IR 05000333/1989017

Insp Rept 50-333/89-17 on 890731-0804.No Violations Noted. Major Areas Inspected:Radiological & Nonradiological Chemistry Program,Confirmatory measurements-radiological, Std analyses-chemistry & Lab Qa/Qc

ML20246L678
Person / Time
Site:	FitzPatrick
Issue date:	08/28/1989
From:	Bores R, Kottan J, Mcnamara N NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20246L665	List: IR 05000333/1989017 ML20246L661
References
50-333-89-17, NUDOCS 8909070022
Download: ML20246L678 (12)

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U.S. NUCLEAR REGULATORY COMMISSION-REGIO Report N /89-17 Docket N License No. DPR-59: Category C

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Licensee: New York Power Authority 4 P. O. Box 41 Lycoming, New York'

Facility Name: James A. FitzPatrick Nuclear Power Plan In spectiori 'At: Scriba, New Yor Inspection Conducted: July 31 - August 4, 1989 Inspectors: NQ/dC4 T. W MN TIK 87 I N. T. MgNamara, Laboratory Assistant, ERPS date-m .

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--N - M ", l'aboratory Specialist, TRPS 7'- ZS~d

.J. J. Kottan "

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l- Approved by: F 2F-#

R. J. Befes, Chief, Effluent Radiation date Protection Section, FRSS Branch l

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L 4: Inspection Summary: Inspection on July 31 - August 4, 1989 (Inspection Report 3 No. 50-333/89-17)

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Areas Inspected: Routine unannounced inspection of the radiological and non-radiological chcmistry program. Areas reviewed included: confirmatory

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measurements-radiological, standards analyses-chemistry, and laboratory QA/Q Results: Of the areas reviewed, no violations were identified.

l lJ l 9909070022 890630 1 PDR ADOCK 05000333 Q FDC

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DE_ TAILS 1.0 Individuals Contacted

• W. Fernandez, Resident Manager

• Liseno, Superintendent of Power

• E. Mulcahey, Radiological and Environmental Services Superintendent

• A. McKeen, Chemistry General Cupervisor

• C. Boucher, Chemistry Supervisor

• W. Hamblin, Radiochemistry supervisor

• D. Vandermark, QA Engineer

• G. Vargo, Radiological Engineering General Supervisor

• Denotes those personnel who attended the exit meeting on August 4, 1989.

The inspectors also interc:ewed other licensee personnel including other members of the chemistry .taf .0 Purpor3 The purpose of this routine inspection was to review thc following area . The licensee's ability to measure radioactivity in plant syste;n and effluent samples and chemistry parameters in ,

various plant system j

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. The licensee's ability to demonstrate the acceptability of his analytical results through implementation of a laboratory QA/QC progra .0 Radioicgical and Chemical Measurements 3.1 Confirmatory Measurements (Radiological)

During this part of the inspection liquid, airborne particulate (filter) and iodine (charcoal cartridge), and gas samples were analyzed by the licensee and the NRC for the purpose of intercomparison. The samples were actual :plit samples with the exception of the particulate filter, charcoal cartridge, and offgas samples. In these cases the samples could not be split, and the same samples were analyzed by both the licensee and the NRC. Wnere possible, the samples are actual effluent samples or inplant samples which duplicated the counting geometries us.ed by the licensee for effluent sample analyses. The samples were analyzed by the licensee using routine methods and equipment and by the NRC:1 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 te Technical Specification and other regulatory requirement In addition, a lie,uid effluent sample was sent to the NRC reference i

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laboratory, Department of Energy, Radiological and Environmental Sciences Laboratory (RESL), for analyses requiring wet chemistr The analyses to be perfornied on the sample are Sr-89, Sr-90, Fe-55, gross alpha, and H- The results of these analyses will be compred with the licensee's

