IR 05000293/1985023

Insp Rept 50-293/85-23 on 850812-16.No Violation Noted.Major Areas Inspected:Analytical Procedures Evaluation Using Stds, Split Samples for Chemical Analyses & Analytical Measurements QC Program

ML20132D827
Person / Time
Site:	Pilgrim
Issue date:	09/24/1985
From:	Kottan J, Kramaric M, Pasciak W NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20132D808	List: IR 05000293/1985023 ML20132D806
References
50-293-85-23, NUDOCS 8509300304
Download: ML20132D827 (10)

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i U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report No.

50-293/85-23 Docket No.

50-293 License No.

DPR-35 Priority Category C

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Licensee:

Boston Edison Company 800 Boylston Street Boston, Massachusetts 02199 Facility Name:

Pilgrim Station Inspection At:

Plymouth, Massachusetts Inspection Conaucted: August 12 - 16, 1985 Inspectors: M ' Q

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7 ~/[GI J. J. Kottan' Radiation Laboratory Specialist 7 date GLf.1%usk ci/vilV

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N. E.

ra ri} Radiatio ecialist

' date Approved by:

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W. "J.

iakYChief, BWR Radiological

iate Protec n Section Inspection Summary:

Inspection on August 12-16, 1985 (Report No. 50-293/85-23)

Areas' Inspected:

Routine, unannounced inspection of the licensee's chemical and radiochemical measurements program using the NRC:I Mobile Radiological Measurements Laboratory and laboratory assistance provided by DOE: Brookhaven National Laboratory and Idaho National Engineering Laboratory, Radiological and Environmental Sciences Laboratory. Areas reviewed included:

analytical'

procedures evaluation using standards, split samples for chemical analyses, performance on radiological analyses of split actual effluent and inplant samples, and program for the quality control of analytical measurements. The inspection involved 109 inspector hours on site by three NRC regionally based inspectors.

Results: Of the areas inspected, no violations were identified.

8509300304 850925 PDR ADOCK 05000293

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DETAILS l

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Individuals Contacted

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• J. Crowder, Senior Compliance Engineer

R. Smith, Chief Chemical Engineer l.

A. Shatus, Senior Chemical Engineer l

C. Grevenitz, Chemical Engineer

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• S. Stinson, Chemical Engineer l'

• C. Mathis, Plant Manager D. Fountain, CC and RP Technician

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l C. Goddard, CC and RP Technician i

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The inspector also interviewed other licensee employees, including members

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of the chemistry and health physics staffs.

• Denotes those present at the exit interview.

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Analytical Procedures Evaluation During the inspections standard chemical solutions were submitted to the licensee for analysis.

The standard solutions were prepared by the Brookhaven National Laboratory (BNL) for the NRC region I, and the stan-l dards were analyzed by the licensee using normal methods and equipment.

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The analysis of standards is used to verify the license's capability to monitor chemical parameters in various plant systems with respect to Technical Specification requirements and other regulatory requirements.

In addition, the analysis of standards is used to evaluate the licensee's analytical procedures with respect to accuracy and precision.

The results of the standard measurements comparison indicated that, with l

the exception of two measurements, all of.the results were in agreement under the criteria used for comparing results.

(See Attachment I.) The two disagreements, both metal analyses, are not considered significant.

Both values, although in disagreement, were within ten percent of the NRC values. The results of the comparisons are listed in Table I.

The licensee performed all analyses in triplicate.

The chloride and fluoride analyses were performed using ion chromatography, the metal analyses by plasma emission spectroscopy, and the boron analyses by the mannitol titration method.

No violations were identified in this area.

3.

Chemistry Confirmatory Measurements During the inspection actual inplant water samples were split between the licensee and the NRC in order to verify the licensee's measurement cap-abilities on actual plant water samples.

The analyses will be performed l

by the licensee using normal methods and equipment and for the NRC Region l

I by BNL.

The analyses to be performed are chloride and fluoride on a i

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reactor water sample; and iron, copper, nickel, and chromium on a feed-water filter sample. On completion of the analyses by both laboratories, the results will be compared, and the intercomparison will be documented in a subsequent inspection report.

