ML20065R280

Forwards 940420 Request to Use Sodium Bromide as Treatment Chemical in Cooling Towers.Reporting Did Not Occur Same Time Change Submitted & Will Be Listed as EPP non-compliance in Annual Environ Operating Rept for CY94

ML20065R280
Person / Time
Site:	Catawba
Issue date:	04/28/1994
From:	Rehn D DUKE POWER CO.
To:	NRC OFFICE OF INFORMATION RESOURCES MANAGEMENT (IRM)
References
NUDOCS 9405100315
Download: ML20065R280 (18)

Text

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• DukeIbwer Company D. L Rms

' Catawba Nuclear Generation Department Vice President 4800 ConcordRoad (803)M13205 Ollice York, SC29745 (803)Ml3426Fux i

DUKEPOWER

., l 4 April 28,1994 j U. S. Nuclear Regulatory Commission ATTN: Document Control Desk

Washington, DC 20555 l

Subject:

Catawba Nuclear Station i Docket Nos. 50-413 and 50-414 ,

j Environmental Protection Plan Reporting I The Environmental Protection Plan (Appendix B to the Catawba Facility Operating .

License) requires that proposed changes to the NPDES Permit be reported to the )

l NRC at the same time the request is submitted to the permitting agency.

Attached please find a request to use sodium bromide as a treatment chemical in i the cooling towers submitted to the South Carolina Department of Health and Environmental Control April 20,1994.

This reporting did not occur the same time the change was submitted and will be i

listed as a Environmental Protection Plan non-compliance in the Annual l Environmental Operating Report for calendar year 1994. i t

Very truly yours l

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! $D.L.Rehn N u ( w) j I Attachments a

i JTH/EPP 1994 L

i900G2 f j 9405100315 940428 PDR ADOCK 05000413 /l P

} nma~rmma PDR l/ l ' p q v

U. S. Nuclear Regulatory Commission April 28,1994 l Page 2 xc: S. D. Ebneter Regional Administrator, Region 11 R. J. Freudenberger Senior Resident Inspector Catawba Nuclear Station R. E. Martin, ONRR

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Oube n>urt Company l

• Ger!rrahan Sernces Department

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In t'lliagers imy Road llantennile. NC 2M?8-?929 DUKEPOWER April 20,1994 '

l Mr. Timothy M. Eleazer l Industrial and Agricultural Wastewater Division South Carolina Department of Health and Environmental Control 2600 Bull Street Columbia, SC 29201 j

Subject:

Catawba Nuclear Station -NPDES Permit No. SC0004278 l Sodium Bromide Usage in RC Cooling Towers File: CN-702.13 i

{

Dear Mr. Eleazer:

This letter is to request permission to use sodium bromide in the condenser circulating water system (RC) cooling towers at Catawba Nuclear Station on a permanent basis.

To support this request please find as Attachment #1 a report titled Toxicity ofCooling Tower Water Following 2:1 (Chlorine to Bromine) Treatment which indicates the solution to be non-toxic.

Duke Power also requests that references made to Free Available Chlorine (FAC) be changed to Free Available Oxidant (FAO) for the RC cooling towers. The existing testing requirement for the RC cooling tower blowdown line (Outfall 005) is for FAC.

(See Part III Item #16 and P.13 cr 31) To allow for the usage of sodium bromide, it is i

requested that references to FAC be changed to FAO within the permit. When chlorine is the only oxidant utilized, then the FAC is the same as the FAO. However, now that an additional oxidant is to be used, FAO is the more appropriate parameter to reference in the permit. Catawba is presently using the DPD Colormetric Method for determination of Free Available Chlorine. Per Standard Methods, (4500-Cl), this analytical method will detect both free chlorine and free bromine.

Background Information Duke Power Company requested permission to begin using sodium bromide on a trial basis in one of the two RC cooling towers systems at Catawba Nuclear Station in a letter dated May 27,1993. The State responded to this letter and requested toxicity

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l testing data be provided on the sodium bromide and sodium hypochlorite solutions it i a letter to Duke Power dated September 16,1993.

Duke Power then proposed to State by fax (See Attachment #2) a request to perform toxicity testing on the sodium bromide and sodium hypochlorite solution as it would be discharged to Lake Wylie. The test was then conducted and the results are provided in Attachment #1.