> results when received at a later date and will be documented in a subsequent inspection repor The results of a liquid sample split between the licensee and the NRC during a previous inspection on October 21-25, 1985 (Inspec u n Report No. 50-333/85-27) were also compared during this $nspectio The results of.the sampie measurement comparisons indicated that all'of the measurements were in agreement under the criteria for comparing results (see Attachment 1) with the exception of a Kr-87 result of one offgas san,ple. The disagreement was due to the fact that the 402 kev photopeak used to quantify the Kr-87 concentration in the sample is subject to interferences from other short-lived isotopes present in the sample. The licensee's procedures require a decay time of at least 15 minutes prior to coun".ing the sample to reduce this interference. However, in counting this sample, the licensee did not observe the minimum decay time so that the sample could be quickly given to the NRC for analysis. The licensee performed a hand calculation on this sample using the 845 kev photopeak, a photopeak without interference, and this result was in agreement with the NRC result. The inspector noted that the Kr-87 results of other offgas samples listed in Table I, although in agreement with the NRC result, were also biased high by about 40 percent even after waiting the required time prior to counting the sample. The inspector discussed with the licensee that although his results were in a conservative direction relative to the NRC results, an improvement in the accuracy of the Kr-87 measurement could be made. The licensee stated that this area would be reviewed. The inspector stated that this area would be examined during a subsequent inspectio Also noted by the NRC inspector was the fact that all of the licensee's offgts sample measurement values were biased high relative to the NRC values. Through discussions with the licensee, the inspector determined that the licensee used a solid source to

, calibrate his counting system for the offgas samples without making l attenuation corrections. The inspector discussed this matter tiith the licensee and noted the availability of low density simulated gas standards. The licensee stated that an appropriate standard would be procured for calibrating this counting geometr The inspector stated that this area would also be reviewed during a subsequent inspectio _ _ _ _ - _ _ _ _ - _ .

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The~ data comparisons are presented in Table The inspector had no further questions-in_this area. No violations were identifie .2 Standards Analyses (Chemical)

1. - During this art of the inspection, standard chemical solutions were submitted to che licensee for analysis. The' standard solutions were pre'p ared 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 niant systems i; with respect to Technical Specifications and other regulatory

requirements. In addition, the analysis of standards is used to evaluate the licensee's procedures with respect to accuracy and precisio A spiked sample of reactor building closed loop cooling (RBCLC) water was sent to BNL for analysis. The analyses tc be performed on the sample are for chloride and sulfate. The licensee will perform the I same analyses, and the NRC results will be' compared with the licensee's results when received af a later date. These will be documented in a subsequent inspection report. The analysis of a

spiked sample of the licensee's RBCLC permits comparison of results l . from an actual sample matri The results of a spiked sample split between the licensee and the NRC during a previous inspection on September 19-23, 1988 (Inspection Report No. 50-333/88-20) were also compared during this inspectio The results of the standards measurement comparisons indicated that all of the measurements, with one exception, were in agreement under the criteria used for comparing results. (See Attachment 2.) The results of the comparisons are listed in Table II. Thc standards were submitted to the licensee for analysis in triplicate at three l concentrations spread over the licensee's normal calibration range.

L The one result in disagreement under the NRC criteria, a fluoride l analysis at approximately 40 ppb, was within five percent of the NRC l known value. This disagreement was due to the statistical nature of the NRC comparison criteria and was not judged to be significant.

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The silica results shown in Table II are from reanalyses of the NRC '

l standards. The results of the first silica analyses were biased low by about 10 percent for all three concentrations. The reanalyses l ~- were performed using fresh reagents and newly prepared standard The boron analyses performed by the titration method ceuld not be compared using the NRC criteria since only one standard could be analyzed at each concentration due to the limited volume available from the NRC standards. However, even with only one analysis at each I concentration, it appears the licensee's boron analysis procedure, using 1.0 Normal sodium hydroxide (NaOH), does not produce the w__-__---____---__-_--_-_-___--____--____- . _ - _ - _ - - - _ - _ _ _ _ _ _ _ _ _ - - - - _ _ =

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. idesired accuracy at the 2000 ppm lower limit specified in.the

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licensee's procedure. The in:pector discussed this matter with the licensee. The'libensee stated that the procedure would be

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revised to raise the owest boron concentration thtt would be analyzed using 1.0 Normal NaO <

