IR 05000423/1989019

Insp Rept 50-423/89-19 on 890828-0901.No Violations Noted. Major Areas Inspected:Radiological & non-radiological Chemistry Program Including Confirmatory Measurements, Chemistry & Lab Qa/Qc

ML20248G834
Person / Time
Site:	Millstone
Issue date:	09/22/1989
From:	Bores R, Kottan J, Mcnamara N NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20248G807	List: IR 05000423/1989019 ML20248G806
References
50-423-89-19, NUDOCS 8910110046
Download: ML20248G834 (11)

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U.S. NUCLEAR REGULATORY COMMISSION.

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REGION-I-Report No. 50-423/89-19

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, Docket No. 50-423 o '

I: , . License'N NPF-49 LPriority -

Category C K Licensee: Northeast Nuclear Energy Coinpany .P. O. Box 270-(. Hartford, CT 06101 l

D Facility Name: Millstone Nuclear Power Plant, Unit 3'

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. Inspection Ati Waterford,~C Inspection Conducted: 'AugustD28 - September 1, 1989 Inspectors: @-7 N Nancy T. McNamara, Laboratory Asst. ERPS

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N James;J. Kott(n, Laboratory Specialist, ERPS date

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Approved by! 9-2E-8f Robert # Bores, Chief. Effluents Radiation date-

. Protection Section, FRSS Branch Inspection Summary: Inspection on August 28 - September 1, 1989 (Inspection Report No. 50-423/89-19)

Areas Inspected: Routine unannounced inspection of the radiological and

.non-radiological chemistry program. Areas reviewed included: confi r.matory measurements - radiological, standards analyses - chemistry, and laboratory 4 QA/Q !

Results: Of the areas reviewed, no violations were identifie l

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DETAILS'

l.0 Individuals Contacted

• T. Burns, Asst. Chemistry Supervisor, Unit 3

• C; H. Clement, Station Superintendent, Unit 3

-*G. L. D'Auria,-Analytical Chemist

• H. Haynes~, Station Services Superintendent

• D.' G. Peiffer, QA Specialist

• Denotes those personnel who attsnded the exit meeting on September 1, 198 The inspector also interviewed other licensee personnel including other members of the chemistry staf .0 Purpose The purpose of this routine inspection was to review the following area . The licansee's ability to measure radioactivity in plant systems and effluent samples and chemistry parameters in various plant system . The licensee's ability to demonstrate the acceptability of analytical results-through implementation of a laboratory QA/QC progra .0 Organization The Millstone Chemistry Department is a site-wide department under the direction of the Millstone Chemistry Supervisor. Reporting to the Millstone Chemistry Supervisor are Assistant Chemistry Supervisors for each unit (1, 2, 3), as well as other professional staff including the

. Site Chemist, Analytical Chemist, Unit 2 Chemist, and Unit 3 Chemis Also reporting to the Chemistry Supervisor is the Chemistry QA Specialist who reports to the Chemistry Supervisor through the Analytical Chemis Reporting to the Assistant Chemistry Supervisors are Chemistry Specialists

. and Chemistry Technician The Millstone Chemistry Supervisor reports to the Millstone Station Services Superintendent, who in turn reports to the Millstone Station Superintendent. The Chemistry QA Specialist is responsible for the

' implementation of the chemistry laboratory QA/QC progra '

4.0 Radiological and Chemical Measurements .

4.1 Confirmatory Measurements (Radiological)

During this part of the inspection liquid, airborne particulate !

(filter) and iodine (charcoal cartridge), and gas samples were l

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• analyzed by the licensee and the NRC for the purpose- of .

