IR 05000254/1987032

Insp Repts 50-254/87-32 & 50-265/87-32 on 871102-06.No Violations or Deviations Noted.Major Areas Inspected: Chemistry Program,Including Procedures,Organization & Training & Qa/Qc Program in Lab

ML20236X434
Person / Time
Site:	Quad Cities
Issue date:	12/04/1987
From:	Holtzman R, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III)
To:
Shared Package
ML20236X431	List: IR 05000254/1987032 ML20236X430
References
50-254-87-32, 50-265-87-32, NUDOCS 8712090189
Download: ML20236X434 (10)

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_ UiS L N!!H EAR L REGULATORY; COMMISSION '

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ReportfNo.450-254/87032(DRSS);-No.a50-265/87032(DRSS);

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J00cket1N'os[50-254;50-265- Licenses.No. DRP-29; DRP-30

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x -Licensee: Commonwealth Edison Compan y '

Post Office Box 1767 :

g . Chicago, ILc.60690-

• Facility:Name: 1 Quad.' Cities Nuclear Generating Station, Units l',and~2-Inspdction Ad Quad Cities Site, Cordova, Illinois'.

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Inspection

ConductedF November 2-6, 1987 (Onsite).

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. November-13 and December 2,L.1987 (Telephone Conversations');

(Inspector: Ak/hbow

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1 R. . B.;. Holtzm '-

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] Approved'By:) 49 M (v y3/e///7 M.;C. Schumacher, Chief- ..

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' Radiological Effluents'and Chemistry 2Ser, ion

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Inspection Summary Inspection on November 2-6, 1987, and November 13 and December 2, 1987<

N LTielephone) (Reports No. 50-254/87032(DRSS); No. 50-265/87032(DRSS))-

Areas Inspected:. Routine announced. inspection of: (1).the chemistry program, y< including procedures, organization, and training; (2) primary and secondary y systems, water quality.controliprograms; (3) quality assurance / quality control program'in the laboratory; and-(4) .nonradiolgical confirmatory' measurement 'Results: Ho. violations or deviations were identifie .

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DETAILS 1. Persons Contacte R. L.'Bax, Station Manager, Quad Cities Nuclear Power Plant (QCNP)

1R. Robey, Services Superintendent, QCNP 1J. R. Wunderlich, Regulatory Assurance, QCNP 1'2P. A. Behrens, Lead Chemist, QCNP 2C. Norton, QA Engineer, CECO-2G. Spedl, Assistant Superintendent,- Technical Services,'QCNP 1J. Sirovy, Rad / Chem Supervisor, QCNP

, R. Knight, Chemist, QCNP K. Engle, Radiation Chemistry Technician (RCT), QCNP R. Schroeder, RCT., QCNP M. J. Melton,: Instructor, QCNP 1R. Higgins, Senior Resident Inspector, NRC The. inspector also interviewed other licensee personnel in various departments in the course of the inspectio ,

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2 Denotes those present at the plant exit interview on November 6, 198 Telephone. discussion held on November 13 and December 2, 198 . Licensee Action on Previous Inspection Findings (Closed) Open Item (50-254/85006-06; 50-265/85006-06): Licensee plans to upgrade process systems and instrumentation. The inspector reviewed the progress of the plan to modernize and upgrade the in-line process instrumentation. The funds have been approved, the program scheduled, a contract completed., and bids on various aspects obtained. The contractor has set up prototype sampling panels and completion dat'es.for the two units are expected in 1989. This item is closed, but progress will be followed along with other water quality improvements during routine chemistry inspection (Closed) Open Item (50-254/86018-04; 50-265/86018-04): Resolve high variability in RCT results of Cr analyses by atomic absorption. The inspector's review of the results indicate that these problems have been resolved as demonstrated by good agreement of the licensee values with those from the corporate interlaboratory crosscheck and from results of the confirmatory measurements of this insp.ection (Section 6). (Closed) Open Item (50-254/86018-01; 50-265/86018-01): Licensee to revise by March 1, 1987, the water chemistry control procedures to reflect the current Corporate NSD Directive NSDD-517, "BWR Water Chemistry Control Program," Revision 1, August 25, 1986. A review of the licensee's chemistry procedures showed that they conform to the Directive and to the BWR Owners Guidelines:

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• QCP 200-3, " Reactor Water Chemistry," Revision 7, March 11, 1987.