, The inspector ha.1 no further questions in this area. No violations were' identifie ,0 Laboratory: QA/QC Program The' inspector r'eviewed the licensee's chemintry'and radiochemistry laboratory QA/QC program. This- program is detailed in a non procredural

, document entitled, " Quality Assurance / Quality Control _ Program", Rev. 7, July 1988. This document provides. for the control of analytical performance through a number of mechanisms including the use of control

harts to assess instrument and analytical procedure performance, and intralaboratory and interlaboratory spiked sample programs. The inspector reviewed selected data generated by the licensee's QA/QC program for 1988 and 1989 to date and noted that the licensee appeared to be implementing the laboratory QA/QC pro. tram as required. All results were properly documented and plotted on control charts. Also well documented were the corrective actions taken when a sample exceeded a limit or acceptance criteri The licensee participated in a quarterly interlaboratory spike program for radioactivity -

with measurement 'an independent laboratory They received spiked(Analytics, samples for Inc.)both gamma isotopic analysis and more complex, time consuming radioactivity analyses requirin wet chemistry. The licensee performs the gamma isotopic analysis inhouse, then . sends the samples requiring the wet chemistry to another vendor laborutory (Teledyne Isotopes, Inc.) for analysis. The licensee waits for the results from Teledyne Isotopes, Inc. before submitting all of the results to Analytics, Inc. for comparison. This results in a delay of up to four or five months in receiving the actual known values of the spiked samples from Analytics, Inc. With a delay of four to five months, it becomes difficult for the licensee to correct any discrepancies-between the gamma isotopic results and the known values of the independent laboratory. In fact, there were two disagreements on a 1988 comparison of the offgas spiked sample data. The inspector discussed this matter with the licensee. The licensee stated that the results were not investigated because the long delay between analysis of the spiked samples and the receipt of the known valces made it impossible to go back and research the problem. The itspector discussed the need to obtain results in a timely manner from a crosscheck program of this kind. The gamma spectrometry results should be obtained promptly and be intercompared while awaiting the results of other more complex, time consuming analyses. The inspector further roted that offgas samples split between the licensee and the NRC

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during this inspection indicated the-licensee's results were biased in'

the same direction and by approximately the same ratio as the 1988 offgas crosscheck results were relative to the know act'iv1ty. (See Section 3.1).

In-addition, the inspector noted that Table 2 of the Quality Assurance / Quality Control document required both spiked samples and an independent laboratory sample split. In reviewing the licensee's QA/QC data, however, the . inspector noted that the licensee was using the same interlaboratory-crosschecks in order to satisfy the requirements for bot types of splits. The licensee stated that Table 2 of the QA/QC docurr.ent

- would be modified to reflect actual laboratory practices. Also the'

inspector noted that the licensee-participates in an interlaboratory split sample progrEm for Standby Liquid Control Tank sampler, on a conthly basis '

but did not include this data iri the laboratory QA/QC program. The~

licensee plotted and trended the results of this program routinely. The inspector suggested ~that these data also be-included in.the !icensee's laboratory QA/QC progra The inspector stated that all of the above'QA/QC praceices would be reviewed during a subseqeent inspection. The inspector had no further questions in this are No violations were identifie .0 Exit Intery,iew-The inspectors met with.the licensee representatives denoted'in Section 1 of' the conclusion of the inspection or. August 4.1989. The inspectors summarized the purpose, scope and findings of the inspectio l

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d Table I-

_F itfatric> verification Test Results

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SAMPLE ISOTOPE NRC VALUE LICENSEE VALU eARIS0N

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O Results in Microcuries Per Milliliter Nortn Drywell 1-131 (8.410.2)Ec12 (8.3 0.3)E-12- Agreeme ~ CAM J-133- (5.4 0.2)E-11 (5.31 0.16)E-11 Agreement Charcoal Cartridge- I-135 ( 9. 4tl .0)T.-11 (9.411.3)E-11 Agreement 8-1-89 hrs

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(Detect a #1)

