IR 05000352/1993001

Insp Repts 50-352/93-01 & 50-353/93-01 on 930111-15.No Violations Noted.Major Areas Inspected:Radiological & non-radiological Chemistry Programs,Including Confirmatory Measurements

ML20128G464
Person / Time
Site:	Limerick
Issue date:	02/04/1993
From:	Kottan J, Mcnamara N, Mark Miller NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20128G448	List: IR 05000352/1993001 ML20128G446
References
50-352-93-01, 50-352-93-1, 50-353-93-01, 50-353-93-1, NUDOCS 9302160015
Download: ML20128G464 (14)

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U.S. NUCLEAR REGULATORY COMMISSION REGION I .

Report No.: 50-352/93-01 j 50-353/93-01 4

Docket No.: 50-352 50-3$3 License No.: NpF-39 HPEM  ;

Licensee: Philadelphia Electric Con 1 patly 2301 Market Street  :

Philadelohla. Pennsylvania 19105 ,

i Facility Name: Limerick Generating Station. Units 1 and 2 Inspection At: Limerick. Pennsyltania  !

Inspection Conducted: - January 11-15. 1993  !

Inspectors: ON T NW MAC 2hb N. McNamara, Laboratory Specialist Date Effluents Radiation Protection Section (ERPS)

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[8 2-+93 J.7Kottanp, [bo"ratory Specialist, ERPS Date Facilities Radiological Safety and Safeguards -

Branch (FRSS13)

. Approved By: N E' D NE M. Miller, Chief, ERPS, FRSSB . Date

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Division of Radiation Safety and Safeguards Areas Inspected 1 Announced inspection of the' radiological and non radiological chemistry programs. -- Areas reviewed included: : Confirmatory Measurements - Radiological, Standard ,

' Analyses - Chemis;ry, Laboratory QA/QC, and Audit Rentils The licensee had in place effective programs for measuring radioactivity in process and .

effluent samples and for measuring chemical parameters in plant systems samples. No safety concerns or violations of regulatory requirements were observe '

9302160015 930204 PDR ' ADOCK 05000352-O PDR

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11El%11E huilthhtah_Cmihtdtd hiucipal Littmtcl.ntploires

• J. Doering, Plant Manager

• J. Dougherty, QA/QC Chemist D. Fay, Technical Monitor E. Frick, Chemist K. Gordon, Supervisory Chemist

• T. Jackson, Senior Chemist M. Kaminski, Engineer, QA

• O. Madsen, Regulatory Supervisor

• J. Phillabaum, Engineer

• G. Roach, Services Superintendent i NRC Employees T. Kenny, Senior Resident Irapector

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• Denotes those present at the exit meeting on January 15, 1993. The inspectors also interviewed other licensee personnel, including the chemistry technicians who performed th' analy,es for this inspectio .0 BirpsSt The purpose of this inspection was to review the following area . The licensee's ability to measure radioactivity in plant systems samples and effluent samples, and the ability to measure chemical parameters im various plant systems sample . The licensec's ability to demonstrate the acceptability of analytical results through implementation of a laboratory QA/QC progra .0 lbidinlogical and Chrmical Measurements - CaulltInator1Mcalurementi _Rndiochemist ry During this part of the inspection, liquid, airborne pa-ticulate (filter) and iodine (charcoal cartridge), and gas samples were analyzed by the licensee's chemistry departmer.t and the NRC for the purjme ofintercomparison. The samples were actual split samples with the exception of the particulate filter, charccal cartridge, _

and offgas samples. In those cases, the samples could not be split and the same samples were analyzed by the licensee and :he NRC. Where possible, the

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samples were actual effluent samples or in plant samples which duplicated the counting geometries used by the licensee for ef0uent sample analyses. The samples were analyzed by the licensee using routine methods and equipment and by the NRC Region I Mobile Radiological Measurements Laboratory. Joint analyses of actual samples were used to verify the licensee's capability to measure radioactivity in efnuent and other samples with respect to Technical Speci0 cations and other regulatory requirement In addition, a liquid sample was sent to the NRC reference laboratory,  !

