IR 05000454/1987036
| ML20235L255 | |
| Person / Time | |
|---|---|
| Site: | Byron  |
| Issue date: | 09/23/1987 |
| From: | Holtzman R, House J, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III) |
| To: | |
| Shared Package | |
| ML20235L139 | List: |
| References | |
| 50-454-87-36, 50-455-87-33, NUDOCS 8710050403 | |
| Download: ML20235L255 (12) | |
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U.S. NUCLEAR REGULATORY COMMISSION
REGION III
Reports No. 50-454/87036(DRSS); 50-455/87033(DRSS)
Docket Hos. 50-454; 50-455 Licenses No. NPF-37; NPF-60 Licensee: Commonwealth Edison Company Post Office Box 767 i
Chicago, IL 60690 Facility Name:
Bryon Generating Station, Units 1 and 2
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Inspection At:
Byron Site, Byron, Illinois Inspection Conducted:
August 31 through September 4, 1987 (Onsite)
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Inspectors:
R. B. Holtzmanj F Date J.
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Approved By:
M. C. Schumacher, Chief i
Radiological Effluents and Date Chemistry Section Inspection Summary Inspection on August 31 through September 4, 1987 (Reports No. 50-454/87036(DRSS);
No. 50-455/87033(DRSS))
Areas Inspected:
Routine announced inspection of:
(1) the chemistry program, including procedures, organization, training, quality assurance, and water quality control, and (2) confirmatory measurements of nonradiological samples, Results:
No violations or deviations were identified.
l 8710050403 870923 PDR ADOCK 05000454 g
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I DETAILS 1.
Persons Contacted
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- R. E. Querio, Station Manager
- R. C. Ward, Services Superintendent
- R. A. Flahive, Rad-Chem Supervisor
- D. J. Herrmann. Station Chemist
- D W. Berg, Nuclear Safety
- M. Snow, Regulatory Assurance Supervisor
- R. B. Klinger, Senior QA Engineer
- W. D. Pirnat, Regulatory Assurance
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- E. M. Zittle, Regulatory Assurance
"V. Junlowjiraya, Analytical Chemistry Group Leader
- K. L. Lurkins,. Chemistry Engineering Assistant W. Scheffler, Operational Group Leader,, (Chemistry)
M. E. Burgess, Supervisor, Group Leader, Analytical Chemistry Services, j
Nuclear Services, Maywood, Ceco
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S. Wilson, Radwaste Coordinator J. Hamm, Chemistry Foreman G. Rood, Rad-Chem Technician (RCT)
M. Kersch, RCT T. Schlieder, RCT G. Quaca, RCT
- P. Brochman, Senior Resident Inspector, NRC
- Denotes those present at the plant exit interview on Septeinber 4,1987.
2.
Licensee Action on Previous Inspection Findings a.
(Closed) Open Item (50-455/86037-01):
Licensee to consider improvements in the procedures for the collection of post-accident samples from the High Radiation Sampling System (HRSS).
In a previous inspection, the inspector noted that rotation of the dilution valve in the Unit 2 system was reversed, so that during the dilution operation, the valve handle pointed against, rather than with the sample flow into the collection vial.
The licensee corrected this deficiency by marking the mimic board with an arrow to note the direction in which the handle should be turned for sample collection.
The RCTs were trained on various aspects of the system and tested in their ability to rapidly (within three minutes) recognize and operate ten valves on each of the HRSS panels, including the dilution valve (RCDV-1); most did it in less than two.
The licensee completed the training on June 30, 1987.
It appeared to be adequate and to address the previous concerns about the rapidity of the operations under accident conditions.
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LOpen) Open Items'(50-454/87013-01; 50-455/87012-01):
Licensee-to
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improve the nonradiological QA/QC program with charts, the use of j
multiple standards, and the improved testing of the RCTs.
The j
licensee has implemented control charts on a large group of analyses,
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including'the boron titration, silica and hydrazine by UV/ visible spectrophotometry, chloride and sulfate by ion chromatography (IC)
and metals by direct coupled plasma (DCP).
The program was well underway, but some charts had not been started because of too few data points.
Further,.the inspectors suggested that the analyses on the IC could better be controlled by using as the' main performance
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parameters the concentrations of the control standards rather than their peak heights (conductivity); the latter parameters are highly variable and dependent on the condition of the conductivity cell and room temperature;'they do not represent the accuracy of a calibrr,ed system.
The inspectors also noted that the control limits on the charts were determined by calculating the standard deviations from the first 15 points of the data collection period (ust c)ly monthly).
However, the use of the data from the previous period, a standard laboratory practice, would give somewhat more accurate limits, and would simplify the maintenance of the charts.