! Reactor Building 'Co-58 (6.9 0.5)E-13 (6.5 1.4)E-13 Agree:ent l h rticulate Filter Co-60 (7.0 0.6)E-13 (6.8 1.1)E-13 Agreement l 7-31-89 Zn-65 (1.4110,02)E-11 (1.65 0.06)E-11 Agreemsnt 0800 hrs L

(Detector #3)-

Stack Gas 8-2-89 Kr-85m (1.1 0 2)E-7 (1.0 0.4)E-7 Agreement 1030 hrs (Detector #3) .,

Liquid Radio- Na-24 (6.010.3)E-6 (6.010.6)E-6 Agreement active Waste Zn-65 (3.4 0.5)E-6 (3.310.8)E-6 Agreement (Weste Filter Outlet) 8-3-89

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0850 hrs l Filtrate (Detector #4)

Liquid Radio- Co-60 (9.4 1.4)E-7 (1.06 0.11)E-6 Agreement active Waste Zn-65 (3.4 0.2)E-6 (1.2 0.2)E-6 Agreement (Waste Filter Mn-54 (5.4 0.9)E-7 (6.6t0.9)Ee7 Agreement Outlet) 8-3-89 0850 hrs Filter (Detector #3)

Liquid Radioactive Fe-55 (1.3 0.5)E-7 <8E-7 No Comparison Waste (Waste H-3 (1.44 0.02)E-3 (1.5 0.1)E-3 Agreement Filter Outlet) Sr-89 (1.2 1.0)E-8 <2Ea8 No Comparison 10-23-85 Sr-90 (7 4)E-9 <5E-9 No Comparison 0810 hours0.00938 days <br />0.225 hours <br />0.00134 weeks <br />3.08205e-4 months <br />

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Table I (centinue_d)

FitzPatrick Verification Test Results

SJ.MPLE ISOTOPE NRC VALUE LICENSEE "ALUE C0MPARISON

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Results in Micyp uries Pee Milliliter Reactor Water Na-24 (2.6710.02)E-3 (2.8510.03)E-3 Agreement 8-1-89 I-132 (5.2 0.2)E-4 (5.2 0.3)E-4 Agreement 1425 hrs I-133 (1.54 0.07)E-4 (1.83 0.11)E-4 Agreement (Detectar #4) I-134 (1.7 0.2)E-3 (2.71 0.08)E-3 . Agreement I-13S (4.0 0.5)E-4 (4.it0.4)E-4 Agrececnt Sr-02 (6.910.2)E-4 (6.8t0.2)E-4 Agreement Mn-E4 (4.95 0.14)E-4 (4.3010.14)E-4 Agreement i Co-60 (1.4310.02)E-3 (L.33 0.02)E-3 Agreement l

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Zn-65 (2.49 0.04)E-3 (7.46 0.04)E-3 Agreement Zn-69m (2.54:0,08)F-4 (2.73i0.11)E-4 Agreement Offp u Pre- Kr-87 (4.210.3)E-4- (5.6 0.6)E-4 Agreement .

Treatment Xc-138 (8.0tu.3)t-3 (9.2 0.2)E-3 Agree nnt 8-2i89 Xe-135 (3.1810.13)E-4 (3.5 0.2)E-4 Agreement 1350 brs Xe-135m (1.70 0.09)E-3 (2.26:0.07)E-3 Agreement l (Detecter #4)

(15 min decay time)

, Offgas Pre- Kr-87 (4.2 0.3)E- 4 (5.0 0.5)E-4 Agreement treatment Xe-138 (8.0ip.8)E-3 (1.0410.04)E-2 Agreement 8-3-89 Xe-135 (3.01 0.11)E-4 (3.910.2)E-4 Agreenent 1308 hrs Xe-135m (2.1 0.3)E-3 (2.24 0.12)E-3 Agreement (Detector #3)

(30 min decay tiine)