Department of Energy, Radiological and Environmental Sciences Laboratory (RESL) for analysis requiring wet chemistry. The analyses to be performed on

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the sample are Sr-89, Sr 90, Fe-55,11-3 and Eross alpha. The results of these analyses will be compared with the ilcensee's results when received at a later date and will be documented in a subsequent inspection report. The results of a liquid sample split between the licensee and the NRC during a previous inspection on February 5-9,1990 (Combined Inspection Report No. 50-352/90-0F, and 50-353/90-07) could not be compared at the time of this inspection because the licensee could not retrieve the sample analysis results. The licensee stated that they will forward to RI the results from the sample split from this inspection as soon as they are receive The results comparisons for all of the above samples, for which results were available, which are presented in Table I, indicated that all of the measurements were in agreement under the criteria for comparing results. (See Attachment I to Table 1). No safety concerns or violations were identined in this are : Standards Analyses - Chemical During this part of the inspection, standard chemical solutions were submitted to-the licensee for analysis. The standards were prepared by Oak Ridge National Laboratory (ORNL) for the NRC and were analyzed by the licensee using routine methods and equipment. The analysis of standards is used to verify the licensee's capability to monitor chemical parameters in various plant systems with respect to Technical Speci0 cations 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 standards were submitted to the licensee in triplicate at three concentrations spread over the ilcensee's normal calibration.-

and analysis rang The boron analyses were performed at only one, concentration on the auto-titrator in order to duplicate the concentration normally_

encountered during standby liquid control tank boron analysis. The remainder of -

the boron standards were analyzed on the inductively coupled plasma emission spectrometer (ICp) in order to duplicate the boron concentrations which would be encountered when performing a post-accident sampl =_,-- -, . , - . = - ---- .. . - - - . - _ - . . = .

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Also, a feedwater sample was spiked with a standard anion solution and sent to ORNL for analysis. The analyses to be performed on the sample are chloride and sulfate. The licensee will perform the same analyses on an aliquot of this spiked sample. The results of these analyses will be compared when received at a later date and will be documented in a subsequent inspection report. The analysis of spiked sampics permits comparisons from an actual sample matri The results of the standards measurements comparisons indicated that all of the measurements were in agreement or qualified agreement under the criteria used for comparir.g results. (See Attachment I to Table 11). The chloride results, which are approximately eight parts per billion (ppb) as reported in Table 11 werc

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obtained after the recalibration of the ion chromatograph (IC). The licensee calibrated the IC at 40,20 and 10 ppb and implemented a lower limit of detection (LLD) at two ppb. Thus, the licensee routinely reported results which were below the lowest calibration point (10 ppb) and above the LLD. The inspector discussed this matter with (Se licensee and noted that the licensee had not formalized the definition of LLD and the method for determination of the LL The licensee stated that this area would be examined and appropriate corrective action taken. The inspector stated that this area would be reviewed during a subsequent inspection. Additionally, the inspector noted that the licensee had put a new ICP and IC into service and was in the process of formalizing plans for an expanded chemistry laboratory. The new instrumentat!on and the expanded laboratory were indicative of licensee management support for the chemistry program. No safety concerns or violations were identified in this are .0 latimntinry OA/ The licensee's laboratory QA/QC program was described in general terms in Procedure CH-1000, " Chemistry QA/QC Program." This procedure denned the administrative program used by the licensee to assure the quality of analytical measurements and referenced specific implementing procedures. The specific implememing procedures provided for both an intralaboratory and interlaboratory QC progra The intrataboratory program consisted of the use of instrument and procedure control charts for trending performance, and the analysis of spiked samples on a semi-annual basi ' The interlaboratory program consisted of the analysis of unknown samples from outside laboratories for both chemical and radiochemical constituent Included in the interlaboratory program was the vendor laboratory utilized by the licensee for performing selected radiochemical analyses of efnuent samples. Also, the QC procedures contained detailed instructions for the preparation and use of control charts, spiked sample analyses and the evaluation of laboratory QC dat The inspector reviewed selected data generated by the licensee's laboratory QC program for 1992 and 1993 to date and noted that the licensee was implementing the program as required. in particular, the inspector noted that the control limits for the gamma

