ML20095J542

Responds to NRC 951025 RAI on LaSalle Unit 1 RPV Surveillance Matls Testing & Analysis, Submitted by Util

ML20095J542
Person / Time
Site:	LaSalle
Issue date:	12/20/1995
From:	Benes G COMMONWEALTH EDISON CO.
To:	NRC OFFICE OF INFORMATION RESOURCES MANAGEMENT (IRM)
References
NUDOCS 9512270158
Download: ML20095J542 (45)

Text

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December 20,1995 U.S. Nuclear Regulatory Commission Attn: Document Control Desk Washington, D.C. 20555

Subject:

LaSalle County Nuclear Power Station Units 1 and 2 Response to October 25,1995 NRC Request For Additional Information On LaSalle Unit 1 RPV Surveillance Material Testing and Analysis, Reactor Vessel Material Surveillance Program - Appendix H NRC Docket Nos. 50-373 and 50-374

References:

See Attached 4

In accordance with Appendix H of 10 CFR 50, Comed provided the original LaSalle Unit 1 RPV Surveillance Materials Testing and Analysis, March 1995 submittal (Reference 1). Due to an error which was discovered in the surveillance specimen chemical analyses, Comed provided the Revision 1 LaSalle Unit 1 RPV Surveillance Materials Testing and Analysis, June 1995 submittal (Reference 2).

In Reference 3, the NRC Requested Additional Information (RAI) on this matter.

The following is Comed's response to the Staffs Request For Additional Information (RAI). The Comed response retains the numbering sequence of the Staffs RAI, although Question 1. has been reformatted for clarity.

1. Provide a chronology of events [see A. below] including a description of the following items:

Why was the surveillance material retested? [see B. below]

What was the root cause of the error in the previously reported data?

[see C. below]

What corrective action has been implemented to assure the error is not repeated? [see D. below]

A.

A chronology of significant events follows:

i 270037 9512270150 951220 PDR ADOCK 05000373 i

P PDR

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USNRC (2)

December 20,1995 Surveillance Specimen Capsule pulled from LaSalle County Station Unit 1, March 25,1994.

Prepared Specimen Capsule shipped from LaSalle to General Electric (GE) Vallecitos Nuclear Center (VNC) on July 29,1994.

1 Capsule received at VNC on or about August 5,1994.

Initial test results were received by Comed from GE on March 9,1995.

j Initial Surveillance Specimen Capsule report docketed with NRC on March 23,1995 (Reference 1).

On April 11,1995 discussions were held with ABB/ Combustion Engineering (ABB/CE), GE, Nuclear Energy Institute, and Wisconsin Public Service's Kewaunee Station lead Comed to believe that a problem potentially exists with the initial GE chemistry results.

Comed verbally requests that GP aview the initial chemistry results for possible errors on April 12,1%E.

GE determines that a systematic but conservative error was made on initial chemistry analysis and verbally informs Comed on or about April 20,1995. GE subsequently documented this in a letter (Reference 4, attached) to Comed on April 25,1995, which also addressed root cause and corrective action.

Problem Identification Form (PIF) 373-200-95-00877 initiated at LaSalle April 21,1995.

LaSalle Nuclear Licensing Administrator verbally informs LaSalle NRC Project Manager of the error on May 1,1995.

Portions of the specimens (five each of weld and plate Charpy halves) are shipped from VNC and received at Argonne National Laboratory (ANL),

May 4,1995 On May 23,1995 Comed requests additional information from GE on corrective actions implemented by GE (Reference 5, attached).

ANL check chemistry results received by Comed on or about May 31,

1995, i

1

USNRC (3)

December 20,1995 Comed reviews results of ANL " check" chemistry, and the revised GE chemistry, with ABB/CE on or about June 2,1995.

Revised Surveillance Specimen Capsule report with corrected GE chemistry results docketed with NARC on June 21,1995 (Reference 2).

Comed receives additional information on GE corrective actions on September 26,1995 (Reference 6, attached).

On September 28,1995 Comed verbally requests additional information from GE on selection of standard reference materials.

PIF closed at LaSalle, October 27,1995.

l Comed receives additional information from GE on selection of standard i

e reference materials for chemical analysis on October 30,1995 (Reference 7, attached).

RAI (Reference 3) received at LaSalle, November 1,1995.

B.

The initial GE chemistry values were shared with ABB/ Combustion Engineering, NEI, and Kewaunee Nuclear Power Plant. Discussion between Comed and these parties lead Comed to request that GE review the initial testing and verify that the results were accurate. In the process of this review, GE discovered that an error had indeed been made during the initial chemistry j

testing. This lead Comed to request that the specimens be retested.

