IR 05000245/1993014
| ML20036C305 | |
| Person / Time | |
|---|---|
| Site: | Millstone  |
| Issue date: | 06/08/1993 |
| From: | Bores R, Kottan J NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I) |
| To: | |
| Shared Package | |
| ML20036C301 | List: |
| References | |
| 50-245-93-14, 50-336-93-10, 50-423-93-12, NUDOCS 9306160081 | |
| Download: ML20036C305 (11) | |
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U.S. NUCLEAR REGULATORY COMMISSION
REGION I
50-245/93-14 50-336/93-10 Report Nos.: 50-423/93-12 50-245 50-336 Docket Nos.: 50-423 DPR-21 DPR-65 License Nos.: NPF-49 Licensee:
Northeast Nuclear Energy Company P.O. Box 270 Hartford. Connecticut 06101 i
Facility Name:
Millstone Nuclear Power Station. Units 1. 2 and 3
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Inspection At:
Waterford. Connecticut
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Inspection Conducted:
May 17-21.1993 sV
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.i Inspector:
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J. K[ttan, liboratory Specialist Date Effluents Radiation Protection Section (ERPS)
Facilities Radiological Safety and Safeguards Branch (FRSSB)
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Approved By:
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R.
res, Chief, ERPS, FRSSB g Date l
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Di sion of Radiation Safety and S'afeguards Areas inspected: Announced inspection of the non-radiological chemistry programs. Areas reviewed included: Confirmatory Measurements - Chemical and Laboratory QA/QC.
Results: The licensee had in place effective programs for measuring chemical parameters in plant systems samples. Nc safety concerns or violations of regulatory requirements were observed.
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Details
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1.0 Individuals Contacted Principal Licensee Employees G. D'Auria, Senior Chemist
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Fontancz,12boratory Supervisor - Unit 3 R. Griffin, Chemist -
D. Harris, Licensing Engineer
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Itteilag, Chemistry Supervisor - Unit 2 i
J.
Kangley, Senior Engineer
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J.
Kelly, Laboratory Supemsor - Unit 1
P.
Lutzi, Licensing
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Macklin, Chemistry Supervisor - U' nit 3 C. Palmer, H.P. Support Manager
D. Peiffer, Chemistty Supervisor, Technical Services
M. Peterson, Chemistry QA
R.
Poole, Laboratory Supervisor - Unit 2 J.
Waters, Chemistry Manager
D. Wilkins, Chemistry Supervisor - Unit 1 USNRC Emnloyees P.
Swetland, Senior Resident inspector
Denotes those present at the exit meeting on May 21, 1993. The inspector also
interviewed other personnel, including the chemistry technicians who performed the analyses for this inspection.
2.0 Purpose The purpose of this inspection was to review the following areas:
1.
The licensee's ability to measure chemical parameters in various plant systems
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samples.
2.
The licensee's ability to demonstrate the acceptability of analytical results through
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implementation of a laboratory QA/QC program.
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3.0 Laboratory Oreanization and Ooeration Millstone Nuclear Power Station, Units 1,2 and 3 had two chemistry laboratories. Units I and 2 shared a combined chemistry laboratory while Unit 3 had a separate chemistry
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laboratory. Some instrumentation and procedures in the Unit I and Unit 2 laboratory l
were utilized for the analyses of samples from either unit and some instrumentation and procedures were dedicated to only the analysis of samples from a specific unit. The data which are presented in Table I note whether the results are from a specific Unit 1 or
Unit 2 instrument and procedure or a combined instrument and procedure.
The chemistry organization was a site-wide organization under the direction of a site
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l chemistry manager.
Reporting to the chemistry manager were unit chemistry supervisors, chemists, chemistry specialists, and technicians. The chemistry organization also included a Technical Support Group which was responsible for implementation of the laboratory QA/QC program.
4.0 Chemical Confirmatory Measurements During this part of the inspection, standard chemical solutions were submitted to the licensee for analysis. The standards were prepared by Oak Ridge National Laboratory (ORNL) for the NRC and were analyzed by the licensee using routine methods and equipment. The analysis of standards is used to verify the licensee's capability to I
monitor chemical parameters in various plant systems with respect to Technical Specifications and other regulatory requirements. In addition, the analysis of standards is used to evaluate the licensee's analytical procedures with respect to accuracy and l
precision. The standards were submitted to the licensee for analysis in triplicate at three I
concentrations spread over the licensee's normal calibration and analysis range. The i
Unit 3 laboratory ammonia results at approximately 250 parts per billion (ppb) were analyzed only in duplicate due to lack of sufficient volume of the NRC standard.
Also, a sample was spiked with a standard anion solution and sent to ORNL for analysis.
The analyses to be performed on the sample are chloride and sulfate. The licensee will perform the same analyses on an aliquot of this spiked sample. The results of these analyses will be compared when received at a later date and will be documented in a subsequent inspection report. The analysis of spiked sample permits comparisons from l
an actual sample matrix.
