IR 05000317/1993009
| ML20035H075 | |
| Person / Time | |
|---|---|
| Site: | Calvert Cliffs  |
| Issue date: | 04/22/1993 |
| From: | Bores R, Kottan J, Mcnamara N NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I) |
| To: | |
| Shared Package | |
| ML20035H072 | List: |
| References | |
| 50-317-93-09, 50-317-93-9, 50-318-93-09, 50-318-93-9, NUDOCS 9305030075 | |
| Download: ML20035H075 (13) | |
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U.S. NUCLEAR REGULATORY COMMISSION
REGION I
50-317/93-09 Report Nos.: 50-318/93-09 50-317 Docket Nos.: 50-318 DPR-53 License Nos.: DPR-69 Licensee:
Baltimore Gas and Electric Company P.O. Box 1475 Baltimore. Maryland 2.1703 Facility Name:
Calvert Cliffs Nuclear Power Plant. Units 1 and 2 Inspection At:
Lusby. Maryland Inspection Conducted:
March 29 - April 2.1993
!3 Inspectors:
/ ftw T /}lA buC
Ba N. McNdmara, Laboratory Specialist Date Effluents Radiation Protection Section (ERPS)
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J.'Kott'an/ Laboratory Specialist, ERPS Date Facilities Radiological Safety and Safeguards Branch (FRSSB)
NR/PB Approved By:
,R. Bord ( Chief, ERPS, FRSSB
' Date Division of Radiation Safety and Safeguards Areas Instsected: Announced inspection of the radiological and non-radiological chemistry programs. Areas reviewed included: Confirmatory Measurements - Radiological, Standards Analyses - Chemistry, Laboratory QA/QC, and Audits.
Results: The licensee had in place effective programs for measuring radioactivity in process and efDuent samples and for measuring chemical parameters in plant systems samples. No safety concerns or violations of regulatory requirements were identified.
9305030075 930422 PDR ADOCK 05000317 O
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DETAILS 1.0 Individuals Contacted Principal Licensee Emolovees
- G. Barley, Chemist
- P. Chabot, Technical Support Superintendent
- C. Earls, Chemistry General Supervisor E. Eshelman, Chemist
- D. Muth, Compliance Engineer B. Nuse, Chemist J. O'Neill, Quality Verification - Operations - Supervisor
- W. Ramstedt, Quality Audits Engineer
- S. Sanders, Plant Chemistry Supervisor l
R. Sprecher, Chemical Analyst J. Wood, Quality Audits Senior Engineer
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NRC Emolovees
- F. Lyons, Resident Inspector P. Wilson, Senior Resident Inspector
- Denotes those present at the exit meeting on April 2,1993. The inspectors also interviewed other personnel, including the chemistry technicians who performed the i
analyses for this inspection.
2.0 Purnose
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The purpose of this inspection was to review the following areas.
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The licensee's ability to measure radioactivity in plant systems samples and effluent samples, and the ability to measure chemical parameters in various plant
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systems samples.
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The licensee's ability *a demonstrate the acceptability of analytical results through implementation of a laboratory QA/QC program.
3.0 Radiolocical and Chemleal Measurements f
3.1 Confirmatory Measurements - Radiochemistry
During this inspection, liquid, airborne particulate (filter) and iodine (charcoal -
cartridge), and gas samples were analyzed by the licensee's chemistry department and the NRC for the purpose ofintercomparison. The samples were actual split
samples with the exception of the particulate filter and charcoal cartridge. In
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these cases, the samples could not be split and the same samples were analyzed
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by the licensee and the NRC. Where possible, the samples were actual effluent samples or in-plant samples which duplicated the counting geometries used by the licensee for effluent sample analyses. The samples were analyzed by the licensee using routine methods and equipment and by the NRC Region I Mobile Radiological Measurements Laboratory. Joint analyses of actual samples were
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used to verify the licensee's capability to measure radioactivity in effluent and j
other samples with respect to Technical Specifications and other regulatory requirements.
In addition, a liquid sample was sent to the NRC reference laboratory, Department of Energy, Radiological and Environmental Sciences Laboratory
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(RESL) for analyses requiring wet chemistry. The analyses to be performed on
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the samples are Sr-89, Sr-90, H-3 and gross alpha. The results of these analyses will be compared with the licensee's results when received at a later date and will be documented in a subsequent inspection report. The results of a liquid sample split between the licensee and the NRC during a previous inspection on January 14-18,1991 (Combined Inspection Report No. 50-317/91-04 and j
50-318/91-04) were also compared during this inspection.
