter final volume of test solution.

The DT-1 addition to each solution was accomplished by adding 8 mL of a 9000 mg/L DT-1 solution to -1600 mL of test solution.

The addition of ammonia was accomplished by adding 25 uL of Dilute Ammonia, Code 287, to -1200 mL of each test solution. The Dilute Ammonia solution contains -20(v/v)%

of aqueous ammonia.

OBSERVATIONS:

When the pH of the high hardness test solution was adjusted, a white precipitate formed (presumably Ca3(PO4)2). The hardness of this solution was measured (via the EDTA titration method). The hardness level reported was that of the filtered solution (0.22um filter). The precipitated hardness should not have effected the testing. It did, however, cause an emulsion to form in the Clam Trol CT-1 testing procedure. It was difficult to work with this emulsion. As a result of this, it is possible that the 1,2-dichloroethane was not dried completely prior to the absorbance measurement. This could have caused slightly higher absorbance readings for the sample measurements.

REFERENCE:

Laboratory Notebook 1540-266 (MSM)

TABLE 1A'XPERlMENTALFLOVf FOR pH STUDY PREPARE 16 mg/L CT-1 STANDARD IN pH ADJUSTED SOLUTION (1) pH 6.42 pH 7.24 pH 8.09 SOLUTION SOLUTION SOLUTION MEASURE ORIGINAL t'CT-1] IN SOLUTIONS SPIKE SOLUTIONS WITH 45 mg/L DT-1 (2)

MEASURE t'CT-1] IN SOLUTIONS SPIKE SOLUTIONS VflTH 2 mg/L NH3 (3)

MEASURE tCT-1] IN SOLUTIONS WAIT 24 HOURS MEASURE tCT-1] IN SOLUTIONS NOTES 1 100 mL of a 0.1 M KH2PO4 solution was added to 2 liters of water. 0.1 M NaOH was added to bring the pH to the correct level. In the pH study, laboratory tap water was used to make all of the test solutions.

a 2 Solutions were spiked with a 9000 mg/L DT-1 solution such that the final concentration of DT-1 was DT-1.

45 mg/L as 3 To spike the solutions with ammonia, 25 uL of a 20% (v/v) ammonia solution was added to 1200 mL of the test solulio 4 The measurements for tap water, p H 7, 15 mg/L CT-1 is shown for both experimental schemes. It was only run in the pH study section of the testing.

TABLE 18: EXPERlMENTAL FLON FOR HARDNESS STUDY PREPARE 16 mg/L CT-1 STANDARD IN SOLUTIONS CONTAINING VARIOUS LEVELS OF HARDNESS (I)

DEIONIZED WATER TAP WATER HIGH HARDNESS WATER MEASURE ORIGINAL fCT-1] IN SOLUTIONS SPIKE SOLUTIONS WITH 45 mg/L DT-1 (2)

MEASURE [CT-1] IN SOLUTIONS SPIKE SOLUTIONS WITH 2 mg/L NH3 (3)

MEASURE [CT-1] IN SOLUTIONS WAIT 24 HOURS MEASURE [CT-1] IN SOLUTIONS NOTES the pH to the 100 mL of a 0.1 M KH2pO4 solution was added to 2 liters of water. 0.1 M NaOH was added to bring correct level. In the pH study, laboratory tap water was used to make all of the test solutions.

DT-1 was 45 mg/L as 2 Solutions were spiked with a 9000 mg/L DT-1 solution such that the anal concentration of DT-1.

1200 mL of the test solutior 8 To spike the solutions with ammonia, 25 uL of a 20% (v/v) ammonia solution was added to for tap water, pH 15mg/L CT-1 is shown for both experimental schemes. It was only run in the 4 The measurements 7, pH study section of the testing.

TABLE 2A EXPERIMENTAL DATA: CLAMTROLCT-0 TESTING

1) BLANK MEASUREMENTS WATER TYPE 5 cm CELL 1 cm CELL (abs) (abs)

TAP WATER 0.0408, 0.041 9 0.0090, DEIONIZED WATER 0.0362, 0.0445 0.0077, 0.01 01 DEIONIZED WATER 0.0031, 0.0032 0.0001, 0.0032 W/45 mg/L DT-1 0.0041

2) CLAMTROLCT-1 CONCENTRATION OF PREPARED SOLUTIONS (PRIOR TO DETOX TESTING)

WATEFt TYPE 5 cm CELL [CT-1] {in ~(({q (abs)

TAP WATER, pH 6.42 1.0454, 1.0688 13.7 mg/L TAP WATER, pH 7.24 1.041 6, 1.0945 13.9 mg/L TAP WATER, pH 8.09 1.1284, 1.0696 14.3 mg/L DDEIONIZED WATER, 1.0404, 1.061 1 13.6 mg/L pH 7.11, 1 mg/L as CaCO3 TAP WATER, pH 7.00, 1.0228, 1.0307 13.3 mg/L 480 mg/L as CaCO3

3) CLANlTROL CT-1 CONCENTRATION OF TEST SOLUTIONS (AFTER DETOX)

FACT-11 WATER TYPE 6 cm CELL (I<<g/L)

{abs)

TAP WATER, pH 6.42 0.0040, 0.0082 <0.2 TAP WATER, pH 7.24 0.0058, 0.021 3 <0.2 TAP WATER, pH 8.09 0.0081, 0.0094 <0.2 Dl WATER, pH 7.11 0.021 6, 0.0269 <0.2 1 mg/L as CaC03 TAP WATER, pH 7.00 0.0375, 0.0245 <0.2 480 mg/L as CaCO3

4) CLAMTROL CT-1 CONCENTRATlON OF TEST SOLUTIONS (AFTER DETOX AND ADDlTION OF NH3)

WATER TYPE 6 cm CELL [CT-'I ] (In mg/L)

(abs)

TAP WATER, pH 6.42 0.0004, 0.01 01

<0.2 TAP WATER, pH 7.24

<0.2 0.0100, 0.0066 TAP WATER, pH 8.09 0.0084, 0.0079 <0.2 Dl WATER, pH 7.11 0.0167, 0.0156 <0.2 1 mg/L as CaCO3 TAP WATER, pH 7.00 0.0229, 0.0199 <0.2 480 mg/L as CaCQ3

6) CLAMTROLCT-5 CONCENTRATlONS IN TEST SOLUTlONS

{AFTER DETOX AND ADDITION OF NH3, 24 HOURS)

VfATER TYPE 6 cm CELL tCT 1] (Inmg/L)

(abs)

TAP WATER, pH 6.42

<0.2 0.0078, 0.0061

<0.2 TAP WATER, pH 7.24 0.0172, 0.0141 TAP WATER, pH 8.09 0.01 40, 0.0190 <0.2 Dl WATER, pH 7.11 0..036, 0.01 21 <0.2 1 mg/L as CaCO3 TAP WATER, pH 7.00 <0.2 0.0230, 0.01 66 480 mg/L as CaCO3

AMMONIA (0 to 0.61 mg/L NH3)

Salicylate Method

SUMMARY

OF METHOD Nitrite 40 mg/L as NO2-Nitrate 440 mg/L as NO3-Ammonia compounds combine with chlorine to form Orthophosphate 300 mg/L as PO43-monochloramlne. Monochloramlne reacts with salicy-Sulfate 300 rng/L as SO42-late to form 5-amlnosallcylate. The 5-aminosalicyiate is oxidized in the presence of a sodium nitroprusside cata- Sulfide will intensify the color.

lyst to form a blue-colored compound. The blue color is masked by the yellow color from the excess reagent Iron will interfere with the test; eliminate iron interference present to give a final green-colored solution. This meth- as follows:

od was adapted from Clln. Chlm. Acta., 14 403 (1966). 1. Determine the amount of iron present in the sample following the Iron, Total procedure.