Please note that Attachment #1 references Calgon H-940 which is - a Calgon Corporation product. This is only a typical product name and other suppliers of sodium bromide will/may be selected in the future.

For you convenience, please find as Attachment #3 the original description of sodium bromide usage. This is the information which is required in Part III Item 9 of the NPDES permit.

Summary To summarize, Duke Power is requesting approval to use sodium bromide as a .

maintenance chemical in the RC cooling towers. The original request was fo trial usage. However, if this initial trial is considered successful, Catawba would like to immediately begin using the sodium bromide without seeking further approvals.

It is requested that referenc i the permit for Free Available Chlorine (FAC) be changed to Free Available  ;AO) as described above. The existing permitted limits for FAC should be a, FAO.

The solution of sodium bromide and sodium hypochlorite will not be discharged directly to Lake Wylie. The compounds will be allowed to decay until the concentration of FAO (as measured with presently certified DPD Colormetric Method fo'r determination of FAC) in the RC cooling tower being treated drops to less than current permit limits. Once a less-than-detectable FAO is reached in the RC cooling tower being treated, residual byproducts will be discharged to Lake Wylie via Outfall 001 by means of the cooling tower blowdown line (Outfall 005). Therefore, only the by-products of these compounds will be seen in tlx 6.al discharge.

The toxicity testing provided shows these by-products to be non-toxic. The toxicity testing was performed under worst case scenanos. Typical field conditions are eight l parts of once through RC cooling water to one part of RC cooling tower blowdown ,

water (1:8). The toxicity tests performed at various ratios as low as 1:2 were not toxic. '

Your approval is requested as soon as possible in order to begin using the sodium l bromide within the RC cooling towers. The use of sodium bromide, if successful, will substantially reduce the volume and concentrations of maintenance chemicals used in l the RC cooling towers.

l

J Should you need additional information to support this request please feel free to call John Estridge at (704) 875-5965 or Christine Odom at (704)8754201.

Sincerely, ,

om. arter, echnical System Manager Environmental Division, Water Protection jte/311 Attachments l

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ATTACHMENT #1 1

Toxicity of Cooling Tower Water Following 2:1 (Chlorine to Bromine) Treatment 1

khn S. velte. Duke Power Company. Envirmmental Division.13339 Itagm Ferry Rd.. Iluntmville. NC 28078 EXECUTIVE

SUMMARY

I A sample of cycled-up (Le., concentrated via recirculation and evaporation) cooling ,

water from a Catawba Nuclear Station (CNS) cooling tower was treated with I chlorine to a free residual of 3 ppm. Half as much Bmmine was then added to the sample (Le., a ratio of 2:1). The sample was stirred at 40.6-43.3*C_(105110*F) to simulate the physicochemical conditions typical in a cooling tower, until the

concentration of free available oxidant declined to less than background. The sample was then diluted with various volumes of intake (raw) water from the CNS intake (Le., Lake Wylie) and tested for toxicity. CNS personnel have estimated that cooling tower " blowdown" waste is typically diluted with raw water to 11.2% waste (a ratio of 1

8) during discharge. This test of simulated waste demonstrated tha; no toxicity occurred among Ceriodaphnia, even when exposed to 33.4% waste (a 1:2 dilution). These test results support the proposed maintenance chemical trial of sodium bromide (Calgon H.940) in conjunction with sodium hypochlorite to control biofouling. -

INTRODUCTION A bench test designed to simulate the behavior of sodium bromide under cooling tower i conditions was developed by Duke Power Company. The bench test was used to produce a simulated waste that would allow the evaluation of toxicity from sodium bromide, bromine residuals, and other waste components in the projected " worst-case" ratio of chlorine (Cl) to bromine (Br). South Carolina Department of Health and Environmental Control (SCDHEC) officials identified the need for this information (to ensure that the receiving water body would not be harmed) as a condition for approval to conduct a maintenance chemical trial with sodium bromide.

