IR 05000461/1987021

Insp Rept 50-461/87-21 on 870601-05.No Violations Noted. Major Areas Inspected:Chemistry Program,Including Procedures,Training & Qa,Lab & Water Chemistry Control & Confirmatory Measurements of Nonradiological Samples

ML20234B845
Person / Time
Site:	Clinton
Issue date:	06/22/1987
From:	Holtzman R, House J, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III)
To:
Shared Package
ML20234B822	List: IR 05000461/1987021 ML20234B819
References
50-461-87-21, NUDOCS 8707060230
Download: ML20234B845 (8)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION III

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Report No. 50-461/87021(DRSS) )

l Docket No. 50-461 License No. NPF-55 Licensee: Illinois Power Company 500 South 27th Street Decatur, IL 62525 j

Facility Name: Clinton Nuclear Power Station, Unit 1  !

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Inspection At: Clinton Site, Clinton, Illinois Inspection Conducted: June 1-5, 1987 (Onsite)

Inspector: ." !3 zm [/2c2/87 '

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Inspector:

1. dn J. E. House 4/,6MT7 1

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Approved By: M. C. Schumacher, Chief 7 N Radiological Effluents and Date Chemistry Section i

Inspection Summary i Inspection on June 1-5, 1987 (Report No. 50-461/87021(DRSS))

Areas Inspected: Routine, announced inspection of the chemistry program, j including (1) procedures, training and quality assurance, (2) the chemistry )

laboratory and water chemistry control, and (3) confirmatory measurements )

of nonradiolgical sample Results: No violations or deviations were identifie I l

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B707060230 DR 870626 ADOCK 05000462 PDR L l

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I DETAILS l 1. Persons Contacted

• D. P. Hall, Vice President, IP

• J. W. Wilson, Manager, CPS, IP

• J. Greenwood, Manager, Power Supply, Soyland/WIPC0

• R. A. Schultz, Director, Planning and Programs - Nuclear Planning and Support, IP

• S. H. Daniel III, Supervisor, Chemistry, IP

• E. A. Till, Director, Nuclear Training, IP

• F. A. Spangenberg, III, Manager, Licensing and Safety, IP i;

• R. E. Campbell, Manager, Quality Assurance, IP

• J. S. Perry, Manager, Nuclear Programs Coordination, IP ,

• J. A. Brownell, Project Specialist Licensing, IP j J. R. Stonestreet, Assistant Supervisor, Chemistry Operations, IP l K. L. Harper, Chemist, Nuclear, IP 1 P. R. Otis, Chemist, Nuclear, IP i P. Hunter, Chemistry Technician, Contractor l H. H. Brophy, Chemistry Techician, IP l The inspector also interviewed other licensee personnel in the course l of the inspectio * Denotes those present at the plant exit hterview on June 5, 198 . Management Controls, Organization and Training The licensee had reorganized the Chemistry Department since the previous inspection.2 The Supervisor-Chemistry, who reports to the Director-Plant :

Operations, has two Assistant Supervisors, one for Chemistry Operations and the other for Chemistry Support. Two Chemists-Nuclear under Chemistry Operations supervise the laboratory with 12 plant Chemistry Technicians (CT) and seven contract cts. Plant management has authorized two more cts, with the contract cts to be phased out. The support group has three I contractor staff members and a Chemistry Specialist / Engineering, with two more positions in the latter category authorize The staffing appears to be adequate to perform the required chemistry operations.

l The qualifications of the recently hired Supervisor-Chemistry meets the requirements of ANSI 3.1-1978 and of the operational needs of the plan He has a Ph.D. in Radiochemistry and many years of supervisory experienc l Prior to assuming the present position, he headed the Radiochemistry i Section at Shoreham Nuclear Power Station for about a year. Several )

years experience at research reactors and at operating nuclear power plants satisfy the requirements of the ANSI standar l No violations or deviations were identified, t

2 Region III Inspection Report No. 50-461/87016,

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3. Implementation of the Chemistry Program

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The inspectors reviewed the chemistry programs, including physical I facilities and laboratory operations. The laboratories had adequate bench, floor and fume hood space and the housekeeping was good. The reagents were properly labeled and none had passed its respective  !

expiration dat The laboratory was reasonably well equipped. The 1 instrumentation included an Orion 701 Ionalyzer, an IL 457 AA/EE i Spectrophotometer, an HP 5890 Gas Chromatograph, a Dionex 20101 Ion i Chromatograph, a Dohrmann Total Carbon Analyzer, and a Perkin-Elmer i Lambda 3 UV/VIS Spectrophotomete ;

Equipment maintenance schedules for both in-line and laboratory instrumentation were computer generated for weekly and monthly maintenance j items. Daily maintenance schedules were controlled by check sheet l While no central logbook was maintained for the documentation of reagent 1 preparation, a record of weighings was maintained at the analytical  !

balanc This concern of a lack of a definite record was discussed with licensee. They agreed to consider a more thorough documentation for  !

reagent preparatio (See Open Item 50-461/87021-01, Section 4).

