ML20076N405

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1990 Annual Nonradiological Environ Operating Rept for Fermi 2
ML20076N405
Person / Time
Site: Fermi DTE Energy icon.png
Issue date: 12/31/1990
From:
DETROIT EDISON CO.
To:
Shared Package
ML20076N402 List:
References
NUDOCS 9105070133
Download: ML20076N405 (69)


Text

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1990 Annual Nonradiological Environmental Operating Report for Ferml 2

-(In accordance with Appendix B to Facility Operating

- License No, NPF-43) l1 1.

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9105070133 9'10501' PDR- ADOCK 05000341 PDR R<

i Table of Contents Section i Executive Summary Section ll Appendices Appendix 1 1990 Remote Sensing and Vegetation Ground Truth Program Final Report

. Appendix 2 Spill Reports L

Appendix 3 Zebra Mussel Mor:ltoring and Treatment Program Reports l

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Executive Summary in 1990, Fermi 2 generated power for over 284 effective full power days and had an overall capacity factor of 77 percent.

The Environmental Protection Plan (EPP) provides for protection of environmental values during any additional construction and the operation of Fermi 2. The principal objectives of the EPP are as follows:

1. Verify that Fermi 2 is operated in an environmentally acceptable manner, as establisherl by the Final Environmental Statement (FES) and environmental impact assessments.
2. Coordinate NRC requirements and maintain consistency with oth6 State and local requirements for environmental protection.
3. Keep the NRC informed of the environmental effects of facility construction and operation and of actions taken to control those effects.

Environmental concerns identified in the FES which relate to water quality matters are regulated by way of Fermi's National Pollutant Discharge Elimination System (NPDES) permit. As such, water quality issues are not required to be addressed in this report.

The components of the EPP are:

1, A terrestrial monitoring program to detect long-term or sudden changes in vegetation due to operation of Fermi 2.

2. A program to establish the controlled use of herbicides on transmission rights-of-way.
3. A program to ensure that changes to Fermi's design or operation and potential tests or experiments are adequately reviewed prior to implementation to avoid adverse environmental impacts not previously evaluated. Changes in plant design, operation or the performance of tests or experiments which do not effect the environment or which are required to achieve compilance with other Federal, State or local environmental-regulations. are not subject to the requirements of this EPP.
4. Routine monitoring for evidence of unusual or important environmental events.

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A terrestrial monitoring program was conducted to messure k.cy terrestrial parameters after startup of the Fermi 2 facility for cumparison with corresponding measurements obtained prior to startup. This study focuses on effects due to the operation of the cooling towers at Fermi 2. The Ferm! 2 t:nvironmental Protection Plan requires aerial remote sensing during the first July-September period after the station has been in operation for one year. Because this type of study focuses on effects caused by the operation of the cooling towers at the Fermi 2 site, Detroit Edison's first post-operational survey was performed during the July-September 1987 period and the first followup of the survey program was performed during the July to September 1988 period. The second of four required followup post-operational surveys was performed during the August-September,1990 period.

Additional followup surveys are required to be performed in 1992 and 1994.

Color infrared aerial photographs < vere used to delineate cover types, vegetation stress i patterns, and crop land use in the 39 square-mile Fermi 2 survey area. Soil samples were

collected and analyzed from areas expected to receive a wide range of cooling tower salt drift deposition on soils. These analyses provided the third opportunity since the plant began operation to evaluate vegetatinn stress that cou'd be attributable to plant operation.

In 1990, the signs of vegetation stress were distributtd in such a way as to suggest no correlatiors w.th the predicted pattern of solid deposition from the cooling towers as described in the Environmental Report-Operating License Stage, Section 51.4 2.6. This would suggest that other explanations (i.e. localized soil water logging) appear to be more probable. Soil analyses varied little for 1990 data. No correlation between pH and conductivity values and their respective zones of $ position could be found. The pH and conductivity of the samples continue to be ccasistor,t with good fertility and low lonic stress. Although 1990 chloride values wors higher th5 n previous years, the highest value remains an order of magnitude below soil-water chlorido concentrations that have been associated with severe injury to salt-sensitive plants. Again, no correlation of the 1990 values with deposition zones could be found.

A copy of the 1990 REMOTE SENSING AND VEGETATION GROUND TRUTH PROGRAM report and a set of aerial photograph transparencies covering the area withm a 2.5 kilometer radius around the Fermi 2 cooling towers are enclosed (Appendix 1).

The use of herbicWes at Fermi 2 must conform to the approved use of '. elected herbicides as registered by the Environmental Protection Agency, approved by State authorities, and applied in accordance with State requirements. Records are maintained at the sito concerning herbicide use. These records include the following information: commercial and chemical names of material used, concentration of active material in formulations diluted for field use; diluting substances other than water: rates of apphcation; method and frequency of application; location; and the date of application.

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1 Page 3 I Defore engaging in additional construction or operational activities which might affect the environment, Fermi 2 would prepare and record an environmental evaluation of such activity, if the evaluation should Indicate that the proposed activity would involve an unreviewed environmental question, Detroit Edison would provide a written evaluation of the activity and obtain prior approval from the Director, Office of Nuclear Reactor Regulation. Activities are excluded from this requirement if all measurable, non-radiological effects are conf!ned to the on-site areas previously disturbed during site prt.paration and plant construction. During the period covered by this report, there were no changes to station design or operation, tests, or experiments which involved potentially

significant unreviewed environmental issues.

Any unusual occurrence or important event which indicates, or could result in, sigolficant environmental impact _susally related to p!r.7t operation is reported to the the NRC within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> followed by a written report. The ;ollowing are considered examples of unusual or important environmental events; excessive bird impaction events, onsite plant or animal disease outbreaks, mortality or unusual occurrence of any species protected by the Endangered Species Act fish kills, and an increase in nuisance organisms or conditions.

During the reporting period, several environmental incidents / concerns occurred, none of which posed any significant environmental impact causally related to plant operation. As such, they did not warrant classification as unusual or important environmental events ,

(Appendix B to Facility Operating License No. NPF-33, section 4.1). Accordingly no non-routine reports were submitted. However, these incidents are noted in this report to provide an all-encompassing record of environmental incidents at Fermi 2. These are

summarized below

o One spill occurred at Fermi 2 during the reporting period. On January 28,1990, approximately 50 gallons of raw sewage entered the storm sewer system. The spill was due to a blockage of the sewage forwarding station discharge line, and

. subsequent failure of septic tank high level alarms. Sewage backed-up into the septic tank and overflowed to an adjacent storm sewer, The system was isolated and flow to the tank terminated. Maintenance crews cleared the blocked discharge line and repaired the faulty level alarms. This was a minor spill and did not produce any observable environmental impact. A copy of the Spill Notification Follow-up Report submitted to the Michigan Department of Natural Resources is included in Appendix 2.

o Monitoring of Fermi 2 raw water cooling systems for the presence of Corbicula (Asiatic clam) and Zebra mussels continued in 1990 in accordance with the Corbicula Monitoring Program (see Annual Non-Radiological Environmental Monitoring Report - 1989, previously submitted).