MATERIALS AND METHODS

. Samole Preparation A 4-L sample of CNS cooling tower water was collect as it spilled to ground level in a Unit-2 cooling tower. The sample had been cycled up to normal blowdown l

concentration but no maintenance chemicals had been added. Immediately following the ,

collection of this sample,10 L of subsurface CNS intake water were collected for use as  :

i control and dilution water during the planned test. Both samples were placed  ;

immediately on ice for transport, logged into the Biomonitoring Lab at < 4*C, and held  !

in a refrigerator at 0 to 4*C thereafter.

Duke Power Company's proposal is that Br in the form of sodium bromide be added to the CI (presently added as sodium hypochlorite) to improve biofouling control while

potentially reducing the amount of Cl presently used. Bromine for this test came from a l

i product called Calgon H-940@ (Calgon Corporation) which is 40% sodium bromide.  !

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I For convenience, the Ci source was Chlorox@ Bleach (Chlorox Company) which contains 5.25% sodium hypochlorite. CNS uses an industrial source of sodium hypochlorite that differs only in the percentage of active ingredient, so with appropriate dilution, no meaningful chemical difference in the lab and field situation existed.

The procedure for sample manipulation was prescribed by Duke Power Nuclear ,

Chemistry personnel to produce a bench-scale sample of effluent that would simulate waste from the cooling towers if treated with the proposed biofouling agents. Hat procedure is summarized here:

1. Approximately 2.5 L of cooling tower water was warmed quiEkly to 43.3 C in a water bath. Exactly 2000 mL were measured from the warmed sample, and poured into a 2000 mL glass beaker.

2. The beaker was set on a magnetic stirrer and a large Teflon-coated stir bar was ,

placed in the sample. These components were set up inside a drying oven which l had previously been calibrated to operate at 43.3"C. The oven provided an air-l tight, dark, and thermally stable environment.

! 3. A digital thermometer with remote temperature probes was installed with one probe in the sample being stirred and one measuring the air temperature within the oven. ,

4. The sample was dosed with 6 mL of a 1000-ppm Cl stock solution; sample temperature at this point was 403*C. He oven was sealed following this addition .

and continuously thereafter except when sample meas'ures or manipulations were underway.

5. After 15 minutes, the free available oxidant (FAO) of the sample (i.e., chlorine) was measured with a colorimetric procedure (Hach Company). This required the l

removal of 25 mL of sample via pipette. The measured FAO was 3.0 ppm.

6. Three mL of a 1000-ppm Br stock solution was added.' The sample was then allowed to react in the apparatus for 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> and 45 minutes. Another 25 rnL .

subsample was withdrawn and FAO in that sample (i.e., chlorine and bromine) was l measured at 0.2 ppm. The temperature had increased to 42.5*C.

7. Five hours and 15 minutes after Br addition, a third withdrawal of 25 mL showed I that FAO had declined to 0.11 ppm; temperature was 43.1 C.

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8. The sample treatment was stopped after 7 hours8.101852e-5 days <br />0.00194 hours <br />1.157407e-5 weeks <br />2.6635e-6 months <br /> and 5 minutes (post Br addition) when the fourth and final 25-mL aliquot revealed that FAO was < 0.1 ppm. A simultaneous test of untreated cooling tower water gave an FAO of 0.12 ppm, so it was assumed that dissipation of Cl in the manipulated sample was complete.

Achievement of this endpoint, as determined by CNS Chemistry personnel, is necessary before discharge from the cooling towers is begun. The final temperature reading was 43.3*F.

9. The manipulated sample was refrigerated (0 to 4*C) in a sealed polyethylene container, with no head space, for toxicity testing.

Page 2 of 5 i

Toxicity Evaluation Toxicity testing was begun the fellowing day (i.e., the cooling tower sample was 50 -

- hours post collection and approximately 17 hours1.967593e-4 days <br />0.00472 hours <br />2.810847e-5 weeks <br />6.4685e-6 months <br /> post manipulation; the CNS intake dilution water sample was approximately 49.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br /> post collection). Toxicity test '

methods were those prescribed by the U.S. Environmental Protection Agency (1989) and SCDHEC (1989). The procedure was a definitive Ceriodaphnia urce Brood Survival and Reproduction Toxicity Test with a control and series of four treatments. Dilutions of the simulated cooling tower waste were prepared on test days 0,2, and 4; and solutions in test cups were renewed daily, Cooling tower water that is discharged during