4.

Radiochemistry Confirmatory Measurements During the inspection, liquid, particulate filter, charcoal cartridge, and gas samples were split between the licensee and NRC for the purpose of s

intercomparison. The split samples are actual effluent and inplant samples normally analyzed by the licensee. The samples were analyzed by the licensee using normal 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 radio-activity in effluent samples with respect to Technical Specification requirements and other regulatory requirements.

In addition a liquid effluent sample was sent to the NRC reference labora-tory, Department of Energy, Radiological and Environmental Sciences Labor-atory (RESL), for analyses requiring wet chemistry.

The analyses to be performed on the sample are Sr-89, Sr-90, gross alpha, Fe-55 and tritium.

The results 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 an effluent sample split between the licensee and NRC:I during a previous inspection on May 9-13, 1983 (Inspection Report No.

50-293/83-13) were also compared during this inspection.

The results of the sample measurements comparison indicated that all of the measurements, with two exceptions, were in agreement under the criteria used for comparing results.

(See Attachment II.) The results of the comparisons are listed in Table II. At the beginning of this inspec-tion the licensee's chemistry gamma spectroscopy system was inoperative.

The licensee counted samples on the health physics gamma spectroscopy system (the backup system) until the chemistry system was repaired.

The sample counting system used for each sample is noted in Table II.

The As-76 disagreement on a particulate filter sample resulted from an incor-rect half life value being used by the licensee. The result was in agree-ment when calculated with the correct half life. The licensee corrected the isotope library prior to the conclusion of the inspection. The dis-agreement on a tritium measurement intercomparison will be resolved when the sample requiring wet chemistry which was split during this inspection is compared for the tritium results. This intercomparison will be per-formed as soon as both sample results are available.

No violations were identified in this area.

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5.

Laboratory QC program The inspector reviewed the licensee's program for the quality control of analytical measurements. The licensee maintains both an intralaboratory i

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and an interlaboratory QC program for chemical and radiochemical analyses.

The intralaboratory program consists of daily or periodic source and back-ground checks, and where applicable, gain and resolution checks in the radiochemistry area; and daily or periodic standard analysis in the chemistry area. All results are plotted on control charts.

The inter-laboratory program consists of periodic spike sample analyses in both the radiochemistry and chemistry areas.

The data from this program is also plotted and includes graphs for the mean and range as well as technician performance. The inspector reviewed the QC data for the period January, 1985 to date.

No violations were identified in this area.

6.

Exit Interview The inspector met with the licensee representatives denoted on Paragraph 1 at the conclusion of the inspection on August 16, 1985.

The inspector summarized the purpose and scope of the inspection and the inspection findings.

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TABLE 2

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VERIFICATION TEST RESULTS PILCRIM STATION SAMPLE ISOTOPE NRC VALUE LICENSE VALUE COMPARISON Results in microcurie per mi1iiiiter

1. Drywell Pa rt icu l a te fi l te r C-19 Cr-51 (2.85 1 0.03) E-10 (2.81 1 0.02) E-10 Ag reement -

August 10, 1985 Mn-54 (8 1 2) E-13 (1.2 1 0.2) E-12 Ag reemen t Co-60 (8.5 1 0.5) E-12 (1.04 i O.03) E-11 Ag reemen t As-76 (8.5 1 0.4) E-11

'(8.2 1 0.3) E-12

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Mo-99 (1.29 i O.07) E-10'

(1.31 1 0.04) E-10 Ag reement Np-239 (4.7 1 0.3) E-11 (5.51 i O.10) E-11 Ag reement

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l-131 (6.1 i O.2) E-12 (5.9 i 0.2) E-12 Ag reement Te-132 (4.5 1 0.4) E-12 (4.4 1 0.2) E-12 Ag reemen t I-133 (2.30 1 0.05) E-10 (2.35 1 0.04) E-10 Ag reemen t Cs-137 (912) E-13 (1.74 1 0.14) E-12 Ag reement Ba-140 (2.3 1 0.2) E-11 (1.9 1 0.8) E-11 Ag reement

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i Na-24 (2.50 1 0.04) E-9 (2.67 1 0.04) E-9 Ag reemen t CO-58 (8.1 1 0.3) E-12 (8.4 1 0.2) E-12 Ag reement

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1. Drywe l l Cha rcoa l Ca rtridge C-19 l-131 (1.000 1 0.014) E-10 (9.72 1 0.06) E-11 Ag reemant August 10, 1985 1-133 (1.33 i O.02) E-9 (1.33 i 0.01) E-9 Ag reement

• corrected result is (8.8 1 0.3) E-11 This result is in agreement. See Pa ragraph 4.