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Page 4 Zebra mussels were first discovered in 1989, colonizing the General Service Water (OSW) intake structure and OSW cooled heat exchangers. Zebra mussel monitoring conducted in May 1990 revealed a 9.4% increase in Zebra mussel densities present on GSW intake structures over 1989 results, in September 1989, the Zebra mussel populations consisted primartly of young-of-the-year mussels (2/3 of the individuals were less than 2 mm in length). By May 1990, most of the population was 2 - 7 mm in length (see Technical and Engineering Services Report 90H19-1, Appendix 3). Populations of this magnitude did not impose sufficient threat to the OSW supply to warrant the cost of mechanical cleaning of the intake structure. The need for mechanical cleaning will be evaluated again pending results of the May 1991 Inspection.

The OSW and Fire Protection systems received two molluscicide applicctions in 1990. Betz Clam-Trol CT-1 was applied to these systems on July 3,1990 and November 29,1990. Zebra mussel mortality due to treatment was estimated at 100% and 85% respectively (see Zebra Mussel Sterilization Reports, Appendix 3).

Approximately three weeks following the July 3,1990 treatment, while operating at 100% power, reduced heat exchanger efficiency was noted on the top Main Turbine Lube Oli (MTLO) cooler. The standby cooler (bottom MTLO cooler) was placed in service to allow the top cooler to be opened for inspection.

inspection revealed approximately 85% blockage of the OSW Inlet tube sheet with dead Zebra mussel shells. The cooler was hydrolased to remove the shell debris and returned to service. The bottom MTLO cooler was then removed from service and strMlarly cleaned. Performance testing was subsequently performed on all remaining OSW supplied heat exchangers in service (Reactor Building Closed Cooling Water, Turbine Building Closed Cooling Water, and Generator Hydrogen Cooling heat exchangers). Decreased heat exchanger efficiencies were observed on the Reactor Building and Turbine Building closed

' cooling system heat exchangers of varying degree. Thermal loads for these heat exchangers were shifted to standby coolers to allow for inspection.

Inspection revealed varying degrees of fouling by dead Zebra mussel shells.

The coolers were cleaned and placed back in service.

The second Zebra mussel sterilization conducted in November 1990 did not result in any decrease in thermal efficiencies for OSW supplied heat exchangers, it is anticipated that reoccurrence of fouling problems such as were experienced in July 1990 will be prevented by scheduling future treatments at sufficient frequency to prevent any newly attached mussels from growing to lengths in excess of the smallest GSW supplied heat exchanger tube dian ster (MTLO coolers-5/8' tube diameter). Periodic Zebra mussel sterilizations coupled with increased frequency performanco testing and cleaning of OSW supplied heat exchangers should maintain control of Zebra mussels at Fermi.

Page 5 l 0 On July 19,1990, Fermi's NPDES Permit No. M10037028 was approved for reissue by the Michigan Water Rosources Commission. The Permit, which consolidated the plant's previously eusting four permits, contains several new provisions as summarized below:

Previous New Previous New Outfall Outfall Effluent Effluent Number Number Parameter Limitation Limitation 001

  • Total Chromium 200 ppb 81 ppb Permit No. Total Zinc 1000 ppb 86 ppb M10037028 pH 6-9 6.5-9 009
  • pH 6-9 6.5-9 Permit No.

M10037028 001 011 pH 6-9 6.5-9 Permit No. Heat Addition 17.9E8 BTU /hr Pararneter deleted M10001830 00A 00C Permit No.

M10001830 008 000

  • Permit No.

M10001830 002 012 Permit No.

M10001830 001 013 pH 6-9 6.5-9 Permit No, M10039365 002 Deleted N/A N/A N/A Permit No.

M10039110

  • Indicates no change

Page 6 In addition, several Special Conditions were mandated by the new permit; as follows:

1. Fermi must conduct a one-time short term waste characterization study for Outfall 001. The study requires Fermi to quantify concentrations of metals discharged to Lake Erie (Part I, Special Condition A.14).
2. Fermi must conduct an analysis of a grab sample on Outfalls 009 and 011 for a GC/MS Scan for Volatile compounds , Acid compounds and PCBs (Part I, Special Condition A.15).
3. Fermi must provide the Michigan Departmett of Natural Resources with sufficient data to demonstrate that conce.itrations of water additives currently used do not exceed specifiec' effluent limitations (Part I, Special condition A.18).

In accordance with Section 3.2 of the Fermi 2 Environmental Protection Plan, a copy of reissued NPDES Permit No. M10037028 was submitted to the NRC on August 17,1990 (NRC-90-0137).

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Appendix 1 Appendix 1 consists of the Fe mi 2 Power Plant Remote Sensing and Vegetation Ground Truth Program 1990 Fliel Report, and a full set of aerial photograph transparencies covering all imagery within a 2.5 kilometer radius around the Fermi 2 cooling towers.

Appendix 2 Appendix 2 consists of the follow-up spill report submitted to the Michigan Department of Naturel Resources for a sewage spill that occurred January 28,1990.

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February 8,1990 1

Mr. P. D. Zugger, Chief )

Surface Water Quality Division i Michigan Department of Natural Resources I P. O. Box 30028 Lansing, MI 48909 Ret Spill Notification Follow-up Repcrt Egrmi-2 power plant NPDES permit No. M10037008 Dear Mr. Zugger In accordance with T -t F d 't NPDES Permit No. MIOO37028 and the Part V Rules of the he ; , sources Commission, the Detroit Edison Company is submitting this follow-up report to the spill notification made by the Nuclear Shif t Supervisor of the Fermi-2 Power plant on January 28, 1990 at approximately 2039 hours0.0236 days <br />0.566 hours <br />0.00337 weeks <br />7.758395e-4 months <br /> to Mr. Roy Schrameck of the Detroit District Office.

At approximately 2005 hours0.0232 days <br />0.557 hours <br />0.00332 weeks <br />7.629025e-4 months <br /> on January 28,1990, a plant operator on routine rounds discovered that approximately 50 gallons of sewage had overflowed from a backup sewage collection tank into the plant parking lot and flowed by way of the storm sewer into Swan Creek through Outfall 002. The system was isolated and flow to the tank i terminated. A contractor was called to pump out the contents of the

, tank and dispose of the sewage.

The cause of the spill was a blockage in the line between the plant and the municipal sewer system and the failure of the high level alarm l on the tank. The sewer line has been cleared and the high level alarm repaired. The system has been returned to service.

The plant staff is reviewing the system's preventive maintenance program and the system design to determine if further medial action is required to prevent a reoccurrence of the incident.

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Mr. P. D. Zugg;r, Chi:f i F0bruary 8,1990 Page 2 If you have any questions relative to the incident or this report, please contact see on (313) 237-7021.

Sincerely, x

Arthur Hr.id' rich, Jr.

Administrator Water and Land Use Pzcarams Environmental Protection AH:D cc: R. Schrameck Hae-Jin Yoon bec: J/Flynn A.Lehmann M. Sterling W. Terrasi I

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Appendix 3 Appendix 3 contains a copy of Detroit Edison - Technical and Engineering Services Report 90H19-1 delineating the status of the Zebra mussel infestation at Fermi.