The comparisons for all of the above sample results that were available indicated that all of the measurements were in agreement under the criteria for comparing results (see Attachment I to Table I) with one exception. The one exception was the Co-60 result from the liquid radioactive waste sample. All of the licensee's
gamma isotopic results were biased high when compared to the NRC results for i
this sample. However, only the Co-60 result was in disagreement. The inspector j
discussed the matter with the licensee, and the licensee stated that a new calibration standard for this particular counting geometry was scheduled to be received in April 1993. The licensee further stated that this counting geometry calibration would be evaluated after receipt of the new standard and any q
appropriate corrections made. The inspector stated that this area would be reviewed during a subsequent inspection in this area. The inspector further noted that the licensee's results were biased in a conservative direction and would not result in the licensee exceeding any liquid effluent release limits. The data are presented in Table I. No safety concerns or violations were identified in this area.
3.2 Standard Analyses - Chemical 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 monitor chemical parameters in various plant systems with respect
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to Technical Specifications and other regulatory requirements. In addition, the
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analysis of standards is used to evaluate the licensee's analytical procedures with respect to accuracy and precision. The standards were submitted to the licensee for analysis in triplicate at three concentrations spread over the licensee's normal l
calibration and analysis range. The boron standards were not analyzed in triplicate at each concentration due to the lack of sufficient volume of the NRC standards. Also, the anion standards were analyzed at only one concentration on the licensee's hot laboratory ion chromatography system.
Additionally, an actual sample was spiked with a standard anion solution and sent to ORNL for analysis. The analyses to be performed on the sample are chloride, fluoride, and sulfate. The licensee will perform the same ar.alyses 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 samples permits comparisons from an actual sample matrix.
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The results of the standards 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 II.) The cold lab anion I
results were obtained after a recalibration of the ion chromatography system. The initial anion results (at approximately 20 parts per billion (ppb)) obtained from
this system were approximately 25 percent higher than the NRC standard (s)
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known values. The licensee then analyzed a control standard at 20 ppb which
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was also biased high by about 25 percent, indicating a calibration error with this system. The licensee maintains a control chart for this system at approximately
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two ppb, but at this concentration the control limits are so broad that the
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calibration error was not detected. After recalibration, all of the anion results
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were in agreement or possible agreement with the NRC known values. During l
the recalibration, however, the licensee noted that the recalibration data were not stored in the IC method analysis files of the computer. (The IC is interfaced to
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j a computer.) This resulted in the initial results after recalibration being calculated
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with the incorrect calibration data. The inspector discussed this matter with the
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licensee and the licensee stated that the appropriate procedures would be modified
so that the IC method analysis files would be manually checked in order to ensure
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that the proper calibration data were stored in the appropriate file. The licensee
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further stated that calibration curve check criteria would be implemented in order
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to detect an erroneous calibration. The inspector noted the licensee's prompt
response to these matters and stated that the above items would be reviewed i
during a subsequent inspection in this area. The data are presented in Table II.
l No safety concerns or violations were identified in this area.
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4.0 Laboratory OA/OC
The licensee's laboratory QA/QC program was described in procedure CP-103,
" Chemistry Quality Assurance and Quality Control Program". This procedure provided for both an intralaboratory and an interlaboratory QC program. The intralaboratory program consisted of instrument and procedure control charts for trending performance
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and the analysis of spiked samples. The interlaboratory program consisted of the analysis of unknown samples received from outside laboratories for both chemical and radiochemical constituents. Included in the interlaboratory program was the vendor laboratory utilized by the licensee for analysis of radioactive effluent samples that require separation chemistry.
The procedure also addressed the construction, use, and interpretation of control charts. The licensee's laboratory QA/QC procedure provided for a comprehensive laboratory QA/QC program.
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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. The licensee has a specific individual assigned to review and maintain the laboratory QC data. This included maintaining the computerized database ofintralaboratory and interlaboratory QC data and
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generating periodic reports which documented and evaluated the QC data. The inspector noted that plots of the interlaboratory analytical chemistry QC data had been generated and provided to the laboratory personnel for use in reviewing their performance and were posted in the laboratory area. The inspector stated that this was a good practice, but observed that interlaboratory radiochemistry crosscheck data were not included. 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. No violations were identified in this area.