APPARATUS REQUIRED 2. Add the same iron concentration to the deionized water sample in step 5.

Cell, sample, 2&mL mark, 2.5 cm Code 2601 (2 required) The interference from iron in the sample willthen be suc-Cylinder, graduated, plastic, 25 mL 495 cessfully blanked out in step 11 ~

Clippers, large 2635 Extremely acidic or alkaline sample should be adjusted Stopper, polyethylene 2601A Photometer, DR/2000 to approximately pH7. Use1 N Sodium Hydroxide Stan-2776 dard solution(Code 255) for acidic samples or1 N Sulfu-ric Acid Standard solution (Code 2066) for basic sam-CHEMICALS REQUIRED ples.

Ammonia Cyanurate Reagent Code 2348 Less common lnterferences such as hydrazine and gly-Powder Pillows clne will cause intensified colors in the prepared sam-Ammonia Salicylate Reagent Powder 2347 ple. lbrbidity and sample color will give erroneous high Pillows values. Samples with severe interferences require distil-Deionized Water 243 lation. Albuminoidnitrogen samples also require distilla-tion.

INTERFERENCES ACCURACY CHECK The following ions may Interfere when present In concen-trations exceeding those listed below: Prepare a 0.2 mg/L Ammonia Standard by dissolving 0.636 g of anhydrous ammonium chloride ln deionized Calcium 1000 mg/L as CaCO3 water and dilute to1000mL in a volumetric flask. Use this Magnesium 6000 mg/L as CaCO3 standard in place of the sample.

AP 337 9012 O1990 BETZ LABORATORIES, INC. ALLRIGHTS RESERVED. Page 1

PROCEDURE 655 ntn PROO ASS 3 8 5 READ ENTER READ ENTER

1. Enter the stored 2. Rotate the wavelength 3. Press: READ/ENTER 4. Pour 25 mL of sample program number for dial until display into a 2&mL mixing ammonia (NH3), shows: The display will show: graduated cylinder, salicylate method. 655 nm mg/I NH3 Salle (the prepared sample).

Press: 385 READ/ENTER Note: Sample cells can be used in place of the mixing The display will show: cylinders.

DIAL nm TO 655 Note: Or, use the up and down arrows to scroll the display to:

385 mgll NHs Salle Press: READ/ENTER TIMER SHIFT 7

5. Pour 25 mL of 6. Add the contents of 7. Press: SHIFT TIMER 8. When the tlmei beeps deionized water into a one Ammonia after 3 min, add the second cylinder (the Salicylate Reagent A 3-min Period will . contents of one blank). Powder Pillow to each begin. Ammonia Cyanurate cylinder. Stopper. Reagent Powder Shake to dissolve. Pillow to each cylinder. Stopper.

Shake to dissolve.

Note: A green color will develop ifammonia nitrogen is present.

Page 2 o1990 BETZ LABORATORIES, INC. ALL RIGHTS RESERVED. AP 337 9012

SHIFT 7 ZERO

9. Press: SHIFT TIMER 10. When the timer beeps 11 ~ Press: ZERO 12. Fill a second cell with after 15 min, pour the the prepared sample.

A 15-min period will blank Into a sample The display will show: Place the cell into the begin. cell. Place the cell WAIT cell holder. Close the Into the cell holder. Then: light shield.

Close the light shield. 0.00 mg/I NH3 Note: The Pour-Thru Cell Salle can be used with this procedure.

READ ENTER

13. Press: READ/ENTER The display will show:

WAIT Then the result in mg/L ammonia (NH3) will be displayed.

Note: In the constants mode, pressing READ/ENTER Is not required. WAIT willnot appear. When the display stabilizes, read the result.

AP 337 9012 o1990 BETZ LABORATORIES INC ALL RIGHTS RESERVED Page 3

<<E TABLE 28 EXPERlMENTAL DATA: AMMONlATESTlNG AMNlONIALEVEL (mg/L as NH3)

SAMPLE AFTER DETOX AFTER NHS AFTER 24 HR.

TAP WATER, pH 6.42 0.46, 0.52 1.95, 1.90 1.90, 1.90 TAP WATER, pH 7.24 0.61 0.55

~ 1,85, 1.80 1.85, 1.90 TAP WATER, pH 8.09 0.61, 0.62 1.95, 1.90 200, 2.00 Dl WATER, pH 7.11 0.15, 0.15 1.10, 1.10 1.15, 1.15 1 mg/L as CaCO3 TAP WATER, pH 7.00 0.50, 0.45 1.25, 1.20 1.15, 1.25 480 mg/L as CaCO3

CLAMTROL CT-1 TEST PROCEDURE Place 200 mL of sample into a 500 mL separatory funnel.

2. Add 20 mL of CT-1 Buffer Reagent to the funnel.

3. Add 20 mL of 1,2-dichloroethane to the funnel.

4. Stopper the funnel, vent, and shake for 30 seconds. Vent. Allow to stand for 10 minutes.,

5. Remove the lower layer of liquid (the 1,2-dichloroethane) from the funnel.

6. Add two plastic dippers ( 3 grams) of Drying Reagent to the beaker containing the solvent. Stir for 10-20 seconds. Allowto stand for 2-3 minutes.

7. Transfer the solvent into a sample cell (1 cm for the high range test, 5 cm for the low range test) and measure the absorbance at 416 nm versus a reference of 1,2-dichloroethane in a similar path length cell.

8. Determine the corrected absorbance for the sample.

corr. abs. = sample abs. - blank abs.

9 Use the calibration curve to determine the concentration of ClamTrol CT-1 in the sample.

• ~

Calibr ation Curve f or CT-1 (1 cm cell, 20/20/200)

1. 60 1.44

1. 28 1.12 A 0.88 b

r 0.80 a

n c

0.64 0.48 0.32 0.18 0.00 0 8 10 12 14 16 18 20 22 Concentration CT-1 (mg/L) 0.075105NX +0.026896

4 I

P 4

4 W k W

4 W ~

4 ~

I I

~ 4 ~

~ 4

~ "I ~ 4 I I k>III' 'V 'W

44. i 0 I 'i A J4 g

CT-1 CALIBRATION CURVE (5 cm cell, 20/20/200)

0. 44 0.40 0.38 0.32 0.28 A

b S

0 0.24 r

b a

0.20 c

e 0.18

0. 12 0.08 0.04 0.00 1.100 0.000 0.100 0.200 0.300 0.400 O.SOO 0.800 0.700 0.800 0.800 1.000 Concentration CT-1 (mg/L) 0.409625NX +8.074999e-03

CLAM TROLo CT Mollusk Control Agent METHYLORANGE METHOD

.APPARATUS REQUIRED CT-1 Buffer Reagent 1591

=

Beaker, glass, 50 mL (2 required) Code Methanol (reagent grade or equivalent) 322 Cylinder, graduated, 25 mL 2622 Drying Reagent, with a plastic dipper 1271 Funnel Rack, separatory 936

SUMMARY

OF METHOD Funnel, separatory, with a Teflon stopcock, 250 mL (2 required) In this procedure the dye in the CT-1 Buffer Reagent com-plexes with the active ingredients in Clam-Trol CT-1. This Glass Rod 114 complex is extracted into 1, 2- dichloroethane. The or-Optical Cell, (2 required)- ganic layer containing the complex ls separatedfrom the aqueous layer and driedwith a drying reagent containing Safety Bulb, rubber 1575 anhydrous sodium sulfate. The color Intensity of the 1, 2 Spectrophotometer dlchloroethane layer is then measured in a spectropho-tometer at 415 nm.