- Appendix 3 also contains copies of Zebra mussel sterilization reports prepared by Betz Industrial for molluscicide applications conducted at Fermi in 1990,

Detroit

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Date: July 10, 1990

. To: F. M. Lehmann Nuclear Operations From: W. p. Kovalak 6 R / .A Technical and Engineering Services

Subject:

Abundance of Zebra Mussels at Fermi 2 Technical & Encineerino Services Report 90H19-1 This report summarizes results of quantitative sampling of zebra mussels (Dreissena polymorpha) on concrete surfaces at the general service water (GSW) pumphouse at Fermi 2. Sampling was carried out on September 8, 1989 and May 7, 1990. These studies were part of Company-wide monitoring of zebra mussels at cooling water intakes.

Similar sampling procedures were used on both dates. The sampler was a metal sleeve with a square opening at one end and a round opening at the other (Figure 1). The round end is fitted with a knee-length nylon stocking.

In September 1989 the sampler was used as a scraper. It was pushed vertically along the concrete surface over a distance of 8 inches. The dislodged mussels accumulated in the stocking. In May 1990 the sampler was held perpendicular to the concrete surface while a spatula was used to remove mussels around the sampler. The spatula was then used to dislodge the mussels enclosed by the sampler and direct them into the stocking.

Twelve quantitative samples were collected on each date.

Samples were collected near surface, mid-depth and near bottom at 4 locations on vertical concrete surfaces of the GSW pumphouse. In September 1989 samples were collected 1,5 and 10 feet below surface and in May 1990 samples were collected-4, 7 and 12-14 feet below surface.

In September 1989 the area of each sample was 32 sq. ,

inches whereas in May 1990 sample area was 16 sq. inches.

In September 1989 mean density was 26,415 (range 4,408-69,411) mussels per sq. meter. There was no consistent relationship between density and water depth although the highest density was near the surface. In May 1990 mean density was 28,893 (range 1,356-50,666) mussels per sq.

meter. Densities were greater near the bottom than near the surface.

Serving Customers

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90H19-1 Page 2.

In September 1989 the population was composed primarily of young-of-the-year mussels spawned during 1989. More than 2/3 of the individuals were less than 2 mm in length (Figure 2). By May 1990 growth and mortality produced a more even size distribution. Most of the population was 2-7 mm in length.

There are several notable differences in the demographic characteristics of mussels at the GSW pumphouse at Fermi 2 and the cooling water intake at Monroe Power Plant.

First, the density of mussels is about 30 times less at Fermi 2. Lower densities appear to be related to lower flow rates. At capacity Monroe draws about 1.4 million gpm whereas Fermi 2 draws about 35,000 gpm; the difference is about 40-fold. High flow rates concentrate large numbers of larvae in the intake resulting in rapid development of high population densities. Second,. growth rates at Fermi 2 are lower than at Monroe Power Plant.

In September 1989, 40 percent of the mussels at Monroe were less-than 2 mm in length whereas at Termi 2 70 percent were less than 2 mm in length. In May 1990 at Monroe 70 percent of mussels were 9-16 mm length whereas at Fermi 7 60 percent were 3-6 mm in length. Higher growth rates at Monroe probably were attributable to higher flow rates. Dr. R. Griffiths (Ontario Ministry of ,

the Environment) indicated that in European waters growth rates are higher in flowing waters, including industrial water systems, than in still waters of lakes.

Overall, flow conditions at the GSW pumphouse operate to minimize infestation and fouling by zebra mussels.

However, this does not preclude the possibility of serious fouling in tne future. In Lake Erie the mussel population is growing at an explosive rate.

Consequently, each spawning will yield increasing numbers of larvae to colonize intake structures and water '

systems. It is prudent to expect that this will continue until food or some other factor limits population growth.

Presently, there-is no way of predicting how large the ,

population will grow before stabilization occurs.

Minimization of operational problems depends on effective monitoring and control-programs. Monitoring should be most intense between late July and early-November. Newly spawned mussels become visible in late July-early August.

During this period, routine visual inspections allow rapid determination of control needs.

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90H19-1 Page 3.

Where possible, mechanical removal, which is more environmentally acceptable, should be used. Chemical control should be used prudently. Indiscriminate use of toxicants allows rapid development of resistant strains as has occurred with a large number of insect pests.

Approved by: h- c = =' !N# 4 D. P. Cross ' '

Supervisor, Environmental and Regulatory Compliance VPK/Pah copies to W. D. Gilbert G. A. Horuczi (file)

G. D. Longton R. D. Smithee en~~., ,--n-*

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Front View FIGURE 1: Design of sampler used to collect quantitative samples of zebra mussels.

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FIGURE 2: Comparison of the size frequency distribution of zebra mussels from the general service water putiphouse at Fermi 2 in September 1989 and May 1990

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DETROIT EDISON FERMI II NUCLEAR PLANT ,

NEWPORT, MI, ZEBRA MUSSEL STERILIZATION JULY 17, 1990 c

PREPARED BY:

77 LEN WALL TECHNICAL SPECIALIST 1

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TABLE OF CONTENTS A. INTRODUCTION B. PROCEDURES C.

APPLICATION SYNOPSIS D.

MONITORING AND RESULTS E. CONCLUSION F. APPENDIX 2

A. INTRODUCTION:

The following is a synopsis of the recent zebra mussel steriliza-tion. This bi-annual sterilization is part of your macrofouling control program for the GSW and fire protection systems. The goal of this program is the control of zebra mussel infestation into these systems before the organisms reaches macrofouling sizes, thus preventing reduced ef ficiencies , increasing system reliability and eliminating potential downtime.

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B. PROCEDURE

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The following is a guideline for the CT-1 sterilization of the GSW and fire protection systems. These procedures were modified due to the system being down during the sterilisation.

1) Run a CT-1 demand test of the water to be treated.

2)-Run baseline and CT-1 residual standards for the analyti-cal test curve.

3) Place the system into recirculation mode.
4) Feed the CT-1 product to the suction side of the GSW j circulating pumps. The product is fed via a positive j displacement pump and through a sparger line. The exact product feedrate -(gph) will be determined by a system demand'and the number of circulating pumps in operation.
5) Feed the product such that at least 15 ppm. of product is in contact with the GSW systems for a period of six I
  • l hours. The application duration was based on a water l

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6) Run hourly tests on the bio-box monitor and throughout i

the treated systems in order to assure a 15 ppm product -l l

concentration.

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7) Once the GSW system concentration has been verified at 15 I ppm or greater, flush the fire protection system until a i concentration of 15 ppm. is verified at the discharge.

Upon residual verification, button up this system for a period of at least six hours.

8) Once a six hour application to all systems has been achieved, discontinue product feed.
9) Run a CT-1 test on the pond water to determine if detox.

feed is needed. If required, feed appropriate quantity of detox.