5.0 Audit Activitics i
The inspector reviewed QA Audit Report No. 92-14, " Chemistry", which was performed j
on September 4 - October 29,1992. This audit was conducted using a detailed checklist, and the audit team included a technical specialist. Through discussions with licensee personnel, the inspector determined that QA audits of chemistry were performed on a biennial basis. The inspector also reviewed the results of selected Quality Verification (QV) surveillance reports for 1992 and 1993, to date. The surveillances were not conducted at a fixed frequency, but the data reviewed indicated that in some months approximately 20 surveillances were performed which involved some aspect of plant chemistry.
The surveillances were performed using detailed check-off sheets and included aspects of laboratory Q.
Based on the review of the above audit and surveillance activities, the inspector determined there was independent oversight and assessment of chemistry activities. No safety concerns or violations were identified.
6.0 ExitJJeeting The inspectors met with the licensee representatives denoted in Section 1.0 at the conclusion of the inspection on April 2,1993. The inspectors summarized the purpose, scope and findings of the insivxtion.
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TABLE I Calvert Cliffs Radiochemistry Test Results SAMPLE ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON Results in microCuries ocr milliliter Unit 1 1-131 (8.4i0.4)E-3 (8.7i0.7)E-3 Agreement Reactor Coolant I-132 (8.37i0.08)E-2 (1.047i0.014)E-1 Agreement 0850 hrs I-133 (7.27i0.06)E-2 (7.74i0.10)E-2 Agreement 03/31/93 I-134 (1.23i0.02)E-1 (1.50i0.04)E-1 Agreement (Detector No. 2)
I-135 (1.13i0.02)E-1 (1.18i0.04)E-1 Agreement Liquid Radioactive H-3 (3.03i0.03)E-2 (2.53i0.3 %)E-2 Agreement Waste Sr-89 (-15i6)E-8 (1.12i23%)E-7 No Comparison (#12RCWMT)
Sr-90 (1.9i0.5)E-8 (3.92i13%)E-8 No Comparison 1135 hrs 01/16/91 Unit 1 Co-58 (6.79i0.08)E-5 (7.9i0.5)E-5 Agreement Reactor Coolant I-132 (1.73i0.08)E-4 (1.65i0.09)E-4 Agreement Particulate Filter I-133 (1.195i0.010)E-4 (1.19i0.06)E-4 Agreement 0850 hrs I-135 (1.81i0.06)E-4 (1.9i0.2)E-4 Agreement 03/31/93 (Detector No. 3)
Unit 2 I-131 (2.17i0.06)E-9 (1.97i0.13)E-9 Agreement Messurizer Charcoal Cartridge 0831 hrs 03/30/93 (Detector No. 2)
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TABLE I - continued Calvert Cliffs Radiochemistry Test Resul.ls SAMPLE ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON Results in microCuries per milliliter Waste Gas Decay Xe-133 (1.670i0.009)E-2 (1.74210.005)E-2 Agreement Tank #13 Kr-85 (3.4i0.2)E-2 (3.38i0.09)E-2 Agreement 1451 hrs 03/31/93 (Detector No.1)
Liquid Radioactive Co-58 (8.47i0.06)E-5 (9.76i0.15)E-5 Agreement
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Waste Mn-54 (2.0i0.2)E-6 (2.5i0.4)E-6 Agreement (#12RCWMT)
Co-60 (3.2i0.2)E-6 (4.5i0.4)E-6 Disagreement 1400 hrs Ag-110m (5.4i0.2)E-6 (6.410.6)E-6 Agreement 04/01/93 Cs-134 (4.04i0.04)E-5 (4.9410.13)E-5 Agreement (Detector No. 3)
Cs-137 (4.46i0.040E-5 (5.20i0.11)E-5 Agreement Note: Reported uncertainties are one standard deviation counting uncertainties for both NRC and licensee results.
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ATTACHMENT 1 TO TABLE I i
CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS j
This attachment provides criteria for comparing results of capability tests and verification
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measurements. The criteria are based on an empirical relationship which combines prior experience and the accuracy needs of the program.
In these criteria, the judgement limits are variable in relation to the comparison of the NRC Reference Laboratory's value to its associated uncertainty. As that ratio, referred to in this program as " Resolution," increases, the acceptability of a licensee's measurement should be more selective. Conversely, poorer agreement must be considered acceptable as the resolution decreases.