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QCP 200-S1",u 'l Reactor 1Startup Surveillance,": Revision 6', March 11,

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f , :e',lQCP.100-T20, " Action Levels'for,BWR, Water Chemistry Control,"J >

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. , :f lIn thetinspectof's discussion with the' Lead Chemist on December 2,

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1987, the.latter stated that the administrative procedures-

.g' g ,:.* fQA' 4P300-22, '.' Water Chemistry Cont'rol, Revision 5, , September; '

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.* IQAP!300-T19, " Values Prior to Startup/ Power Operation,"

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?Wl, essentially duplicated the Directive. The last procedure provided

the bases for the limits in QCP 200-S1, above. - Further, he noted '

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that.his recordsL(a NSD Worksheet)Lshowed that these procedures had '

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been submitted prior: to the March I compliance date.' This= program

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will be tollowed in subsequent routine chemistry inspections.

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, l3i ; Management Controlsi Organization'and. Training

' M The. management structure of the' Chemistry Group is' essentially unchanged usince'the previous inspection in;this area.) One Chemist with about-fou '

k%* s byear's: experience has b6en replaced by.another with similar' experience int the CorporateLTechnical-Center.>

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The. Rad / Chem Department has lost one RCT'and now has 3 expres' sed his conce'rn to licensee representative'esLabout.the RCTs being--

The inspector rotated between health. physics 'and' chemistry. Licens'ee representatives-y,

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recognized this problem.and;noted that:this is a corporate policy-that the= company is presently a'ttempting to resolve. The staffing appears-to

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be' adequate 1to perform the required chemistry lfor plant ~ operations.

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.The: licensee's RCT training program was certified by INP0;on January 28,

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,:1987. .

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e -No violations or deviations were identifie . Water Chemistry Control Progr'am

n The' inspector reviewed aspects of the Water chemistry control program in

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the plant. The' licensee maintains trend charts on the various parameters, u

l including sodium 'pentaborate concentrations-in the Standby Liquid. Control Tank', silica concentration and conductivity in the reactor cleanup system, nitrates in the. HRSS, RBCCW, and TBCCW,'.and dissolved oxygen, chloride, lp a . sulfate, silica, and conductivity in the. reactor' coolant system. He also charts'and reports monthly on the percentage of time and hours L, ~Out-of-Specification'for both the reactor-related and auxiliary systems

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pr 2RegionLIII Inspection' Report Nos. 50-254/86018; 50-265/86018.

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fand the averages-for'a11LBWRs.,"The plant maintained' generally low levels-n fof contaminants;inothe water, with most.of the out-of specification E 4 excursions occurring'duringlstartup and' power change iThs M'akeup Demineralized (MUD)' system is schedulsd to' be rebuilt;by the

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, end:of.1989 to improveTits ease.of operation and the quality of waterLit-y4 ,

supplie Theilicensee ..is installing: equipment for hydrogen injection into the'

reactor coolantito' reduce oxygen levels in the.RCS water. ,It~is expected g

b Lto.beioperational:toward the end of 1988.'

clicensee'managementSappe'arstol6every'awareofjthev'alue.ofagoodwater quality control. program,Tand has . scheduled substantial improvements-over.-

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theLnext-few years. . Progress in upgrading _the'in-line process v ,

instrumentation and systems (Sectionf2a), rebuilding-the MUD, and

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. implementation'of.-the RCS hydrogen injectionisystem will,be-followed in a '

/ subsequent routine inspection '

/ No violations or deviations were identifie >

i c Implementation of the Chemistry Program

.g ' Thn: inspector reviewed .the chemistry programs, including physical

'N ' facilities' and laboratory operation Housekeeping and bench space 4 R ?were adequate forlthe analyses performed. The laboratories'were welt equipped,l including a three-unit DionexJIon Chromatographic system,

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T ; 'UV/ visible spectrophotometers, a Perkin-Elmer Model 5000 Atomic

, Absorption Spectrophotometer (AA), and total organic carbon analyzer .The inspector-observed several RCTs analyze the confirmatory measurements-

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. samples;byl titration, UV/ visible spectrometry, AA, and ion. chromatograph They' appeared to.be generally knowledgeable about the procedures, and did well.in the' analyses.

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'Overall, the laboratory appeared to be adequate for the proper operation

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of the plant and to be operating satisfactoril No violations or deviations were identifie . Nonradiological Confirmatory Measurements The -inspector submitted chemistry samples to the licensee for analysis as part of a. program to evaluate the laboratory'.s capabilities ~to monitor

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nonradiological chemistry parameters in various plant systems with respect to various Technical Specification ~and other regulatory'and i administrative requirements. These samples had been prepared, j i ,

. standardized, and periodically reanalyzed (to che::k for stability) for ;

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, thelNRC;by'theLSafety and Environmental Protection Division of Brookhaven !