The results of the standard measurements comparisons indicated that all of the measurements were in agreement or qualified agreement under the criteria used for comparing results (see Attachment I to Table 1) with one exception. The one exception was the ammonia result at approximately 100 ppb as determined by the Unit 2 laboratory ion chromatography (lC) system. The IC ammonia calibration curve was non-linear, but the licensee used a straight line, point to point fit to the three point calibration data. The licensee utilized this method of calibrating the IC because the IC software would not
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perform a curve fit to the ammonia calibration data. The inspector discussed this matter with the licensee and the licensee stated that this area would be reviewed and appropriate action taken. The inspector stated that this area would be reviewed during a subsequent
inspection in this area. Additionally, the licensee was unable to provide sulfate results j
from the Unit 3 laboratory IC. The licensee's initial sulfate results were not as precise l
as the results obtained by the licensee's Unit 1 IC and Unit 2 IC. The licensee then began to " trouble shoot" the Unit 3 IC and had not completed the " trouble shooting" by
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I the conclusion of the inspection. The inspector discussed this matter with the licensee, l
and the licensee stated that the Unit 3 IC method of analysis would be changed to that
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used on the Unit 2 IC. The inspector stated that this area would be reviewed during a subsequent inspection in this area. The data are presented in Table I.
No safety concerns or violations were identified in this area.
5.0 Laboratorv OA/OC The licensee's laboratory QA/QC program is described in Procedure CP 800/2800/3800,
Quality Control Program. This procedure provided for both an intralaboratory and an interlaboratory QC program. The intralaboratory program consisted ofinstrument and procedure control charts for trending performance and the semi-annual analysis of spiked samples. The interlaboratory program consisted of the semi-annual analysis of unknown samples received from an outside laboratory. In addition, the licensee maintained a
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separate procedure for the preparation and use of control charts.
The inspector reviewed selected data generated by the licensee's laboratory QA/QC program for 1992 and 1993 to date and, based on this review, noted that the licensee was implementing the laboratory QA/QC program as required. In particular, the inspector noted the detailed statistical analyses and reviews of the laboratory QC data. The inspector further noted the licensee's proactive approach to using the laboratory QA/QC program results for refining and improving analytical methods. The inspector concluded that the above aspects of the licensee's laboratory QA/QC program were noteworthy.
No violations were identified in this area.
6.0 Exit Meetine The inspector met with the licensee representatives denoted in Section 1 at the conclusion of the inspection on May 21,1993. The inspector summarized the purpose, scope and Endings of the inspection. The licensee acknowledged the inspection Dndings.
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. TAllLE I Millstone Nuclear Power Station Analytical Chemistry Test Results
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Chemical Method of
'NRC Licensec Analysis Analysis Known Value Value Comparison
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Results in parts per billion foob)
l.94 0.05 1.86iO.06 Agreement 3.65 0.11 3.65 0.03 Agreement 7.7i0.3 7.60 0.06-Agreement Sulfate IC'
l.94 0.03 2.13 0.08 Agreement 3.88 0.06 4.243 0.005 Agreement 7.9i0.2 8.60 0.07 Agreement Results in carts per million (ppm)
Zine ICP'
O.109i0.003 0.108 0.002
' Agreement 0.522 0.007 0.522 i 0.008 Agreement 1.03 0.01 1.057 0.006 Agreement Results in parts per billion (opb)
- Sodium IC 5.30.2 4.81 0.07 Agreement 10.2io.3 9.5i0.2 Agreement 15.5 0.4 14.5 i 0.3 Agreement
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TABLE I - (Cont'd)
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Millstone Nuclear Power Station Analytical Chemistry Test Results Chemical Method of N_Rf Licensee Analysis Analysis Known Value Value Comparison Results in parts per billion (oob)
Fluoride IC 2.02 0.08 1.94 0.07 Agreement 4.0i0.2 3.97 0.09 Agreement 8.4 0.4 7.9i0.2 Agreement
Chloride IC 1.94 i 0.05 2.03 0.12 Agreement 3.65 0.11 3.66 0.06 Agreement 7.7 0.3 7.58 0.11 Agreement Sulfate IC:
1.94 0.03 2.04i0. I1 Agreement 3.8810.06 3.83 0.15 Agreement 7.9i0.2 8.0i0.02 Agreement
Ammonia IC 110 3 129 2 Disagreement 305 5 317il3 Agreement 482 i 7 506 8 Agreement
Hydrazine SP 13.23 i 0.06 11.69 0.12 Qualified Agrmnt.
34.1 i 0.3 30.9 i 0.5 Qualified Agrmnt.
56.5 i 1.0 51.3 i 0.2 Qualified Agrmnt.
