IR 05000346/1989024
| ML19325F370 | |
| Person / Time | |
|---|---|
| Site: | Davis Besse  |
| Issue date: | 11/08/1989 |
| From: | Holtzman R, Schumacher M NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION III) |
| To: | |
| Shared Package | |
| ML19325F369 | List: |
| References | |
| 50-346-89-24, NUDOCS 8911200237 | |
| Download: ML19325F370 (13) | |
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U.S. NUCLEAR REGULATORY COMMISSION
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REGION III
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L Report No. 50-346/89024(DRSS)
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l Docket No. 50-346 License No. NPF-3
P Licensee: Toledo Edison Company
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l Edison Plaza i
L 300 Madison Avenue
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Toledo, Ohio 43652 Facility Name:
Davir-Besse Nuclear Power Station, Unit 1
Inspection At:
Davis-Besse Nuclear Power Station Site l
Dak Harbor, Ohio
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l-Inspection Conducted:
October 16-20, 1989 (Onsite)
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///f/d Inspector:
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L Approved By: M.C.bhumacher, hief
"/6/85 Radiological Controls and Date i
Chemistry Section
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l Inspection Summary
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Inspection on October 16-20, 1989 (Report No. 50-346/89024(URSS))
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Areas Inspected:
Routine announced inspection of:
(1) the" chemistry program, L
incleding procedures, organization, and training (IP 79701); (2) primary and
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secondary systems water quality control programs (IP 79701); (3) quality
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assurance / quality control program in the laboratory)(IP 79701); and (4)
nonradiological confirmatory measurements (IP 79701.
Results: The licensee has an extensive water quality control program that
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conforms to the EPRI Steam Generator Owners and Primary Systems Guidelines.
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Morpholine is used in the secondary system to improve pH control and obtain higher pH levels in the water.
This reduces erosion-corrosion of the
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secondary system piping, reduces iron concentrations in feedwater and results in lower buildup of scale on the steam generator tubes.
Except for
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dissolved oxygen concentrations in feedwater, the chemistry parameters in
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these systems were generally maintained well within the guidelines.
The QC c
procedure is very good for both laboratory and inline process instrumentation.
The nonradiological confirmatory measurements results were about average.
Progress in the chemical measurements QA/QC and chemical parameters trending
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programs was good.
No violations or deviations were identified.
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DETAILS
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Persons Contacted
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- R. Coad, Radiological Protection Supervisor, TE/RC
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- R. T. Holliday, Acting Compliance Supervisor TE
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- J. Stor, Engineer-Planning, TE
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- R. Gaston Licensing Engineer, TE
- E.A.Dellcate,AssistantEnvironmentalComplianceTechnologist,TE
- P. Byron, Senior Resident Inspector, NRC
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- K. Walton, Resident Inspector, NRC
- D. Miller, Senior Radiation Specialist, RIII, NRC The inspector also interviewed other licensee personnel in various departments in the course of the inspection.
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- Denotes those present at the plant exit interview on October 20, 1989.
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2.
Licensee Action on Previous Inspection Findings (IP 92701)
a.
(Closed) Open Item No. 50-346/88008-02:
Licensee to improve the
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nonradiologicil chemistry QA/QC with an expanded program.
The
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licensee expanded the QC control with a new procedure (Section 7).
b.
(Closed) Open Item No. 50-346/88008-03:
Licensee to split with Brookhaven National Laboratory (BNL) spiked samples of reactor coolant and feedwater, to analyze them, and to submit the results to Region III.
The licensee analyzed a reactor coolant sample spiked
with fluoride, chloride and sulfate ions and a feedwater sample
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spiked with iron and copper ions.
The results are compared in
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Table 1; the acceptance criteria are presented in Attachment 1.
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relative standard deviations were taken as 5%, which appears to be
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reasonable for these analyses.
Four of the five analytes were in
agreement, c.
(Closed) Open Item No. 50-346/88008-04:
The licensee to improve
the fluoride analysis and to implement iron and copper analyses in the plant laboratory.