2 Misc. Tank 1020 hours0.0118 days <br />0.283 hours <br />0.00169 weeks <br />3.8811e-4 months <br /> C r-51 (2.5 1 0.4) E-6 (3.4 i O.8) E-6 Ag reement August 14, 1985 Mn-54 (2.7 1 0.8) E-6 (412) E-7 Ag reemen t Co-60 (6.6 1 0.2) E-6 (8.3 1 0.4) E-6 Ag reement Cs-137 (5.96 1 0.11) E-6 (6.6 1 0.3) E-6 Ag reemen t

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As-76 (1.14 i O.14) E-6 (1.2 i'O.3) E-6 Ag reemen t a

Cs-134 (2.9 i O.8) E-7 (2.5 i 1.2) E-7 Ag reement i

Main Stack Cas

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1325 hours0.0153 days <br />0.368 hours <br />0.00219 weeks <br />5.041625e-4 months <br /> K r-85m (6.5 i O.3) E-7 (6.93 1 7.91%) E-7 Ag reemen t August 15, 1985 Kr-88 (3.7 i O.8) E-7 (4.71 1 26%) E-7 Ag reement

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1st count Xe-133 (3.84 1 0.08) E-6 (3.89 i 4.65%) E-6 Ag reemen t

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Xe-135 (8 i 2) E-8 not identified No Comparison

Main Stack Cas

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1325 hours0.0153 days <br />0.368 hours <br />0.00219 weeks <br />5.041625e-4 months <br /> K r-85m (6.5 1 0.3) E-7 (6.67 i 9.69%) E-7 Ag reement August 15, 1985 Xe-133 (3.84 1 0.08).E-6 (3.61 1 4.19%) E-6 Ag reement j

2nd count Xe-135 (8 1 2) E-8 (1.24 1 29.8%) E-7 Ag reement

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NOTE: Samples identified with an asterisk were counted on the Health Physics counting system, i

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TABLE 2 (con't)

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. VERIFICATION TEST RESULTS PILCRIM STATION SAMPLE ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON Results in microcurie Der milliliter Rzactor Water 1-132 (4.58 1 0.06) E-3 (4.66 1 1.54%) E-3 Ag reement 1333 hours0.0154 days <br />0.37 hours <br />0.0022 weeks <br />5.072065e-4 months <br /> 1-134 (1.40 1 0.03) E-2 (1.38 1 4.64%) E-2 Ag reement August 14, 1985 l-135 (4.65 1 0.15) E-3 (4.44 1 2.22%) E-3 Ag reement 1st count Rsactor Water I-131 (1.5 1 0.2) E-4 (1.06 i 4.56%)-E-4 Ag reement 1333 hours0.0154 days <br />0.37 hours <br />0.0022 weeks <br />5.072065e-4 months <br /> 1-133 (1.76 1 0.03) E-3 (1.68 1 1.03%) E-3 Ag reement

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August 14, 1985 2nd count

1. Main Stack 1-131 (6.0 1 0.3) E-3 (5.62 1 0.12) E-3 Ag reement Cha rcoa l Ca rt ridge 1-133 (1.11 1 0.05) E-1 (1.13 1 0.02) E-1 Ag reement August 9, 1985