" blowdown" of the towem is typically diluted at a ratio of 1:8 with raw water that is pumped through the station. That ratio was used as the basis of the treatment series in an attempt to establish a " dose-response" relationship between the waste, and the test organism (Ceriodaphnia dubia).

l RESULTS The measured sample volume after manipulation was 1827 mL Considering the starting l volume of sample, C1 and Br stock solution additions, and FAO sample withdrawals,82  !

mL were missing due to evaporation. The timing of additions and withdrawals 1 complicates the interpretation of evaporative effects on the sample. Evaporation had the effect of concentrating the test sample by less than 5% under these test conditions. That -

effect is considered negligible for this study because ongoing evaporation is a function of full-scale cooling tower operation too. De comparability, however, of evaporation'-

modeled in this study with that which actually occurs in the cooling towers was not -

determined.

The following table summarizes the survival and reproduction that occurred during the toxicity test in the control and treatments. The tested ratios of cooling tower waste to raw intake water (i.e., 1:16.1:8,1:4, and 1:2) are presented as waste percentages to simplify interpretation.

i Percent of Cooling # C. dubia i

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Tower Waste in Females Percent Total Young Mean Young g

Lntake Water Exposed Survival Produced Per Female 0 (Control) 10 100 302 30.2 5.8 10 100 283 28.3 11.2 10 100 295 29.5 20.0 10 100 293 29.3 33.4 10 100 297 29.7 I g.

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l These data were evaluated as specified by USEPA for significant (alpha = 0.05) survival and reproduction effects. The lack of any mortality during the test negated the need to look for survival effects. The untransformed data were found to be normally distributed according to a Shapiro-Wilks Test. Bartlett's Test further confirmed that the data are homogeneous. Consequently, Dunnett's T-Test for determining significant differences l between the reproductive mean of the control and all treatments was applied. No

! significant differences between the control and any treatment were found. Copies of the raw test data sheets and a printout of the statistical evaluation are attached as Appendix A.

DISCUSSION The lack of a " dose-response" curve from this data preclude the determination of the 7-day EC20 value (as specifically requested by SCDHEC) or any other chronic endpoint.

The data do, however, demonstrate that the simulated cooling tower waste was safe for .

C. dubia even at a concentration that was 3 times greater than is expected under actual station discharge conditions. There was no significant difference observed in C. dubia survival or reproduction between the control, which consisted of 100% intake water, and any treatment (the highest of which was 33.4% cooling tower waste). A full-scale trial l

of sodium bromide (used in a manner consistent with the protocol described in this report) would be environmentally compatible based on this test outcome.

REFERENCES CITED -

South Carolina Department of Health and Environmental Control.1989. South Carolina Environmental Laboratory Certification Criteria: Biological Parameters.

Columbia, SC U.S. Environmental Protection Agency.1989. Short-term methods for estimating the chronic toxicity of effluents and receiving waters to freshwater organisms. 2nd i ed. EPN600/4-89/001. Cincinnati, OH I l

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SP0394J2 Ceriodophnic dubla Data Shast for 2:1 Cl to Br Cooling Tower Wasta Chronic Toxicity Tsst

, Proceduto Number 810 260.0 l March 1994 CONTROL (100% Row Water) Replicate 1 2 3 4 5 6 / 8 9 10 vouno N *cn commenis l p.] *C

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( L3 ) (W) (t% ) ( L3 ) ('A)

Numbers in potentheses indicate the otiginofing brood sites. All organisms in a rephcote are ftom the some adult.

H Record in order gNen. a) L = Alive. b) 0-30 = Number of live young, c) E e A borted embryos observed D= Dead (0-30) = Number of dead young l

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SP 0394J.2 Csriodophnic dubio Test Information and Activity Log for 2:1 Cl to Br Cooling Tower Waste Chronic Toxicity T:st. Procedura Number BIO-260.0 ,

Ceriodophnla dubio Young Production Doto - DPC Lab Cu'tures Obution water for odu!!: - 20% Perrier in Mim - Q woter: PER - WAS Adultssegregated: Date 3/&V'Q The MA Int!bh[Y) .