The fluroide analysis has been improved by bringing the fluoride peak out of the water dip in the ion chromatographic analysis by gradient elution, as shown by che
comparisons of the results of the NRC unknowns samples in Table 2.
The licensee now analyzes for iron and copper in the plant
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laboratory.
3.
Management Controls and Organization (IP 79701)
The structure of the Chemistry Group is essentially unchanged since
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the previous inspection in this area,1 except for changing the titles I
1 Region III Inspection Report No. 50-346/88008
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of the chemistry foremen to Supervisors-Chemistry (one General
Supervisor-Chemistry, four Supervisors-Chemistry and one i
Supervisor-Chemistry for Training).
There are now 18 technicians (Testers);. the five Assistant Chemistry Testers are in training.
The personnel and organization appear to be adequate to perform the
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required laboratory analyses.
No violations or deviations were identified.
4.
Water Chemistry Control Program (IP 79701)
The water quality control program is similar to that previously described,8 but with revised procedures; primary chemistry is controlled L
by DB-CH-03001, " Reactor Coolant Chemistry," Revision 00, January 6, 1989.
This procedure is consistent with the Technical Specifications and
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the EPRI Primary System Guidelines, except that sulfur as sulfate is not yet determined by the laboratory.
The licensee is pursuing various aspects of chemistry control, including the estimation of high
temperature pH, rather than only that at 25' C.
This is important because high-and low-temperature pH values are not directly correlated; different chemical species affect pH differently at different i
temperatures.
i The secondary system chemistry specifications procedure DB-CH-06900,
" Operational Chemical Control Limits, Revision 00, April 26,1988, is i
consistent with and references the EPRI PWR Secondary Water Chemistry Guidelines, April 1985 and, Revision 1 September 1986.
The EPRI Action Levels may be waived by the plant manager.
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The licensee is in the process of rebuilding the secondary system sampling panel and upgrading the in-line process monitors with digital instrumentation.
These will be monitored continuously by computer.
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The sample cooling system has been improved to maintain the samples at 25 t 1* C, and an in-line ion chromatographic system (presently onsite)
for anion, cation and organic analyses will be installed after the panel area is enclosed in an air conditioned room.
The new instrumentation r
includes specific and cation conductivities, pH, dissolved oxygen, and hydrazine in the various systems.
Computer terminals will provide information to the chemistry office and other sites around the plant.
Monitoring of the makeup water system is being improved with the installation at various sampling points in the system of new instrumentation, including conductivity, sodium, silica and dissolved oxygen meters.
Licensee representatives stated that they have spent considerable effort since the previous inspection to lower the feedwater (FW) dissolved oxygen concentration from about 11.5 ppb to below the guideline levels of 10 ppb.
The condenser tubing was " staked" to reduce steam-impingement vibration, which allows lower condenser pressures, and hotwell crackt were sealed.
Nevertheless, the levels measured at the condensate pump outlet are still in the 10 ppb range.
The next step appears to be checking for 2 Ibid
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L deficiencies in the Steam Jet Air Ejector (SJAE).
However, while the high oxygen levels adversely impact the INPO Chemistry Performance Index j
(CPI), the effect on the actual performance of the steam generators (SG)
j appears to be negligible due to deaerators that lower the FW oxygen levels L
to below one ppb prior to entry into the SGs.
An inherent characteristic of the B&W once-through steam generators (SG)
of this plant is that they are sensitive to iron scaling on the SG tubing, I
which reduces heat-exchange capacity, causes a rise in SG water level, and l
eventually may require derating of reactor power.
To slow this effect, j
the licensee has reduced the iron content of FW by the use of morpholine in the secondary system, a compound that gives better pH control and increased pH levels in the water phase, compared to that of the more volatile ammonia.