GENERAL APPARATUS

• This methodmust be customized to each specific appli-Cylinder, graduated, 100 mL Code 121 cation. Varythe volumes of sample, CT-1 Buffer Reagent, Cylinder, graduated, 250 mL 917 and 1, 2- dichloroethane according to the test range (see Table 1). If a higher absorbance is needed, increase Flask, volumetric, 1 L, glass (4 required) 935 the volume of sample or decrease the volume of 1, 2-Pipet, glass, graduated, 1 mL 140 dlchloroethane. When increasing the sample volume it may be necessary to increase the volume of CT-1 Buffer Pipet, glass, volumetric, 1 mL 866 Reagent used. For samples <150 mL use 10 mL of CT-1 Pipet, glass, volumetric, 3 mL Buffer 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 enough 1, 2- dichloroethane is used to leave a small Pipet, glass, volumetric, 10 mL 123 plug of solvent in the separatory funnel when the bottom Pipet, glass, volumetric, 15 mL 861 layer of solvent is removed and to fill the optical cell properly.

Pipet, glass, volumetric, 20 mL 1278 Pipet, glass, volumetric, 25 mL 117 GENERAL PROCEDURE Pipet, glass, volumetric, 30 mL Use a weil-ventilated or hooded area to run the test.

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

mined by the specific test procedure used.

• • Apparatus not available through Betz Lab Supply 1,2- Dlchloroethane (also known as Ethylene Dichlo-ride) is a priority pollutant and a specifically-listed should be obtained through a local supplier. RCRA-regulatedmaterial subject to specific disposal re-strictions and/or prohibitions. For this reason, all used CHEMICALS REQUIRED 1,2- dichloroethane should be segregated from other 1,2-Dichioroethane(reagent Code 1666 waste streams. Dispose of waste 1,2- dlchloroethane in grade or equivalent) an approved manner (e.g., labpacking or Incineration).

AP 368 9009 o1990 BETZ LABORATORIES, INC. ALL RIGHTS RESERVED. Page 1

1. Refer to Table 1 for the appropriate range and vol- CALIBRATIONCtjRVE PREPARATION umes to use in this procedure. Transfer an aliquot of

1. Prepare a 1000 mg/L CT-1 stock solution by accu-the water sample to a separatory funnel (the sam-ple). Transfer the same volume of distilled (or deion-

'ately weighing 1.00 g of CT-1 into 1 L of distilled (or deionized) water.

ized) water to a second separatory funnel. (the',

blank). Run the blank once for each set of samples 2. Pipet designated volumes of the stock solution into tested (see Notes 1, 2, and 3). 1-L volumetric flasks. These are the standard solu-tions used in preparing a calibration curve. Use

2. Add CT-1 Buffer Reagent to both the sample and the Table 2 to make appropriate dilutions of the stock blank. solution for each specific application.

3. Using a pipet, add 1, 2- dichloroethane to both se- 3. Follow the General Procedure using the specific so-paratory funnels. lution volumes that have been determined for the

4. Insert the stoppers in each of the separatory funnels. application and prepare a calibration curve. Deter-Invert and briefly open the stopcock to vent the fun- mine the absorbance of a blank solution using dis-nels (see Notes 4 and 5). When venting the funnels, tilled (or deionized) water. ~is blank can be.sub-point the tip of the funnel away from yourself and tracted from the sample absorbance or used to others. zero the spectrophotometer so that the caIIbrhtion

5. Shake the funnels moderately for 30 sec, vent the cuwe goes through the origin. The calibration funnels, then allow them to stand for10 min (but no curve should be linear over the indicated longer than 15 min). ranges.

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

water. Concentration CT-1 Stock Solu-

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

Wait approximately 1 to 2 min (but not more than 5 0.2 0.2 8.

min). Then carefully decant the extract off of the dry- 0.4 0.4 ing reagent into an optical cell. 0.6 0.6

9. Set the spectrophotometer at 415 nm and zero with 0.8 0.8 1,2-dichloroethane. Measure andrecord the absor-bance of the blank and the sample (see Note 6). 1.0 1.0

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

11. Clean the cells after each measurement 25.0 25.0 (see Note 7).

Table 1. Suggested Volumes for Various Ranges of CT-1 Range Volume Volume Volume Optical CT-1 (mg/L) CT-1 Buffer Dlchloro ethane Sample Cell Size (mL) (mL) (mL) 0.2 - 3.0 15 10 250 1.0 cm

• 1.0 - 25.0 10 30 2.5 cm **

0.2 - 1.0 15 20 5.0 cm ***

• The1.0-cm cell (Code 1312) can be used with Hach spectrophotometers using a 1-cm cell adapter (Code 2776C).

• • The 2.5-cm'cell Is the standard Hach 1-in."cell (Betz Code 2601).

• • • Five centimeter cells are not available for use with the Hach photometers. Many laboratory spectrophotometers require an adapter to accommodate 5-cm cells. Check with the instrument manufacturer Page 2 AP 368 9009

NOTES 7. It is imperative that the sample cells are kept clean during the running of the test. It is recommended that

1. For maximum accuracy the calibration curve should the cells are cleaned after each measurement using .

be checked by every operator using this test and the following procedure:

shouldbe verified a minimum of twice per monthus-ing a freshly prepared CT-1 standard. a) Rinse the cell three times with distilled (or deionized) water.

2. A blank measurement (the blank should be a sam-ple of the system water prior to CT-I treatment) must b) Rinse the cell three times with methanol.

be recorded for each set of samples. The blank reading may vary slightly; however, the absolute dif- c) Rinse the cell three times with 1, 2- dichloro-ference between the sample and the blank remains ethane to remove methanol from the cell.

relatively constant.

3. Chlorine causes a negative interference in the test. 8. Turbidity can interfere with this test procedure.

This can be eliminated by adding 0.1 N Sodium Turbidity may:

Thiosulfate (Code 235) to the water sample before o create an emulsion iri the 1,2, - dichloro-running the test. The amount added is based on the ethane layer that does not separate after concentration of chlorine in the system. For a standing for 10 min when the funnel is 100-mL water sample containing 0.3 mg/L chlorine, shaken.

add 10 drops of 0.1 N Sodium Thiosulfate to remove the interference. o create a positive Interference. ( A yellow color is extracted into the 1,2- dichloro-

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

samples. When this happens, vary step 5 of the procedure. Shake the funnel for 30 sec, vent it, then These problems can be removed by centrifuging the allow it to stand for 5 min. Gently Invert the funnel sample(10mln at3500rpm or30min at2500rpm) before once then allow the funnel to stand for 5 min. performing step 1 of the procedure.

5. It Is important to vent the separatory funnel bothbe- 9. Ifyouneedto change test conditions(i.e., usediffer-fore and after shaking it. Otherwise, a pressure will ent volumes than those in Table 1), contact the Ana-build up in the funnel that can cause the stopper to lytical Testing and Development Group In Trevose be forced out of the top of-the funnel. for assistance.

6. Use caution when inserting or removing the sample 10. This methodis adaptedfrom Wang, L. K.; Langly, D.

cell In the photometer. The 1, 2- dichloroethane can F. Ind. Eng. Chem., Prod. Res. Dev., 1975, 14, 3, damage the cell compartment. 210-212.

AP 368 9009 o1990 BETZ LABORATORIES,INC. ALL RIGHTS RESERVED. Page 3

Lr

&t t f+ ~

~ ft ~ ~ ~ Wgf r r )

~ < <<

Q/Jf+ rVT H Qp p

~

P.~P .~gtf fr Q~ >L <Q~ r Tht ~ ~"=g e

~ ~

r J

~ 4

• tr It rt ~ ~

tlat ~ r '

~ ~ t t furr . -s t rp>> t ~rrqp ~

g p rr r T, pg.'er r,,-/ r , t.'t c 1

P" ~

'Y ',W ~

~ t, ~ 'p ~ tt), . g m

",, Q rg ~

~

t

~ t

'\

t I

(~ t ~ k ~ It t~

BETZ LABORATORIES,INC.