'intercomparison. The samples were actual split samples with the exception.of the particulate filter, charcoal' cartridge,. and reactor coolant gas samples. In these cases.the samples 'could not be split, and the same, samples were analyzed by both the licensee and the NRC.-

Where possible, the samples are actual effluent samples or inplant 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:I Mobile Radiological Measurements Laboratory. ' Joint analyses of actual effluent samples are- used to verify the licensee's capability to measure radioactivity in effluent and other samples with respect to

' Technical Specification and other regulatory requirement In. addition, a liquid effluent sample was sent to the NRC reference r laboratory, Department of Energy, Radiological and Environmental Sciences Laboratory (RESL), for analyses requiring wet chemistr The analyses to be performed .on the sample are Sr-89, Sr-90, Fe-55, gross alpha, and H- 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 repor The licensee's Unit.3 Health Physics Department also possesses a

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gamma spectrometry system. Therefore, the particulate filter and charcoal cartridge were also analyzed using this counting system and compared with the NRC results. These are the types of samples which are routinely analyzed by this departmen The results of the sample measurement comparisons indicated that all of the measurements were in agreement under the criteria for comparing results (see Attachment 1). The results'of the comparison are listed in Table The inspector had no further questions in this are No violations l were identified, i 4.2 Standards Analyses (Chemical) '

During this part of the inspection, standard chemical solutions were submitted to the licensee for analysi The standard solutions were prepared by Brookhaven National Laboratory (BNL) for the NRC, and were analyzed by the licensee using routine methods and equipmen The analysis of standards is used to verify the licensee's capability to monitor chemical parameters in various plant systems with respect to Technical Specification and other regulatory requirements. In addition, the analysis of standards is used to evaluate the licensee's procedures with respect to accuracy and precisio _ _ _ _ ___ ___ _ _ _ _ . I

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3 A spiked feedwater sample was sent to BNL for analysis. The analyses to be performed on the sample are sulfate and chlorid The licensee will perform the same analyses, and the .NRC results will be compared with the licensee's results when received at a later date. These.will be documented in a subsequent inspection repor The analysis of an actual spiked sample permits the comparison of results from an actual sample matri The results of the st'andards measurement comparisons indicated tha three of-the 31 measurements were in disagreement under the criteria used for comparing results. (See Attachment 2) The results of the comparison are listed in Table II. The standards were submitted to the licensee for analysis in triplicate at three concentrations spread over the licensee's normal calibration range. The fluoride analysis was performed at only one concentration because of the licensee's narrow calibration range (5-10 ppb) for this analyte on the ion chromatography syste The disagreements were judged not to be significant since all of the values which were in disagreement were within 10% of the BNL valu The disagreements were due to the statistical nature of the NRC comparison criteria and were not judged to be significan The sodium results which are presented in Table II are those from a reanalysis of the NRC standards using only a sodium calibration standard. The licensee's routine procedure requires calibration using a standard containing both sodium and potassium. When the NRC sodium standards were analyzed using the sodium / potassium calibration, the results were biased low by approximately 20 percent at the five ppb concentration and approximately 10 percent at the'15 ppb concentration. The inspector discussed this matter with the licensee, and the licensee stated that this area would be reviewed and appropriate corrective action taken. The inspector had no further questions in this area. No violations were identifie . Laboratory QA/QC The inspector reviewed the licensee's chemistry and radiochemistry laboratory QA/QC program. This program is described in Procedure No. CP 3800, " Chemistry Quality Assurance Program". The procedure provides for the control of analytical performance through a number of mechanisms including intralaboratory spiked sample programs in the chemistry area, interlaboratory spiked and split sample programs in both the chemistry and radiochemistry areas, and the use of control charts to assess instrument and analytical procedure performance. In addition, the procedure also addresses such areas as training, calibration of j instrumentation, preparation of QA reagents and standard solutions, and a duplicate and spiked sample program for the vendor laboratory used for l L performing Sr-89, Sr-90, Fe-55, and gross alpha analyses of effluent l L samples. The inspector reviewed selected data generated by the '

licensee's laboratory QA/QC program for 1988 and 1989 to date and noted

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that the licensee appeared to be implementing the laboratory QA/QC program as required. All results were properly documented and plotted on-control charts as require In reviewing the above data the inspector noted that, in practice, the licensee was actually implementing.a larger QA/QC program than required by his laboratory QA. procedure. Specif_ically, the licensee was conducting.an intralaboratoy spiked sample program in the radiochemistry

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area, was participating in a spiked sample program with NIST.(formerly NBS), and was analyzing Millstone 1 and 2 chemistry laboratory calibration standards as unknowns as part of the interlaboratory-program. -The inspector noted the the licensee was currently in the

