IR 05000295/1990016

Insp Repts 50-295/90-16 & 50-304/90-18 on 900702-06,16 & 20. No Violations or Deviations Noted.Major Areas Inspected: Chemistry Program,Procedures,Organization & Training

ML20058N025
Person / Time
Site:	Zion  File:ZionSolutions icon.png
Issue date:	07/30/1990
From:	Holtzman R, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III)
To:
Shared Package
ML20058N024	List: IR 05000295/1990016 ML20058N020
References
50-295-90-16, 50-304-90-18, NUDOCS 9008130173
Download: ML20058N025 (10)

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jL U.S. NUCLEAR REGULATORY COMMISSION q,'w

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. REGION III

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' Report Nos. 50-295/90016(DRSS); 50-304/90018(0RSS)

Docket Nos. 50-295; 50-304 License Nos. DRP-39; ORP-48

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Licensee: ' Commonwealth Edison Company o

Post Office Box 767

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Chicago, IL 60690

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Facility Name:

Zion Generating' Station, Units 1 and 2

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+f" Inspection At: Zion Site, Zion, IL 60099

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Inspect onducted:

July 2-6,1990 (On-site)

16 and 20, 1990 (Telephone discussions)

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Inspector:

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M Approved By:

H. C. Schumacher, Chief

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Radiological Controls and Date Chemistry Section

Inspection Summary Inspection on July 2-6 and 16-19, 1990 (Report Nos. 50-295/90016(DRSS);

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50-304/90018(ORSS))

Areas Inspected:

Routine unannounced inspection of: (1) the chemistry program, including procedures, organization, and training (IP 84750);

(2) primary and secondary systems water, quality control programs (IP 84750);

':j (3) quality assurance / quality control program in the laboratory (IP,79701, IP 84750); (4) nonradiolgical confirmatory measurements (IP 84750);'and (5) audits and assessments (IP 84750).

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Results:

The licensee has an extensive water quality control program that conforms to the EPRI Steam Generator Owners and Primary Systems Guidelines.

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The inspector noted the following strengths and weaknesses:

Very good'laborai,ory instrumentation.

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Good secondary system water quality for plant without condensate polishers.

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Slow development of the laboratory QA/QC program.

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j ho violations or deviations were identified.

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' sT., P. Joyce,; Station Manager, Zion, CECO

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20. Schultz, Quality Control Supervisor, Zion:

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1L. -Prorok,; Corporate Chemist, CECO'. o

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1,2D. - Hemmerle, Lead ' Chemist', Zioni

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2T.- Saksefski, Regulatory Assurance, Zion

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2B; Brandolino, Nuclear Quality Programs, Ceco

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'2R. Hastings, Analytical' Chemist, Zion

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^2R.;Leemon, Resident Inspector, NRC

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uTheLinspector also interviewed other licensee personnelJin various -

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J1Denot'es those present at the plant exit interview onfJuly,6; 1990.t n '-

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2 Telephone discussions held July 16-and 20, 1990;

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Licensee Action on Previous Inspection Findings'(IP 92701')

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J(Closed)[0penItem(50-295/89031-0];50-304/89027-01):

Licensee to.

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n" split' for' analysis with Brookhaven' National Laboratory (BNL); samples

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of; secondary system water spiked with anions. ;This item is' closed

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because of,the NRC. reference laboratory for this-work'is not-

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b...(Closed)L0 pen Item (50-295/89031-02; 50-304/89027-02):

Licensee to.

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'1 submit a' letter.by November'3.0,.1989 to Region-III outlining plans 4

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f or1 improvements inLthe laboratory QA/QC-program along with the.

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proposed schedule. The licensee 7 submitted,a' letter on. improvements

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to the_QA/QC pro 0 ram,Lwhich had satisfactory proposals to be<

implemented. This11s discussed in Section17;

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ManagementControl' sand 0rganisation(IP84750f, l

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Y i-was <some turnover in staff, since the previous' inspection-in this area.,

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A' new Chemittry Supervisor was appointed. ' He reports'directly to the

' V'LTechnical"Sup rintendentband the Lead Chemist; Quality Control (QC)

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" Chemist, and Wee Chemistry ' Laboratory Supervisors report directly tou N

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Chim.' Four' Chemists ar.d two Engineering Assistants report to:the Lead

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The U A2demist and an additional Analytical Chemist

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1 Region III; Inspection Report Nos. (50-295/89031; 50-304/89027)

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TCorporateDChemistry Services group.

