IR 05000483/1989017

Insp Rept 50-483/89-17 on 890821-25.No Violations or Deviations Noted.Major Areas Inspected:Chemistry Program, Including Procedures,Organization,Training,Primary & Secondary Sys Water QC Programs & Qa/Qc Program in Lab

ML20248A577
Person / Time
Site:	Callaway
Issue date:	09/22/1989
From:	Holtzman R, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III)
To:
Shared Package
ML20248A565	List: IR 05000483/1989017 ML20248A562
References
50-483-89-17, NUDOCS 8910020251
Download: ML20248A577 (13)

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x, U.S. NUCLEAR REGULATORY COMMISSION REGION.III

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Report No. 50-483/89017(DRSS)

Docket No. 50-483 License No. NPF-30 Licensee: Union Electric Company Post Office Box 149 - Mail Code 400 St. Louis, M0 63166 Facility Name: Callaway Plant, Unit 1 Inspection At: Callaway Site, Steedman, Missouri Inspection Conducted: August 21-25, 1989 (Onsite)

August 31 and September 6, 1989 (Telephone discussions)

Inspector:

0 0l R. B. Holtzman 7/dd/N D&te Approved By:

Y M. Cl Schumacher, Chief 6f>/7 Radiological Controls and Date Chemistry Section Inspection Summary Inspection on August 21-25 and 31 and September 6, 1989 (Report No. 50-89017(CRSS))

Areas Inspected: Routine, unannounced inspection of the chemistry program, including (1) procedures, organization, and training (IP 84750); (2) primary and secondary systems water quality control programs (IP 84750); (3) quality assurance / quality control program in the laboratory (IP 84750); and (4) nonradiological confirmatory measurements (IP 79701). Also reviewed were past Open Items and audit Resul ts: The licensee has an extensive water quality control program that conforms to the EPRI Steam Generator Owners and Primary System Guideline The licensee's QA/QC chemical measurements program was improved over that of the previous inspection, but the initial results of the nonradiological confirmatory measurements were only fair and demonstrated some weaknesses-in the QA/QC program. The licensee agreed to correct deficiencies in the progra !

l No violations or deviations were identified during this inspectio ,

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DETAILS Persons Contacted l G. L. Randolph, General Manager, Nuclear Operations, UE l 2 J. R. Peevy, Assistant Manager, Technical Services, UEN0

J. R. Polchow, Superintendent, Chemistry and Radwaste, UENO C. A. Riggs, Supervisor, Chemistry, UEN0 L

R. R. Roselius, Superintendent, Health Physics, UENO I 1 W. R. Robinson, Assistant Manager, Operations and Maintenance, UE

G. W. Hamilton, Supervisor, Radwaste, UEN0 2,20. J. Voeller, Rad / Chem Foreman, UEN0

J. .Little, Engineer, UEQA

N. Lombardi, Engineer, UEQA

F. W. Eggers, Engineer, UEQA K. R. Bryant, Reactor Engineer,UEN0 D. Sievel, Radchem Technician (RCT), UEN0 R. D. Kelley, RCT, UEN0 R. L. Manning, Assistant RCT, UENO

B. H. Little, Senior Resident Inspector, NRC The inspector also interviewed other' licensee personnel in various departments in the course of the inspectio Denotes those present at the plant exit interview on August 25, 198 Telephone discussions held on August 31 and September 6, 198 . Licensee Action on Previous Inspection Findings (IP 92701)

(Closed) Open Item (50-483/88017-02): Licensee to spike and split with BNL a sample of RCS and S/G water and analyze and submit the results to Region III for comparison with those from BNL. A comparison is given in Table 1 only for the metal ion results for the split samples; Brookhaven has no record of receiving the other sample. The comparison criteria are presented in Attachment 1. Although, the ratios appear to be large, the results are in agreement. Since a new split san.ple will be submitted in this inspection, this item is close . Management Controls, Organization and Training (IP 84750)

The organization of the Chemistry Department is similar to that in the previous inspection in this area (Inspection Report No. 50-483/88017).

The Supervisor, Chemistry reports to the of Superintendent, Chemistry and Radwast A Chemist and Chemical Engineer, along with four laboratory foremen and 15 Radiation Chemical Technicians (RCT), operate the laboratory. All the RCTs are qualified under ANSI /ANS-3.1-197 .