10) Run analytical CT-1 test to insure complete product detoxification.
11) Resume normal system operation once product is verified detoxified.

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C. APPLICATION SYNOPSIS:

The CT-1 sterilization was initiated at 8: 46 AM on July 3, 1990.  ;

The chemical feed pump was set at approximately 17 gph. This feedrate was based on a water demand of 2. 5 ppm (total product feedrate of 17. 5 ppm. ) and two GSW circulating pumps in opera-tion.

At 9:45 AM, analytical test results indicated a CT-1 residual of

18. 8 ppm at - the bio-box (see monitoring section) outlet. At this time (since the CT-1 residual was greater than the minimum 15 ppm required), various auxiliary cooling systems and the fire header system were valved into service. The fire protection system was flushed until a residual of greater than 15 ppm. was achieved (21.1 actually achieved) and then the system was buttoned back up.

The CT-1 feed was continued until 5: 00 PM. The extended time period was needed to insure a six hour contact time to some of the auxiliary cooling systems that were valved in last. As.you l

can see from the feedrate chart and graph, the chemical feedrate

! was around 15 gph throughout the application. Unfortunately, I

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signed for a system operation of four GSW circulating pumps and i

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the corresponding feedrate (the outage allowed for reduction to two pumps) and could not be lowered below the 7% stroke i+. was set at during this application. The total product usage amounted to 132 gallons of CT-1.

The analytical results from the bio-box monitor outlet indicated that CT-1 residuals of 18. 8 to 21. 7 ppm, were achieved for the desired six hour exposure (see chart and graph). Additionally, various samples from the GSW and fire protection system indicat-ed a 15 ppm residual was achieved throughout.

At 5:00 PM, the chemical feed was stopped. Analytical tests of the cooling pond revealed a CT-1 residual of 0.14 ppm. The i- discharge permit was for less than 0.10 ppm. The feed of two drums of detox was therefore, necessary. This product was added l

at 5:45 PM. A subsequent pond test at 6: 30 PM, indicate a resid-ual of less than 0.10 ppm and the system was soon returned to t normal _ operation.

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CT-1 RESIDUALS DATE SAMPLE ELAPSED CT-1 PT. TIME TIME ABSORBANCE CONC.

07/03/90 BIOBOX 8:45 AM 0.00 TREATMENT 0. 0 STARTED 07/03/90 BIOBOX 9:10 AM 0.42 0.155 4.2 07/03/90 BIOBOX 9:45 AM 1.00 0.014 18.8 07/03/90 BIOB0X 10: 45 AM 2.00 0.842 26.1 07/03/90 BIOBOX 11: 45 AM 3.00 0.780 24.1 07/03/90 BIO *'X 12:45 PM 4.00 0.725 22.4 07/03/90 Bl e3X 1: 45 PM 5.00 0. 7 17 22.1 07/03/90 BI0 BOX 2:45 PM 6.00 0.697 21.5 07/03/90 BIOBOX 3:45 PM 7.00 0.705 23.0 07/03/90 BIOBOX 4:45 PM 8.00 0.704 21.7 07 /03/90 POND 4 : 15 PM 7.50 0.043 0. 0 07/03/90 POND

  • 4:30 PM 7.75 0.153 0.14 07/03/90 POND 5: 00 PM 8.25 TREATMENT STOPPED 07/03/90 POND 5:45 PM 9.00 DET0X ADDED 07/03/90 POND
  • 6:30 PM 9.75 0.100 < 0.1

DATE SAMPLE CT-1 PT. TIME ABSORBANCE CONC.

07/03/90 GSW HEADER 10: 15 AM 0.579 17. 7 07 /03/90 FIRE HEADER 12:45 PM 0.350 10.6 07 /03/90 FIRE HEADER 1: 15 PM 0.471 14.3 07/03/90 FIRE HEADER 3: 15 PM 0.084 21.1 i

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FEED TOTAL ELAPSED RATE USAGE TIME TIME (GPH) (CUMULATIVE) 8:45 AM 0.00 START ---

9:45 AM 1.00 17.9 17,9 10: 45 AM 2.00 16.2 34.1 11:45 AM 3.00 15.7 49.8 12:45-PM 4.00 17.0 66.8 2:00 PM 5.25 14.6 84.3 2:45 PM 6.00 16.2 96.5 3:45 PM 7.00 15.8 112.3 4:45 FM 8.00 16.0 128.3 5:00 PM 8.25 15.9 132.3 TOTAL: 132.3 GALLONS CT-1 L

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D. MONITORING AND RESULTS:

The CT-1 application effectiveness was monitored through the use of a flow-through bio-box. This piece of equipment is a plexi-glass container with six separate compartments in it. It was installed such that water flow from the GSW header was continual-ly passing through the unit. In this way, the test mussels would see the same conditions as the systems being treated.

The bio-box cas installed five days prior to the start of the system sterilization and approximately 1000 zebra mussels were placed in the various bio-box compartments. The mussels were thus, allowed to acclimate to the water conditions and resume normal feeding similar to any mussels in the systems to be t reat-ed. These mussels would be monitored for latent mortality once the sterilisation was completed.

The mussel mortality achieved was 100%. As you can see from the enclosed graph, there was a 95% mortality achieved after 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> .

and a 100% mortality af ter 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />. The time lapse between the stoppage of treatment and mortality is due to the latent toxic effect of the CT-1 molluscicide.

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24 72 ELAPSED TIME (HOURS)

f lE; CONCLUSION:

- The CT-1 sterilization of your GSW and fire protection systems achieved the product dosage rate of at least 15 ppm for the desired six hour exposure period. This application resulted-in 132 gallons of CT-1 and 600 pounds of detox being fed.

This

. product'_ usage-corresponds to a total-system sterilization cost of

only $2000 ($2300 for CT-1 and $600 for detox).

-2 The monitoring of.the sterilization effectiveness resulted in a zebra mussel mortality _of 100%. With the continued monitoring of your systems for zebra mussel fouling potential and correlating I this monitoring with subsequent CT-1 applications, your system will be protected from macrofouling. The net result is increased system reliability, optimum efficiencies and prevention of downtime,'

D 9

4

y , u BASELINE TESTS 4

HIGH RANGE CONCENTRATION ABSORBANCE 5 ppm. 0.180 10 ppm 0.289 20 ppm 0.701 LOW RANGE CONCENTRATION ABSORBANCE 0 ppm 0.031 0.1 ppm 0,109 0.5 ppm 0.486

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l l l l F. Appendix Clam-Trol CT-1 Analytical Method

This method must be customized to each specific application. This is l done by varying the volumes of sample, CT-1 Buffer Reagent and 1,2-dichloroethane used in the procedure. Table 1 lists several combinations of reagents that can be used to obtain three different test ranges. When optimizing the procedure, if a higher absorbance is needed, the volume of sample should be increased or the volume of 1,2-dichloroethane should be decreased. When increasing the sample volume it may be necessary to increase the volume of CT-1 Buffer Reagent used. For sample volumes of less than 150 mL use 10 mL of the CT-1 Buffer Reagent; for volumes between 150 and 300 mL use 15 mL of CT-1 Buffer Reagent. When determining the amount of 1,2-dichloroethane to use it is necessary to make sure that the volume used is large enough to have sufficient 1,2-dichloroethane to leav9 a small plug of solvent in the separatory funnel when removing the bottom layer of solvent while having enough solvent to fill the optical cell properly. GENERAL PROCEDURE FOR TEST _____________________________________i

                                   ,_________________ilated or hooded area to run the test.1 1 Use a well vent l Always use a safety bulb when pipetting liquids.                                       l i______________________________________________________i
1. Transfer an aliquot of the water sample to a separatory funnel (the sample). Transfer the same volume of distilled (or deionized) water to a second separatory funnel (the blank) .