4636 SOMERTON ROADS TREVOSEi PA 19053 BETZ MATERIAL SAFETY DATA SHEET EMERGENCY TELEPHONE (HEALTH/ACCIDENT) 800-877-1940 (PAGE 1 OF 3)

PRODUCT: CLAM-TROL CT-1 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 ---

I INFORMAT ON ON PHYS'I CAL HAZARDS i HEALTH HAZARDS i PEL S AND TLV S FOR SPEC F C PRODUCT INGREDIENTS AS REQUIRED BY THE OSHA HAZARD COMMUNICATIONS STANDARD IS II LISTED. REFER TO SECTION 4 (PAGE 2) FOR OUR ASSESSMENT OF THE POTENTIAL ACUTE AND CHRONIC HAZARDS OF THIS FORMULATXON.

ETHYLENE GLYCOL***CAS(107-21-1;LIVER, KIDNEY AND BLOOD TOXIN CNS DEPRESSANTgANIMAL TERATOGEN(HIGH ORAL DOSES);PEL/TLV:50PPM-C.

ALKYL DIMETHYL BENZYL AMMONIUM CHLORIDE***CASg68424-85-15CORROSXVE(EYES)i PEL NONEiTLV NONES ISOPROPYL ALCOHOL(IPA)***CASg67-63-0 FLtQKABLE LIQUID CHRONIC OVEREXPOSURE MAY CAUSE LIVER AND KIDNEY TOXICITYgPEL/TLV:400PPM (500PPM-STEL) ~

ODECYLGUANIDINE HYDROCHLORIDE***(DGH) i CAS) 13590 97 1 i CORROSIVE i PEL NONE g TLV:NONES ETHYL ALCOHOL(ETHANOL) ***CASg 64 17 5 i FLAMMABLEi EYE IRRITANTi MAY CAUSE DEFATTING DERMATITIS,DIZZINESS AND HEADACHE;PEL/TLV:1000PPM.

-- -SECTION 2 - ----TYPICAL PHYSICAL DATA PH: AS IS (APPROX. ) 5.3 ODOR: MILD FL. PT. (DEG. F): 116 SETA(CC) SP.GR.(70F)OR DENSITY: 1.022 VAPOR PRESSURE(mmHG) 23 VAPOR DENSITY(AIR=1): )1 VISC cps70F: 23 %SOLUBILITY(WATER): 100 EVAP.RATE: <1 ETHER=l APPEARANCE: COLORLESS PHYSICAL STATE: LIQUID FREEZE POINT(DEG.F): <-30

---SECTION 3- ------REACTIVITY DATA LE.MAY REACT WITH STRONG OXIDIZERS.DO NOT CONTAMINATE.BETZ TANK OUT CATEGORY 'B THERMAL DECOMPOSITION (DESTRUCTIVE FXRES) YIELDS ELEMENTAL OXIDES.

( . ~

) 'rfV >>>ICZ>>P' C7(

irrrlhl

~ h <<r ~ QIC 3I,~ 'l kW "ial<<(l' I .C">>r 'p >.,lc 'i <' ~

zQ7.

~

p"..., i Y vr C c>> ~ ji,

c. ".-PO.':"A. Sic '1.-'. = Ui:.i;,.::-. r I I

"-'" ("0 "Y~' ~,Pi J hccc ve>>r

~

' '" cr h

~

'l

~

--.'0 C"":

"~"=C'Z Z Dt'G3".>-";l'.!" ""-.. P"-C,~ ","

"c( r

~ \

i k ('"

krhC4- ~,

l'f <,Irr g

~

Ii(fI'I, r7'v.'"r4 vq ~

p,g gq g g Prvi ~

Pl/r7 If c

'8 'i'.,Crp'hcv If I'~ frfV rrl('.+~y h (vhc Cr

" q

,,'l P'

',, i ),h, I ~ L...' ~ le C ~

harv KrZ 3I CC 'XJ <<() (( r 'f>>$ I

~

r'

~'

A(kv h A ~a.. ". 4 Y I A.CCRC, X 'O'O',.X C P.a'i i ( tr,( ( << I~ I+i ~

p rf ,r ~

pr Cv>>

I",C.'".. =C. e

>>. Cvl 1

~ ~

rher 7~C"'. ' "'F q, rq,p p, pn <<>>~

'hr r r>> "

>q rp. v gy r y v7p!1, cp(I7 'l1 '

p ~

~

r Iv PCT'I I Cwegr ~ Cl C'rllh i4h! ar pt7 l r kv L(vI 'I I'v r,r I'(qr I ((C ~ r ~

hr rC ~

%(h/g 2 ~

v

"-"('IiOZ"( V' ""7(. '. '"7 C.i(<

P ' l kr~'C:" C'72 ~

"-<<.I-:, S'=P.".,"'-HQ3,7,.-C!qB-<- ZTPC51 I".~

(i'A TD17CQFi I .ZP. J'"'~lr.F (.

"1"

~ r 3 JP

'.~.'<WB. ~2: "7" -'7"i.' i':.ri."... i l rhrh

( uc

~' I

'5

>> Ch (.

C ~ I I..t'(fr(y I v r, s Plg ) I

.(,'TPl."!~iZ'.!J 9A ~f,".DT 'r-rL: .=.'i:R "D7::..(>=.~~&A

'r, )cShCJ( ~

'::,', I C

~

~>> r p

'r h ~ ~ - ~

~

'g~crhrgg vi'r,r I w gTr grI r r cv,v.I7c , - lh ~,

Cl T~JIJ r r(j,( 0 Ir I f. I gr) w rh"ITrf r.'Tcc., I rvli

-'fi'"""" "%3, c kc )(g,"r I.( 3 p.;

rv JP 'Q (i)'\,P~<~""';: .',(

Iik(C 7pr p-p,rr.

A r.

(

'( <<rvcric

(~(.'<<

r 0 f "1fc.",

~

r (.Ihg

( '.

r'3."~i

~

cp (A rh f P

~ C II ~

hr chIhg

~

L I

V h

BETZ MATERIAL SAFETY DATA SHEET (PAGE 2 OF 3)

PRODUCT: CLAM-TROL CT-1

-SECTION 4 HEALTH HAZARD EFFECTS UTE SKIN EFFECTS *** PRIMARY ROUTE OF EXPOSURE ORROSIVE TO SKIN.POTENTIAL SKIN SENSZTIZER TE 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 EFFECTS OF OVEREXPOSURE***

PROLONGED OR REPEATED OVEREXPOSURES MAY CAUSE: TISSUE NECROSIS;BLOOD CELL DAMAGE OR IMPAIR BLOOD CELL FUNCTION; REPRODUCTIVE SYSTEM TOXICITY'KIN SENSITIZATION.

MEDICAL CONDITIONS AGGRAVATED ***

NOT KNOWN SYMPTOMS OF EXPOSURE ***

INHALATION 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.IMMEDIATELYCONTACT PHYSICIAN EYE CONTACT***

IMMEDIATELY FLUSH EYES WITH WATER FOR 15 MINUTES.IMMEDIATELYCONTACT A HYSICIAN FOR ADDITIONAL TREATMENT I LATION 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 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 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***

ZREFIGHTERS SHOULD WEAR POSITIVE PRESSURE SELF-CONTAINED BREATHING PPARATUS(FULL FACE-PIECE TYPE). PROPER FIRE EXTINGUISHING MEDIA:

DRY CHEMZCALJCARBON DIOXIDEgFOAM OR WATER

)~ v,*S.2'a. g>>'a e t J t>>t't a l r tTe ~ e ase e ~ e>> egeeS t e ~ 7P>>- e e Cp ~ .L. ~ J, I '>>t4a) A>>a.(t

'."DUQO>A i'k'.="3:::YS~ ..Ct ..(.'..J. "Ti.. "'. '>.'."