The higher pH reduces pipe corrosion / erosion and
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Since the morpholine treatment was started, i
the water level appears to have remained constant.
i The licensee is studying the depletion in the RCS of the boron-10 i
isotope, the isotope with the large neutron absorption cross section.
l The initial results showed the depletion to be about 4% compared to boron samples from other sources, including the BWST, SFP and boric acid addition tanks (BAAT).
A licensee representative noted that accounting i
for depletion removes the discrepancies in the reactivity calculations
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based on the " natural" isotopic composition of boron.
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The inspector reviewed the boron concentration data for the past i
year from the various systems having Technical Specification (T/S)
requirements, the BWST, Core Flood Tanks, and the Spent Fuel Pool.
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They all appeared to be within specifications during this period.
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l-The licensee maintains trend charts on the various chtmistry and radiochemistry and parameters, including secondary system FW cation
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conductivity, chloride, sodium, hydrazine, and dissolved oxygen
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concentrations, and primary system pH, lithium, boron, and radioiodine i
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parameters.
They also maintain charts on the chemistry performance
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index (CPI).
These charts are generated monthly, or as needed, from the
computerized chemistry database.
They are used by chemistry management, j
and selected charts are sent to plant and corporate management in a
monthly report.
Both monthly and yearly charts are produced.
A new
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database is being developed that will allow automatic and timely entry of data and extended versatility in the chart plotting, chart comparison, and data management.
In general, the various parameters appe6rs to be well controlled, with i
few out-of-specification problems.
The licensee appears to have put much j
effort into improving and maintaining water quality control.
The
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programs are satisfactory and well run, i
No violations or deviations were identified.
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Implementation of the Chemistry Program (IP 79701)
The inspector reviewed the chemistry programs, including physical
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facilities and laboratory operations.
The operations and instrumentation
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I were generally good.
The laboratory was somewhat'small and crowded for
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the amount of analytical apparatus and the number of operations done.
The licensee has plans to expand the operations into a nearby room.
The i
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Dionex Chromatograph was operated in the gradient elution mode to
separate fluoride and organic-acids from the other anions.
A Milton Roy Spectronic Model 501 UV/Vis Spectrophotometer with a 50-mm cells was used L
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for the silica and hydrazine analyses.
A Perkin Elmer (P-E) Model 5100 i
Atomic Absorption Spectrophotometer (AAS) with a Zeeman Effeet background corrector has replaced the P-E Model 5000 AAS..
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The inspector observed several Testers analyze routine samples by titration and AAS.
They appeared to be generally knowledgeable about
the work and followed the procedures.
They appeared to do well in the i
analyses.
l Overall, the laboratory appeared to be adequate for the proper operation i
of the plant and to be operating satisfactorily.
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No violations or deviations were identified.
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Nonradiological Confirmatory Measurements (IP 79701)
The inspector submitted chemistry samples to the licensee for analysis as
.i part of a program to evaluate the laboratory's capabilities to monitor l
nonradiological chemistry parameters in various plant systems with respect to various Technical Specification and other regulatory and
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administrative requirements.
These samples had been prepared, j
standardized, and periodically reanalyzed (to check for stability) for
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the NRC by the Radiological Sciences Division of Brookhaven National y
Laboratory (BNL).
The samples were analyzed by the licensee using
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routine methods and equipment.
Two dilutions for each sample were made by licensee personnel as j
necessary to bring the concentrations within the ranges normally analyzed
by the laboratory.
Each dilution was run in duplicate in a manner similar J
to that of routine semples.
The results are presented in Table 2 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
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deviations (SD) of the measurements.
Modifications made to these criteria J
(Attachment 1 Notes) are based on the consideration that the uncertainties (SD) of the licensee's results were not necessarily representative of the l
laboratory's because they were obtained by one analyst over a short period of time, j
The licensee will also prepare a sample of secondary system water spiked l
with the anion analytes fluoride, chloride and sulfate to be split with i
BNL.
The licensee will determine the concentrations of the analytes and the results will be submitted to Region III and compared to those determined by BNL.
This will be followed under Open Item No. 50-346/89024-01.