An interlaboratory crosscheck program is maintained with vendors (Analytics, Inc. and ERA) to assist in the laboratory QA progra i The inspectors reviewed recent results of the CT performance check program. Measurements were made by each of 18 cts on pH, conductivity and chloride and the results were analyzed and summarized by a superviso The pH and conductivity measurements were all within the acceptance limits; four of the chloride results were outside of the limits and were satisfactorily reanalyze This program appears to be adequate for testing CT performance capabilitie No violations or deviations were identifie . Water Chemistry Control Program The inspectors reviewed aspects of the water chemistry program based on Procedure CPS 1819.00, " Plant Water Chemistry Control," Revision 0, January 28, 1986, and the plant Technical Specifications. The sampling and maintenance schedules along with the data were examined and appear

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l to be adequate. Trend charts are plotted for various chemical parameters '

relating to water quality control, including dissolved oxygen and conductivity measurements to compare in-line values with those of grab samples, and the concentrations of silica, chloride and sulfate. These i were determined at various sampling points in the reactor systems, including

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reactor water, condensate, feedwater and polisher systems. Some control parameters were given on the plots, such as action levels and " achievable" concentrations. As the plant has been operational for only a short time and still coming up to power, the licensee has had difficulties, as is to be expected in a new plant, of maintaining the desirable parameter limit This program is still under development, so that not all parameters were trended and long-term trends were not available. This program will be followed under the chemistry reviews in future inspection .

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No violations or deviations were identifie . Non-radiological Confirmatory Measurements The inspectors 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 various plant systems with respect i to various Technical Specification and other regulatory and administrative requirement These samples had been prepared, standardized, and !

periodically reanalyzed (to check for stability) for the NRC by the Safety and Environmental Protection Division of Brookhaven National Laboratory (BNL). The samples were analyzed by the licensee using routine methods and equipmen The samples were diluted by licensee personnel as necessary to bring the concentrations within the ranges normally analyzed by the laboratory, and l run in triplicate in a manner similar that of routine samples. The 1 results are presented in Table 1 and the criteria for agreement in Attachment These criteria for agreement are based on comparisons

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of the mean values and estimates of the standard deviations (s.d.) of the measurements. Consideration was given to the fact that the uncertainties (s.d.) of the licensee's results were not necessarily representative of the laboratory's because they were obtained by one analyst over a short 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 of the ratio 2 (S zin Attachment 1).

While only one of the 27 licensee results was in disagreement with those I of BNL, some potential problems did appear. Low-level chloride and iron differed from the BNL values by more than 15%, but because of the high s.d.s in the BNL results, they were agreements. Further, the copper results had biases of more than 10%, which, from their examination of the calibration curves, the inspectors attributed mainly to the nonlinearity of the instrument over the calibration range. The inspectors' replots of the curves using the lower calibration point at 1.0 ppm and the control standard at 3 ppm, gave a three point straight line through zero; the ratios for the two higher concentrations of 1.12 each, were then reduced j to 1.09 and 1.06. The calibration curves of the other metals showed !

similar effects, but with substantially lower corrections. The boron j results had good precision, but the biases of up to 2.7% appeared to be !

somewhat high for this analysis. The inspectors noted to the licensee 1 representatives that part of this may be due to the CT not reading of the I buret to its maximum precision of about 0.01, and to not using a check l standard and control chart. The inspectors noted their concerns that j the laboratory did not have a policy of using dual stock solutions for the '

standards, in which the calibration standards were from different lots than the check standards. The chemists agreed, that within two months they would consider procedure changes and laboratory practices relating to the concerns with the nonlinear calibration curves, the lack of controls on the boron analysis, the use of different standard solutions

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j for the calibrations and control standards, and the implementation of a reagent preparation logbook (Section 3). Progress in these items will be followed in subsequent inspections under Open Item No. 50-461/87021-0 The licensee also prepared three samples to be split with BNL. To these 1 were added analytes supplied by the inspectors. Reactor water was spiked j with the anions, chloride and sulfate, and samples of condensate and i feedwater were spiked with copper, iron, nickel and chromium ions. The l

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licensee will determine the analytes in each and the results will be sent l to Region III for comparison with the values determined by BNL. This will be followed under Open Item No. 50-461/87021-0 !

l The licensees QA/QC program using control charts and multipoint calibrations i of the instruments appears to have been a substantial factor in accounting {

for the good agreements achieve '

No violations or deviations were identifie . Licensee Internal Audits The inspectors reviewed the findings of a recent audit from the QA Departmen Six findings were listed along with likely corrections to be taken by the Chemistry Department. However, since the reply was not yet due, the audit was not complete. The Supervisor-Chemistry noted that these items were being addressed. The nature of the questions addressed in the findings lead the inspectors to believe that the audit system is ,

adequat ]