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'The personnel.have changed within the organization. The previous Chemist

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left and was replaced in an acting position by a Laboratory Foreman. He, appears to be well-qualified; he has a degree in chemistry and is working on.a Master's degree in Nuclear Engineering; his experience includes nine

' years at the plant and six years as a Navy ELT. Two foremen supervise-the hot and cold laboratories, while the'other two work on various otherL projects. The personnel complement and organization appear to be adequate for the chemistry program.

_ No' violations or deviations were identifie . Water Chemistry Control Program (IP 84750)

The_ licensee's water chemistry control programs are essentially the same as those in the previous report in this area'(Inspection Report No. 50-483/88017).

The Post Accident Sampling System was designed to limit the radiation exposure to workers under accident conditions by incorporating remotely-operated sampling and measurement systems operated from the counting room; RCS boron concentrations (by neutron absorption) and gamma activities by a Ge spectrometer are monitored inlin The Chemistry Department stores most of the measurement results in a computerized data management system (CDMS) from which various reports are compiled regularly. Trend charts of the chemistry parameters for th various system are plotted on a monthly basis, including chloride, sulfate, fluoride, specific and cation conductivities, hydrogen, boron, lithium and dissolved oxygen. Relevant operational. parameters are also plotted,. including reactor power levels and steam generator blowdown rates. They also submit a monthly letter to the Assistant Plant Manager, Operations with information on significant trends and event The water quality of the secondary systems during normal operations was generally very good; the concentrations of the contaminant control and indicator parameters, including chloride, sulfate,- sodium and silica were generally well below the licensee /EPRI secondary system guidelines. The primary system parameters appear to be maintained within their respective guideline The inspector also reviewed some of the data on the chemistry parameters with T/S limits, including the boric acid storage tanks (BAST) A and B and~

the refueling water storage tanks (RWST). 1hese all appeared to be within the specified concentrations, or were brought within specifications in the required time No violations or deviations were identifie i l

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.i 5. Implementation of the Chemistry Program-(IP 84750)

The inspector reviewed the chemistry programs including physical facilities and laboratory operations. Both the. hot and cold laboratories had sufficient room, good instrumentation, and good maintenance. The inspector noted that the temperature of the cold laboratory was high, over 80 F and variable. -This could impact on the instrumentation, especially the ion chromatograph, and technician performances. The Chemist noted that management-was investigating this problem. A check on the air conditioner showed it to be working at its specified capacity; they are now looking 'j into modification to increase its outpu The inspector observed several technicians analyze the confirmatory measurements samples, including boron by an autotitrator, and metals by atomic absorption spectrophotometry (AAS). They appeared to be generally knowledgeable about the work and followed the procedure Overall, the housekeeping was good and the laboratories appeared to be adequate for the proper operation of the plan No violations or deviations were identifie . Nonradiolegical Confirmatory Measurements (IP 79701)

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 requirement These samples had been prepared, standardized, and periodically reanalyzed (to check for stability) for the NRC by the Radiological Sciences Division of Brookhaven National Laboratory (BNL).

The samples were analyzed by the licensee using routine methods and equipmen 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 2 and the criteria for agreement in Attachment 1. These criteria for agreement are ba. sed on comparisons of the mean values and estimates of the standard deviations (SD) of the measurements. Modifications made to these criteria (Attachment 1 Notes) are based on the consideration that the uncertainties (SD) 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 tim The licensee also prepared a sample of secondary system water spiked with the anion analytes fluoride, chloride and sulfate to be split with BN _ _ _ - - - _ - _ _ - - - - _ _ - - . - _ _ __ .1

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The licensee determined the concentrations of the analytes and the results '

will be compared to those determined by BNL. This will be followed under Open Item No. 50-483/89017-0 The licensee determined 11 analytes at three concentrations each. Of the initial 33 analyses, 19 were in agreement (58%). The disagreements were in the fluoride, and two of the three samples of chloride, sulfate, iron, copper and sodium. The fluoride results were low, indicating that the licensee's calibration standards were high, while those for chloride and sulfate appeared to be low. Reruns of the samples at higher concentrations ar.d new standards, brought the results into agreemen The problems with the metal analyses appeared to be due both to the use of the graphite furnace, which appears to be a generic problem with this type of analysis and to the sample matrix which contains copper, nickel and chromium. Additionally, the very small concentrations of the analytes (4