, National Laboratory (BNL). The' samples were analyzed by the licensee

'using routine methods and equipment,

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<The' sampler were' di1Uted by: licensee: personnel as necessary to bring the

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concentrations.within.the ranges normally. analyzed by the laboratory, and ,

run in' triplicate in~a manner similarito that of routine. sample The l results-are presented in' Table 1,and the criteria for agreement in Attachment These criteria for agreementJare based on comparisons of the mean. values and estimates'of the standa'rd deviations (s~.d.) of the measurements. Consideration was.given to the fact that the. uncertainties

.(s.d.) of the3 11censee's res.ults were not_necessarily_ representative of the . laboratory's because they were obtained by one analyst over a short i period.of. time. Consequently when the licensee s.d. was less than'that .

. of BNL, and a disagreement' resulted, the BNL value was substituted for that of the licensee in calculating the s.d. of the ratio'Z'(S in 2 Attachment 2).

The licensee also prepared two samples to'be split with BNL. To these-were added analytes supplied by the inspector. Reactor. water was spiked-with the anions, chloride and sulfate, and samples of condensate were ,

spiked with the. cations, copper, iron, nickel and chromium. The licensee will determine the concentrations' of the analytes in each and the results will be sent to Region'III for comparison with the values determined by B N L.' This will;be.followed under the Open Item Nos. (50-254/87032-01; 50-265/87032-01).

The licensee analyzed 10 mater.ials at three concentrations each. Of he -

30 analyses, 26 or 87% were'in agreement with the BNL values. The disagreements included all three. sulfate. concentrations,.which were about 20% low relative to the BNL values. The inspector noted an error in the preparation procedure.for.the 1000 ppm sulfate solution ~(QCP 600-2,

" Reagent Preparation," Revision 4, dated March 12,1987), which states that 1.814 g of anhydrous sodium, sulfate solid, rather than the proper amount of 1.478 g, should be'added<to 1000 ml of deionized water. On compensating the sulfate values by.the ratio of 0.815, they were brought-into agreement (Table 1). These results are also consistent with those found by the licensee in the latest corporate interlaboratory comparison in which they were low by about'14%. . In a telephone conversation, the Lead Chemist stated that the Chemist had also found this problem and the procedure has been revised and is awaiting final approva The high level chloride result with a low bias was also in disagreement and, in addition, the low concentration chloride with a bias of about 20%

low,' was a borderline igreement. This suggests that the chloride calibration and performance check standards are also somewhat hig The intermediate silica analysis result at 9% low was borderline, which may be a problem *

in the future. The licensee is looking into the cause of these problem : Progress in resolving these problems and revision of the procedures will be followed in subsequent inspections under Open Item (50-254/87032-02; 50-265/87032-02). (

The licensee utilizes multi point calibraHcns on the AA and spectrophotometer and is obtaining IC integrators that will also take-such curves, uses independent performance check standards, and has p control charts on some of the analyse While presently the licensee i t ~ uses arbitrary control limits, e.g. , i 10%, the laboratory will shortly l

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. revise them to use statistically-derived limits, and charts.will'be-

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implemented for all analyses.(Section 7). (

L No violations or deviations were identifie ' : Implementation of the QA/QC Program in the Chemistry Laboratory i

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The. inspector reviewed the nonradiologi. cal QA/QC program in the laborator 'The' program is; required by the Corporate directive, NSDD-25,." Nuclear Stations Chemistry Quality 1 Control Program," January 1987' and will be implemented by. procedure QCP 1400-11,." Verification.of Analytical

c Performanc ," Revision 3, currently in the onsite review stag It requires;that control charts be used in.most assays with statistitdly-derived control limits'at the two-sigma leve The inspector' discussed his concerns about the procedure'with licensee

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repres entatives: (1) Control limits for most analyses should be determined more frequently than the required' semiannual assessment, and.(2) the

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' control and other relevant data should be tabulated on logsheets for easier access for assessment and calculatio The. licensee. representative agreed 1 to' consider these concerns during revision of the above. procedure. He

expected to have most.of the improved-control charts' implemented by the-firstof the year-and.is: committed to-fully implement the procedure by April 1, 1988. Progress in the~ implementing the procedure will.be followed-under Open Item Nos. (50-254/87032-03;- 50-265/87032-03).