Check odutts eight hours or less ofter the segregalon Emo for ihird or later broods of eight or more neonales.

Adults checked for neonotes: Date 3 /3'1/*Q The MG InRbis MD Troy G Number of occeptoble broods M Ntsnber of Neonotes W ics metoin extra neonates unts after the one hour post-Iniflation mortaW check has been completed.

Test information Test initb!lon: Dore 5 /w/M Time ttC45 Test Terminatbn: Date / / Time Test beation: Duke Power Company Blomonitoring Laborofory.13339 Hogers Ferry Rd..Huntersvtle. NC 20075 Age of test initiation < Go h incubator ID / sher A/a Renewotfrequency - Do!y Test vessel Composition = Polystyrene. Anchor Hocking PI-I CopocRy = 30rr.L Solutionvolume = 15mL Day Datuent Treatment Treotment Feec no Temperature inniotion. Transfers Counts Survivol &

tPtt*t Preparoflon Delivery Transfer or by by Counts N RAW by by 100 ut YiC 100 ut Aigoe Measured Recorded terminotion Recorded Nic ti. RC (YTC - )/Init. (SC - }/init. by . by Time by WN

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• Neonores Checked I h offer initiation for rondom morfo8fles cIEC.) - reploCS rondom mortolfles and doctInent in the Comments teCilon Cs oppropriate.

Diluent Cycled 43p Coollnc Tower Wcter (recieved 03-2844)

Toxicaris Br (as 40% NoBc Colgon H440) and CI(os 5.25% NoOCt Chlorox) Source = Nuclear Chemistry (Steve Davenport)

Cl Stock Solution Preparation: 4.0 mL product d!!uted to 100mL <lth dNent = 1000 ppm Ci stock soution Br Stock Solution Preparation: 0.322 mL product diluted to 100mL with d!iuent = 1000 ppm sto k soution Duution Scheme Recorded by A&I m 1. h X-X1 1 Checked by 2 d bt.b 3[29/9y .

DUte 167 mL of frected coolhower water to 500 mL wth diluent for a finalconconfration ci 12 333 N. f)Au M - D #/a Dkte 100 mL of treated cooing tower water to S00 ml wth diluent for a f!not concentrotion of 1:4

[ ' '  : q c: O "

ao *A Dilute 56 mL cf trected cooling tower water to 500 mL with diluent for a finct concentration of 1:8 = 'it.p{ ,- i t . t"j.

DAte 29 mL of treated cooling tower woter to 500 mL with di!uent for a finoi concentr'o tion of 1:16 :93I .- 3'f, Dote O mL of treated cootno tower water to 500 mL with d!tuent for o final concentrotlon of 100% tow water Control =gg3 ~ O%

Food YTC odjusted to 1800 mg/L totol solids. Procedure Number BO48.0. Daphnid YTC Food Preparotton Setenastrum capricornutum ceu density = 3A2 a 10E7. Procedure Number 8044.1. Moss Algot Culture for Daphnid Feeding Temperature test temperatures measured by device: ELENV- 3t M . Procedure Number BIO-2CO.O.Temperoture Determinotion DO NOT DISPOSE OF SOLUTIONS OR DILUENT UNTIL REPOT*NtMS HAVE BEEN APPROVED Finot Dato Sheet Check by - O- Date '/ [W 9evised 3/29/94

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SP0394J2 .

2:1 Cl to Br Cooling Tower Waste Toxicity Test 7-Day Carlodaphnia Survival and Reproduction Test Water Chemistry Data Control . .., M

. Parameter Day 0 Inittels Day 1 l Initials l Day 2 l Initials l Day 3 l Initials l Day 4 l Initials l Day So llnitials l Day 6 Initials Day 7 Initials D.O. (mgt) (initia0 86 X5M 8.3 l19) l 9,7 l kW l % .7 lt(A6 l M. 7 l 67C l 8 Mb" l kb^I l (Fina0 8. t [Af 83 l MA) l 9.3 lVKAFl RM l 01C l 6.h l %N l R5 lr h l pH (Units) (Initia0 7.T MA/ 7, (, l # 'd l75 l MW l 7.4 l KAF l 7. 6 lOfCl 7.V l MN l V

77 41C b

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(Final) ') . Q 7.7 ,.

