IR 05000483/1987016

Insp Rept 50-483/87-16 on 870511-15.No Violations Noted. Major Areas Inspected:Chemistry Program,Including Procedures,Training & QA & Confirmatory Measurements of Nonradiological Samples

ML20215A861
Person / Time
Site:	Callaway
Issue date:	06/08/1987
From:	Holtzman R, House J, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III)
To:
Shared Package
ML20215A841	List: IR 05000483/1987016 ML20215A839
References
50-483-87-16, NUDOCS 8706170117
Download: ML20215A861 (10)

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U.S. NUCLEAR REGULATORY COMMISSION l

REGION III

Report No. 50-483/87016(DRSS)

Docket No. 50-483 License No. NPF-30 Licensee: Union Electric Company l Post Office Box 149 - Mail Code 400  !

St. Louis, M0 63166 Facility Name: Callaway Plant, Unit 1 Inspection At: Callaway Site, Reform, Missouri

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Inspection Conducted: May 11-15, 1987 (On-site)

May 22 and 26, 1987 (Telephone conversations) l k,0 / w Inspectors: R. B. ko tzm $/6'/[-]

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Date Q// ,4/w'A-Approved By: M. C. Schumacher, Chief Y O Radiological Effluents and Da'te Chemistry Section Inspection Summary Inspection on May 11-15, 22 and 26,1987 (Report No. 50-483/87016(DRSS))

Areas Inspected: Routine announced inspection of: (1) the chemistry program, including procedures, training and quality assurance, and (2) confirmatory measurements of nonradiological sample Results: No violations or deviations were identifie t l

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l DETAILS Persons Contacted

J. D. Blosser, Plant Manager, UENO

J. R. Peevy, Assistant Manager, Technical Services, UEN0

V. J. Shanks, Superintendent Chemistry, UEND 1,2C. A. Riggs, Supervisor, Primary Chemistry, UEN0

T. Stotlar, Supervisor, Engineering QA, UEQA

D. R. Brownawell, QA Engineer, UEQA

D. A. Widmer, QA Engineer, UEQA  ;

J. J. Cassmeyer, Assistant Engineer, UEQ J.' V. Kerrigan, Chemistry Foreman, UENO E. C.' Olson, Chemistry Engineer, UENO B. L. Allen, Supervisor, Secondary Chemistry, UENO ,

D. E. Martin, Radiation / Chemistry Technician (RCT), UEN0

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I W. R. Johnson, RCT, UEN0 i The inspectors also interviewed other licensee personnel in various departments-in the course of the inspectio j

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20enotes those present at the plant exit interview on May 15, 198 .l 2 Telephone conversations held on May 22 and 26, 198 ' Licensee Action on Previous Inspection Findings (Closed) Open Item (50-483/86001-01): Licensee to perform improved evaluations of nonradiological analytical results obtained from ,

chemistry interlaboratory crosscheck program. The inspectors reviewed !

the results of the RCTs' analyses of samples supplied from a recent set of samples for the interlaboratory'crosscheck program with Analytics, Inc. The actions on the results 'are now based on Chemistry Technical Procedure, CTP-ZZ-04702, " Quality Control Verification l Program," Revision 1, July 29, 1986. The acceptance limit is based l on the uncertainties derived from the control chart for the-respective analysis (See Section 5). Unsatisfactory values result in the RCT !

being required.to analyze another, similar sample prepared by a chemist; further unsatisfactory results require supervisory evaluation and actions, including possible retraining of the RCT-until he reports a satisfactory value. The inspector confirmed that.the results had been tabulated and that the unsatisfactory ones had be'en resolved by a second analysis. This program will be'followed in future inspections-of the QA/QC program. This item is close . Management Controls, Organization and Training No changes in management controls _or staffing structure of the Chemistry Department have occurred since the previous inspection-in this area 1 (Inspection Report No. 50-483/86014). In discussions with the Superintendent Chemistry and Primary Chemistry Supervisor, the inspectors