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The RCT performance te'st records were' reviewe During the year, each RCT performed about 15 different analyses'of vendor supplied-(ERA)

' unknowns, including pH, conductivity', chloride, sulfate, and boro The acceptance limits were usually within i 10% of the known value and

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unacceptable. values resulted in the'RCT repeating the analysis. The results were statistically assessed by type of' analysis and by individual-RCT.~ 'The inspecter noted that the performance check and blird samples

used in testing of assays;could.be incorporated into to the RCT performance checks to improve the credibility of the testing or redu'ce the need for

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the vendor unknown i The. licensee results in the corporate interlaboratory comparison appear to be improving according to the performance standard defined as the fraction of the results within 10% of the.." calculated" value. The licensee had 73% of the values within 10%'in June,rcompared to 67% in March. This is somewhat poorer than the other BWR stations in the group. This performance may be improved somewhat in the future with the improved sulfate standard. The licensee' is also participating in interlaboratory comparisons with other plants through a vendor (NWT).

The inspector noted to licensee representatives that the QA/QC program .

has advanced somewhat slowly since the previous inspection. However, it is progressing and the planned program appears to be good.

ll No. violations or deviations were identified.

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s Thejinspect$r.reviewedthelatestcorporate1auditrelatingto. Chemistry,:

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.{ : Quality; Assurance : Aud_it. ReportL O4-87-02, 'of January .12-19,:1987, whic '

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found chemicals without; certificates and;someEminor errors-by.a technician:

." iduring an analysis These problems wereiresolved in,a timely manne . ' 7^

JThe Inspector also discussed withLthe a;QA Engineer, who was chairman o ithe corpor' ate committee to. revise-the? Chemistry. Surveillance? forms, the possibility'of adding'aLquestion to the" form specifically addressingLth 'controlscharts.for'the analytical procedures,being audited. This would:

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e make;both:the: chemists and the QA Department;more aware-that~these were

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definitely'part of the.QA program. In .a very timely response to. the NRC-

• concerns,-he stated during the exit interview, that this question:was -

approved.and would be i. incorporated-into the CECO: surveillance forms within'.

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Thel audit and surveillanceLreports: indicate that the licensee's mechanisms

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for" responding;to audit findings' are~ adequat ,g

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4j - No' violations: or~-deviations:were identifie !!?' '

1 Open Items l ,

Open'itemscare matters which have.been discussed with the licensee,-which

'will be reviewed further by the inspector, and which involve;some action

.on.the partJof the NRC or licensee, or both. 0 pen items' disclosed during

the' inspection areidiscussed in Sections 6 and .I l E1 Exit. Interview'

LThecscope'and findings of the-inspecti6n were reviewed with licensee representatives (Section 1) at the'conclusionTof the inspection on

.. . November 6,'1987. The' inspector-discussed'the Open Items in Section 2

~ L' and' observations on thec quality- control program and the confirmatory 1 measurements'. Licensee representatives; agreed.'to modify'the QC' charts

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andLto' consider other modifications of the program, as discussed in Section 7.- The inspector noted the progress in the QA/QC program since the previous inspection. Telephone discussions were held with Mr. P. Behrens on November 13 and December 2,~198 l' During the. exit interview, the inspector discussed the likely informational content of.tte inspection report with regard-to documents

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or' processes reviewed by the inspector during the inspection. i.icensee h '

' representatives did not identify any such documents or processes as y  : proprietar _

11 j h i Attachments:

Table 1,~Nonradiological Interlaboratory

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, ' Test Results,iNovember 2-6, 1987

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: Attachment 11, Criteria.for' Comparing i -Analytical Measurements'(Nonradiological)

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TABLE 1

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. . _ Nonradiological Interlaboratory Test Results

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LQuad Cities Nuclear Generating Station, Units-1 and 2 November 2-6, 1987 m ,

Ar.alyte Analysg Dil'ution , NRC Licensee Ratio Comparisonc ,

Method 1; x - Y i s.d.(n) X i s.d.(n) Z * s'. ' 2 Concentration, ppb

~ Fluoride':I .