The licensee representative. agreed to modify the program by using the concentrations as the control parameters and to calculate the control limits from the previous month's results.
The inspectors alr.o reviewed the formal semiannual RCT testing program. Unknowns of chloride, fluoride, lithium, silica and boron prepared inhouse are submitted to each RCT.
Results, except those for boron, were considered acceptable if they were within ten percent of the known value, acceptable with a caution to the RCT for values greater than ten percent and less than 15%, and unacceptable if greater than 15%.
The limits for boron were set at two and four percent, respectively.
A technician failing an analysis is retestd and if a second failure occurs, he is retrained on that particular assay.
A review of the data from the previous year indicated that the RCTs were tested as required and that all passed.
This item will remain open and the development of the program and the suggested changes will be examined in a subsequent inspection.
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(Closed) Open Items (50-254/87013-02; 50-455/87012-02):
Licensee to implement the use of data sheets for collecting the results of the performance check sources in the radiological QA/QC program and to increase each performance checle count to greater than 10,000 counts.
The licensee implemented the use of data sheets to keep track of the data for the performance checks on the counters to better follow trends of the instruments.
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To reduce'the number of performance test failures when the control limits for these tests were set at two standard deviations based on counting statistics, the corporate Technical Center-Nuclear (Memorandum JMD-84-006, Dated July 17,1984) had previously recommended that the corporate laboratories use performance test sources that gave 2000-5000 counts.
However,-in the previous inspection,1 the inspector had noted that with few counts the variabilities in the count 1rtg statistics will hide the instrumental and operational variabilities cf the counters themselves and defeat the purpose of the performance check, whfth is to test the instrument.
To alleviate this problem, the Tech Crmier re-examined the problem and recommended in Memorandum RRL-87-008,
" Performance Test for Detector Quality Control,"= dated August 10, 1987, that to test counter stability, the laboratories use sufficiently active check sources and count times to obtain more than 10,000 counts.
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In conformance with this recommendation, the licensee has recently
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obtained and is using more active sources.
This item is closed.
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3.
Management Controls and Organization
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The inspectors reviewed the organization and staffing of the Chemistry Group and changes since the last inspection.2 The Group is headed by the Station Chemist, who reports to the Rad / Chem Supervisor.
Two chemists have been added to the group.
One is taking over radiochemistry from the Engineering Assistant who has been moved to work full time supervising the nonradiological chemistry laboratory.
The group has recently added two new Chemistry Foremen, for a total of three. This organization cppears to be adequate for operating the laboratory and doing the required analyses.
During the inspection the licensee announced that the Station Chemist and Radwaste Coordinator would be exchanging positions with each other on September 14, 1987.
The inspectors interviewed and reviewed the
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qualifications of the Station Chemist designate.
He has a Bachelor i
of Science degree in Chemical Engineering, two years at the corporate Tech Services-Nuclear and was a Chemist at this station for over two years.
He has been the Station Radwaste Coordinator.since October 1985.
In the latter position, he has had to deal with many aspects of radiation and radioactivity, has taken courses in radiochemistry, and is formally qualified (signed off on qualification cards) to operate the radiological instrumentation in the chemistry laboratory.
He appears to be knowledgeable
i in chemistry and radiochemistry and to be well-qualified for this position in conformance with the standard ANSI-N18.1, 1971, required by the Technical Specifications.
The inspectors' review of the licensee's records of the training program for the Rad / Chem Technicians showed that it was accredited by INPO in May 1987.
No violations or deviations were identified.
1 Region III Inspection Reports No. (50-454/87013; 50-455/87012)
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Water Chemistry Control Program
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.The inspectors reviewed the secondary water system, including computer j
generated. trend charts on steam generator blowdown, feedwater and
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condensate.
A review of selected records showed that secondary water.
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parameters were maintained within the plant action levels.
Steam generator blowdown is monitored for cation conductivity, sodium,
sulfate, chloride, silica and pH.
Feedwater is monitored for pH, i
dissolved oxygen, hydrazine and iron.
Condensate is checked for
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dissolved oxygen and air inleakage.
The trend charts indicated that j
secondary water is held below Action Level 1 when the reactor is at
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power levels over ten percent.
In general. this Action Level is exceeded
.only when the plant is in shutdown, or startup, or a transient power change
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The plant has three inline Dionex Ion Chromatography for the continuous monitoring of various parameters.
One unit is in the laboratory for steam generator blowdown, and two are in the plant for measuring secondary system pararreters, including fluoride, chloride, sulfate, ammonia and sodium at ppb concentrations in feedwater, main steam and hotwell condensate.