It is only necessary to run the blank once for each set of samples tainted (see notes 1 and 2). Table 1: Suggested Volumes for Various Ranges of CT-1 Range volume (mL) volume (mL) volume (mL) optical ag/L CT-1 CT-1 Buffer dichloroethane sample call size 0.2 - 3.0 15 10 250 1.0 cm

  • 1.0 -25.0 10 30 50 2.5 cm **

0.2 - 1.0 10 15 100 5.0 cm ***

  • The 1.0 cm cell can be used with Hach spectrophotometers utilizing a 1 cm call adapter.
                          ** The 2.5 cm cell is the standard Hach 1 inch cell (Betz code 2601)                                        .

that can be used with Hach spectrophotometers.

                          *** 5 cm cells are not available for the Hach photometers. Many laboratory spectrophotometers require an adapter to accommodate 5 cm cells. Check with the instrument manufacturer.
2. Add the CT-1 Buf fer Reagent to both the sample and the blank (see note 6).
3. Using a pipette, add the 1,2-dichloroethane to both separatory funnels.

r, j

4. . Insert the; stoppers in each of the separatory funnels, invert and briefly open the stopcock-to vent the funnels (see notes 3 and 4).

When venting-the funnels point the tip of the funnel away from  ! yourself and others.-

5. Rhaka the funnels moderately for 30 seconds, vent the funnels,  ;

then allow to stand for ao minutes (but no longer than 15 minutes) .

6. Collect the ' lower layer from each funnel -(the 1,2-dichloroethana) in 50 mL beakers. It is most convenient to allow a small amount of the -1,2-dienloroethane (-1-2. mL) to remain in the funnel. This prevents any significant removal of water from the separatory funnel when the 1,2-dichloroethane is being removed.
7. Using the plastic dipper, add 2 scoops of Drying Reagent to each beaker and stir with a glass rod for 10 seconds (but no longer
                .than 20 seconds).                                .
8. Wait approximately 1 to 2 minutes (but not more than 5 minutes) then carefully decant the extract off of the drying reagent into an optical cell.
9. Set the spectrophotometer at 415 nm and zero with 1,2-dichloro-ethane. Measure and record the absorbance of the blank and the sample.
10. The sample absorbance minus the blank absorbance is used to determine.the concentration of CT-1 in the sample. From a prepared calibration' curve, determine the CT-1 concentration in the sample (see Calibration Preparation).

11._ Clean the calls after each measurement (see note 5).

 ~

l' CALIBRATION PREPARATION

1. - Prepara a 1000 ag/L CT-1 stock solution by-accurately weighing out 1.00 gram of-CT-1 into 1 liter of distilled or deionized h water.
2. Pipet designated volumes of the stock solution into 1 litar volumetric flasks. These are the standard solution-to be used ..

in preparing a. calibration curve. Use Table 2 to determine the appropriate dilutions-to make of the stock solution for each specific application. l-l

o - CLAM-TROL CT METHYL ORANGE METHOD APPARATUS REQUIRED Beaker, glass, 50 mL (x2) Code --- Cylinder, graduated, 25 mL 2622 Funnel rack, separatory 936 Funnel, separatory, w/ teflon stopcock, 250 mL (x2) --- Glass rod 114 optical cell, (x2) Spectrophotometer GENERAL APPARATUS

  • Cylinder, graduated, 100 x1, Code 121 Cylinder, graduated, 250 ud, -

917 Flask, volumete.c, d 1 liter, glass (x4) 935 Pipette, glass, volumetric, 1 mL 866 Pipette, glass, 1 mL, graduated 140 Pipette, glass, volumetric, 3 mL Pipette, glass, volumetric, 5 mL 124 Pipette, glass, volumetric,10 mL 123 Pipette, glass, volumetric, 15 mL 861 Pipette, glass, volumetric, 20 mL Pipette, glass, volumetric, 25 mL 117 Pipette, glass, volumetric, 30 mL

  • The general apparatus required for the test is determined by the specific test procedure used.

CHEMICALS REQUIRED 1,2-Dichloroethane (reagent grade or equivalent) Code 1666 CT-1 Buffer Reagent 1591 Methanol (reagent grade or equivalent) 322 Drying Reagent w/ plastic dipper 1271 ______________________________i ,

   ;_______________________________________iApparatus l Mote:                                                              and' chemicals not ava lable through Bet l'should be obtained through a local supplier.                                                                l l_____________________________________________________________________l DISCUSSION OF THE METHOD In this test procedure, methyl orange complexes with the active ingredients in Clam-Trol CT-1. This complex is extracted into 1,2-dichloroethane. The organic layer containing the complex in separated from the aqueous layer and dried with anhydrous sodium sulfate. The color intensity of the 1,2-dichloroethane layer is then measu od at 415 nm.

1Tablo 2 'D11utionof fer Calibration curvo Proparation (based on finni colution volumo of 1'11 tor)- Conc. mL.CT-1 Stock ag/L CT-1 solution added to desired. make 1 litar

                                                                       -0. 2                                          0.2 0.4                                           0.4 0.6-                                          0.6 0.8.                                          0.W 1.0                                           1.0 5.0-                                          5.0 10.0                                           10.0 15.0                                           15.0
                                                                     ~20.0                                           20.0 25.0~                                          25.0
3. Follow the procedure listed (utilizing the specific solution volumes that have been determined for the application) and-prepara a calibration curve.. Determine the absorbance of a blank
                                                      -solution ~using distilled-or deionized-water. This= blank can be subtracted from the sample absorbance or used to zero the photometer _so that the calibration curve goes through the origin.

f The calibration curve should be linear over the indicated ranges. NOTES- . 1. For maximum accuracy.the calibration curve should be checked by

                                                        'every operator using the test and should be verified a minimum of twice per month using a freshly prepared CT-1 standard.-
2. A blank measurement =must be recorded for each set of samples.
The blankJreading.may vary slightly, however the absolute.

difference between the sample and tte blank remains relatively constant.

              -3.                                           Aislight emulsion may form when using natural water samples.