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TABLE I - (Cont'd)
Millstone Nuclear Power Station Analytical Chemistry Test Results Chemical Method of N_R_C Licensee Analysis Analysis Known Value Value Comparison Results in parts per million (opm)
Lithium IC 0.493 0.007 0.502 i 0.009 Agreement 1.24 i 0.02 1.25 0.02 Agreement 2.43 i 0.03 2.56 i 0.04 Agreement Iron ICP'
O.398iO.004 0.399 0.002 Agreement 0.796 i 0.008 0.796iO.003 Agreement 1.59 i 0.14 1.576 0.015 Agreement Copper ICP'
O.404 0.004 0.4057 0.0015 Agreement 0.806 i 0.008 0.7977 i 0.0015 Agreement 1.62i0.02 1.580 i 0.010 Agreement Nickel ICP'
O.398 0.004 0.4027 0.0015 Agreement 0.800 0.008 0.800 i 0.003 Agreement 1.60 i 0.16 1.57 0.02 Agreement Chromium ICP'
O.400 0.004 0.403 i 0.002 Agreement 0.804 i 0.008 0.798 0.002 Agreement 1.608iO.014 1.56 i 0.02 Agreement
Boron T
506 i 8 504.1 1.0 Agreement 1049ill 1030.9 i 0.5 Agreement 3040 i 40 3030.8io.8 Agreement
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Millstone Nuclear Power Station Analytical Chemistry Test Results Chemical Method of NRC Licensee Analysis Analysis Known Value Value Comoarison Results in parts ner billion foob)
- Silica SP'
12.17 i 0.13 13.454 0 Agreement 28.4 i 0.4 26.908 0 Agreement 60.1 1.0 61.3 i 0.7 Agreement
Sodium AA-GF 5.30.2 5.7 0.4 Agreement 10.2 0.3 10.6 i 0.3 Agreement 15.5 0.4 16.3 0.2 Agreement Fluoride IC*
5.110.2 4.8i0.4 Agreement 10.0 0.5 10.1i0.2 Agreement Ammonia IC*
110 i 3 118.3il.0 Agreement
241 i 4 240 2 Agreement 305 5 318.4 1.2 Agreement flydrazine SP2 13.26 i 0.06 13.37 0.15 Agreement 34.1iO.3 35.2 0.6 Agreement 56.5 1.0 56.8 i1.0 Agreement Silica SP8 12.17 0.13 11.67 0.12 Agreement 28.4 0_.4 24.97 i 0.15 Qualified Agrmnt.-
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60.I 1.0 60.2 i 0.6 Agreement _
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TABLE I - (Cont'd)
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Millstone Nuclear Power Station Analytical Chemistry Test Results Chemical Method of NRC Licensee Analysis Analysis Known Value Value Comoarison Results in parts per billion foob)
Chloride IC 1.94 0.05 1.85 0.10 Agreement 3.65 i 0.11 3.4i0.3 Agreement 7.7 0.3 6.8310.15 Qualified Agrmnt.
Results in parts per million (com)
Boron T*
506 i 8 510.6 0.9 Agreement 1049 11 1039.6 i 1.2 Agreement 3040 40 3052.4 1.6.
Agreement Lithium
'd 0.493 i 0.007 0.457 i 0.013 Agreement 1.24 0.02 1.183 0.006 Agreement 2.43 0.03 2.377 i 0.006 Agreement Iron ICP*
0.398 0.004 0.397 0.011 Agreement 0.796 i 0.008 0.779 i 0.004 Agreement 1.59 0.14 1.58 i 0.02 Agreement
Copper ICP 0.404 i 0.004 0.389 0.007 Agreement 0.806 i 0.008 0.772 i 0.010 Agreement 1.62 i 0.02 1.6000 0.0010 Agreement
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TABLE I - (Cont'd)
Millstone Nuclear Power Station Analytical Cliemistry Test Results Notes:
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Unit 1 procedure / instrument
Unit 2 procedure / instrument
' Combined Ul/U2 procedure / instrument
Unit 3 procedure / instrument 5 Duplicate analysis only IC lon Chromatography
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UV-Vis Spectrophotometry SP
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Potentiometric Titration T
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Inductively Coupled Plasma Emission Spectrometry ICP
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AA-GF = Graphite Furnace Atomic Absorption Spectrometry
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ATTACHMENT 1 TO TABLE I
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Criteria for Comparing Analytical Measurements from Table 11 This attachment provides criteria for comparing results of capability tests. In these criteria the
judgement limits are based on data from Table 2.1 of NUREG/CR-5244, " Evaluation of Non-
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Radiological Water Chemistry at Power Reactors." Licensee values within the plus or minus two standard deviation range (i2Sd) of the ORNL known values are considered to be in agreement. Licensee values outside the plus or minus two standard deviation range but within z
the plus or minus three standard deviation range ( 3Sd) of the ORNL known values are
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considered to be in qualified agreement. Repeated results which are in qualified agreement will receive additional attention. Licensee values greater than the plus or minus three standard deviations range of the ORNL known value are in disagreement. The standard deviations were computed using the average percent standard deviation values of each analyte in Table 2.1 of
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the NUREG.
The ranges for the data in Table 11 are as follows.
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Agreement Qualified Agreement Analyte Range Range Chloride 8%
12 %
Fluoride 12 %
18 %
Sulfate 10 %
15 %
Silica 10 %
15 %
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Sodium 14 %
21 %
Copper 10 %
15 %
Iron 10 %
15 %
Baron 2%
3%
i Ammonia 10 %
i 15 %
Hydrazine 8%
12 %
Lithium i 14 %
21 %
Nickel 6%
9%
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Chromium 10 %
15 %
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