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Tot Alk.(mg/L) 3 f T. 4

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Tot.Hard (mg/L) dS.T 9 "L.

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Ij ?.f Cond. (uS/cm) ,

1 Part Waste : 8 karts Raw Water (expected discharge conc.)

, Paramster Day 0 Initials Day 1 l Initials l Day 2 l Initials l Day 3 l Initials l Day 4 l Initials l Day 5 l Initials l Day 6 Initlais Day 7 Initials D.O. (mg/L) (Initia0 B.5 M/ O.l l VA l85 l M\/ l 8.S l VAF l L ')  ! OfC l85 lW l (Final) 8,0 )8Al 9.3 l% l %.3 l WAf l ff.9 l 01&l 8.3 l16V l @.5 lyb l pH (Units) (Initia!) '7. b T.9/ 7.6 l M l 7. 6 l VW l 7.5 l 1(AP l 7,5 l ort l 7. 4 l yo I (Finan 71 M '

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u .p p7g 7, ~ ,, y4 yg M

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Tot. Alk (mg/L) y a . lL , , . , . .

v y -f.; 3,,]Mg{fgpq h ~ , . J l.3 *. ; , . . , (. . _ .,}

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Tot.Hard (mq/L) 30. Ls

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Cond. (uS/cm) 13 0 7,4A) . . _

W _ _'M W Ai U

+

1 Part Waste : 2 Parts Raw Water (high conc.)*

Parameter Day 0 Initials Day 1 l Initials l Day 2 l Initials l Day 3 l In!tlets l Day 4 l Initials l Day 5 l Initials Day 6 Initials Day 7 Initials D.O. (mg/L) (initial) 3.4 kraj g,g l gA) l 6. (. l yfj l g,g l yAF l Q,7 l grCl 8, Q lW

, (Final) 8.O 'f/f] 9.';L lM l S.3 l" b/AF l Cf. 3 l CJL l R.1 l M l 8.y l Urpm pH (Units) (Initia0 'l . 7 VA/ 7.7 l%J l 7 7 liM/ l 7 . 84 l VAF l 7. 6 l "$10 l ~L L3 l 16Al V

(Final) ] . '7 T/.A.) -

41C .. . , 7.7 I ".

7ot. Alk.(mq'L) MS M .

a f. -

' ' % -.43- ; . _ i ;, ~ ,, fg)

.M.T M '

A i%sid

~

Tot Hard (mg/L) -

. .. j .., j*

W*

. , ~

~~'

Cond (uSicm) 'M t M _.f ~, _ _ _. ._ _ . . . / _ __ c .

U l

• In the event that mass mortality makes this concentration inappropriate, monitor the next highest concentratfor' and note when this occurs on the data sheet i

1

2:1'Cl TO Br COOLING TOWER WASTE CHRONIC TESF, }0:07 Thursday, April 7, 1994 l 'CNS RAW (INTAKE) WATER DILUENT ?B M JTS. VELTE D j FILE NO.: SP0394J2 NO MORTALITY OCCURRED, THUS FISHER'S EXACT TEST FOR SIGNIFICANT MORTALITY' i DOES NOT APPLY. '

SHAPIRO-WILKS TEST FOR NORMALITY OF UNTRANSFORMED REPRODUCTION DATA

• Analysis Variable : YOUNG

---

TREAT = control --------------- -----------.-

Minimum Maximum Sum Mean Std Dev

---

__......__________.... .___________..________..__________--- =__ l 27.0000000 33.0000000 302.0000000 30.2000000 2.2509257

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . . _ _ _ _ . . _ _ = = _ . = - . ______ .._____,_ . ___..______

---

_------ TREAT =treatl -====- - -----------------  !