C...'<<5'"

'~"< Z/D~"

~t'X

"'Ct'.P ','('e Ga '"J E1B Zr)J ",

~ a ' "" 'apt C~'".i~i,'T'u-A 8 ~l. .... ~

T S!8 ~)'4 Ne C;DC) rea /s1et re Atar ')C ~'

~ p ~,

guyot p rt p)p C,>> rps d.T">p., C,Tasp,sse CTp Z I g' r 'aa~'9 Tt; re lr C, '~ ' e,ip.>>S >>>> p'aJ( vt, 'I'I" f,; '4 SSlg 1 ~ a) . " ~

C a ~ r.. P (ae ee L L>> T ~

~.

)C ) a1 P Jar' J(<

• "aw T':)' T!T' )t.1 T 5 s')'Ctx+%T) )) "i)TTC p'T T T) Hsx~'ps T):T T'. >> )1 "* v TTi:+>> x Jpx>> "..

<" r Pr "'

~.r rPa' T).

t s

a.

)

1r)

~

' f e

~ a Ce, tea (e Te>> ae>>>>f J 0 ) ~,' 4La e aJ aw.,de p, Ceca a>>le.J C

~

+c s( ~T) Tcw.w)):ie 4 0-:. 1 w<<a)) T.T T T x T)))sx <<x-.'

(1'" v t >> Qg r a ~ ~

s e 1 ww+>>aw) cxi..ax)es:)

Tct t v '(aJ r, ) ~ ~ +,

r

<<t e')

'p'ss(

~ a3

~

~

')re p +sar)

~

)r, rla>>r,

>>4 r>>

C a

IT>>

P)>>

ps

~

P.C'.T pate, r

C" TC(e>>g e1pp

'a t'I r, t tt." )>>rC'ee>>>>aa

'(a 1q gtt "g

p>><<>>L(rr r e>>

nt:

I L>>')

~

T

<<PT

)TC

~

ep t )

A 't qs;ea Cb T.","

PSJ

~,

tre e

)

L p

a.

p J~:.4. 2 r

ia d

~

a>>

~

~

~

r, L

- se) wS

~

p-)q C-tI ra e \s ~ ae XIIe>>

TTp'r a au a' C'>>

rr a

) Sare~ I er <<>

J T

pterk a

.SVQ taV r

Cp ~

p)Tp aJ ~ ~ e'C

'e ear <<'t5

~ .a>>l

~ p>> e tP r

a C

"e'f '>>t>>

~ ia

~ ~

) p e a rp ep ~

~

~ '<<O'Sai 'aa a"aS

>>t>>t(p vt>>

~ tr <te,r p~Zt.p, Sea C ~

e TTPT apC Q+>> a r

~JQE".P'I CU8;fC~

C;.~S(.7R'.""J AE "'r TC'<7:)7;., (fera tla rr e>>

c Tt T.

PT re ~

~ (>> reg 4aJ CTa p

I ~

e,e ee ~ 'p Y.F.. (.V.C'T g ) IM) t yr

BETZ MATERIAL SAFETY DATA SHEET (PAGE 3 OF 3)

PRODUCT: CLAM-TROL.CT-1

- SECTION 7- - -SPECIAL PROTECTIVE EQUIPMENT-PROTECTIVE EQUIPMENT XN ACCORDANCE WITH 29CFR SECTION 1910.132-134. USE PIRATORS WITHIN USE LIMITATIONS OR ELSE USE SUPPLIED AIR RESPIRATORS.

TILATION PROTECTION***

ADEQUATE VENTILATION TO MAINTAIN AZR CONTAMINANTS BELOW EXPOSURE LIMITS RECOMMENDED RESPXRATORY PROTECTION***

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

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

SPLASH PROOF CHEMICAL GOGGLES. FACE SHIELD

-- -SECTION 8 - STORAGE AND HANDLING PRECAUTIONS STORAGE INSTRUCTIONS***

KEEP DRUMS 6 PAILS CLOSED WHEN NOT IN USE.

STORE IN COOL VENTILATED LOCATION. STORE AWAY FROM OXIDZZERS HANDLING INSTRUCTIONS***

COMBUSTIBLE. DO NOT USE- AROUND SPARKS OR FLAMES. BOND CONTAINERS DURING FILLING OR DISCHARGE WHEN PERFORMED AT TEMPERATURES AT OR ABOVE THE PRODUCT FLASH POINT.

• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 4*

THIS MSDS WAS WRITTEN TO COMPLY WITH THE OSHA HAZARD COMMUNICATION STANDARD APPENDIX: REGULATORY INFORMATION CONTENT OF THIS APPENDIX REPRESENTS INFORMATION KNOWN TO BETZ ON THE ECTIVE DATE OF THIS MSDS. THIS XNFORMATION 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 ZS EXEMPT FROM TSCA INVENTORY REQUIREMENTS

...FIFRA(40CFR):EPA REG.NO. 3876- 145

...REPORTABLE QUANTITY(RQ) FOR UNDILUTED PRODUCT:

NOT APPLICABLE

~ ~ ~ RCRA IF THIS PRODUCT XS DISCARDED AS A WASTE i THE RCRA HAZARDOUS WASTE IDENTIFICATION NUMBER IS: D001=IGNITABLE D002=CORROSZVE(SKIN)

. .DOT HAZARD/UN)/ER GUIDE/ XS: CORROSIVE TO SKIN.COMBUSTIBLE UN1760/560

~

...CALIFORNIA SAFE DRINKING WATER ACT (PROPOSITION 65) MATERIALS: NONE

...SARA SECTION 302 CHEMICALS: NONE

~ ~ ~ SARA SECTION 313 CHEMICALS ETHYLENE GLYCOL(107 21 1) i 21 ' 30 04F g

~ ~ ~ SARA SECTION 312 HAZARD CLASS: IMMEDIATE(ACUTE),DELAYED(CHRONIC) AND FIRE

...MICHIGAN CRITICAL MATERIALS: NONE NFPA/HMIS : HEALTH - 3 i FIRE 2 REACTIVITY - 0 SPECIAL - CORR PE - D

Ir g Vl v ;P PI (It ~

4 gj I j(

~

~ v Ih ~

V jh v <<jtp ~

rh I Cv

~ I a! a(

-' l L" .">>' Vg r f:r. I j I j>> Q)

m. ee, v $>> ~ t<<l <<l (p Al ~

~

'<< '4' I Ph I

C c'

I I rv 0 h"L IT iv L'"

I jl. A c ill'c

. I, vr H lr

'= f;.;

( +fr j." KF kz,  ! f', lv R.' A>> I I

'g l.

~ . gg'g

<>

5 j",.' I J Il I> fi q

1 4 v ~I h(

F j'j .I ~

j~

'~ ~,ggg>>>>.

4

!j P cr j 'I- 4 Cl '

I t V<<

4 r l( I'~ Lh '

4 rr I I

<<cva ( ~ ' r 4'>a

~

'g r v

~ I P

I ~ ~

t

\ V

't '

~

4 v

j

. P'j I

C ll C

l r

~ ~ ~ v

>I V .-; fi

~

. 4 c~ I 4

~"

V I

' V r 4 Irtht h ~ Pt P~

~ 4, Vl c I* V 4 (.