No violations or deviations were identifie . Open Items Open items are matters which have been discussed with the licensee, which will be reviewed further by the inspectors, and which involve some action on the part of the NRC or licensee, or both. Open items were disclosed during the inspection in Section . Exit Interview j The scope and findings of the inspection discussed in Section 4 were !

reviewed with licensee representatives (Section 1) at the conclusion of the inspection on June 5, 198 During the exit interview, the inspectors discussed the likely informational content of the inspection report with regard to documents or processes reviewed by the inspector during the inspection. Licensee representatives did not identify any such documents or processes as proprietar Attachments: Table 1, Non-radiological Interlaboratory Test Results, June 1-5, 1987 1 Attachment 1, Criteria for Comparing Analytical Measurements

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DRAFT TABLE 1 Non-Radiological Interlaboratory Test Results Clinton Power Station Unit 1 June 1-5, 1987 a Anal- Analysis Dilu- NRC Licensee Ratio Compari-b c yte Method tion, son 1:x Y 1 s.d.(n) X 1 s.d.(r; Z 1 (x)

Concentration, ppm i B Titr 1 985 1 10(7) 1010 1 14 1.025 1 0.018 A 1 2980 1 50(7) 3002 1 15 1.007 1 0.018 A 1 4870 1 60(7) 5005 1 37 1.027 1 0.015 A Cl- IC 2000 24.1 2 3.1(7) 19.9 1 0.46 0.825 1 0.108 A 2000 37.4 1 1.2(7) 40.3 1 .077 1 0.048 A l 2000 80.5 1 2.2(8) 83.44 1 0.95 1.037 1 0.031 A i l

Sul f- IC 2000 20.0 1 0.9(7) 19.4 1 0.71 0.970 1 0.056 A ate 2000 41.0 1 2.4(8) 40.2 1 1.14 0.980 1 0.064 A 2000 80.8 1 3.0(7) 82.05 1 0.84 1.015 1 0.039 A Sil- Spec 2000 54.3 1 5.6(7) 53 1 .976 1 0.140 A ica 2000 109 1 7(7) 109 2 .000 1 0.076 A 2000 160 1 5(7) 155.7 1 .973 1 0.034 A (

Cu AAS 10 4.68 1 0.24(12) 4.6 1 .983 0.055 A 10 9.66 1 0.49(14) 10.8 1 .115 1 0.076 A 10 14.5 1 0.6(12) 16.2 1 0.21 1.117 1 0.062 A* '

Fe AAS 10 4.89 1 0.35(13) 4.0 1 0.11 0.818 1 0.092 A*

10 9.55 1 0.34(14) 9.3 1 0.60 0.974 1 0.035 A ,

10 14.7 1 0.42(13) 13.4 1 0.32 0.912 1 0.039 D* '

Ni AAS 10 5.09 1 0.26(6) 5.0 1 .982 1 0.050 A*

10 10.2 1 0.3(7) 10.7 1 0.06 1.049 1 0.031 A 10 15.3 1 0.4(6) 15.1 1 0.32 0.987 1 0.033 A Cr AAS 10 5.1 1 0.3(6) 4.9 1 0.15 0.961 1 0.064 A 10 9.41 1 0.3(6) 9.8 1 .041 1 0.046 A 10 14.3 1 0.8(6) 14.9 1 0.12 1.042 1 0.059 A Na AAS 10 4.58 1 0.5(6) 4.9 1 0.36 1.070 1 0.14 A 10 9.23 1 0.8(6) 8.9 1 0.05 0.964 1 0.084 A i 10 14.4 1 0.8(6) 13.7 1 0.15 0.951 1 0.054 A Value i standard deviation (s.d.); n is number of BNL analyses. The number of licensee analyses is 3 unless otherwise note l

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DRAFT b. Analytical methods: Titr - titration IC - Ion chromatography Spec - Spectrophotometric AAS - Atomic absorption spectrophotometry c. A = Agreement

, D = Disagreement

• Substituted the BNL uncertainty for licensee's uncertaint i

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ATTACHMENT 1 Criteria for Comparing Analytical Measurements This attachment provides criteria for comparing results of the capabilit The acceptance 14:cits are based on the uncertainty (standard deviation) ofythe test ratio of the licen ee's mean value (X) to the NRC mean value (Y), where (1) Z = X/Y is the ratio, and (2) S is th pfopaga'euncertaintyoftheratiodeterminedfromtheion of the uncer Sx , and of U;e NRC's mean value, S .1 Thus, y

z _ s2 s2 S2 x

Y ~ V * 11', so that

[S*2 s2%

Y S

z =Z*! +

(X2 y2)

' 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 i

equal to twice the uncertainty in the ratio, l 1-Z l < 2*S 7 l National Council on Radiation Protection and Measurements, i A Handbook of Radioactivity Measurements Procedures, NCRP l Report No. 58, Second Edition, 1985, Pages 322-326 (see Page 324). 4

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