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spectrometry were now based on an experimentally determinal estimate of the standard deviation. During the previous inspection in this area, the licensee used fixed values or tolerance limits for the control limits but stated that consideration would be given to changing to statistically determined limits. The licensee had implemented this chang )

No violations were identined in this are .0 Atid1LAtlhliks i

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The inspector reviewed the report for Audit No. A0391330, LOS Chemistry / Radio-chemistry, which was conducted from May 21,1992 through August 21,1992. The audit was performed using detailed check lists, which had comprehensive comments in each reviewed area, and the audi' ' cam included a technical specialist. Additionally, the inspector reviewed an industry audit, NUPIC Audit-NYPA Audit No. 9218, of the lleensee's vendor laboratory used for selected radiochemical analyses of efnuent samples, which was conducted on August 3-6, 1992. The above audits were of good technical depth, suf0cient to identify programmatic problems in the areas being auditM. The inspector also reviewed the licensee's master audit plan and audit schedule, in order to verify the frequency at which audits of the licensee's chemistry program were conducte The licensee also performed surveillance activitics of specific chemistry tasks and documented these activities in technical monitoring reports. The inspector reviewed selected monitoring reports for 1992 and noted that the reports were generated following specinc guidelines for each monitored activit Ilased on the review of the above audits and technical monitoring activities, the inspector determined there was independent oversight and assessment of chemistry activities. No safety concerns or violations were identifie .0 Exit Mrt.llug The inspector met with the licensee representatives denoted in Section 1.0 at the conclusion of the inspected on January 15,1993. The inspector summarized the purpose, scope, and findings of the inspectio _

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TABLFJ Limerick Units 1&2 Verification Test Results

. LICENSEE

. SAMPLE- , IS_OTOPE NRC VALUE VALUE COMPARISON

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Results in MicroCuries per milliliter

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.ED Surge Tank Cr-51 - (1.33i0.02)E-4 (1.3310.06)E-4 Apowient

0934 hrs- Mn-54 (6.4i0.2)E-6 - (6.2i0.7)E4 Agreement

'01/14/93' Co-58 (6.Si0.3)E-6 (6.3i0.2)E-6 ApwTst (Detector No. 2) - Co-60 (1.27 0.04)E-5 . (1.33i0.03)E-5 ' Agreement Zn-65 (2.81i0.08)E-5 (2.70i0.09)E-5 Agreement Ba-140 (1.46i0.09)E-5 . (I.4210.05)E-5 Agreement Cs-13 (7.0i0.2)E-6 - (6.7i0.2)E-6 Apwnst l I-13 ; (5.9i0.2)E-5 (6.810.4)E-5 - Agreement

I-133 (5.68i0.04)E-5 (6.2iO.2)E-5 Aycwst I-131- i-

- (1.02i0.03)E-5 (1.07i0.04)E-5 .Apcsst Na-24 (1.09i0.04)E-5 (9.8 0.5)E-6 Agreement j;

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j TABLE I - Continued Limerick Units 1&2 Verification Test Results LICENSEE ISOTOPE NRC VALUE VALUE COMPARISON SAMPLE Results in MicroCuries per milliliter Cr-51 (1.33 0.02)E-4 (1.51i0.07)E-4 Agreement ED Surge Tank 0934 hrs Mn-54 (6.4 0.2)E-6 p.5 0.3)E-6 Agreement 01/14/93 Co-58 (6.510.3)E-6 p.0 0.3)E-6 Agreement