~.

~

I I ~ l4 >V I

~ I E

~I a

g>>

>c '4 '>

.4 I 'C I D r r. ~

~,

<< r I rl I It 4 I

-I I << ~

4 ~ '

v ~

l R

4 r

<< L<<v j 'I. v v' v~ V I t (

I '<< ~ ~

' IV 1 V t j'et, t>

I~  !>>' ~ 4 t 6 v-. ~

Lh 4 ~ h  !

I V M V ~ ~ 4 1 4 4

I a

fI I

~ ~

~ ' '!'r.

S - >.'.

~ h V 4 r,S ~

I' IV>> ti" vr 'j  !

~

v t

~ k V li V 11 ~

rt 4

t j>jj(cjlR >r'- ~ <<c ~ ~

V V' 4 ~

C>>I V 5 ~

I t~ '

fV>ajar+ Fl ~ ~

I ~ r ~

F f 4 4

\,

~

e) I I Q

~ ~ ~

1 T

v 4 t j,,j '"-

t<< V I 'I I 4 tr (jj 4 CI kr. R 9 c 4 j>v, p ~

llV t<< I ~ r t 4 "

~

. >Cjj<<%6m&'C C'.",".'

I

~'

~ II rI'- C I> ~" 4 ~

~ V ~ 'I 4

V 4

(j (C" I ~. 4

'j; I (rr V

V I 'I 4 44 0 Vl I<<

~'

~ 'I ~

R'.

v'j jt', g, 't,'-;I I

v<<AC j 0 ( I t>'t t '

4

[t

~

4 c.

C t V 4 ~

V <<p V' 1 4 Acth+<<

'4 I 4

.4 4

4 I j 1

I ~ 4a I

~

j I I I.

I ~ I

~ I I~

~ J I

~

't

~ I rhj I f I'I ~ <<4 jQ j t' ~ 4' ~ j ~

t V t ~

ET,R C l GLm-tro I Act he la)it (it its I Deftcylyeaatl tn lyirocihrlh........5.0I K P 0 AC R I GER Ndltyl (CI2-1)l> C11-501. C16-101) OBHlsER STATEPIE)iT OF PRACTICAL TREATMENT CORROS IUE. ETE AMD SL'lN OAHACE.HNI-ilrtllylltatylsrroaler cilerlit....e.it I~ cast sf csatsct Nlti stia Nssi lrrtihtti) Nltl )hat) if sos) sai Nshi.lrorihttt) ceahct FUL If SHAILOHED.DO Net CET INIO EYES>ON tacit la)rtiltahr......................e).OI )lpicIII.

SKIN OR ON CLOTllINC.OO N01 INH4LE UAPCR OR Total..................100.01 la cess ef ctshct Nlti tps>flail )rer)tly sai tlenellly Nltl char wttr fsr at Inst 15 a!act ts.

HIST.USE NITN AOENNTE L8ITILATION.DEN Irors(htII) ciatsct )1$ 51ch ~ . L RUSHER SLOWS>COCCLES OR FACE SHIELD RIEN ls cast sf tapstiet Irertihhty csatsct )iplclsa. C HAKXIMC.IMHDIATELYREHOOE A)K) RASH MI- Set hft slh )seel fet s(iitloaal )rtcsetltsny ststtrtats.

L TNIINATEO CLOIHINC SETOSE ROSE.NSH MR- NOTE 10 PHYSICIAN: Hecesat itrs)t rsy ceatnlailcatt tlt est ef pstric hee)I.Desserts C(HIENI)5 1TOUID EPA EST. NO spiast clr-OUCHLY AFIER INC%K.IHC.

POUNDS FER CA(LONI 0.5 <<CF) ctlstiry slecb rts)lnlory A)rtnlts ni ceaielslia rly lt anhi.

EPA REC. NO.C 3076-1$ 5 4 Hsttrht Safety Data Sleet ciatalalay ren hhllti Iafsrrstlsa nhtln te tilt )relict Is aislhlle ENUIRtHOKNIAL HAZARDS ~ Ia n II5t.

IRIS PESIICIDE IS TOIIC 10 FISH AND NILDLIFE OXRECTIOHS FOR USE- I I Inl IN ~ I5t 5 )n Ic s I INntr acIa515 ta N 5 Is)Illa).

OO NO1 DISCHNCE EFFLUENT CONIAINIRC THIS STORAGE AND DISPOSAL ACT IUE INCHED IFNT INIO LAKES> SIREAHS> PONDSr SIORAK:Ktt) ctatslstr ti)ltly clnti.Prehct frtr Frnzla).)tert I ~ a 4ry )lect.ee ott stere st tltntti ttr)treteits.

ESTUARIES> OCEPLMS> DR PUOLIC INTERS UNLESS PESTICIDE DISPOSAL:Di att csahriastt Niter>ftii sr ftti iy stere)t or ils)nal.Pntlclh rsstts srt scottly ianrhes nihr ttxic.lr)re)tr ils)enl sf txcns HIIS PESTICIDE IS SPECIFICALLY IDENTIFIED )tstlclh.s)ny rlxtort>tr tlssate 15 I iielatit~ tf Ftitnl ln.lF titst rsstts cssatt lt ils)tsti if ly sst sccer4ls) te hltl lasttectltas>coitsct ynr Shts C-i50 NKE)ESSED IN Nl I(FOES PERPLII.OO NOT OIS- Pntlclh or Esitroarntsl Ceatrel Aytacy tr tit Hsnriios Ntstt re)nnahtln st ttt atartst EPA Rt)least Of)let For plhsct. c I

NARK I)FLUENT CONIAINIMC THIS PESTICIDE TO I CONTAINER DISPOSAL:HDAL AND PLASTIC CONTAINER)Ctrl)te rlsst (er ttehsltat).tits offer fer rtcyclll) tr rtcesilllttla)r sr )eactert sa4 ils)ist of la a sialtsry C SEDER SYSIEIS HIIHNT PREEIIOUSLY NOtlfTINC lsaifllh sr leclatrsts tr lira IF allerti ly state asi lscsl astierltles.lf inati. stet eet ef irate.

THE )ONCE TREATHEHT )LNII NIIHORIIY.FOR FIRER ORNS NITH LINERS:Cir)httly tr)ty llatr iy slstiay sai ts))ley slits soi letter h htsta clio)la) )sitlchs.tiyty nslht late INllcstloa stol)rtat.tits CUIDAMCE C(HTACT YOUR STATE NTER BOARD OR ils)nt of Ihn sai irer la I snitary Isa(fill or hclanstt If ellirti ly state sa4 Iieet nthrlths.OI aot rent tr)t) irer or Ilier.

RECIONAL OfFICE OF THE EP4.4PPLY THIS PES-R C CUL EG COOLING AT YST PIS TICIDE NLY AS SPECIFIED ON THIS LASEL. Ills )nhct slit I ~ tit ceatrel ef rellesca sa4 ef lscttrlsb fsspl sa4 slpl QRSEOUENT OOSEC IHta coatnl Is telhat> ail tilt yrihct st tit rats sf 0.15 te 5llrts la tel)trstht cia(tastes> ltat excise)t rater 5)ster> cirortrcisl say 1.5 )Ies(5 (le te 100 Nr) )tr 1000 plhas ef rsttr la tit 5)stir titry 3 Ap er ss Ia(sstrht castle) tertrs> hfinst spttrs sici as fler tiros)l fllttrs ssi h- anhi ti rslatsi ~ ctalrel.

PHYSICAL AN NCAL HAIARDS pns> Ie(estrhl aster scrobila) spttrs as4 irtrtry pstterlxns.