Inline mounted ion chromatographic instrumentation is relatively new in nuclear plants and this station is one of the few plants in the country to use this type of monitoring system. These analyzers should provide valuable data on overall secondary water quality and enable the plant to maintain secondary water parameters within prescribed limits.
No violations or deviations were identified.
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Implynentation of the Chemistry Program a.
Nonradiological Chemistry
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The inspectors reviewed the conditions in the primary and secondary chemistry laboratories.
The licensee has recently made additional effort to improve the housekeeping which is now very good.
Space is adequate and the laboratories are well equipped.
State of the art equipment includes Dionex 20201 Ion Chromatography, Orion Ionalyzers, an OI Total Organic Carbon Analyzer, a Tracor 565 GaF Chromatograph, Brinkman Autotitrators, Altex 5000 Ion Analyzers, Hitachi 110A Spectrophotometers, a Perkin Elmer Model 5000 Atomic Absorption Spectrophotometer with a graphite furnace and an Autosampler, a Beckman Spectraspan VI Plasma Spectrometer, and Hewlett-Packard Integrators.
Each of the instruments now has a logbook containing the tabulated performance check data for independent controls, control charts, other parameters that monitor instrument performance, and maintenance schedules and records Reagents were properly labeled with expiration dates listed.
No outdated reagents were observed.
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' Radiochemistry-A licensee representative ncted t'at the calibration problem with h
'their alpha counters (previously discussed in Open Items-
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-(50-454/85011-03; 50-455/86009-03)- and closed in Inspection Reports No.'(50-454/87003; 50-455/87005)) apparently resulted from the use of calibration standard solutions that contained sufficient-dissolved solids.to produce substantial 'self-absorption losses when dried on the j
standard' sample. planchets.,However,'when they recalibraced the counters-with standards made from small volumes ~of solution, e.g.,
200 pl., the self-absorption losses were greatly reduced and the calibrations were reasonable ~and comparable to those from vendor produced standards.
No violations or deviations were identified.
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.Nonradioloaical Confirmatory Measurements The inspectors submitted chemistry samples to the licensee for analysis as
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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 requirements. 'These samples had been prepared, standardized, and periodically reanalyzed (to check for stability) for the 11RC by the Safety and Environmental Protection Division of Brookhaven National Laboratory (BNL).
The samples were-analyzed by the licensee using routine methods and equipment.
The samples were diluted by licensee personnel as necessary to bring the
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concentrations within the ranges normally analyzed by the laboratory, and
.run in triplicate;in a manner similar to that of routine samples.
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'results are presented in Table 1 and the criteria for agreement in Attachment 1.
These criteria for agreement are based on comparisons.of the mean values and estimates of the standard deviations (s.d.) of the measurements.
Consideration was given to the fact that the uncertainties j
(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, I
and a disagreement resulted, the BNL value was substituted for that of the licensee in calculating the s.d. of the ratio Z (5 in Attachment 1).
The licensee also prepared two samples to be split with BNL. To these were added analytes supplied by the inspectors.
Reactor water was spiked with the anions, chloride and sulfate, and a sample of condensate was spiked with copper and iron ions.
The licensee will determine the analytes in each and the results will be sent to Region III for comparison with the values determined by BNL.
This will be followed under the Open Items
(50-454/87036-01; 50-455/87033-01).
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.The" licensee analyzed ten materials at three. concentrations each.'
Of the initial'30 analyses, seven,resulted:in disagreements with the BNL values.
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.The high and low fluoride analyses were in disagreement and the middle
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Concentration required substitution of the BNL standard deviation to be
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in agreement.
The biases of 15,to 20% low appeared to'somewhat large,
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< standard was. faulty.
They then recalibrates with a' vendor prepared solution rather than their internally prepared one..Preanalysis brought the high. fluoride level into agreement and-all of the absolute values-of the' biases decreased substantially.
The low concentration was still-in.
disagreement..The licensee agreed to' continue working on instrument calibration and electrode maintenance.
Additional samples will be analyzed and reported to Region III under the Open Items (50-454/87036-02; 50-455/87033-02).
The chloride analyses had one disagreement, due possibly to the poor precision of this: analysis, as illustrated by the two lower concentration results having biases of 12 percent, one low and one high.
This should improve as the licensee modifies the performance check control charts to plot' concentrations rather than peak heights vs. time (Section 2b).
Two
, disagreements occurred in analyses involving graphite furnace atomic absorption spectrophotometry.
The high concentration of iron and sodium exhibited low biases of 16 and 24 percent, respectively.