- 24 ppb) may have compounded the difficulties. Rerunning these with the flame and at higher concentrations brought them into good agreement and showed that the standards were good. Sodium presented similar problems; the precision of the sodium analysis in other laboratories has also been generally poor at the low concentrations used her Following adjustment of the concentrations and recalibration, the results of the reruns were then all in agreement. If one takes into account the possibility of matrix effects in the metal ion analyses and the initially low concentrations of the analytes, overall, the results of the analyses were good. Some particular problems were identified, mainly the large biases and wide control limits in the QC charts, as discussed in Section The licensee is in the process of assessing and rectifying the problem Progress in the improvements in the analyses and the control charts will be followed in subsequent inspections in this are No violations or deviations were identifie . Quality Assurance and Quality Control for Nonradiological Chemistry (IP 84750)

The inspector reviewed the nonradiolagical QA/QC program for both the ,

primary end secondary systems laboratories. This program is controlled by '

Chemistry Departmental Procedures reviewed in the previous inspection (Region III Inspection Report No. 50-483/88017):

CDP-ZZ-00300 Control of Chemistry Instrumentation and Equipment, Revision 13, January 6, 1988, and j CDP-ZZ-00700 Laboratory Quality Control Progrem, Revision 9 August 22, 198 The related Chemistry Technical Procedures have been revised since the previous inspection: 4

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CTP-ZZ-04701 Control Chart Construction and Use, Revision 6, June 29, 1989; CTP-ZZ-04702 Quality Control Verification Program, Revision 3, November 29, 1988; The second procedure above gives the key nonradiological parameters for analysis as boron, chloride, fluoride, sulfate, silica, iron, copper' and sodiu Control charts were implemented for these analyses with warning I limits'of two standard deviations (SD) and control limits of three SD' Control charts have been revised to' implement control limits of two standard deviations (SD). The procedures require that the results from the performance standards be within the control limits before the RCT may proceed with the analyse This program has been modified extensively to address the concerns expressed in the previous inspection in this area. The mean and SD values are calculated quarterly from the performance check standard data, and the previous QC chart remains in the book. The mean and control limit values, expressed as recovery (the ratio of the measured value to the expected value of the check standard) of the performance data are shown on the charts. All of the more significant analytical procedures now have control charts, and separate logsheets were implemented for the performance check data. The calibration and control standards are now from different sources, i.e. different manufacturers or different lot The procedures also take into account the possible nonlinearity of calibration curve The inspector noted some concerns about the QA/QC program: On many of the charts, the mean values had substantial biases with respect to the stated values of the standards, such as 5 % for chloride, 15 -25% for sulfate, 23% for total organic carbon (TOC),

and 9% for copper. These varied from time to time. When this happens the problem should be checke The control limits should be recalculated when a substantial bias is seen. If this is not done it can lead to very wide control limit It appears that the check standard data need to be assessed more frequently than is done presently. Licensee representatives noted that the check standard data are calculated monthly, although the QC charts are revised only quarterly. They agreed to check and assess the parameters monthly for changes.

l The laboratory also started in December 1988 under procedure CTP-ZZ-04704,

" Equipment Trending Charts," Revision 0, June 5, 1989, a similar QC program for inline instrumentation, including conductivity, sodium, dissolved oxygen, and pH, in which instrument readout is periodically compared to laboratory or check standard values and plotted. This appears to improve the credibility of data from these sources.

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The licensee has' an extensive Interlaboratory Crosscheck program with a vendor. (Analytics, Inc.) where they analyze sets of unknown samples quarterly. Each technician analyzes each of the samples, so that each is

!- . tested at least twice a year. The acceptance criteria are based on three sigma. derived from the instrument QC control charts. The inspector noted two weaknesses in the program: the results are not used to asse.s the laboratory as a whole, and technician performance is not formally intercompared.-

Licensee representatives acknowledged these concerns and agreed to consider them. Progress in this and the QA/QC program will be followed in subsequent inspections under Open Item 50-483/89017-0 No violations or deviations were identifie . Audits and Surveillance (IP 84750)

The inspector reviewed some recent audits and surveillance of the Chemistry Department progra QA Audit AP 88-019, November 23, 1988 found that the procurement and receipt of chemicals used in safety-related systems, i.e. the RCS, were poorly documented, botn for manufacturers specifications and of tests made on the materials by the licensee. The licensee has corrected this with a system that includes a checklist, document control and acceptance limits for material No violations or deviations were identifie . Defective Fuel Rods in the Spent Fuel Pool (SFP) (IP 79701)