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l noted that the Chemistry Department management has the authority to make decisions and to rapidly implement procedure changes in response to NRC initiative )

l A licensee representative stated that the technician training program has ]

been approved by INP l l

No violations or deviations were identifie { Implementation of the Chemistry Program The inspectors reviewed the primary and secondary chemistry programs incleding physical facilities and ' laboratory operations. Housekeeping is good, space appears to be adequate and the laboratory is well equippe Instrumentation includes a Dionex Ion Chromatograph, a Mettler Memotitrator, a Dohrman. Carbon Analyzer, a Perkin Elmer Atomic Absorption Spectrophotometer, a Hach. Gas Chromatograph, an Orion Digital Ionalizer, a.Perkin Elmer UV/Vis Spectrophotometer.and several Hewlett-Packard integrators. In-line instruments monitor pH, sodium, conductivity and dissolved oxygen on the secondary side. Short-term trends on these instruments'are tracked by technicians, while long-term trends are monitored by chemist Preventative maintenance schedules for both laboratory'and in-line l instruments are computer generated with a printout-for each instrument i denoting the necessary checks on calibration along with a form.to record :1 completion of the wor The inspectors observed two RCTs perform a number of analytical procedures including fluoride (specific ion electrode); chloride and ]

sulfate (ion chromatography); sodium,. nickel, copper and iron (atomic 1 absorption); and boron (automatic titration).' The RCTs appeared to l be knowledgeable in both operation of the instraments and procedure Laboratory techniques were adequat l Reagents were properly labeled and expiration dates liste No outdated reagents were observe No violations or deviations were identifie . Quality Assurance and Quality Control for Nonradiological Chemistr The inspectors reviewed the nonradiological QA/QC program for-both the primary and secondary systems laboratories. This program is controlled by Chemistry Departmental Procedures CDP-ZZ-00300 Contrdi of Chemistry Instrumentation and Equipment, Revision 10, March 9,'1987, and CDP-ZZ-00700 Laboratory Quality Control-Program,.

Revision 8, July 30, 1986,

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I and Chemistry Technical Procedures CTP-ZZ-04701 Control Chart Construction and Use, I Revision 1, July 24,1986, and CTP-ZZ-04702 -Quality Control Verification Program, Revision 1, July 29,198 The second pro'cedure above gives the key nonradiological parameters'for analysis as chloride, fluoride, sulfate, silica, iron, copper and' sodiu ;

Control charts were implemented-.for these analyses with warning limits of !

'one standard deviation (s.d.) and control limits of two s.d.' Other analytical methods. required that the results from the performance- ;

standards give values of the results within certain limits before the- '

RCT may proceed with the, analyse ,

The inspectors expressed concerns about the QA program: The source of the limits for the control charts appeared 'to be 'h statistically weak. ' They were derived from a set of measurements .j made about a' year ago, at the time the charts were set up. The y limits were based on measurements of standards covering the range a of values expected'in-..the respective analyses using percent recovery J and the associated s.d.'s. However, the daily _ performance checks 1 were run with standards of fixed concentrations in'the ranges i normally expected for the. samples. Thus, for various reasons, such as increased experience of the RCTs, these _ checks generally had much lower variabilities'than did the original test data, i.e., )

most of the results from the check samples fell within the one- W warning limits, while, if the s.d. had represented the data, only about 67% of them would have done s The data from the performance checks, while recorded on the laboratory daily logsheets,-were not collected and tabulated for each type of tes No control charts were used for the high-level boron analyses f (> 100 ppm). Although they required that the value of a 1000 ppm boron performance standard run prior to each batch of samples _ be-within +1% of the known value, this represents only a limited control of the analysis, e.g., the current statistics, such as s.d. and trends are not known quantitatively (the laboratory had determined these previously), The calibration standards and control standards' are not necessarily ,

made from solutions from independent sources, i.e., different-manufacturers or different lots. The use of independent sources would afford a check on the stability of these standard Many of the analyses were performed with one point calibrations, which implies that the instrumental' outputs _ are linear _ with the . '

quantity determined. The applicability of_this assumption should be checked periodically to assure the proper ~ quality of the result . .