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Co-60 (1.27 0.M)E-5 (1.46 0.03)E-5 Agreement

_(Detector No. 4)

Zn-65 (2.81 0.08)E-5 (3.00 0.09)E-5 Agreement Ba-140 (1.46 0.09)E-5 (1.73 0.06)E-5 Agreement Cs-137 p.0i0.2)E-6 p.7 0.3)E-6 Agreement I-135 (5.9i0.2)E-5 (6.48i0.15)E-5 Agreement I-133 (5.6Si0.N)E-5 (6.6 0.2)E-5 Agreement I-132 (9.0 0.4)E-6 (1.Ii0.3)E-5 Agreement I-131 (1.02 0.03)E-5 (1.25i0.05)E-5 Agreement Na-24 (1.09 0.@)E-5 (1.08i0.M)E-5 Agreement South Sta': I-131 (6.2 0.7)E-13 p.2 0.9)E-13 Agreement I-133 (1.4iO.3)E-11 (l.21 0.15)E-11 Agreement Charcoal Cartridge 2052 hrs 01/08/93 (Detector No. 4)

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TABLE I - Continued Limerick Units 1&2 Verification Test Results

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LICENSEE ISOTOPE NRC VALUE VnLUE COMPARISON SAMPLE Results in MicroCuries per milliliter Kr-85m ~ (3.6iO3)E-7 (4.2i0.2)E-7 Agreemeat Unit 2 OfTgas'-

Xe-133 (1.18 0.03)E-7 (1.4i0.6)E-7 Agreement Post Treatment 1356 hrs 01/13/93

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(Detector No.1)

'I-132 (4.3Si0.08)E-2 (5.40i0.12)E-2 Agreement Unit 2 .

1-133 (2.59i0.04)E-2 (2.92 0.09)E-2 Agreement

~ Reactor Water -

.I-134 (1.63i0.06)E-1 .(2.13i0.Gt)E-1 A p w nient

- 0800 hrs .

^ I-135 (7.0io.2)E-2 (7.0i0.2)E-2 Agreement 01/14/93 j . (Detector No.1)

(3.48i0.09)E-5 (3.6i0.2)E-5 Agreement Unit l' . Cr-51

~ Mn-54 . (5.21i0.13)E-6 (53i0.2)E4 : Apament Reactor Water Co-58 (4.80 0.13)E-6 (4.9 0.2)E4 A p w nient

. Particulate Filter Co-60 (6.1iO.2)E4 (6.4i0.2)E-6 ~A p wrnent 0730 hrs

- (9.0i0.4)E4 Agreement -

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01/11/93 12n-65 (8.0 03)E4

. (Detector No. 5)-

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[. TABLE I - Contmued Limerick Units I&2 Verification Test Results LLCENSEE SAMPLE - ISOTOPE NRC VALUE VALUE COMPARISON Results in MicroCuries per milliliter

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, Unit 1 1-132 (5.0 0.4)E4 (5.7i0.2)E4 Agreement Reactor Water I-133 (1.49 0.12)E-4 (1.33iO.10)E4 Agreement -

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0730 hrs 1-134 (1.41iO.16)E-3 (1.57 0.CG)E-3 Apwust 01/13/9 (Detector No. 5).-

Unit 2 Offgas ..Kr-85m - (1.8i.0.2)E-2 (1.8110.06)E-2 Agreement 6 1232 hrs' Kr-87 (1.15610.010)E-1 (1.22iO.04)E-1 Agreement 01/12/93 Kr-88 p.1610.07)E-2 p.4i0.2)E-2 Agrament (Detector No. 6) Xe-133 (5.8 0.2)E-3 - (6.5i0.4)E-3 Agreement Xe-135m (4.0 0.2)E-I (4.2810.14)E-1 A p warent

!' Xe-135 p.69i0.G*)E-2 p.810.3)E-2 Apccuat Xe-138 (2.0110.08) (2.09 0.06) Agreement

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Note.- Reponed uncertainties are one standard deviation (IS) cou.ning uncertdnties for both NRC and licensee result ~ , , . .. ~ :- . . ., .- - . . . . - . :- . . -- - . . . - . . - .