Laboratory personnel could not identify the source ~ of these disagreements, but the problem may be due to the nonlinear calibration curves and the use of the Perkin-Elmer two point calibration (zero plus two additional points) in which the instrument fits straight-line segments between the points, which could result in substantial differences in the slopes of the calibration curves. While the procedure requires a check with a control standard, this was done only on the lower curve, i.e. between zero and the first point, but it was not-done above this point.
The licensee is investigating this problem.
Iron was also analyzed on a DCP Spectrometer and the three levels j
agreed with BNL.
Laboratory personnel stated that a new atomic absorption j
instrument will be acquired in the near future as the current unit has been troublesome and difficult to operate.
The licensee agreed to continue work on calibration curves and will provide the region with additional analytical j
J The hydrazine analyses resulted in two disagreements at the medium and high concentrations.
The bicses for these analyses were low by about ten percent.
Because the precisions of both the BNL and the licensee data for hydrazine are very good (small standard deviation), a small bias can result in disagreement.
A review of the procedure and observations of the reaction (color development) by laboratory supervisors along with the laboratory temperature (64 F) suggested that the development time be increased.
This produced an agreement in the high concentration, but the middle sample was still in disagreement with a low bias of about seven percent.
Due to the precision - bias relationship in the acceptance criteria, the repeat analyses of hydrazine appear to be adequate.
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l The licensee uses multiple point calibration curves where possible and included independent controls as a calibrator check that also serve to improve calibration of instruments where a one point curve is used due I
data processing design.
This set of intercomparison analyses demonstrated several weaknesses in the laboratory:
(1) some standards prepared in this laboratory were inaccurate (fluoride), (2) the hydrazine procedure apparently needs to be modified, (3) problems were noted with the AAS calibration method, and (4) the control charts, especially those for the IC, need to be improved.
Part of the difficulties stemmed from weaknesses in the quality control program, which has a recently gotten a good start, but is still under development.
The chemists were knowledgeable about the analyses, they were receptive to the inspectors' suggestions, and, most importantly, they, themselves, initiated corrective actions to solve most i
of the problems.
The licensee is reviewing those methods that produced
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disagreements and the results will be followed in subsequent inspections under the above Open Items (50-454/87036-02; 50-455/87033-02).
No violations or deviations were identified.
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7.
Licensee Internal Audits The inspectors reviewed the findings of a recent available internal audit of the Radiation-Chemistry Department (6-87-I, March 1987) conducted March 8-13, 1987.
None of the findings or observations related to Chemistry.
A more recent audit was not yet available, but it will be reviewed in a subsequent inspection.
No violations or deviations were identified.
8.
Environmental Monitoring:
TLD Collocations
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The inspectors reviewed the location of all 16 colocated TLD's and determined by physical inspection of each that they were located on the same pole as the licensee's TLD.
A few discrepancies in distance and azimuth were noted on NRC and licensee locator charts but these were resolved by reading distance and azimuth from maps.
No violations or deviations were identified.
9.
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 licensse, or both.
Open items disclosed during the inspection are discussed in Sections 2 and 6.
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10. Exit Interview The scope and findings of the inspection were reviewed with licensee representatives (Section 1) at the conclusion of the inspection on September 4, 1987.
The inspectors discussed the Open Items in Section 2 and observations on the quality control program and the confirmatory measurements.
Licensee representatives agreed to change the QC charts as discussed in Section 2b.
The inspectors noted the great progress in the QA/QC program since the previous inspection.
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 proprietary.
Attachments:
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Table 1, Nonradiological Interlaboratory Test Results, August 31-September 4, 1987 2.
Attachment 1, Criteria for Comparing Analytical Measurements t
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TABLE 1 Nonradiological Interlaboratory Test Results 8yron Nuclear Generating Station, Units 1 and 2 August 31-September 4,1987 Measured Concentrations a
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Analyte
'Analysgs Dilu-NRC Licensee Ratio Comparison Method tion, 1:x Y i s.d.(n)
X i s.d.(n)
Z i s.d. i 2 s.d.