The QC chemist'left-and was-

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. T > technicians are now permanently assigned to'the laboratory, and spend ;

minimal;timecin* radiation protection duties.

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requirements for newly hired cts =have been 'nhanced by requiring higher e

A7 educationalllevels,.usually a1 minimum of an associates degree in a G

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+ ; cts are on shift,- and five are to start initial training shortly. :The?

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poJtion.' ' He has a Bachelor. of Chemistry degree with 11 years of "

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cche the* remainder of his experience was in supervisory por,itions

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.The' chemistry offices were temporarily' moved.whi.lel thepermanentafeain'

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I 6%, a 4-Water Chemistry Control Program (IP 79701, 84750)

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s-LThe. water quality ^ control program is essentially: identical ~to that in

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' tne previous report in' this : area,2 with minor revisions..The secondary D L

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system p,r_ogram is consistent with the Steam-Generator Owners' Group

'W Secondary Water Chemistry Guidelines (EPRI(SG0G), Westinghouse '

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Guidelines for Secondary Side Water Chemistry, and other contaminant--

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concerns.; Since'the turbine vendor (Brown-Boveri) hasino limitation on, silica,'thisspecies'is.notincludedinfthe:basicplantcontrol'

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procedure A0P 5.2.. However, Ait is1 determined in: various system samples F

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' as a diagnostic parameter., The primary system program is consistent Twith the EPRI: Primary System Guidelines.

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'The secondary system sampling and inlino process-panels have digitali instrumentation, including specific andLeation conductivities, pH, '

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Ldissolved oxygen, sodium and hydrazine at various points inLthe. systems.

A computerized.Datalogger system continuously collects, stores, and plots j

data from these-irstruments.

The licensee completed interfacing the

u process monitoring system with the Unit-2 with-a computer system and is,

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completing the Unit l' system. After the Chemistry Department returns to

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its permanent' offices, the licensee-plans to insta11Ldata terminals to: y

~make real time information readily available to the chemists.

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laboratory has a QA/QC program for these instruments.in which they are

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recalibrated an'd-performance checked periodically.

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', y The Makeup Demineralizer' System (MUD)Eis' a : vendor-operated (Ecolochem)'

system: based on three semitrailers; The demineralizer. system is -

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supplied:byfa reverse osmosis (RO) system that removes the:nonionic'

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-organic materialsifrom the-lake water that in thc-radiation fields of-f.

the RCS'become acidic.

This produces'high quality water,,which' appears:

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to bealow in silica;($ Sppb).

The-licensee has decided to'make th,is--

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• "1 system' operated by_the vendor to be;the permanent one.

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The plant's Chemistry Performance: Indices (CPI) have been near the

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f:.>' '. median values for all:PWR plants.

This appears to be good,for4a plant.

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M]7 thatlackscondensate. polisher,hasrecentlyhadseveraloutages,andN

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operates a substantial:part'of the time with load.following,o The n g i f gl' j m.

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inspector reviewed selected boron concentration data from.the the ' Boric!

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Acid Storage Tanks (BAST) with operational limits of 11.5-13% boricf

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acid.

These were generally within sp':ifications, or demonstratedsto bel 1,, "</br></br>Y k~</br></br>_~</br></br>?</br></br>,</br></br>l'</br></br>'</br></br>'</br></br>'</br></br>'</br></br>~</br></br>JQ(</br></br>t The' licensee maintains trend charts on the various chemistry 'nd fy m;</br></br>a</br></br>..</br></br>,,,</br></br>radiochemistry parameters,-including lithium, pH,'</br></br>boron,? dissolved:</br></br>J a</br></br>' @y oxygen,1 cation conductivity, [[Atomic Element" contains a listed "[" character as part of the property label and has therefore been classified as invalid., sulfat'e, sodium, compon'ent' s

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f~ 4, p cooling system chromate and daily CPI's1These are put info monthly-

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' p reports that are sent to various levels of management. The reports

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contain both short-term'(monthly) and lo'ng-term (six-month) plots,.

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infresponse to the previous'NRC comments.

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In_ general,-the various; parameters-appear lto be well' controlled, with n

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few ou;.-of-specification problems 2., Sulfate concentrations in the i,

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t secondary system appear to be somewhat higher than in most.other' plants,f

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but are well belowsthe Action-Level 1 limits of 20; ppb.

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The plant $has placed a new emphasis on the-stabilization of lithium

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4 control: radiation levels.