Correct.for this bysusing a variation-in step 5 of the procedure. Shake the funnel'for 30 seconds-than allow to stand for 5 minutes. Gently: invert that funnel once then allow the funnel to stand for ( 5_ minutes (don't forget to vant the funnel) . L -14 . - ~.It:is important to vent the separatory funnel both before and L after shaking it.-otherwise, a_ pressure will build up in the L funnel'that can cause the stopper to be forced out of the top l of the funnel. E

5. It.is imperative that the sample cells are kept clean during the running.of,the test. It is recommended that'the cells are cleaned after each measurament.by the following procedures a)~ Rinse the call-three times with distilled or deionized water.
                                                                             'b) Rinse the cell three times with methanol.
 -------__&__   _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ . _ _                              .s_.-, a          .     .                         .,         e - , , , - . . , , ,,v 6- ,7 .

c) Finally rinse the cell three times with 1,2-dichloroethane to remove any methanol from the cell.

6. Chlorine causes a negative interference in the test. This can be eliminated by adding 0.1 N sodium thiosulfate (code 235) to the water sample before running the test. The amount to be added must be determined based on the concentration of. chlorine in the system.

For a 100 mL water sample containing 0.3 mg/L chlorine, 10 drops of 0.1 N sodium thiosulfate will remove the interference.

7. This method is based upon L. K. Wang and D. F. Langly, Ind.

Eng. Chem., Prod. Res. Dev., (1975) Vol. 14, No. 3, 210-212 t l

a Betz0mdam@oofm0 DETROIT EDISON FERMI II NUCLEAR PLANT NEWPORT, MI. ZEBRA MUSSEL STERILIZATION DECEMBER 28, 1990 PREPARED BY: 47 LEN WALL TECHNICAL SPECIALIST . 1

Betz0xdm89T0m0 _ TABLE OF CONTENTS A. INTRODUCTION B. PROCEDURES C. APPLICATION SYNOPSIS D. MONITORING AND RESULTS E. CONCLUSION F. APPENDIX i 2

Betz0xdm@r0m0 A. INTRODUCTION: The following is a synopsis of the recent zebra mussel steriliza-tion. This bi-annual sterilization is part of your macrofouling control program for the GSW and fire protection systems. The goal of this program is the control of zebra mussel infestation into these systems before the organisms reaches macrofouling sizes, thus preventing reduced efficiencies, increasing system reliability and eliminating potential downtime. 3

Betz0xaGm@Mm0

B. PROCEDURE

The following is a guideline for the CT-1 sterilization of the GSW and fire protection systems. These procedures were modified due to the system being down during the sterilization.

1) Run a CT-1 demand test of the water to be treated.
2) Run aseline and CT-1 residual standards for the analyti-cal test curve.
3) Place the system into recirculation mode.
4) Feed the CT-1 product to the suction side of the GSW circulating pumps. The product is fed via a positive displacement pump and through a sparger line. The exact product feedrate (gph) will be determined by a system demand and the number of circulating pumps in operation.

l

5) Feed the product such that at least 15 ppm. of product is
  • in contact with the GSW systems for a period of aprox. 12 to 18 hours. The application duration was based on a water temperature of 45 F.

i 4 l

7 Betz0xd m M m0 6)- .' Run . ~bi hourly- the

                                                                  'tes ts . on                 bio-box           monitor    and 5throughout              the ' treated systems              in     order to assure the product? concentration obtained is greater than 18 to                                        20       i ppm.
                         = 7 ')    Once'the GSW system concentration has been verified at 20 ppm'or greater,               flush the fire protection system,until a concentration of 20 ppm.~is- verifled                             at          the discharge.

7 Upon residual -verification,  : button up this system for a

                                 . period of at least eighteen hours.

8).'Once-;an eighteen- hour application to all systems has been achieved,. discontinue product feed. 9);Run a CT-1 test on.the pond water to determine if detox.

                                  ~ feed'is needed.              If required,.-feed appropriate quantity fof1 detox.

10)Run analytical- CT test to insure complete product detoxification. i- .

                          .11 ) Resume' normal system-operation once product is verifled-1::                                 'detoxifled.

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      'I C. APPLICATION SYNOPSIS:

The CT-1.-sterilization was initiated at 10:30 AM on November 29,

                    .1990. The: chemical' feed pump was set at approximately 19 gph.

This feedrate was based ~ on a . water demand of 2. 0 ppm (total t product feedrate of 25. 0 ppm. ) . and two GSW circulating pumps in. operation. LAt 12: 30 PM, analytical test results indicated a CT-1 residual of. f

26.9 ppm at the bio-box- (see monitoring section) outlet. .At this
                                                                                         ~

time (since.the CT-1: residual was greater than the minimum 20 ppm required):, various ' auxiliary cooling systems and the fire header-

                   .l system _were. valved.into service.                 The fire protection system was flushed '~until a residual of . greater -than 20 ppm. .was- achieved  _

J(26.4 actually achieved) L and then the system- was- -buttoned back

                   ! up.

The CT-1: feed was = continued until 5: 30. AM on November 30,.-1990. .

This feed' duration-amounte'd-to an-application duration of nine-
                    -teen hours.            This extended duration was necessary.due to the i
                   . lower ^ water ~ temperatures at the time of treatment (Note: The EJuly,.-1990 application-was for six hours and was based on a water
temperature of 70 F.) AsLyou can see from the feedrate chart
                    -and   graph,     the chemical feedrate stabilized around                          8.5         to   11 p

}_ 6-

Betz0xdms@Mm0 gallons per hour throughout the application. The lower feedrate was possible due to partial recirculation of treated water from the pond. The total product usage amounted to approximately 213.5 gallons of CT-1. The analytical results from the bio-box monitor outlet indicated that CT-1 residuale greater than 18.0 ppm. were achieved for the desired eighteen hour exposure (see chart and graph). Addition-ally, various samples from the GSW and fire protection system indicated a 18 ppm residual was achieved throughout. At 5:30 AM on November 30, 1990, the chemical feed was stopped. Based on previous application experience, two drums of detox were added to the pond in order to neutralize any active CT-1. Pond test at 8: 50 AM (confirmed at 9: 00 AM) indicated a CT-1 residual of less than detectable (< 0.1 ppm). This was within the permit limits and subsequently, the system was returned to normal opera-tional mode. l 7

Betz0xdm8Mm0 CT-1 RESIDUALS DATE SAMPLE ELAPSED CT-1 PT. TIME TIME ABSORBANCE CONC. 11/29/90 BI0 BOX 10: 30 AM 0.00 TREATMENT 0. 0 STARTED 11/29/90 BI0 BOX 12:30 PM 2.00 1.092 26.9 11/29/90 BIOBOX 1: 40 PM 3. 17 1.522 37.9 11/29/90 BIOBOX 2:30 PM 4.00 1. 3 12 32.6 11: 29/90 BI0 BOX 3:40 PM 5. 17 0.708 18.7 11/29/90 BI0 BOX 4:25 PM 5.92 0,770 18.7 11/29/90 BI0 BOX 6:00 PM 7.50 0.912 22.4 11/29/90 BIOBOX 9:00 PM 10.50 0.7 12 17. 3 11/30/90 BI0 BOX 12:00 AM 13.50 0.892 21.8 11/30/90 BI0 BOX 1: 15 AM 14.75 1.186 29.3 11/30/90 3:15 AM 16,75 1.157 28.6 11/30/90 5: 15 AM 18.75 1.522 38.8 11/30/90 BIOBOX 5:30 AM 19.00 TREATMENT STOPPED 11/30/90 POND 6:00 AM 19.50 DET0X ADDED 11/30/90 BIOBOX