During the inspection, while the licensee was trying to remove defective fuel rods from the SFP two of the rods apparently broke. The inspector reviewed some of the chemistry records to note changes owing to placing the fuel bundles in the pool about October 1987. Of the parameters tabulated in the CDMS records only the chloride appeared to change; when the fuel was placed in the pool the chloride concentrations rose from below 5 ppb to above 25 ppb over a period of few months and then over about six months returned slowly to the present value of about 10 pp The licensee's administrative specification for this system is 100 pp The significance of the change is not clear; it could be due to defective fuel or to just adding additional material to the poo Further, the water is cleaned by a demineralized bed operated at irregular interval One set of gamma spectra was reviewed, one taken just before the second fuel rod was broken in the pool and one just after. The nuclide activities in the water were not much changed, except for Cs-134 activity which about doubled in the second sampl A licensee representative agreed to forward a trend chart showing concentrations of the cesium isotopa from 1987 to the presen The licensee prepared a summary report to assess the fuel defect / leakage problem and has concluded, based on various factors in RCS, such as 1-131/I-133 and Cs-134/Cs-137 ratios and I-131 spikes associated with

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. power changes in the reactor, that several fuel leaks w2re present in the RC Radioactivity in the RCS was well within. technical specification limit No violation or deviations were identifie . Open Items Open items are matters which have been discussed with the licensee, which will be reviewed further by the inspector, 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 6 and . Exit Interview The scope and findings of the inspection were reviewed with licensee representatives (Section 1) at the conclusion of the inspection on August 25, 1989. The inspector discussed concerns about the quality control program and the confirmatory measurements addressed in Sections 6 and Telephone conversations were held with licensee representatives on August 30 and September 6, 1989 relating to the confirmatory measurements result During the exit interview, the inspector 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:

1. -Table 1, Nonradiological Interlaboratory Split Sample Results, August 1988 2. Attachment 1, Criteria for Comparing Analytical Measurements (Nonradiological)

3. Table 2, Nonradiological Interlaboratory i Test Results, August 21-30, 1989 1 o>

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TABLE 1 Non-Radiological Interlaboratory Split Sample Results Callaway Plant August 1988

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Analyte a Analytigal NRC Licensee Ratio Comparison Method Y SD X i SD I i SD i 2 SD -

Concentration, ppb Fe AA/FL 238 7 269 1 26 1.130 0.114 A

.Cu AA/FL 218 12 257 24 1.179 0.128 A-a. A = Agreement D = Disagreement b. AA/FL Atomic Absorption Analysis (Flame)

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l-Criteria for Comparing Analytical Measurements p

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This attachment provides. criteria for' comparing results of the capabilit The acceptance limits are based on the uncertainty (standard deviation) y te of the 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

. propagation of the uncertainties of licensee's :nean value, S , and of the NRC's mean value, Sy.1 Thus, x

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

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ATTACHMENT 1

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NOTES

' The uncertainties may-be modified in cases.of disagreement:

a .' If the;1icensee'.s SD, S is smaller than that of the NRC, the NRC's i -l relative' standard deviafion (RSD) (S /Y) will be substituted for

.that of the licensee (S x/X), and the Yagreement criteria recalculate : If a disagreement and the RS3s appear to be unreasonably low, RSDs H

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of 3% will be substituted fcr those of both the NRC and the. license This will not be done for the boron analyses where the expected RSDs are 0.5-1%.

IJ. 'Due to some uncertainties in the values of the 1987 (87) boron standards, the mean values of the concentrations obtained by the plant laboratories in Regicn III are used as the NRC values. These results appear to have resolved the problem of the consistently negative biases between the licensees and BNL boron analyses. The licensees generally reported similar values of the 1000 ppm standard with a~relatively small RSD of 11.7%, although the analytical methods differe _ _ _ . - - _ - - - - - _ - _ _ - - - _ . - _ _ _ - - - - - _ - _ - - - _ - - - - _ - - . _ - - - - - - - - - - - _ - - - - - - = - - - - - - - - - - - - - - - - - - - _ - - - - - - _ - - - - - - - - - - - - - - - - -

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TABLE 2 I

Non-Radiological Interlaboratory Test Results Callaway Plant August 21-30, 1983 a a b Analyte Analytjcal NRC - Licensee Ratio Comparison Method Y t SD X i SD Z i SD i 2 SD Concentration, ppb Fluoride SIE 45.0 1 .0 1 .733 0.092 D*

l 63.4 i .3 1 .840 1 0.045 D+

82.8 1 .7 1 .854 i 0.025 D*

(rerun) 225 20 220 1 4 0.978 1 0.089 A 423 1 8 426 1 0 1.007 1 0.019 A 414 9 437 1 0 1.056 0.031 A*