The licensee determined 10 analytes at three concentrations each.
Of the initial 30 cnalyses, 21 were in agreement (70%).
The oisagreements were
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mainly in the chloride and silica results, with others in the sulfate, L
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The high biases in the chloride results indicate that the concentration
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of the standard was low, probably due to making it from solid sodium chloride reagent dried at 110' C, rather than the 600' C required to properly dry this reagent (ASTM D-4327-84, Anions by Ion Chromatography).
f The cause of the bias in the silica results appears to be a defective standard, but comparison with a standard from a different source showed
little change.
The results of a rerun done by a second technician were substantially improved with agreement in two of the three samples, and l
a substantially reduced bias in the third, The positive biases in the sulfate analyses indicate that the standard t
concentration was low and that the variabilities were such that the
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last measurement was in disagreement possibly due to statistical variation, l-The initial sodium results had substantial positive biases, which, for this element, indicates either a deficient standard or contamination.
The rerun results still showed the biases, but were now in agreement.
The problems with the iron analyses appeared to be due both to the graphite furnace, which appears to be a generic problem with this type of analysis and to the sample matrix which contains copper, nickel f
and chromium.
Additionally, the very low concentrations of the iron (5 - 15 ppb) may have compounded the difficulties.
The licensee is in the process of assessing and rectifying the problems.
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Progress in the improvements in the analyses and control charts will be followed in subsequent routine inspections in this area.
Overall, the results of the analyses were about average for the plants, L.
but some problems with the analyses were noted.
Laboratory personnel demonstrated a willingness to correct the problems.
No violations or deviations were identified.
7.
Implementation of the QA/QC Program in the Chemistry Laboratory (IP 79703)
The inspector reviewed the nonradiological QA/QC program in the laboratory.
The program operates under Administrative Procedure DB-CH-00010, " Chemistry Quality Control Program," Revision 01, January 6, 1989.
This is a good procedure with comprehensive requirements for
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control charts, analyst and interlaboratory comparison programs, blind and duplicate samples, and independent calibration and check standards.
The description also includes tests for estimating the significance of changes in the parameters and a QC program for in-line process monitors.
One Chemistry Supervisor puts extensive effort into maintaining the program.
i Considerable progress has occurred since the previous inspection in this area.8 The charts have calculated statistical parameters with 1.5-50 warning limits, two-SD control limits, and the mean and expected values of the check standards.
They cover most of the analyses, including fluoride, chloride, lithium, hydrazine, boron, silica, iron, and sodium.
8 Ibid
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Licensee representatives agreed to implement charts for sulfate, which l
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The inspector noted that charts were not always evaluated frequently
enough to maintain good control over the analyses.
Some of the charts
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showe1 substantial biases of the mean relative to the expected values and l
drifts'in the data; e.g., sequential data points were, for the most part,
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either substantially above or below the mean line.
The limits were I
j recalculated infrequently so that the control parameters did not
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represent current operation of the respective analysis.
The inspector l
also noted some minor problems in the pro::edure and how control chart
data could be processed more efficiently.
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i The laboratory maintains good nonradiological interlaboratory comparison i
and technician testing programs.
Each month vendor-supplied (Analytics, l
Inc.) unknowns are distributed to the testers, so that over each quarter i
of the year, each analyst does the required series.
The acceptance
criteria for analyst's results were modified from those of the previous
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inspection, and are based on the measurement precision derived from the i
control charts.
The data from each analysis and for each tester are i
graphed to show the performance of the laboratory and of the individuals j
over time.
More timely evaluation of tester performance iesulted from modification of the acceptance criteria to use laboratory mean and SD
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values, rather than waiting for vendor results.
The quality of the r
results was good for both the laboratory and testers.
Overall, the program appeared to be effective.
j No violations or deviations were identified.
8.
Audits and Appraisals (IP 79701)
The inspector reviewed a recent corporate audit report relating to r
Chemistry, AR-89-CHEMC-01, March 30,1989.