l The chemists agreed with these concerns and are in the process of modifying the control chart procedure to allow for periodic updates of the limits using prior data generated by the performance check samples, j They will implement the use of independent calibration and control standards. The licensee is in the process of obtaining a computer system for tabulation and analysis of the dat However, since the modified control chart procedure requires tabulation for the calculations, anyway, the licensee representatives agreed to set up logsheets for tabulation of the performance check results prior to installation of the l computer system. They had implemented control charts for the boron analyses prior to the end of the inspection with initial control limits of +10 ppm for the 1000 ppm boron standard. A licensee representative ,

agreed to complete these changes by July 25, 1987. Progress in this will i be followed in subsequent inspections under Open Item 50-483/87016-0 i i

Licensee representatives were very aware of the value of a good QA/QC

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program and they had spent much effort on its development and implementation. They were receptive to the inspectors' initiatives for improvement and they acted quickly to implement several of the above change i No violations or deviations were identifie ;

l 6. Non-radiological Confirmatory Measurements i 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 to various Technical Specification and other regulatory and administrative reyjirements. 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 1 run in triplicate similarly to routine sample The results are presented j in Table 1 and the criteria for agreement in Attachment 1. These criteria j for agreement are based on comparisons of the mean values and estimates of i the standard deviations (s.d.) of the measurements. Consideration was i given to the fact that the uncertainties (s.d.) of the licensee's results I were not necessarily representative of the laboratory's because they were I obtained by one analyst over a short period of tim 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 in7Attachment 1).

Initially, eleven of the 32 licensee results were in disagreement with those of BN The laboratory experienced difficulties with the lower-level fluoride analyses partly because these were near the lower levels of detection. These were repeated with a recalibration of the

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probe; one result was then within the acceptance limits and the other l was closer. They had particular difficulties with the silica and ;

hydrazine analyses which are both done by spectrophotometers and may i reflect problems in its calibration. The problems with the silica ma also reflect an excessively large silica blank, which was not corrected in the analysis. Problems with the hydrazine may be partially due to excessive aeration of the dilution deionized water that oxidized the hydrazine before analysis. The disagreements in the high-level . chloride and hydrazine appear not to represent a serious problem in themselves, because they differed from the BNL values by less than 8% and the results had high degrees of precision (1-3% relative s.d.). In general the ,

precision within the. individual samples was good,.with a coefficient o I variation (C V., or relative standard deviation).less than 10%. However,

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problems were noted with the other analyses, even when the results were 1 otherwise in agreement. The iron and sodium results had a fairly large l biases, which indicated possibly defective calibration standard The j analysts were hampered in the metals analyses by some operationa '

problems of the atomic absorption spectrophotometer, so that they could not do all the analyses needed to confirm their results. The main j problems appeared to be due to uncertainties of the accuracies of the calibration standards and'possibly the calibration procedure The chemists believed that they had determined the causes of t'he discrepancies in the results and agreed to reanalyze the relevant sample The inspectors noted that the improvements in the QA/QC program discussed in Section 5 should bring these analyses under better control

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i and result in better performance of the analytical program. The resultw of these reanalyses and improvements in the licensee performance will be examined in subsequent inspections under Open Item (50-483/87016-02).

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 bot Open items disclosed during the inspection are discussed in Sections 5 and . Exit Interview ,

The scope and findings of the inspection were reviewed with license ;

representatives (Section 1) at the conclusion of the inspection on May 15, :

1987. The inspectors discussed their concerns about the quality control program and the confirmatory measurements addressed in Sections 5 and Licensee representatives agreed.to modify items relating to these concerns. Telephone conversations held on these matters on May 22 and'

26, 1987, a licensee representative agreed to complete these modifications by July 25, 198 :

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During the exit interview, the inspectors discussed the likely informational content of the inspection report with regard to documents or processes reviewed by the inspectors during the inspection. Licensee representatives did not identify any such documents or processes as proprietar Attachments: Table 1, Nonradiological Interlaboratory Test Results, May 11-15, 1987 Attachment 1, Criteria for Comparing l Analytical Measurements l

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TABLE 1 1 /

Non-Radiological Interlaboratory Test Results l Cellaway Plant Unit 1 '