Chloride IC 3.70 0.02 i .514 i 0.068 D+

5.59 1 0.09 .8 1.144 1 0.144 A 7.65 1 0.12 . 3 1.163 0.050 D+

(rerun) 18.5 1 .8 1 .070 1 0.048 A+

18.6 1 .1 .081 0.048 A+

19.1 1 .7 1 .030 1 0.019 A

' Sulfate IC .3.90 1 0.28 .2 1.256 0.328 A*

5.74 0.40 .6 1.184 1 0.134 A 7.80 1 0.23 .2 1.167 1 0.042 D*

(rerun) 1 .4 1 .6 1.000 0.078 A 19.2 1 .6 1 .076 0.076 A 19.5 1 .9 1 .021 i 0.040 A Fe AA/FU 8.0 1 .8 i .225 1 0.060 D+

11.7 1 .3 1 .137 1 0.045 D+

2 . 6 24.0 1 .075 1 0.041 A*

'(rerun) AA/FL 111 1 3 118 3 1.059 0.039 A 1327 1 17 1350 1 23 1.018 0.022 A 1838 49 1940 42 1.056 1 0.036 A 1990 25 1980 1 35 0.995 1 0.022 A 1950 1 50 1960 1 35 1.005 1 0.031 A Cu AA/FU 4.0 1 .6 .150 1 0.078 A 6.0 1 . 8 .133 i 0.051 D+

1 .2 1 .125 1 0.050 D+

(rerun) AA/FL 120 1 2 120 1 2 1.002 1 0.022 A 1343 50 1330 10 0.990 1 0.038 A 1976 1 30 2030 1 10 1.027 0.016 A 2015 1 75 2080 1 23 1.032 1 0.040 A 2000 50 2070 25 1.035 i 0.029 A (rerun) AA/FL 120 1 2 120 1 2 1.002 1 0.022 A

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a a b Analyte Analyt NRC Licensee Ratio Comparison Method { cal Y .SD X i SD Z i SD i 2 SD Concentration, ppb Ni AA/FU 8.34 0.14: 10.5 1 .259 0.042 D 12.1- 1 .6 1 .124 i 0.062 A 2 .7 2r,. 7 1 .094 1 0.046 D+

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1390 i'23 1400 20 1.007 1 0.022 A 2006 1 59 2000 i 12 0.997 1 0.030 A

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2017' i 83- 2040 10 1.012 1 0.042 A Na AA/FU 3.03 1 0.3 .1 1 .025 0.123 A 5.05 1 0.29 6.2 1 .228 1 0.098 D*

7.90 0.45 6. 7 1 .848 1 0.068 D*

(rerun) AA/FL 297 1 34 303 1 6 1.022 1 0.120 A

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765 1 44 817 1 12 1.068 0.063 A Li AA/FL 985 20 967 1 12 0.982 0.023 A 1500 1 35 1450 1 18 0.967 t 0.026 A 2065 i 50 1963 21 0.951 1 0.025 A Hydrazine' Spec 19.9 1 .3 1 .020 0.034 A 4 .5 5 . 6 1.036 1 0.043 A+

109 1 1 99.3 i .993 1 0.012 A Silic Spec 52.8 1 .7 5. 8 0.979 0.122 A 106 4 105 1 7 0.990 1 0.076 A 157 2 153 1 11 0.975 1 0.071 A Concentration, ppm d

Boron Titr 1002 10 993 1 4 0.991 1 0.011 A 8/89 2970 23 2947 1 10 0.992 1 0.008 A 4919 47 4863 22 0.989 0.010 A a. Value standard deviation (SD); the number of analyses is from 6 to 9 for BNL and three for the license b. A = Agreement 0 = Disagreement c. Analytical methods: Titr - titration IC - Ion chromatography AA/FU - Atomic absorption Spectroscopy (furnace)

AA/FL - Atomic absorption Spectroscopy (flame)

SIE - Specific Ion Electrode Spec - Ov/VIS Spectrophotometry d. NRC (BNL) Values replaced by mean values of plants in Region II * Substituted the BNL uncertainty for licensee's uncertaint + Assumed a 3% Relative Standard Deviation (3% RSD).

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