It had one finding and four Observations that related to reporting out-of-control conditions to
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management and checks on the quality of bulk chemicals.
The responses
were timely.
The audit appeared to adequately assess the quality of the
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chemistry program.
No violations or deviations were identified.
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Open Items f
Open items are matters which have been discussed with the licensee, which I
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will be reviewed further by the inspector, and which involve some action on the part of the NRC or licensee, or both.
The open item disclosed t'
during the inspection is discussed in Section 6.
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10.
Exit Interview The scope and findings c.f the inspection were reviewed with licensee representatives (Section 1) at the conclusion of the inspection on October 20, 1989.
The inspector discussed the Open Items in Section 2
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and observations on the quality control program and the confirmatory j
measurements.
The inspector noted substantial improvements in the QA/QC
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program with comments mainly on minor problems'(Section 7).
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i During the exit interview, the inspector discussed the likely j
informational content of the inspection report with regard to documents
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or processes reviewed by the inspectors during the inspection... Licensee
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representatives'did not identify any such documents or processes as i
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proprietary.
i Attachments *
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Table 1, Nonradiological Interlaboratory S)11t $ ample Results, March 1988
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Table 2, Nonradiological Interlaboratory
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7est Results, October 17-20, 1989 I
3.. Attachment 1 Criteria for Comparing j
' Analytical Measurements (Nonradiological)
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I TABLE 1
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Nonradiological Interlaboratory Split Sample Results
' Davis-Besse Nuclear Power Station
March 1988 l
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Analyte, Matrix Analysis
.NRC Licensee Ratio Comparison b
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Concentration, ppb
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RCS IC 50.0 1 0.6 47.8 1 1.4 0.956 1 0.030 A
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RCS IC 45.3 1 0.3 52.9 1 0.2 1.168 1 0.082 A'
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Sulfate ~
12 1.214 1 0.041 D'
Fe FW AA/FL 490 1 10 527 1 15 1.076 1 0.046 A'
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Cu FW AA/FL 480 1 10 489
1.019 1 0.022 A
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Matrix:
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Analytical Method:
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IC Ion Chromatography
AA/FL Atoniic Absorption Spectrophotometry / Flame t
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Comparison i
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A Agree
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t (See Notes on Comparison Criteria for agreement criteria.)
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TAliLE 2 Nonradiological Interlaboratory Test Results Davis-Besse 'iuclear Power Station, Unit 1
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October 16-20, 1989 a
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Analyte Analytical NRC License Ratio Comparison b
Method Y i SD X i SD Z t SD 12 SD Concentration, ppb Fluoride IC 7.53 1 0.15 7.65 1 0.03 1.016 1 0.021 A
11.25 1 1.00 10.10 1 0.20 0.898 1 0.082 A
16.27 1 0.31 16.90 1 0.20 1.039 1 0.023 A
Chloride IC 6.95 1 0.11 8.30 1 0.30 1.193 1 0.047 D
i 9.25 1 0.05 11 70 1 0.80 1.265 1 0.087
l 14.35 1 0.23 16.70 1 0.90 1.154 1 0.065 D
Sulfate IC 7.09 i 0.01 7.80 1 0.20 1.100 1 0.046 D+
9.75 1 0.70 10.40 1 0.20 1.067 1 0.079 A
14.73 1 1.04 15.90 1 0.10 1.079 1 0.076 A
l Fe AA/FU 4.65 1 0.1 5. 2 1 0.1 1.120 1 0.048 D+
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9.95 1 0.1 10.8 1 0.1 1.085 1 0.045 A+
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14.6 1 0.1 15.8 1 0.2 1.082 1 0.046'
A+
Cu AA/FL 5.00 1 0.08 5.40 1 0.40 1.080 1 0.082 A
10.08 1 0.38 10.30 1 0.12 1. 022 1 0.040 A
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15.0 1 0.38 14.5 1 0.30 0.967 i 0.032 A