OO NOT 15E FOUR OR STORE NEAR HEAf OR CENIRNK6 FEED lEON OPEN FLNIE. Tits )rehct NI) it sihi t ~ tlt 5)stirs eltltr csstlnnsly sr lahrrlthotly er IyltlALD0SE: Htta tit spttr is aetlctslly hole(. IN tits at tit ntt of u anhi. TII frttetacy sf fttilay ssi feratha ef tie trtstrtat rill A)sa4 s)ea 0.5 to 2.0 )eoais (36 te 210 ))N) )tr 1000 pilots ~ F rater la)rehct tie 5)shr.

tlt snerlty ef tit )relhr.

SD)SEIMJENT OOKI Ceatiainsly ftti tilt )nhct te mhtsis s fisap sf 0.05 to 0.5 OAOLY ANLTD ST)TENS rest lt cltasti Itfert trtstrtst 15 lt)ia.

)Ioai (6 te 60 ))II) )tr 1000 plltt5 tf ratn I ~ tlt 5$ 5ttN.

FOR THE CONTROL OF Qt HOLLO)CA> OACTERIIL FUNCI AN ALC4E I-PATENt PENINC FOR ISE AS 4 IKLLUSICIOE. I INIERHITTENT OR SLUC DEMO CJ TOR Ion RIAL USE. Ttclalnl sieice re@rite) IN1114L 00)Et Iln tit 5)stir ls asticnlly fnhi> sii tils )rehct st tit tits

)self lc site )relltrs 15 nslhilt her ROZ. tf 0.3 te 2.0 )nels (36 tt 210 Nll) )tr 1000 pilots If Ns'ttr I'a 'tlt 5)sttN.

11t 0$ 10 PA)EL 1 OF 2 Rt) tst sat ti cIs'trII 15 sclits14. DSE OIRECTIN5 CONTIN%0 CN )ECON )AREL.

TREUOSE, PB i8047 BUSIHESS PHOHEI 2i5-355-33OO ENERGEHCY(HEBLTH OR BCCIDEHT)I 2i5-355-3300 SP>ECLFIC clam-tro1 Glar-trot CT 1 Chr.tnl Ct-1 HAZARD I Severe 3-CT j NET WT.:

PROPER SHIPPING f(APIE 2- Serious Moserore I Slight LOS. (3%0SIUE LINJIO k 0. S.

0- Mi>>br>et 3 LOT NO. EMIOOLLL HOEECEN r r ',

UH 1768 >>ISCINMKH CUSTOMER PART NO. >> SLPEIY Otety 0 COmE)r(KOIES C OON CLOLIX REACTIVITY AHOI 0 OOOOLEKOLOIEK IPNM(P PEIIOMAL PMOTEOMOM D

Jt, PPg(C S r.:=s C 4 JV a Jr M V 4 p I

~ I @Q eS 4~

~

41 ~ I I 4 ,I Sh L" 4

\I 'I - ~

~ Jlp C

CL P 4 I

I CC Cg r p rv I

~I 4 Je ti I

~I l Ci ~ I

~ A L"I g ~1 'I Ir

~1 ~

evr I

~I I ~ \~ $ 4 iL I r.

~~

C' ~ I 4 I ~- I

~

'e

~

~ 4 I el'r I ~ I 4 e j 4 4 Vh

~ I V gA! V I"

4 Cy 4

V 4 4 A J 4 1 r 7 4 ~ V 4 ~I J

\

VJ r ~ ~ "r Qb

~

~ r I

~

~

r V.

4 ~ \ 4 I

~ 4 4

~ ' ~'

~JV

~ I C J'\I 'II I

~ I 4 ~

~ 'I ~

~I I

' ~

J

~

V * '4

~ 4 e e

ic V

4 v

4 t

rg 4 I ~ tg r I V

4 4

C, ~

~ ~ er h

'e C et

~

~I 4 CJ 0

Vera T; 4 ~C '

~'

~ ~' . i.

a 4 L.l

~

4I

~ I

~'

~I

>C C Pi

'lr 4 4 ~

V av c

~ ~

g:MUPPAth J I.

r I

~ .

'V 4

4' ~ 4 C 1, )

".l4VHkfPe X. 4 5K I, L er 4

'I J

~

~ ~

4 V K>> v

~

r

~ t

~ ~ L ts Je I 4

~ I I at C+

L t*

4 a'e I

4 ee 4 tl I

$ V fNNFSMtqq ~I 4' 4

CCJ

~'

~.

g v 4 4

~

r- .

4

~ tr ~ C ~ '

e 4 V 4 ~ I 4U

~

t I I

4 I~

I' I'

~'

'r,.;

I' r4 4

'I

't ~

4

~' l 4

t '

BBDRBTDR ES, TR lHC.

C I um-tI o I OSE OIRECTIONS C(NINOEO fROO PANEL ONE ONCE-THROUCH AUXILIARY WATER INDUSTRIAL COOLINC WATER SYSTEMS AND WASTE WATER SYSTEFIS Till )niect elis la tlt coatrol ef Kellesca lai oF alpl> llcterhl loi fespl lilacs la eace- Tile )nhct Is tffcctln fer tlt ceatnl ef Kollesca ni ef lier forall) Isf 5)lat.fora)I) llctlrh.

tlrol)l ali cis5ti c'lclt frt5l algal 5n Nltl'r clllll)5)5ttK5> cooll'I) )IIA> cnll5 all hpol5

~ hs)l lll slpt la eextlhr) alter spttK5 seel as fire )rehctlta spttK5 aai )IK) er settee ll)5>

T))5 )rohct Kc) It i(hi te tlt spttK islet Nlttr er lcferl ls) ceatlelaltci am la tlt spttN. Nlstt aeter lli Nlstl Ncttrllt il5)t5ll> lllill)er rccllcr) 5)5ttK5 seel ll Sttnp 'tnt5> 5torl)t Aiiltles of till )rofect slee!i It Klh Nltl I Kcttrh) )Ilyl It Ke) lt ceatlsnn er let tralttcat )litt, lutchtti )l)la). set tlh) )ta(5 er hlools> trial)ort 5)lllalp er cnlls lsi 4)5)enl at)Is.

A)tails) e)oa tlc sclcrlt) ~ F ctetlalaltlea Kits trntecll Is ltpl> lai tll rthatln tice Ia tit 5)5tla. Ills )rtiect KI) lc lfhf te tlt spha I) sh) et Isttraltttat hci er I) 5)Mlle) oat a Kestt

~

)Ilt. Ilt frctotsc) of fni or 5)n) lai tlt Arltle~ of trtltacat Kill A)esi e)os tll sntrlt) tf OAOLT FOOLEO STSTHI Nest It clclati ltfnc trcltatat Is ltpa. 'tlt ctltlNIMWII.A(4 I)toes tt Notes 5)5hK5 5lelli Ic Kefc hrh) tll )IK)ls) I)chile ~ lai ls chn tl tlt )'ll) ls )o55lllt h teslrt IA(lett Nish).

FOR THE CONTROL OF NLLOSCA OACTERIL FONCI ANO ALCAE INIERNITTENT OR SLOO hETHOO INTERNITTHIT OR SLOO OETHOO Oltl trntaclt l5 rcgetrcf> lii 'till )el(tet lt tlt tltt IF 1.5 ts 0.0 )nlis )It 1000 plltss If INITIAL00SEl OICI tie sphK Is aetlcnll) ftehi. Iii tile )rohct lt tlt rlh of 0.2 te 1.0 )nai Nlttr lltni) h tlt spttlh or lch) elhi to tlt spha fer I te 8 lnrs> 1 te ) tlets )ct acct sr (2) te 120 ))K) )cr 1000 plless ~ I Kith lnti oa th fltN rote tlrol)l tlc sphK. NlalKIK trtltecat as ecch( te ac)inc tlt Aslrci Intl ef coalrel. Oita clatrel 15 oltllati> a(4 till )rohct at tlt tahreals sleeli lc 15 Nlaehs. Rc)tlt ntll castro! Is acllelti. rltc ef 0.)5 te 2.0 )nl45 )cr 1000 pilose ef Klhr la tlt $ )5ttN.