At'the start of the fuel icycle the Li is

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kept at the maximum level of 2.2 ppm to conform'to the RCS vendor,

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1" 4 (Westinghouse) specifications.

As the boric ~ acid' concentrations arei

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reduceJ to = compensate" for decreased reactivity,.the Li concentrations -

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are adjusted to= keep the'pH'at 7.1.

To obtain a more realistic view'of-

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4: ' RCS conditions,cthe' licensee.uses pH values"at RCS temperatures.

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values are calculated from the boron and lithium' concentrations rather

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than pH measured at 25 C.

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Theilicensee.has advanced toward 'ts improvement goals noted in

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the previous report 4 by implemWng the inline process monitor

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1 instrumentation QA/QC program; bringing the MUD system to specification'

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by permanently leasing the vendor system; and developing the QA/QC.

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" analytical system in the laboratory (Section 7).

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The licensee's water quality control programs appear to be satisfactory

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'No violations or deviations were identified.

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Implementation of the Chemistry Program (IP 79701)

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.,f The inspector reviewed the chemistry programs, including physical i

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facilities and laboratory operations.

The operations were generally 5 with good.

The instrumentation was the same as previout.ly discussed

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the new ones now being activated.

The Brinkmann PC 800 Colorimeters

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are being replaced with computerized spectrophotometers (Milton Roy Spectronic 1200) with a long (10-cm) cells for the silica, ammonia and hydrazine analyses.

A Perkin-Elmer (P-E) computer-based Model 5100 Atomic Absorption Spectrophotometer (AAS) with a Zeeman Effect background corrector will completely replace the presently used D-E Model 5000 AAS as soon as all the cts qualify on it.

The laboratory is

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using a Waters Ion Chromatographic system in the cold laboratory for anion analyses and the Waters system in the hot laboratory for the anion analyses in both the primary and secondary reactor systems.

The plant was developing new analytical techniques, using the new instrumentation to improve the sensitivities, accuracies, and efficiencies of the analyses.

Overall, the laboratory appeared to be adequate for the

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proper operation of the plant and to be operating satisfactorily.

No violations or deviations were identified.

6.

Nonradiological Confirmatory Measurements (IP 79701)

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The inspector submitted chemistry samples to the licensee for analysis as part of a program to evaluate the laboratory's capabilities to monitor nonradiological chemistry parameters in variot.6 plant systems with respect to various Technical Specification and other regulatory and administrative requirements.

These samples had been prepared,

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standardized, and periodically reanalyzed (to check for stability) for the NRC by the Radiological Sciences Division of Brookhaven National

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Laboratory (BNL).

The samples were analyzed by the licensee using routine methods and equipment.

j A single dilution for each sample was made by licensee personnel as necessary to bring the concentrations within the ranges normally analyzed by the laboratory, and run in triplicate in a manner similar to that of routine samples.

The results are presented in Table 1 with the

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criteria for agreemert presented at the end of the table.

They are j

derived from the BNL results of the present samples and the relative i

standard deviations (RSD) derived from the results of the 1986 s

interlaboratory comparisons from the various plant laboratories in the.

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study (Table 2.1, NUREG/CR-5422).

The acceptance criteria were that the a

ratios of licensee's value to that of BNL should be within 12 SD of

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1.000 for agreement and between 2 and 3 SD for qualified agreement.

However, for lithium because of lack of data f rom the earlier BNL sampl,es, the acceptance limits chosen here are based on the achievable accuracies in AAS flame analyses, values consistent with the INP0 recommendation of 15% (INP0 88-021, December 1988).

Data from the 1987 BNL samples are

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being evaluated.

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• The licensee determined 11 analytes at three' concentrations each., Of; p.

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L Ethe-initial 33 analyses,'27 (82%) were agreements, four were qualified H -f

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' agreements which indicated deficiencies in the assays (94% totalj,

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L agreements),fandtwowerefdisagreements.

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cThr, qualified agreements' included the.high chloride, middle copper,

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low sodlum,~high lithium'and middle hydrazine concentrations.- For-the chicride, the decrease in ratios' with conce'ntration indicates t

isome contamination'of the sample and_a possibly positive bias in the

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standard.

Themlow hydrazine biases also indicstes a high standard.

The positive. biases of'about 8% and good precision in the lithium

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results. indicate that the calibration 'is low." This is consistent with the positive bias.the licensee observed in the control chart mean value.

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cThe;11thium is-of,particular. concern because chemistry procedures and.