Minimum Maximum Sum Mean Std Dev 7

__________________.______________..________ ___ __- _ _ _ _ _ _ = - ____

16.0000000 34.0000000 283.0000000 28.3000000 5.5986109

_ _ . _ _ _ - _ - _ _ _ _ _ _ . _ _ _ . _ _ _ _ _ _ _ _ = = - - - _ _ . - _ _______....._________

-- --- - ---- - ---- --- -- ------- -- -- T RE AT = t r e a t 2 ------ - -- - ----- ----- -------- --

Minimum Maximum Sum Mean Std Dev 25.0000000 37.0000000 295.0000000 29.5000000 4.1699987

---

TREAT = treat 3 ---------- - ---------------

Minimum Maximum Sum Mean Std Dev 25.0000000 34.0000000 293.0000000 29.3000000 2.4966644 i

1 ------------------------------- TREAT = treat 4 ------------------------------

l Minimum Maximum Sum Mean Std Dev

=_____________________..__________________.._____... ___..

25.0000000 33.0000000 297.0000000 29.7000000 2.2135944 Univariate Procedure Variable =DIFF Moments N , 50 Sum Wgts 50 Mean 0 Sum 0 Std Dev 3.453481 variance 11.92653 Skewness _0.55866 . Kurtosis 2.23593 USS 584.4 CSS 584.4 CV . Std Mean 0.488396 l T:Mean=0 0 Pr>lTl 1.0000 l Num ^= 0 50 Num > 0 26 l M(Sign) 1 Pr>= M 0.8877 I

Sqn Rank 17.5 Pr>= S 0.8678 W: Normal 0.965742 Pr<W 0.2641 i

PROBABILITY < W (0.2641) IS GREATER THAN 0.01, SO CONCLUDE THAT UNTRANSFORMED' REPRODUCTION DATA ARE NORMALLY DISTRI8UTED.

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Page 1

. . . . _ ~ ~ - , . - . . _ _

_ _ . _ _ _ _ _ _ - _ _l BARTLETT'STESTFORHOMOGENEITYOFREPRODUCTIONDATAVARIANCEAMONGTREATMENTSk BARTLETT.*S TEST: CHI-SQUI DE=12. 7 2 66 329 4 8 ALPRA=0.0126917128 .

Compare to critical B as approximated from the Chi-square distribution at (p-1) degrees of freedom at a 0.01 level of j significance. If the computed B is less than the critical i (Chi-square) value, the variances are equal. l

, . ALPHA (0.01269) IS GREATER THAN 0.01, SO CONCLUDE THAT DATA ARE HOMOGENEOUS' l

\

l Listing of Input Data i

_-____-__----____------- -- =___-_----.= __-- __--___

Data Checked Total Live Young Per Replicate By: -----___-------_-----------------------

Dates 1 l2 l3 l4 l5 l6 l7 l8 l9 l10

ysgjf4) 4 -__+_'__+---+___+___+--_+-_-+-__+_--+---

l UQN N l N-l N l N lNlN lN lN lN lN

__-____----_+-__+---+---+___+___+--_+---+--_+-__+---

Treatment control 32 29 33 28 33 31 32 27 29 28 treatl 16 31 34 24 34 26 32 25 30 31 treat 2 28 29 30 27 37 25 25 31 27 36 treat 3 28 30 31 25 30 27 28 29 31 34 treat 4 28 30 29 31 32 30 30 25 29 33 i

---

____-- _ -____---__--_---------_----____. --__ l

-DUNNETT'S T-TEST FOR DETERMINING 1sIGNIFICANT DIFFERENCES IN REPRODUCTIONe BETWEEN CONTROL AND TREATMENTS Dunnett's Test at an alpha = 0.05 level of significance General Linear Models Procedure Dunnett's One-tailed T tests for variable: YOUNG' NOTE: This tests controls the type I experimentwise error for comparisons of all treatments against a control.

Alpha = 0.05 Confidence = 0.95 df= 45 MSE= 12.98667 Critical Value of Dunnett's T= 2.222 Minimum Significant Difference = 3.5817 Comparisons significant at the 0.05 level are indicated by '***'.

General Linear Modelo Procedure l l

Simultaneous Simultaneous Lower Difference Upper TREAT Confidence Between Confidence Comparison Limit Means Limit treat 4 - control _4.082 -0.500 3.082 treat 2 - control -4.282 -0.700 2.882 treat 3 - control -4.482 -0.900 2.682 treatl - control -5.482 -1.900 1.682 SIGNIFICANT DIFFERENCES AT ALPHA = 0.05 WERE NOT OBSERVED BETWEEN THE CONTROL' 1 AND ANY OF THE FOUR TREATMENTS. THIS TEST DISPLAYED'WEITHER~ ACUTE TOR $

. CHRONIC TOXICITY OF .THE SINULATED COOLING TOWER WASTE TO .THE TEST,. SPECIES, 7 ERIODAPHNIA DUBIA, AT ANY TESTED DILUTION.