S(NIEOOENT OOSEI Rite ceatrol ls nlhah ail tile )rohct lt tlt nte ef 0.05 tt 0.5 )na4 (6 te 60

))N) )tr 1000 plltas lf Netcr Inti Il 'Ilt floN rett tiros)l tlt 5)5tta llttraltttltl)I5 lcthi tl Nil!tell coatre.

CNTINtNNS FEEO OETHCO INITIALDOSE: Rica tll sptn Is aetlcnll) fnlti lii tits )rehct at tlc rate ef 0.2 te 1.0 pni (2) tl 120 ))I) )cr 1000 pllol5 tf Nettl Ilni ea tll floN rett tlroe)l tll 5)5ttN. Clatlnc I'It!i cntnl I5 acltcocf.

SIISEOOENT OOSEl hite coitrot 15 nlhat> )tK) a ceathens fni ef till )rehct at tlt ntt ef 0.02 to 0.2 )nsi (2.) te 2) ))N) )cr 1000 pilose ef Niter lalci ea tlt flea rett tires)i tlt 5)sttN.

CTIT 8810 PASH. 2  % 2 TREVOSE. PB i8047 BOSXHESS PHOHEO 2i5-355-3300 ENERGEHCY(HEBLTH OR BCCEDEHT)8 2i5-355-3300 SPEDIFIC I-HAZARD 3- Seeeno 3 Serbus More>lle 1 Sag hl 0 Minimal REACTIVITY'

~ PERSONAlPROTEGIlON

f V viXA'.ih )...' Pi c... ' a C P pl'<

Z

~

t If+ v('T

~

~~ VG rb>

hg 3~,pg. u 8 ~ g~5u'.'.f" 8E D 'lxC

~

a ~

E

AQUATIC TOXICOLOGY KS LABORATORIES, INC. LABORATORY SOMERTON ROAOiTREVOSE. PA 1 9047'.S.A. / TEL: 21 5i355-3300'ELEX: 1 ¹ 73 1 48iFAX 355.2869 Acute Toxicity (LCgp~s)

Clam-.,Trol CT-,.1 Marine Or anisms Sheepshead Minnow 96 hr LC5p 7.0 mg/L Mysid Shrimp 96 hr LCgp 1.45 mg/L Silverside (Menidia menidia) 96 hr LC50 6.0 mg/L 96, hr LC5p 1.24 mg/L,

SeLD aP1, 4c, ' i d&Q3~ C B)O c 5%1 <<Zhdd ' \:' " a' vs> rc ~

8.. Di!l.c:~ f f'E&):HQ&~C.

id

~

<CCf.Pal%

/ a ~ C

'l4 VL is

~ggt, ~ ~ ~ w Dii -'

B.'."~E'i 6?~ i",."csT-..XGi!8" 3 Q. ~-" 0".

i. ',7 c;- ~-.0( v',<'.<:. ~ Zl4w l... i 4 JSlti' e ~ ": ~

58~& BcfQ ~ B~>.'c +li'~ &~i! i ~~~0" i " '+F>> c. 3~.~ W Q

A e,s)i~ S-'~3 L'c,~":-ra~,') oi exoa~cxc, vsh-~ e ~ "202; r....'-~<<=9:is=

gynic..P 7 ~

VD&

~ W J

%$ 4liKXObt Q 4J Ctklfkmma 0 I ' j' w v,CI 4 ~ ~ '~ ' ~~ ~

ff

.A r r'V 'J CP J.-C Q>,0 I

%C ~

~-'.S I. QP v,

~ i C'

~

~ a i+a%

.l ~ 0 >

r

~ ~ C 6I L'i

~

I

/ AQUATIC TOXICOLOGY LABQRATQRIES, INC. LABORATORY SOMERTON ROAOiTREVOSE. PA 1 9047iU.S.A. /'EL: 21 5i355-3300'ELEX: 1 73 1 48iFAX 355-2869 4S Chronic Toxicit of Clam-Trol CT-1 to Shee shead Minno A 7-day static renewal toxicity test was conducted to estimate the chronic toxicity of Clam-Trol to Sheepshead minnow, using newly hatched larvae. The endpoints of this toxicity test are based on adverse effects on survival and growth. This toxicity test was conducted in accordance to EPA protocol "Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, EPA/600/4-87/028."

The no observed effect concentration (NOEC) and the lowest observed effect concentration (LOEC) to a 7-day exposure to Clam-Trol CT-1 was 5.0 mg/L and 10.0 mg/L respectively.

Mortality and Growth of the Sheepshead minnow after a 7 day Chronic Exposure to Clam-Trol CT-1.

CT-1 Concentration Mortality D Wei h m Fish m L Mean S.D. Rancae 0 '

0.625 0

2' 1.23 1.14 0

0

'9

'0 1. 13-1 32 1.06-1.24

~

1.25 2' 1.35 0.20 1.12-1 53

~

2 ' 0 1.50 0.35 1.17-2.02 5'

10 '

0 55 1

1

'2

'3 0.11 0.11 1.22-1.47 0.90-1.13

C V i: i:)'G~ I Lgv.'.".'a

'fl" d~C:~DE P~ b P~

h Ncaa&'oft" Qg -r ado'

~

+Z -, .'&BC-'0 -" "~ 'i;i! f~

i'v'~O>J OC'":~-'>>- 3'g 5&,.QQ

,~ jf~ Qp f ~ pg S ~>> "p Qp,+ J +Q~p +eg*+We Qg'r u lg

~

55$ L.">>" ~j . I.6'<'SY'"Uc. "SQ V."6'"." -. ""C:s:z=Z .a ~,'~i< ~ . pl'. C; "A.' 'Giles 'XC BYili fa.~~ ~ "i 5 .9Y.

Af) "'C ~C ~g

~

r 4

"<<0. tI t" " P f' Ck-~ . =li~. C ~

i< J. C r,"r

~ . C I ~ f (! 4 w i P

'.a C

-.i: 4r .Q C

~ I

AQUATIC TOXICOLOGY LABORATORY SQMERTQN RQAQiTREVQSE, PA 1 9047iU.S.A. / TEL: 21 5i355-3300'ELEX: 1 73 1 48iFAX 4 355-8869 Chronic Toxicit of Clam-Trol CT-1 to M sid Shrim A 7-day static renewal

!.'.~!'!.!

toxicity test was conducted to estimate the 7-day old juveniles. The toxicity test incorporated chronic end points of survival, growth and reproduction. This toxicity test conducted in accordance to EPA protocol "Short-Term Methods for was Estimating the Chronic Toxicity of Effluents and Receiving .Waters to Marine and Estuarine Organisms, EPA/600/4-87/028."

The no observed effect concentration (NOEC) and the lowest observed effect concentration (LOEC) to 7-day exposure to Clam-Trol CT.-l is 1.25 mg/L and 2.5 mg/L respectively for survival, growth and reproduction.

day exposure to Clam-Trol CT-1

!. ~!!  !

Average Dry Mean Percentage, of Concentration Mortality .Weight (mg/L) Female with Eggs m L Mean S.D. Mean 0~0 0 .461 .097 0 '2

'3 10 .457 .040 88 93 0 10 .481 .054 98 1 25 5 .463 071 2 '0

~

F 00 100 100

~ 85