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I^ . TABLE II - Continued Limerick Units 1 &_2 Chemical Method of NRC Licensee Analysis : Analysis Known Value Value Commrison 4- , Results in carts ner million (com)

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p Boron ICP 10.49 i 0.11 10.6 i *

ICP 30.41 .8 Ti Agreement R sults in parts ner billion (oob)

Silica SP 12.17 0.13 12.6 i Agreement 28.4 i .9 i Agreement i 60.li .0 i Agreement

' Sodium - IC 10.6 .20 i 0.04' Apsst 20.4 i io.09 - ' Agreement 31.0 i .2io.2 - Agreement

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Sulfate IC 7.9i .90 i 0.08 Qual Agicurst.

, 19.4 .70 10.09' Apwst 4 ;38.8i .113 0.016'- Apdust

• The criteria for comparing boron results were based on the titration ' method. - No criteria exists, at the present time, for comparing boron by ICP. However, these results would be in Agreement under the criteria used for analysg metals by IC "

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TABLE II - Continued Limerick Units 1 & 2 Chemical  ? fethod of NRC Licensee Analysis Known Value V; tine Gnnoarison Analysis --

Results in parts per billion (rob)

IC 7.71 .16 i 0.13 Agreement

- Chloride 19.4 Agreement 36.5 .91 Agreement

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i Notes: ICP- = .fInductively Coupled Plasma Emission

- Tit. - ' = PotentiometricTitration

'SP = L UV-Vis Spu.huphotometry

- IC _ = Ion Chromatography -.

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A'ITACilMENT I TO TADLE I 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 "Resciution," increases, the acceptability of a licensee's measurement should be more selective. Conversely, poorer agreement must be considered acceptable as the resolution decrease Resolution' Ratio for Comparison2

<4 ' No CompaEison'

4-7 0.5 - .6 - 1.66 16 - 50 0.75 - 1.33

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51 - 200 0.80 - 1.25

> 200 0.85 .- 1.18-

'No comparison due to the large uncertainty of the resul l. Resolution-= (NRC Reference Value/ Reference Value Uncertainty)

l 2. Ratio = (Licensee Value/NRC Reference Value)

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ATIACIBtENT I TO TAllLil.J1 CtilcIliL[er Cortlpating_.Anah11caLhiemitttaientLfrom Tablem This attachment provides criteria ior comparing results of capability tests. In these criteria the judgement limits are based on data from Table 2.1 of NURl!G/CR 5244, " Evaluation of Non-Radiological Water Chemistry at Power Reactors". Licensee values within the plus or minus two standard deviation range (i2Sd) of the ORNL known values are considered to be in agreemen Licensee values outside the plus or minus two standard deviation range but within the plus or minus three standard deviation range (i3Sd) of the ORNL known values are considered to be in qualified agreement. Repeated results which are in qualified agreement will receive additional attention. Licensee values greater than the plus or minus three standard deviations range of the ORNL known value are in disagreement. The standard deviations were computed using the average percent deviation values of each analyte in Table 2.1 of the NURE The ranges for the data in Table 11 are as follow Agreement Qualified Agreemem Andlyte lW1gc__ Range Chloride i 8%

Sulfate i 12 %

i 10 % i 15 %

Silica i 10 %

Sodium i 15 %

i 14 % i 21 %

Copper i 10 %

fron i 15 %

10 %

lloron i 15 %

i 2% i 3%

Nickel i 6%

Chromium i 9%

i 10 % i 15 %

Zine 10 %

i 15 %

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