'2000 11.6 1 0.3(8)' 11.3 1 0.4(4) 0.974 1 0.043L -A 2000' 21.8'i 0.95(8)' 20.8 1 0.2(4)' O.954 1 0.043- A-20001 41.8 i 1.4(7) 40.7 t 0.9(4) 0.974 1 0.039 A

' Chloride' IC- 2000' 12.1.1 1.6(7)' -9.78.1 0.36(4) 0.808 1 0.111, A+

F 2000: 18.7: 1-0.6 (7) 19.2 1 0.15(4) 1.027 1 0.034 A-2000 '40.3'i 1.1 (8) 3 .26(4). 0.888 1 0.037*' 0*

Sulfate ' I .0 0.45(7). 7.95 i 0.41(4) 0.7951 0.054 D 2000' 20.5 i 1.2 (8) 16.O i 0.12(4). 0.780 i-0,074' D*

2000 40 4't 1.5 (7) -31.1 i 0.3 (4) 0.770 1 0.047 D*-

. Sul'fateY IC '2000 10.0 i 0.45(7) 9.75 1 0.50'(4) 0.975 i 0.0621 A 2000 20.5 i 1.2-(8) 19.6 1 0.15(4) 0.'956 1.0.056 A 2000 40.4 1 1.5.(7) 3 .4-(4) 0.946 1 0.036 A

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Silica! . Spec- .1000 '54.3 i 5.6 (7) 52.0 i 1.0(6) 0.958 1 0.100 A

't 7 (7) 99.0 i 1.0(6)

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.-1000 109 0.908 i 0.059- A 1000- 160 .

5 (7) 15 i 2.1(6)- 0.981 1 0.033 A Fe AAS 10- 489 i 35 (13) 493 i 58 1.008 1 0.139 A 10 955 1 34 (14) 977 1 15 1.023:i 0.040 A 10 1470 .i 42-(13) 1460 i 16 0.993 1.O.030 A

. Cu AAS 10 468 i 24 (12) 453 6 0.968 1 0.051 A 10 966 i 49 (14) 930 1 .963 1 0.049 ~A 10 1450 i 60 (13) 1397 12 0.963 0.041 A'

N AAS 10 509 1 26 (6) 483 15 0.949 i 0.057 A 10 1020 i 30 (7) 993 i 12 0.974 0.031- A 10 1530 1 40 (7) 1500 1 17 0.980 1 0.028 A

' Cr AAS 10 510 1 30 (6) 487 i 21 0.955 1 0.070 A 10 941 1 30 (6) 897 1 6 0.953 1 0.031 A 10 1430 1 80 (6) 1377 i 6 0.963 1 0.054 A i

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lNa AAS 200 22.9 1 2.5(6). 24.3 1 .061 1 0.168 A 200 46.2 i 4.0(6) 49.2 i 1. 6 1.065 1 0.098 A .

l 200 72.2 i 4.0(6) 73.5 1 .018 1 0.061 A l

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, ( Concentration, ppm B Tit ' i 10(7) 978 1 6 0.978 0.011 A 11 3024L i 46(7)- 2950: 1: 12 0.976 i 0.015: A 1 ,

1- 4947 i 61(6) 4970 1 53 ,1,005 0.016 : ' Val ue . 'i standard deviation (s.d.); n is number of BNL analyse The1 number of licensee analyses is 3 unless otherwise note ' : Analytical methods: Titr - titration IC - Ion chromatography Spec - Spectrophotometric AAS . Atomic absorption Spectroscopy-(flame) A. =. Agreement

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.D = Disagreement A+ = Borderline Agreement -

. d .' The sulfate standard was corrected for an error in preparation by multiplying the uncorrected value by 0.815 (see-text, Section 6).

• . Substituted the BNL uncertainty for licensee's: uncertaint i

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ATTACHMENT l'

Criteria for Comparing Ana'lytical Measurements ThisLattachment p'rovides criteria for comparing results'of'the capabilit-The' acceptance limits are based on.the uncertainty (standard deviation)ofy the- test ratio of the licensee's mean value (X) to the.NRC mean value (Y), where .

(1)/Z=X/Yistheratio,and .

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(2) S is tie uncertainty of the, ratio determined from the 4

. propagation of.the uncertainties of licensee's mean value, Sx , and..of the NRC's mean,value,.S .1 Thus, y

S2 32 s2 ' l Vz ~_ V x ..* V y,.so-that

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.The results are considered to be in agreement when the bias in the ratio --

.(absolute value of' difference between unity and the ratio) is less than or- l equal to twice the uncertainty'.in the. ratio, i h ;Jcl-Zl12*S z National Council on. Radiation Protection and Measurements, A Handbook of. Radioactivity Measurements Procedures;-NCRP

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Report No. 58, Second. Edition, 198b, Pages 322-326 (see '

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