Resolution'
Ratio for Comparison2
<4 No Comparison *
4-7 0.5 - 2.0
8 - 15 0.6 - 1.66
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16 - 50 0.75 - 1.33
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51 - 200 0.80 - 1.25
> 200 0.85 - 1.18
- No comparison due to the large uncertainty of the result.
i 1. Resolution = (NRC Reference Value/ Reference Value Uncertainty)
2. Ratio = (Licensee Value/NRC Reference Value)
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TABLE II Calvert Cliffs Analytical Chemistry Test Results
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Chemical Method of NRC Licensee Analysis Analysis Known Value Value Comparison Results in parts ocr million (Dom)
Boron T
1049 i 11 1034.8*
Agreement 3040 i40 3035.7 i 0.3 Agreement 5060 i 80 5026.2*
Agreement Lithium AA 0.493 i 0.007 0.53 i 0 Agreement 1.24 i 0.02 1.290 i 0.010 Agreement 1.94 i 0.02 2.017 i 0.006 Agreement Iron AA 1.99 i 0.02 1.97 i 0.03 Agreement 3.18 i 0.03 3.163 i 0.015 Agreement 3.98 i 0.04 3.8810.02 Agreement Copper AA 0.0810 1 0.0010 0.092 i 0.003 Agreement 0.202 i 0.002 0.2160 1 0.0010 Agreement 0.403 i 0.004 0.410 i 0.003 Agreement Results in oarts ocr billion (opb)
Hydrazine SP 26.46 i0.12 24.5i0.7 Agreement 68.2 i 0.6 66.6 i 0.2 Agreement 113 i 2 108.4il.0 Agreement
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TABLE II - continued Calvert Cliffs Analytical Chemistry Test Results Chemical Method of NRC Licensee Analysis Analysis Known Value Value Comoarison Results in parts ocr billion (oob)
Silica SP 12.17 i 0.13 13.75 i 0 Qual Agreement 28.4 i 0.4 27.16 i 0.08 Agreement 60.lil.0 59.74 0.15 Agreement Ammonia IC 110 i 3 113.1 i 1.5 Agreement 305 i 5 291 i 4 Agreement 482 i 7 459 i 3 Agreement Sodium IC 5.3i0.2 5.29 i 0.09 Agreement 10.210.3 10.12 i 0.13 Agreement 15.5i0.4 15.67io.10 Agreement Chloride IC 3.65i0.I1 3.5i0.2 Agreement 7.7i0.3 6.8i0.2 Qual Agreement 19.4 i 0.5 20.li0.5 Agreement Fluoride IC 4.0i0.2 4.06 i 0.13 Agreement 8.4i0.4 8.06 i 0.16 Agreement 20.2 i 0.8 21.2 i 0.4 Agreement
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TABLE II - continued Calvert Cliffs Analytical Chemistry Test Results
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Chemical Method of NRC Licensee Analysis Analysis Known Value Value Comoarison Results in parts ocr billion (oob)
Sulfate IC 3.88 i 0.06 3.7i0.3 Agreement 7.9i0.2 7.8io.2 Agreement 19.4 i 0.3 21.66 1 0.12 Qual Agreement Chloride IC'*
19.4 i 0.5 20.8 i 0.5 Agreement Fluoride IC'*
20.2 i 0.8 20.5i0.5 Agreement Sulfate IC'*
19.4 i 0.3 20.46i 0.14 Agreement Notes:
IC = Ion Chromatography T = Potentiometric Titration SP = UV-Vis Spectrophotometry AA = Atomic Absorption Spectrometry The licensee maintains an IC system for anion analysis in both me primary (or hot) laboratory and the secondary (or cold) laboratory.
- Single Analysis Only
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- Hot Lab result
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f A'ITACHMENT 1 TO TABLE II Criteria for Comparing Analytical Measurements from Table II This attachment provides criteria for comparing results of capability tests. In these criteria the judgement limits are based on data from Table 21 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 ( 2Sd) of the ORNL known values are considered to be in agreement. Licensee values outside the plus or minus standard deviation range but within the plus or minus three standard deviation range ( 3Sd) of the ORNL known values are considered i
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 deviation values of each analyte in Table 2.1 of the NUREG.
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The ranges for the data in Table II are as follows.
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Agreement Qualified Agreement Analyte Range Range Chloride i 8%
i 12 %
Fluoride i 12 %
i 18 %
Sulfate i 10 %
i 15 %
Silica i 10 %
i 15 %
Sodium i 14 %
i 21 %
Copper i 10 %
i 15 %
Iron i 10 %
i 15 %
Boron i 2%
i 3%
Ammonia 10 %
i 15 %
Hydrazine i 8%
i 12 %
Lithium i 14 %
i 21 %
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