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the ' vendor require fairly narrow limits in reactor coolant, e.g.,

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1.8-2.2 ppm ^with fresh fuel.

Further, the licensee keeps the concentra-yW tions near. the upper ends of the ranges to maintain higher RCS pH values to minimizei the deposition of activatic% products on primary system.

surfaces.

The sodium biases are large, but less significant than-those.

-q of the lithium, possibly due;to an interference between lithium and s

sodium in.the sample. matrix.

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Overall,theresbitsof-theanalysesweregood,butsomeproblems f

.with the analyses were noted.

The licensee representative stated that

they are in the process of obtaining new standard materials from the

'NIST and elsewhere to resolve the control chart biases.

They agreed to s

work to resolve analytical problems with the lithium.> Progress in

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-solving these problems wil.1 be followed in subsequent routine inspections under 0 pen Item Nos. (50-295/90016-01; 50-304/90018-01),

t No violations or' deviations were identified.

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7, Implementation of the QA/QC Program in the-Chemistry Laboratory (IP 84750)

iheinspector"re'viewedthenonradiological'QA/QCprograminthe

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The program.is required by the corporate directive, Nuclear _

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Mg Operations Chemistry Quality Control Program Manual," Nuclear" Operations U

/1 1 Chemistry Quality Control Programi Revision 4, May '1,1989.2 It is

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several'more ' general activities aresin various procedures, including-

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ZCP-500, " Laboratory Instrume1tation Quality Control Calibration / Maintenance.,"'

Revision 0,' January 12, 1990 and ZCP-500-2, "Inline/0nlinenInstrumentationl j

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Quality Control Standardization / Performance Check Program,". Revision 0,1'

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January 12, 1990. The licensee submitted'a draft copy to the Region of'

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a' comprehensive procedure-to control;the operation of the QA/QC programt

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'(Section 2b), The QC program is still progressing s' lowly, sincejthe

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' previous inspection in this area; 'However,Las a resultiof more care'

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Land experience in the analyses and recalculation of the control ~1imits,

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the limits.on most of:the analytical < procedures have decreased greatly.

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cJ In recognitionof their own and the NRCts concerns over the progress of

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the QA/QC program, the licensee recently' replaced the QC chemist by'a-

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" scorporate chemist experienced in this field; this appears,to" insure that

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implementation of the program will move at a faster pace.4'

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The use of indepe *1t standards has been implemented with performance check standards being from different lots than the calibration standards.

The control charts have calculated statistical parameters with two-SD control limits which essentially cover all of the analyses, h,

including fluoride, chloride, sulfate, hydrazine, boron, lithium, silica, copper, iron, chromate, and magnesium.

Licensee supervisors still do not regularly evaluate the charts to confirm control of the analyses which was also an inspector concern during the previous inspection.

Failure to correct biases evident in the QC data is a likely cat.c

' 3e confirmatory measurements difficulties noted in

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Section 6 of this report.

The laborato"v maintains a nonradiological interlaboratory comparison program mana ed by the corporate Technical Support Center (TSC) which quarterly seaplies unknowns to be analyzed by the laboratory. The acceptance ranges are based on the INP0 criteria, e.g., 110% for most species, 11% for boron, and 15% for lithium.

A review of the results indicated the station achieved about 75% agreement in 1989 and about

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82% agreement in the first quarter of 1990.

The licensee's technician performance program is operated under

procedure ZCP 1021-3, " Radiation Chemistry Technician Proficiency Check Program," Revision 2, May 5, 1990.

It requires Technician testing twice yearly; acceptance criteria are presently based on the instrument

control limits or INP0 criteria for the analyses.

When the CT's results

. '

,

were in disagreement, new samples were run.

The program was run twice

last year after the previous inspection and once so f ar this year. * Data

evaluation has improved.

This program appears sathfactory and the cts have generally done well in it.

i

.

While the QA/QC program has progressed only slowly, the licensee appears

to have taken steps to speed it up.

Progress of this. program will be

,

followed in subsequent routine chemistry inspections.

l I

No violations or deviations were identified.

8.

Audits and Appraisals (IP 84750)

l The inspector reviewed a detailed corporate Chemistry Assessment of Zion Chemistry, February 5-9, 1990 by a team of experienced chemists and

radwaste personnel.

They found five Category I improvement items,

)

including differences between theoretical and measured hydrogen

!

concentrations in primary coolant, excessive times out of specification

,

in diesel generator and closed cooling water systems, problems with the ntilation and insufficient power for new instrumentation in the l

labor atories, and slow implementation of the chemistry QC program.