May 11-15, 1987 l Comparison Analysis NRC Licensee Ratio Comparison Parameter Method Y 1 s.d.(n) X 1 s.d.(n) Z + s. I

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Concentration, ppm j Boron Titra- 985 + 10( 7) 964 + 14 0.979 + 0.017 A tion 2980 150(7) 2943 } .988 - 0.017 A 4870 1 60(7) 4867 1 18 0.999 1 0.023 A Concentration, ppb Fluoride Specific 23.1 1 0.5(8) 27.0 + .169 i 0.050 D Ion 21.8 + 0.95(8) 26.7 7 1. 2' 1.225 + 0.077 D Probe 41.7 7 1.4(7) 43.0 i .031 i 0.042 A Repeat 23.1 7 .8 I .074 7 0.049 A Analyses 21.8 30.95 25.0 3 .14610.065 D Chloride IC 12.05 + 1.6(8) 12.1 + 1.05 1.007 i 0.16 A 1 ~7 0.60(8) 18.6 7 0.16 0.996 + 0.033 A 40.25 1 1.1(8) 37.0 } 0.69 0.923 ~ 0.037 D* ,

Sulfate IC 10.0 1 0.45(7) 11.1 1 .11 1 0.22 A 20.5 1 1.2(8) 18.2 1 0.94 0.888 1 0.069 A 40.4 + 2.5 (7) 35.3 1 0.47 0.874 1 0.049 D*

Silica Spectro- 27.2 + 2.8(7) 28.7 +~ .055 + 0.117 A 54.5 13,5(7) 45.3 1 ~

photo- 0.831 1 0.058 D i metric 80.0 1 2.5(7) 120.0 1 .50 1 0.065 D Copper AAS 4 ~+ 2.4(12) 49.3 + .053 + 0.061 A 9 .9(14) 104.3 7 .080 I 0.063 A 3 i6(12)

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145 153 ~1 2 1.05510.046 A Iron AAS 48.9 + 3.5(13) 39.9 + .816 + 0.092 A*

95.5 7 3.4(14) 89.3 7 .935 7 0.050' A

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147 34.2(13)110 } .748 1 0.044 TT Nickel AAS 50.9 1 2.6(6) 48.9 + .961 + 0.059 A ,

102 +3 (7) 96.6 I .947 7 0.028 A 153 ~+ 4(6) 148 i .967i0.061 A Sodium AAS 4.58 * 0.5(6) 4.2 + .917 + 0.102 A 9.23 i 0.8(6) 7.5 7 .813 7 0.11 A 14.4 {0.8(6) 9.9i 1,3 0.68810.098 D ,

Hydrazine Spectro- 22.3 1 1.4(7) 15.0 1 ). 4 0.673 2 0.075 D photo- 56.9 1 0.7(7) 46.7 3 .821 + 0.015 0 metric 104 1 1.0(7) 96.0 1 .923 1 0.013 D

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a. Value + standard deviation (s.d.); n is number of BNL analyse The number of licensee analyses is 3 unless otherivise note l

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b. A = Agreement D = Disagreement j

Substituted the BNL uncertainty for licensee's uncertaint ;

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ATTACHMENT 1 Criteria for Coinparing' Analytical Measurements This attachment provides criteria for comparing results of the capabilit 1 The acceptance limits are based on the uncertainty (standard deviation)ofy th test J ratio of the licensee's mean value (X) to the NRC mean value (Y), where )

(1)' Z = X/Y is the ratio, and .{ '

(2) S is the uncertainty of the ratio determined from the pfopagationoftheuncertainties'oflicensee'smeanvalue, j

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

S 3 3 Yz ' _Vx, h , so that

[S*2 + S2D SZ =Zel Y--

(X2 y2)

-l The results are considered-to be in agreement when the bias in the ratio I (absolute value of' difference between unity and the ratio) is less than or equal to twice the uncertainty in the ratio, l 1-Z l < 2*S 7 'I National Council on Radiation Protection and Measurements, i A Handbook of Radioactivity Measurements Procedures, NCRP '

Report No. 58, Second Edition, 1985, Pages 322-326 (see Page324).

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