Na AA/FL 3.03 1 0.35 3.26 1 0.08 1.076 1 0.127 A
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5.30 1 0.30 6.46 1 0.33 1.219 1 0.093 D
7.9 1 0. 5 10.2 1 1.1 1.291 1 0.161 A
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3.03 1 0.35 3.26 1 0.08 1.078 1 0.127 A
5.30 1 0.30 5.92 1 0.03 1.117 1 0.063 A
l 7.90 1 0.45 9.02 1 0.08 1.142 1 0.092 A*
j Li AA/FL 985 1 20 1003
1.018 1 0.022 A
1500 1 35 1548
1.032 1 0.024 A
2065 2 50 2052
0.994 1 0.024 A
i Hydra-Spec 19.9 1 0.3 19.8 1 0.1 0.995 1 0.016 A
zine 49.9 1 0. 5 50.0 1 0.2 1.002 1 0.011 A
100 i 1 98.5 1 0.7 0.985 1 0.012 A
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TA8LE 2 (Continued)
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Analyte Analytical NRC" License" Ratio Comparisonc
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. Method Y i SD X i SD Z 1 50 12 SD
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I Concentration. ppb
i Silica Spec 26.4 1 0.04 21.0 i 0.7 0.795 1 0.04?
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L 52.0 1 0.06 43.6 1 1.1 0.838 i 0.032 D+
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26.4 1 1.4 24.3 1 0.1 0.920 1 0.049 A
78.5 1 0.03 62.8 1 0.8 0.800 1 0.024 D+
52.0 1 2.0 49.1 1 0.4 0.944 1 0.037 A
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78.5 1 0.03 71.1 1 0.4 0.906 2 0.039 D+
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Concentration. ppm i
i 8oron Titt 1002 i 10 990 t 9 0.988 i 0.013 A
i 2970 1 23 2950 t 6 0.993 1 0.008 A
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4918 i 48 4853 1 35 9.987 t 0.012 A
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Value i stendard deviation (SD); number of 8NL analyses is 6 to
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The number of licensee analyses is 4.
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Analytical methods:
Titr - titration I
- lon chromatogr phy
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AA/Fu - Atomic Absorpt on Spectroscopy t
(furnace)
I AA/FL - Atomic Absorption Spectroscopy (flame)
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A = Agreement i
D = Disagreement
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i Substituted the BNL uncertainty for licensee's uncertainty, i
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Substituted 3% relative Standard Deviation for BNL and licensee
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SDs.
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ATTACHMENT 1 c.
Criteria for Comparing Analytical Measurements
This attachment provides criteria for comparing results of the capability tests.
I The acceptance limits are based on the uncertainty (standard deviation) of the
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ratio of the licensee's mean value (X) to the NRC mean value (Y), where (1) Z = X/Y is the ratio, and
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(2) S is the uncertainty of the ratio determined from the i
pfopagationoftheuncertaintiesofjicensee'smeanvalue, S, and of the NRC's mean value, S.
Thus, x
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Y~W~*h,sothat r _ x
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S = Z *l(S*2 s 2)h
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Y--
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i 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 or I
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equal to twice the uncertainty in the ratio, i.e.
l 1-Z l < 2+S,.
1.
National Council on Radiation Protection and Measurements,
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A Handbook of Radioactivity Measurements Procedures, NCRP Report No. 58, Second Edition, 1985, Pages 322-326 (see
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i Page 324).
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4/6/87 j
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ATTACHMENT 1
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NOTES i
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The uncertainties may be modified in cases of disagreement:
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If th:
censee's SD, S is smaller than that of the NRC, the NRC's relative standard devia{ ion (RSD) (S /Y) will be substituted for Y
that of the licensee (S /X), and the agreement criteria recalculated, x
b.
If a disagreement and the RSDs appear to be unreasonably low, RSDs
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of 3% will be substituted for those of both the NRC and the licensee.
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i This will not be done for the boron analyses where the expected R$Ds are 0.5-1%.
II.
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 Region 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 reethods differed.
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