. process of revising his laboratory QA procedure and ' suggested the above

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programs be included in the procedure. The inspector also noted the extensive QA/QC data review and analysis performed by the licensee. With regard to the intralaboratory data, for example, the licensee computed a grand average of all results, tested individual results for outliers'and

. recomputed a grand average if necessary, and then performed a t-test to compare the grand average to the known value. The inspector. stated that this extensive data review and analysis was a noted strength of the laboratory l QA program. In' addition, the inspector and the licensee discussed the preparation of spiked samples. In particular, the preparation of. spiked samples for Fe-55 analysis was discussed. The inspector stated that interferences should be present in spiked samples which duplicated those present in "real" samples; at least Fe-59 should be present in Fe-55 spiked samples. The inspector had no furthe'r questions in this area. No violations were identifie ~ Exit Interview The inspector met with the licensee representatives denoted in Section 1 at the conclusion of the inspection on September 1, 1989. The inspector summarized the purpose, scope and findings of the inspectio _ _ _ _ _ _ _ _ _ _ _ _ - _ - _ - _ _ - _ _ _

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Table I Millstone, Unit 3 Verification Test Results SAMPLE- ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON-Results in Microcuries Per Milliliter l

' "B" Waste ~ Mn-54 (5.110.3)E-6 (6.1 0.4)E-6 Agreement Test Tank Co-60 (1.49 0.05)E-5 (1.6310.06)E-5 Agreement 8-30-89 Co-58 (2.1510.05)E-5 '(2.2610.06)E-5 Agreement 0400 hr .

Ag-110M (1.11 0.03)E-5 (1.1010.04)E-5 Agreement (Detector #3)

Reactor Coolant I-131 (1.9610.04)E-3 (2.0 0.2)E-3 Agreement 8-30-89 I-132 (8.6 0.6)E-3 (9.0 0.2)E-3 Agreement 0825 hr (5.8710.08)E-3 (5.90 0.14)E-3 Agreement

' (Detector #2) I-135 (8.5 0.5)E-3 (8.4 0.7)E-3 Agreement RE10B Charcoal Cartridge I-131 (4.4 0.5)E-4 (4.0 0.2)E-4 Agreement 8-30-89'

1140 hr (Detector'#2)

Reactor Coolant Cr-51 (1.6210.12)E-5- (1.5010.05)E-5 Agreement Particulate Filter Mn-54 (1.3310.12)E-6 (1.20 0.07)E-6 Agreement 8-22-89 Co-58 (1.2010.03)E-5 (1.17 0.02)E-5- Agreement

' 0804 Co-60 (3.Si0.2)E-6 (3.4510.10)E-6 Agreement (Detector #3)

. Reactor Coolant Kr-85m (4.2710.07)E-2 (4.62 0.03)E-2 Agreement Gas' Sample Kr-87 (6.410.2)E-2 (6.8610.06)E-2 Agreement 8-30-89 Kr-88 (1.04 0.02)E-1 (1.110 0.008)E-1 Agreement 0825 hr Xe-133 (8.8010.11)E-2 (1.098 0.007)E-1 Agreement (Detector #3) Xe-135 (1.941 0.012)E-1 (2.09910.005)E-1 Agreement

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CMS 22 Xe-133 (7.1 0.2)E-6 (7.09 0.15)E-6 Agreement ,

Gas Sample Xe-135 (3.3 0.3)E-7 (3.510.2)E-7 Agreement '

x 8-30-89

'1400 hr (Detector #2)

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Table I (continued)

Millstone Unit 3 Verification Test Results SAMPLE ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON Results in Microcuries Per Milliliter Health Physics

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Reactor Coolant Cr-51 (1.62 0.12)E-5 (1.59 0.05)E-5 Agreement Particulate Filter Mn-54 (1.33 0.12)E-6 (1.31 0.06)E-6 Agreement 8-22-89 Co-58 (1.20 0.03)E-5 (1.223 0.013)E-5 Agreement 0804 hr Co-60 (3.5 0.2)E-6 (3.50 0.09)E-6 Agreement (Detector #1)