Offgas Post- Kr-87 (1.53 0.06)E-3 (2.77 0.11)E-3 Disagreement Treatment Xe-138 (3.45 0.09)E-2 (3.9010.03)E-2 Agreement B-3-89 Xe-135 (1.46 0.03)E-3 (1.56 0.05)E-3 Agreement l 1537 hrs Xe-135m (8.010.3)E-3 (8.76 0.11)E-3 Agreeme-t j (Detector #4) 2Kr-87 (1.53 0.06)E-3 (1.69 7)E-3 Agreement l 2 Hand calculated value using 845 kev photopeak l

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f L Table II FitzPatrick

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Chemistry Test'Resul+.s-

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Chemica ' Method of NRC License Ratio Parameter. Analysis * Known Value Measured Value (LIC/NRC) _ Comparison Results in parts per billion (ppb)

l p . Fluoride IC 231'2 22.27 0.15 0.9710.08 Agreement 42.3 .31 .0510.02 Disagreement

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8<31 .8 .9410.10 Agreement Chloride' IC 18.5 .3 .1010.08 ' Agreement- 1 37.3 .07 0.11 Agreement 7.6510.12 7.9 .G3 0.06 Agreement-.

Sulfate IC 19.5. .11 .0810.11 Agreement-38 3 40 4 .1.0510.13 Agreement 7.8 .8 .0010.15 Agreement 2 Silica SP 53 3 56i10 1.1 Agreement 104 4 103.01 .99 0.04 Agt cement 157 2 154 2 0.98!0.02 Agreement Chloride .

IC 76.8 t3 _

No Comparisoc**

(From' sample Sp1f t during 50-333/83-20 RBCLC)

Results in parts per million (ppm)

Boron Ti .95 "No Ccoparison 5000 90 85675 1.14 'No Comparit.on !

Iron ICP 0.186 0.005 0.18 0.02 0.97 0.11 Agreement 0.398 0.005 0.37 0.04 0.9310.10 Agreement

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O.58510.015 0.57:0.02 0.9710.04 Agreement Copper ICP 0.20010.003 0.188 Oc005 0.94 0.03 Agreement 0.40310.015 0.4010.02 0.9910.06 Agreement 0.60010.015 0.637 0.012 1.06 0.03 Agreement j i

2Licesisee ar.slyses performed in duplicate; results shown are from second analyses .

onl j 2 Titration performed using 0.1 N NaOH 4

" Titration perfonned using 1 N NaOH

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l T,abj,eII(continuedl FitzPatrick Chemistry Test Results l

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L Chemical Method of NRC Licensee Ratio f Parameter Analysis * Known Vaiue Measured Value (LIC/NRC) Compari_ son, l- Results in parts per million (ppm) ,

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Nickel ICP 0.203 0.006 0.20 0.02 1.00 0.10 Agreement 0.417 0.007 G.41 0.04 0.90 0.10 Agreement 0.60t0.03 0,6210.92 1.0310.06 Agreement Ciromium ICP 0.19810.005 0.19 0.02 0.9620.10 Agreemerit 0.385 0.005 0.40 0.04 1.0410.10 Agreement 0.580 0.010 0.60 0.0?. 1.04:0.04 Agreement Zinc !CP 0.103 0.004 0.10260.014 0.9910.14 Agreement 0.288t0.004 0.31:0.02 1.08*0.07 Agreement 0.480 0.006 0.54 0.06 1.1710.12 Agreeraent Boros ICP 1.040 0.010 1.02 0.03 0.98t0.03 Agreement 3.10 0.10 2.90 0.10 0.9410.04 Agreement 5.0010.09 4.8310.12 0.97 0.03 Agreement

• Note: -$P = UV-Vis Spectrophetemetry  ;

IC = Iun Chromatography Tit. = Titration with PHT endpoint ICP = Inductively Coupled Plasma spectrometry

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l 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 Resol u, tion 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 CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS This attachment provides criteria for comparing results of capability test 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 steps are performed:

(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 propagate If the absolute value of one minus the ratio is less than or equal to twice the ratio uncertainty, (ll-ratiol s 2 uncertainty), the results are in agreemen = x, then * = 3* + bY'

y Z2 x2 y2 2(Fromi Bevincton, P. R., Data Reduction and Errer Analysis for the Physical Sciences, McGraw-Hill, New York, 1969)

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