• Main Stack Ba-140 (1.1 1 0.5) E-3 (8.5 i 1.0) E-4 Ag reemen t Particulate Filter August 9, 1985 Orr Gas 0918 hours0.0106 days <br />0.255 hours <br />0.00152 weeks <br />3.49299e-4 months <br /> Kr-87 (5.55 1 0.07) E-1 (5.46 i 1.8%) E-1 Ag reement August 15, 1985 Kr-88 (4.85 i 0.05) E-1 (4.30 2.2%) E-1 Ag reement 1st count Kr-85m (1.75 1 0.02) E-1 (1.46 1 2.0%) E-1 Ag reemen t Xo-135 (8.08 1 0.03) E-1 (7.01 1 0.5%) E-1 Ag reement Xe-133 (1.86 1 0.02) E-1 (1.89 1 2.9%) E-1 Ag reemen t Xe-135m (2.3 1 0.3) E-0 (2.02 i 7.6%) E-0 Ag reement Orr Gas 0918 hours0.0106 days <br />0.255 hours <br />0.00152 weeks <br />3.49299e-4 months <br /> K r-87 (5.55 1 0.07) E-1 (5.12 i 11.87%) E-1 Ag reement August 15, 1985 K r-88 (4.85 1 0.05) E-1 (4.52 1 3.97%) E-1 Ag reement 2nd count Kr-85m (1.75 1 0.02) E-1 (1.61 1 2.37%) E-1 Ag reement Xe-135 (8.08 1 0.03) E-1 (7.072 1 0.53%) E-1 Ag reemen t Xe-133 (1.86 1 0.02) E-1 (1.946 i 1.87%) E-1 Ag reement Results in total m ic rocu ri es

• Reactor Building Vent Cha rcoa l Ca rt ridge 1-131 (3.8 1 0.3) E-3 (3.87 1 0.09) E-3 Ag reement August 9, 1985 1-133 (1.01 1 0.05) E-1 (1.04 1 0.02) E-1 Ag reement Reactor Building Vent Particulate Filter Ba-140 (8 i 4) E-4 (7.9 1 1.4) E-4 Ag reement

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TABLE 2.(con't)

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VERIFICATION TEST RESULTS--

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SAMPLE ISOTOPE.

NRC VALUE LICENSEE VALUE COMPARISON

. Results in microcurie ner mil l il iter

Misc. Tank gross alpha

.(6.4 i 0.8) E-81 not analyzed No Comparison 1400 hours0.0162 days <br />0.389 hours <br />0.00231 weeks <br />5.327e-4 months <br /> gross beta -

(1.69 i O.06) E-4 (1.4 i O.1) E-4 Ag reement

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.H-3 (1.73 1 0.06) E-5 (1.20 1 0.24) E-5 Disag reement -

S r-89 (2.5 i 1.2) E-7

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Fe-55 (4 i 4) E-8 (8.7 i 0.4).E-5 No Comparison-

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ATTACHMENT I

Criteria For Comparing Analytical Measurements y

This attachment provides criteria for comparing results'of capability tests.

In.these criteria the judgement limits are based on the uncertainty of the

. ratio of the licensee's value to the NRC value. The following -teps are performed:

(1) the ratio of the licensee's value to the NRC value is computed ratio = Licensee Value ;

NRC value

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(2) the uncertainty of the ratio is propagated.1 s

s If the absolute value of one minus the ratio is less than or equal to twice the ratio uncertainty, the results are in agreement.

(11-ratio ls2 uncertainty)

.Z = E' then Sz2 Sx2

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y Z2 X2 y2 (From: Bevington, P. R., Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York, 1969)

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l ATTACHMENT 2 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 program.

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In these criteria, the judgement limits are variable in relation to the comparison of the NRC Reference Laboratory's value to its associated l

uncertainty. As that ratio, referred to in this program as " Resolution",

i increases the acceptability of a licensee's measurement should be more

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selective. Conversely, poorer agreement must be considered acceptable as the

resolution decreases.

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RESOLUTION = NRC REFERENCE VALUE RATIO = LICENSEE VALUE REFERENCE VALUE UNCERTAINTY NRC REFERENCE VALUE Resolution Agreement

<3 0.4 - 2.5 4-7 0.5 - 2.0 8 - 15 0.6 - 1.66 16 - 50 0.75 - 1.33 51 - 200 0.80 - 1.25

>200 0.85 - 1.18

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