RE10B l Charcoal. Cartridge I-131' (4.4 0.5)E-4 (4.010.6)E-4 Agreement-8-30-89 1140 hr (Detector #1)

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[e Table II

Millstone Unit 3 i Chemistry Test Results o'

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Chemical Method of .NRC Licensee Ratio Parameter Analysis * Known Value . Measured Value- (LIC/NRC) Comparison Results in parts per billion (ppb)

Fluoride IC 8.3 .1 .98 0.03 Agreement Chloride IC 1.8510.01 1.8210.10 0.9810.05 Agreement 3.7310.03 3.9310.13 .1.05 0.04 Agreement 7.65 0.12 7.51 .98 0.04 Agreement

. Sulfat IC 1.9510.14 1.91 0.11 0.9810.09 Agreemen .8 .4.00 0.04 1.05 0.08 Agreement'

7.8 .0 .0210.06 Agreement'

Silica SP 53 3 49.5 .93 0.06 Agreement 10414 95.7 .9210.04 Agreement 157 2 150.61 .95910.013 Disagreement-

' Ammonia I .94 0.05 Agreement 301 3 31114 1.0310.02 Agreement 246 12 26416 1.07 0.06 Agreement Hydrazine SP 19.9 .01 .0010.05 Agreement 49.9 .01 .08 0.02 Disagreement 100.01 .02010.010 Agreement-Iron AAG 9.3 .78 0.10 1.05 0.04 Agreement 19.9 .0 .06 0.05 Agreement 14.61 .8 .01 0.05 Agreement Copper AAG 10.00 0.15 10.4 .04 0.02 Agreement 20.2 .81 .9810.04 Agreement 15.01 .2 .0110.06 Agreement Sodium ** AAG 6.0 .15 0.13 0.86 0.10 Agreement 10.6 .92 0.07 0.94 0.05 Agreement 15.81 .71 .93 0.06 Agreement

• • Licensee measured values for sodium are from reanalysis of the NRC sodium standard using only a sodium calibration standar _- - .

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i Table II (continued)

l-Millstone Unit 3 Chemistry Test Results l

l l Chemical Method of NRC Licensee Ratio Parameter Analysis * Known Value Measured Value (LIC/NRC) Comparison Results in parts per million (ppm)

Boron Ti .61 .956 0.009 Disagreement

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3100 100 2938111 0.95 0.03 Agreement 5000 90 4887 4 0.98 0.02 Agreement Lithium IC 1.9710.04 1.90 0.02 0.9610.02 Agreement 3.00 0.07 2.96 0.04 0.99 0.03 Agreement 4.13 0.10 3.96110.013 0.96!0.02 Agreement

• Note: SP = UV-Vis Spectrophotometry IC = Ion Chromatography Tit. = Potentiometric titration AAG = Atomic Absorption Spectrometry with Graphite Furnace

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ATTACHMENT 1 CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS This attachment provides criteria for comparing results of capability tests and verification measurements. The criteria are based on an empirical relationship which combines prior experience and the accuracy needs of this -

progra 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 decrease Resolution 2 Ratio For Agreement 2

<3 No Comparison 4-7 0.5 - .6 - 1.66 16 - 50 0.75 - 1.33 51 - 200 0.80 - 1.25

>200 0.85 - 1.18 2 Resolution = (NRC Reference Value/ Reference Value Uncertainty)

2 Ratio = (License Value/NRC Reference Value)

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ATTACHMENT-2

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CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS j

' This attachment'proviries criteria for comparing results of capability test In these criteria the judgement limits are based on the uncertainty of the ratio of.the lice' nee's value to the NRC value. The following steps are performedi (1) the ratio-of the licensee's value to the NRC value is computed Licensee'Value-(ratio = NRC Value );

(2) 'the uncertainty of the ratio.is c opagate ,

If the absolute value of one minus the ratio is less than or equal to twice the ratio uncertainty .(ll ratio l s 2 uncertainty), the results are in agreemen Zu 5' then UZ* = 3*' + Ef5 y Zr x2 y2 2( From: Bevington, P. R., Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York, 1969)

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