CHECKED BY: _ Af dew DATE: y///fy ' '

Page 2

f

. ATTACHMENT #2 l

CATAWBA NUCLEAR. STATION l COOLING TOWER TOXICITY TEST SODIUM BROMIDE MIXED WITH SODIUM HYPOCHLORITE In order to simulate the field conditions after mixing the sodium hypochlorite and sodium bromide to determine the toxicity, the following steps will be performed.

1. The cooling towers at Catawba will be cycled up to normal blow down concentrations without the use of any maintenance chemicals. A sample of this cooling water would be pulled and deliverd to out toxicity laboratory at Duke Power's Environmental Center.

2. A sunple of raw lake water from Lake Wylie will also be delivered to the Environmental Center at the same time.

l 3. The cooling water sample will be pland into a heated ;tirrer to approximatly 110 F to simulate the temperature of the actual cooling towers.

4. A worst case scenario of sodium hypochlorite and sodium bromide will be added to

! the cooling water sample. Sodium hypochlorite will be added until a free chirorine ,

residual of 3.5 ppm is obtained.

1 Approximately 1 ppm of sodium bromide will then be added to the mixture.

5. The sample will be mixed until no free oxidant is measured.

6. At the point in which no free oxidant is measured, the sample will be mixed with the raw lake water sample in the following quantities: 8 parts raw lake water to i part cooling water.

This 8 to i ratio will simulate the actual conditions prior to the discharge monitoring point. The cooling tower blowdown rate is approximatly 5000 gpm. This is mixed with once through cooling water of approximatly 45,000 to 50,000 gpm prior to being i discharged to Lake Wylie. l l

7. A sample will then be pulled for toxicity testing purposes.  ;

1 l

l

l 4"

n ATTACHMENT #3 CATAWBA NUCLEAR STATION l.

PROPOSED SODIUM BROMIDE USAGE  ;

j MAY 27, 1993

NPDES PERMIT SC0004278 PART III ITEM 9 REQUIREMENTS

1) NAME AND GENERAL COMPOSITION OF THE MAINTENANCE CHEMICAL l

j a) Liquid Sodium Bromide (40 to 46% solution) l

} 2) QUANTITIES TO BE USED

Approximtely 100 gallons of product.

]

l 2) FREQUENCY OF USE Every two days.

I

4) PROPOSED DISCHARGE CONCENTRATION -

! Since chlorine and bromide are both oxidants it is proposed that 1 J the current limits on outfall 005 of 0.2 mg/l monthly average and 1 0.5 mg/l daily maximum for Free Available Chlorine be changed to 4 Free Available Oxidant. (Outfall 005 is an internal outfall that

discharges upstream of Outfall 001. Flow through Outfall 001 i typically allows for an approximate 9 to 1 dilution ratio.) 1 l

5) EPA REGISTRATION NUMBER The EPA Registration Number for one of the. sodium bromide products ,

under evaluation is 1706-168. Once the actual manufacturer / supplier i j is selected an update can be provided if needed.

• q j 6) AQUATIC TOXICITY INFORMATION l

' l a) SODIUM BROMIDE

96 hour0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> static acute LC 50 to Fathead Minnow = 16,479 ppm.

96 hour0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> static acute LC 50 to Poecilia. reticulata = 225 ppm.

j 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> static acute LC 50 to Daphnia magna = 7,900 ppm.

b) HYPOBROMOUS ACID (acid generated from Sodium Bromide)

) 96 hour0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> static acute LC50'to Bluegill Sunfish = 0.52 ppm (as Br2) 96 hour NOEC for Bluegill Sunfish is 0.30 ppm based on no i mortality.

j 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> static acute LC50 to Daphnia Magna = 0.71 ppm (as Br2) 48 hour5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> NOEC for Daphnia magna is 0.41 ppm based on no mortality.

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r - , , ,--