  • 6:40 AM 2 0, 17 0. 19 1 0.84 11/30/90 POND
  • 8:30 AM 22.00 0.058 0.13 11/30/90 POND
  • 8:50 AM 22.33 0.047 < 0.1 11/30/90 POND
  • 9: 00 AM 22.50 0.042 < 0.1
  • LOW LEVEL TEST ,

OTHER PTS. DATE SAMPLE CT-1 PT. TIME ABSORBANCE CONC. 11/29/90 GSW HEADER 12:30 PM 0.362 8.3 11/29/90 FIRE HEADER 1: 40 PM 0.926 22.7 11/29/90 FIRE HEADER 3:30 PM 1. 07 1 26.4

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                                                      . CHEMICAL USAGE                                                                        ,
                                                                                                                                            ~1.

w FEED TOTAL ELAPSED RATE USAGE DATE- 1 TIME . TIME (GPH) -(CUMULATIVE)

                -- 1~1/29 /90 : 10: 30 AM                             0.00                      START                          ---            ;

11/29/90? 12:30 PM 2.00 20.4 40.8 J ' 11/29/90: 4:51.PM 6.35 8.7 78.6 11/29/90- 5:40 PM 7. 17 :12 :2 88.6 11/29/90- 6:40 PM. 8. 17 10.2 -98.8 11/29/901 -7:50 PM 9.34 10.2 110.7 ' 111/29/90- 8:50 PM '10.34 8.5 119.2

                   -11/29/90            9i20 PM                      10.83                        10.2                       124.2
                   '11/29/90            9:50 PM                     11.34                          8.5                      -128.5 11/29/90        11: 50 PM                      13.34                        11.9                       152.3-

.' '11/30/90' 12:50 AM 14.34 10.2 162.5 11/30/90' 1: :20 . AM 14.83 10.2 167.5 11/30/90 1: 50 ? AM 15.34 10.2. 172.7 , 11/30 /90 ~ 2:55 AM. 16.42 11.0- 184.6~ 11/30/90- 4:00.AM- 17.50 11.2~ 196.7

11/30/90: 5:30 AM' 19.00' 213.5-sTOTAL: - 213. 5 G ALLONS CT r i s h 1 l -.

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Betz0xdm@r0m0 MISC, DATA DATE TIME WATER TEMP. 12/29/90 6:00 PM 12 C 11/29/90 9: 00 PM 12 C 11/30/90 12:00 AM 12 C

Betz0xdm@@r0m0 D. MONITORING AND RESULTS: The CT-1 application effectiveness was monitored through the use of a flow-through bio-box. This piece of equipment is a plexi-glass container with six separate compartments in it. It was installed such that water flow from the GSW header was continual-ly passing through the unit. In this way, the test mussels would see the same conditions as the systems being treated. The bio-box was installed three days prior to the start of the system sterilization and approximately 300 zebra mussels were

        -placed in the various bio-box compartments.                                         These mussels had been in a " control" bio-box for a period of five weeks in order to acclimate them to the system and so that they would resume normal feeding similar to any mussels in the systems to be treat-ed. Also, any stressed mussels that died off could be removed and a control group of mussels would be available for any mortal-                                         ,

it.y comparisons (untreated). The treated mussels would be monitored for latent mortality once the sterilization was com-pleted. The mussel mortality achieved was 85%. This corresponded to 275 dead mussels out of a group of 323 total. As you can seen from I l 8

l l Betz0xdx8970x0 the enclosed graph and chart, mortality rates werc ~70% after 1 week, ~80% after two weeks, and a final count of 85%. The first two counts were approximations due to the problems of counting dead mussels while leaving others unaffected. The time lapse between the stoppage of treatment and mortality is due to the latent toxic effect of the CT-1 molluscicide. Finally, it should be mentioned that there was less than a 1% mortality in the untreated control group. 9

Betz0xdm@Mm0 ZEBRA MUSSEL MORTALITY ELAPSED TIME  % MORTALITY

                   'l WEEK                                                     70 "

2 WEEKS 80 % 3 WEEKS 85 %

l l BetzDeom9 nmo . . D, _ _,_ ca ,

                                                                                \

l ZEBRA MUSSEL MORTAUTY: NOVEMBER, 1990 9 0 ,' __M" . _ t n

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ONE TWO THREE ELAPSED TIME (WEEKS)

c Betz0x&Ruktim0 E. CONCLUSION: The CT-1 sterilization of your GSW and fire protection systems achieved the product dosage rate of at least 18 ppm for the de-sired eighteen hour exposure period. This application resulted in 213.5 gallons of CT-1 and 600 pounds of detox being fed. This product usage corresponds to a total system sterilization cost of only $4592 ($3992 for CT-1 and $600 for detox). The monitoring of the sterilization effectiveness resulted in a zebra mussel mortality of 85%. With the continued monitoring of your systems for zebra mussel fouling potential and correlating this monitoring with subsequent CT-1 applications, your system will be protected from macrofouling. Tne net result is increased system reliability, optimum efficiencies and prevention of downtime. l l l l 10

Betz0xdmMm0 l BASELINE TESTS HIGH RANGE CONCENTRATION ABSORBANCE 0 ppm 0.043 10 ppm 0.438 20 ppm 0.817 LOW RANGE CONCENTRATION ABSORBANCE 0 ppm 0.035 0.2 ppm 0.0?1 1.5 ppe 0.301 3.0 ppm 0.628 1 {

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F. Appendix Clam-Trol CT-1 Analytical Method t i ) l i

e l . [ This method must be customized to each specific application. This is done by varying the volumes of sample, CT-1 Buffer Reagent and 1,2-dichloroethans used in the procedure. Table 1 lists several l l combinations of reagents that can be used to obtain three different ' test ranges. When optimizing the procedure, if a higher absorbance is needed, the volume of sample should be increased or the volume of 1,2-dichloroethans should be decreased. When increasing the sample volume it may be necessary to increase the volume of CT-1 Buffer Reagent used. For sample volumes of less than 150 mL use.10 mL of the l CT-1 Buffer Reagents for volumes between 150 and 300 mL use 15 mL of CT-1 Buffer Reagen?.. When determining the amount of 1,2-dichloroethane to use it is necessery to make sure that the volume used is large i enough to have sufficient 1,2-dichloroethane to leave a small plug of solvent in the separatory funnel when removing the bottom layer of solvent while having enough solvent to fill the optical call properly. r V GENERAL PROCEDt'AE FOR UST I I l Use a well ventilated or hooded area to run the test.l1 l ?.1 ways use a safety bulb when pipetting liquids. i i......................................................l

1. Transfer an aliquot of the water sample to a separatory funnel L (the sample). Transfer the same volume of distilled (or deionized) water to a second separatory funnel (the blank) .