The l

last item included several subcategories of problems, some of which

)

related to the counting room and radwaste.

The respor,es were timely, l

and work is progressing.

The resolutions will be fo'. lowed in subsequent routine inspections in these areas.

l t

Ne violations or deviations were identified.

GIbid.

l

'

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w

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-

,

,

.

,

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-

.

~0henithmsfarematterswhichhavebeendiscussedwiththelicensee,'

) N"'

@(.4 / S

^

y.1 which willLbe. reviewed further by:the inspector, and which. involve some,

'

7 T: i g action on the part of-the NRC or: licensee, or both.- One open item was ;

s

,

..

-

".

disclosed in Section 6.

'

, / a,

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,

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.

,

10. Exit Interview

a JG t ' r ",+

L.

... F'

.

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- The-scope"and findings Of: the inspection were reviewed with licensee

.

"

o

+

' representatives (Section~1) at the conclusion of the inspection on

.

e

.l'E

.

. July 6,;1990.

Thejrspector.discussedtheOpenItemstinSection2and-N,

+

'i

'

,

,

~

^

i,

,s observationsLon the quality (control program and the confirmatory

~'

>,

it

. measurements. The i.1spector: noted improvement in!the chemistry trending 3 n

-

,

, y:

and QA/QC" programs;'but since the previous. inspection, progress;in_the.

'

i O latter.has.been slow..The fresults of the confirmatory measurements 4

;.

"

'

Iprogram were good.

Telephone discussions were' held with Chemistry staff.

.

lon July 16 and 19^ 1990. '

4.6

'

,

,

%

a..

o

'

,' 1 i ' m'.

During the exit' interview., the inspector discussedLthe:likely:

' informational content of the' inspection; report with regard to documents

-or processes reviewed by the inspectors during the' inspection.; Licensee

-

V

,: representatives did not identifytany such documents or processes as n

.

proprie}ary.

e

-

i

.

,

'<

-

.

..

!

s Attachments.

,

.

-

. Table 1, Nonradiological;Interlaboratory

~4

'

-

.

c Te'st Results', July: 2-19,.1990

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,

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July 2 - 19,-1990

'

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(k T

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Analyte:

Method 2'

Conenz Ratio 3 Acceptance Ranges *-.

Result 6

s 6 u-

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1'3RSD

+

-e y.

v

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.,

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'A-

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5-1.050-0.875.1~.125e 0.813-1.187:.A

<

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E a;

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.

IQ B A'

(10; 1;117l 0,875-1.125; ;0.813-1.187-A s

.

$~',

lC ~

1.097 )0.875-1.125= 0.813-1.187-A J

.

M:

~f

-

'

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.

,

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,,%g,

, Chloride

'A*

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1.000 0.933-1.067'.0.900-1.100 Al e

r s

'%;..'

,. : +

'B.

0.974' '0.917-1;081 0.879-1.121 Ai q

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0.867-1.133 A,

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Ratio 3

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. Methods:

Titr -; Titration

.

b IC

.'-Ion l Chromatography Colr E--' Colorimetry:

.

+

y AA/FL

.. Atomic absorption spectrophotometry'(flame)

s AA/FL - Atomic absorption spectrophotometry (furnace)-

i

..

..

.

s, f 2.

' Conc:

Approximate concentration-analyzed.-

s

,

,

3.

Ratio _offLicensee mean value to NRC mean value.

'

-m

,

-,: g

,4.

The SD in the'fifth.and sixth columns represents the coefficient."off 0'

,

t variation obtained'from averaging licensee data from the preceding cycle j

'

'

L-(TableL2;1 of?NOREG/CR-5244). iThe-licensee value is considered to be in i

L ay agreement;if it. falls within the-i 2' SD range;' a qualifi.ed agreement ifL

i P

M it lies,outside't:2 SD,fbut within=1 3 SD; andlin disagreement'if'it is-H i

n outside the 1 3.SD~ range.

i

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5.-

result:

-

,

.

.

'

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D 2 A =. Agreeme'nt:

Licensee value is'within.12.50s of th'e NRC~mean l

"

<

value.

~

.

.

.

.

.

,

j'

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3" p A* = Qualified agreement, licensee is b.etween'i 2 and 13 SDs of i

,t'A

>

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, y H 1-the NRC value, i t

qr A i D' = Disagreement: licensee'value-isoutsid i 3 SDs.

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