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Concentration, ppb Fluoride SIP-250 92.4 1 2.0 (7)
75.1 1 1.0 0.813 1 0.021 D 250
.174 1 7.6 (7)
154 1 2.6 0.885 1 0.058 A*
250 334 1 11'
(8)
294 i 1.2 0.880 1 0.029 D Fluoride SIP 250 92.4 1 2.0 (7)
82.9 1 1. 0 0.897 1 0.022 D (rerun)
250 174 i 7 6 (7)
167 1 4 0.959 i 0.048 A 250 334 1 11 (8)
328 i 8 0.982 1 0.040 A Chloride IC 2500 9.64 1 1.24(7)
8.49 1 0.36 0.881 1 0.119 A 2500 14.96 1 0.48(7)
16.8 i D.74 1.123 1 0.061 0 5000 16.10 1 0.44(8)
16.1 1 0.61 1.000 1 0.047 A l
Sulfate IC 2500 8.0 1 0.36(7)
8.55 1 0.38 1.069 1 0.068 A 2500 16.4 1 0.96(8)
15.69 1 1.32 0.957 1 0.098 A q
2500 32.3 1 1.20(7)
34.02 1 0.36 1.053 1 0.041 A Silica Spec 2000 54.3 2 5.6 (7)
52.0 1 1. 7 0.958 1 0.104 A 1000 109 1 7 (7)
103 A 3.2 0.945 1 0.067 A 1000 160 1 5 (7)
155 1 4 0.969 i 0.039 A Cu AAS 1000 4.68 0.24(12)
4.66 0.25 0.996 1 0.074 A 1000 9.66 1 0.49(14)
9.94 1 0.38 1.029 1 0.065 A 1000 14.5 1 0.6 (12)
14.3 1 0.15 0.986 1 0.042 A l
Fe AAS 1000 4.89 i 0.35(13)
4.82 1 0.18 0.986 1 0.080 A 1000 9.55 1 0.34(14)
9.18 f 0.42 0.961 0.056 A 1000 14.7 1 0.42(13)
12.3 1 0.61 0.837 1 0.048 0 Na AAS 1000 4.58 1 0.5 (6)
5.67 1 0.43 1.24 1 0.16 A i
1000 9.23 1 0.8 (6)
8.95 i 1.07 0.970 1 0.143 A I
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1000 14.4 1 0.8 (6)
10.9 1 0.56 0.756 1 0.058 D Hydrazine Spec 1000 22.3 1 1.5 (7)
22.7 1 0.5 1.018 1 0.072 A 1000-56.9 1 0.7 (7)
51.0 1 2.0 0.896 0.037 D 1000 104 1 1 (7)
93.7 1 0.6 0.901 1 0.010 D Hydrazine Spec 1000 22.3 1 1.5 (7)
21.3 1 0.6 0.955 1 0.070 A
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1000 56.9 1 0.7 (7)
52.7 1 0.58 0.926 1 0.015 0 1000 104 1 1 (7)
100.7 1 1.5 0.968 i 0.017 A
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Measured Concentrations
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' Analyte Analysfs Dilu-NRC Licensee Ratio Comparison Method tion, 1:x Y i s.d.(n)
X 1 s.d.(n)
Z i s.d. 1 2 s.d.
Concentration, ppm NHa Spec 100 0.88 i 0.05(7)
0.90 1 0.05 1.023 1 0.081 A 100 3.14 1 0.26(7)
2.51 1 0.04 0.799 1 0.106 A*
100 9.38 1 0.85(7)
9.02 1 0.18 0.962 1 0.089 A Boron Titr
1000 1 10 (7)
993 1 1.7 0.993 1 0.010 A-
3024 1 46 (7)
2999 1 15 0.992 1 0.016 A
'l 4947 1 61 (7)
.4955 1 30 1.002 1 0.014 A a.
Value i standard deviation (s.d.); n is number of BNL analyses.
l The number of licensee analyses is 3 unless otherwise noted.
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Analytical methods:
Titr - titration IC
- Ion-chromatography Spec - Spectrophotometric SIP - Specific ion probe AAS - Atomic absorption Spectrophotometry I
(furnace)
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A = Agreement D = Disagreement
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- Substituted the BNL uncertainty for licensee's uncertainty.
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-ATTACHMENT 1 o
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Criteria for Comparing Analytical Measurements (
This attachment provides criteria for. comparing results of-the capability tests.
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The acceptance limits are based on the ' uncertainty (standard deviation) of the I
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l ratio of the licensee's mean value (X) to the NRC mean value (Y), where
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(1) Z = X/Y is the ratio, and
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-S' is the uncertainty of the ratio determined from the propagation of the uncertainties of licensee's mean.value, S,.and of the NRC's mean value, S.1 Thus, x
y q
S*
S 6*
L Y ~ V, h, so that z _ x s = Z. S 2x., s 2D
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y z
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The results are considered to be in agreement when the biasiin the ratio l
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'(absolute value of difference between unity and the ratio) is less than or
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equal to twice the uncertainty in the ratio, 1.e.
-l l 1-Z l 1 2'S7 I
1.
National Council on Radiation Protection and Measurements,
A Handbook of Radioactivity Measurements Procedures, NCRP i
Report No. 58, Second Edition, 1985, Pages 322-326 (see
Page 324).
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4/6/87
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