It is only necessary to run the blank once for each set of samples tested (see notes 1 and 2). Table 1 suggested volumes for Various Ranges of CT-1 Range volume (mL) volume (mL) volume (mL) optical ag/L CT-1 CT-1 Buffer dichloroethane sample cell size 0.2 - 3.0 15 10 250 1.0 cm

  • 1.0 -25.0 10 30 50 2.5 cm **

0.2 - 1.0 10 15 100 5.0 cm ***

  • The 1.0 cm cell can he used with Hach spectrophotometers utilizing a 1 ca cell adapter.-
        ** The 2.5 cm call is the standard Hach 1 inch call (Betz code 2601) that can be used-with Hach spectrophotometers.                                                   ,
         *** 5 cm cells are not available for the Mach photometers. Many laboratory spectrophotometers require an adapter to accommodate 5 cm cells. Check with the instrument manufacturer.
2. Add the-CT-1 Buffer Reagent to both the sample and the blank (see note 6).
3. Using a pipette, add the 1,2-dichloroethane to both separatory funnels.
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4. Insert the stoppers in each of the separatory funnels, invert and briefly open the stopcock to vant the funnels (see notes 3 and 4).

When venting the funnels point the tip of the funnel away from yourself and others.

5. Shake the funnels moderately for 30 seconds, vent the funnels, then allow to stand for 10 minutes (but no longer than 15 minutes).
6. Collect the lower layer from each funnel (the 1,2-dichloroethane)  !

in 50 mL beakers. It is most convenient to allow a small amount of the 1,2-dichloroethane (~1-2 mL) to remain in the funnel. This prevents any significant removal of water from the separatory funnel when the 1,2-dichloroethane is being removed.

7. Using the plastic dipper, add 2 scoops of Drying Reagent to each beaker and stir with a glass rod for 10 seconds (but no longer than 20 seconds). .
8. Wait approximately 1 to 2 minutes (but not more than 5 minutes) then carefully decant the extract off of the drying reagent into an optical cell.
9. Set the spectrophotometer at 415 nm and zero with 1,2-dichloro-ethane. Measure and record the absorbance of the blank and the sample.

Sc. The sample absorbance minus the blank absorbance is used to l determine the concentration of CT-1 in the sample. From a i prepared calibration curve, determine the CT-1 concentration in the sample (see Calibration Preparation).

11. Clean the cells after each measurement (see note 5).

CALIBRATION PREPARATION

1. Prepara a 1000 mg/L CT-1 stock solution by accurately weighing out 1.00 gram of CT-1 into 1 liter of distilled or deionized water,
2. Pipet designated volumes of the stock solution into 1 liter volumetric flasks. These are the standard solution to be used ,

in preparing a calibration curve. Use Table 2 to determine the appropriate dilutions to make of the sto:k solution for each specific application. 1 ~

1 { CLAN-TROL CT-1 < METHYL ORANGE METHOD f i APPARATUS REQUIREL f Beaker, glass, 50 mL (x2) Code --- Cylinder, graduated, 25 mL 2622 runnel rack, separatory 936 i Punnel, separatory, w/ teflon stopcock, 250 mL (x2) --- - Glass rod. 114 optical cell, (x2) -.. spectrophotometer ... GENERAL APPARATUS

  • cylinder,-graduated, 100 mL code 121 cylinder, graduated, 250 EL .

917 3 Flask, volumetric, 1 litar, glass (x4) 935 t Pipette, glass, volumetric, 1 EL 866 Pipette,_ glass, 1 mL, graduated 140 Pipette, glass, volumetric, 2 mL --- Pipette, glass, volumetric, 5 mL 124 Pipette, glass, volumetric, 10 mL 123 Pipette, glass,. volumetric, 15 mL 861 1 Pipette, glass, volumetric, 20 mL --- Pipette, glass, volumetric, 25 mL 117 Pipette, glass, volumetric, 30 EL -~~ '

  • The general apparatus required for the test is determined by the specific test procedure used.

CHEMICALS REQUIRED 1,2-Dichloroethane (reagent grade or equivalent) code 1666 CT-1 Buffer Reagent 1591 Methanol (reagent grade or equivalent) 322 Drying Reagent w/ plastic dipper 1271

g. . .=====.....: --
                                                    ..........................................l         ,

l Note: Apparatus and' chemicals not available through Betz Lab Supply l l ehould be obtained through a local supplier. l

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             -DISCUSSION OF THE METHOD In this test procedure, methyl orange complexes with the active ingredients in clam-Trol CT.1. This complex is extracted into 1,2-dichloroethane. The organic layer containing the complex is separated from the aqueous layer and dried with anhydrous sodium sulfate. The color intensity of the 1,2-dichloroethane layer is then measured at 415 na-                                                            ,

Tablo 2: Diluticns for Calibration curvo Proporation (baced on finni colutien volumo of 1 liter) i Conc. EL CT-1 Stock j mg/L CT-1 solution added to desired make 1 litar 0.2 0.2 0.4 0.4 O.6 0.6 0.8 0.8 1.0 1.0 5.0 5.0 10.0 10.0 15.0 15.0 20.0 20.0 25.0 25.0

3. Follow.the procedure listed (utilizing the specific solution volumes that have been determined for the application) and prepara a calibration curve. Determine the absorbance of a blank solution using distilled or deionized water. This blank can be subtracted from the sample absorbance or used to zero the photometer so that the calibration curve goes through the origin.

The calibration curve should be linear over the indicated ranges. I NOTES

1. For maximum accuracy the calibration curve should be checked by every operator using the test and should be verified a minimum of twice per month using a freshly prepared CT-1 standard.
2. A blank measurement must be recorded for each set of samples.

The bitnk reading may vary slightly, however the absoluta difference between the sample and the blank remains relatively constant.

3. A slight emulsion may form when using natural water samples.

Correct for this by using a variation in step 5 of the procedure. Shake the funnel for 30 seconds than allow to stand for 5 minutes. Gently invert the funnel once then allow the funnel to stand for i 5 minutes (don't forget to vant the funnel).

4. It is important to vant the separatory funnel both before and after shaking it. Otherwise, a pressure will build up in the funnel that can cauen the stopper to be forced out of the top of the funnel.
5. It is imperative-that the sample calls are kept clean during the running of the test. It is recommended that the cells are cleaneo after each measurement by the following procedures a) Rinse the cell three times with distilled or deionized water.

b) Rinse the cell three ti, mas with methanol.

c) Finally rinse the es11 three times with 1,2-dichloroethans to remove any methanol from the cell.

6. Chlorine causes a negative interference in the test. This can be eliminated by adding 0.1 N sodium thiosulfate (code 235) to the water sample before running the test. The amount to be added must be determined based on the concentration of chlorine in the system.

For a 100 mL water sample containing 0.3 mg/L chlorine, 10 drops of 0.1 N sodium thiosulfate will remove the interfarance.

7. This method is based upon L. K. Wang and D. F. Langly, Ind.

Eng. Chem., Prod. Res. Dev., (1975) Vol. 14, No. 3, 210-212

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