4 i

C.

The root cause of the error in the previously reported data was that incorrect dilution factors for the actual metal specimens being tested were entered into the plasma spectrometer. Since the dilution factors for the reference standards i

being tested were entered correctly, the error was not detected during the testing, or during review of the test results. It was therefore concluded that this error was caused by inadequate process controls in the form oflack of i

independent verifications on the part of GE personnel involved in the original testing and analysis of the LASalle Unit 1 RPV surveillance specimens.

It should also be noted that a predisposition existed on the part of both GE and Comed subject matter experts to accept the variable chemistry results due to prior knowledge ofindustry experience with chemistry variability associated l

with the particular ABB/CE weld metal involved (1P3571).

4 1

USNRC (4)

December 20,1995 D.

The following corrective actions were taken to verify that the chemistry results

]

provided in the revised report are correct:

i The corrected GE chemistry results were independently confirmed by e

ANL.

ABB/ Combustion Engineering reviewed the corrected GE results and the ANL " check" results and agreed with the results for the ABB/CE 1P3571 weld metal.

)

The following corrective actions are in place to assure that the error is not repeated:

In the future GE will independently verify dilution factor calculations.

In the future GE will independently verify spectrometer inputs.

In the future GE will independently verify final chemistry results with spectrometer output.

In the future Comed will pursue re-analysis when chemistry data is unusual in any respect, and will apply GE lessons learned to any future vendor supplied surveillance reports.

General Electric is currently testing a Surveillance Specimen Capsule removed from LaSalle Unit 2 on March 1,1995. It is Comed's belief that the aforementioned corrective actions taken by GE and Comed will prevent recurrence of a similar error in this ongoing testing.

2. Provide a list of surveillance capsules and materials previously tested by General Electric. Are the test results from these surveillance capsules correct? Explain the basis for this conclusion.

See Reference 8 (attached) for the answer to this question. Comed has reviewed and concurs with the bases and conclusions of Reference 8.

4

3. Describe the procedures and actions taken by the licensee and its vendor, General Electric, in meeting the requirement of 10 CFR Part 21," Reporting of Defects and Noncompliance."

USNRC (5)

December 20,1995 As detailed in the above chronology, once it had been confirmed that an error existed in the initial chemistry results, a Problem Identification Form (PIF) was initiated at LSCS in accordance with administrative procedure LAP-1500-8TB.

This document served to track investigation of the root cause of the error, its resolution, and corrective actions. In this case, because the analysis of the RPV specimens was completed under GE's Part 21, Safety Related, Quality Assurance Program, Comed requested that GE evaluate the Part 21 applicability of this error. The results of GE's evaluation (Reference 8, attached) indicate that Part 21 is not applicable in this instance, and that no concern exists with the possibility of past errors in chemistry results. Comed concurs with GE's evaluation.

1

4. Provide the NRC with sample surveillance weld material to confirm the licensees test results. Since this will include irradiated material, packaging and transportation of the material will probably require special handling. The licensee is requested to contact the NRC project manager to arrange for the time and place of delivery of the irradiated surveillance specimens to the NRC contractor.

J Although Comed understands the concerns of the Staffin this matter, it is our belief that the shipment of the irradiated specimens to the NRC's contractor, Oak Ridge National Laboratory (ORNL), is unnecessary. This beliefis based on the i

fact that ANL has already completed an independent chemical analysis of the LaSalle Unit 1 RPV specimens. See attached Reference 9 for a description of the testing performed and the results obtained. Comed initiated this independent analysis as a part of the corrective actions described above. The results of the ANL analysis corroborate the revised GE chemical analyses, as shown in the following table-l 4

l j

l USNRC (6)

December 20,1995 MGOME GE CAPSULE SAMPLE #

CHECK REPORT ANALYSIS PLATE SAMPLES

% Cu

% Ni

% Cu

% Ni 417

.14

.56

.14

.47 433

.12

.49

.14

.57 j

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435

.11

.50

.18

.60 4JC

.13

.50

.14

.54

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4J6

.15

.58

.15

.56 l

l AVERAGE =

.13

.53

.15

.55 1

WELD SAMPLES 443

.20

.75

.19

.69 44A

.20

.76

.18

.70 44F

.22

.83

.19

.71 44M

.22

.73

.18

.64 45E

.23 82

.18

.69

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l 45E (ANL DUPLICATE)

N/A N/A

.18

.64 AVERAGE =

.21

.78

.18

.68 The ANL check analysis was performed under a Quality Assurance Program which is structured in accordance with DOE 5700.6C, incorporates the requirements of ASME NQA-1, and satisfies 10CFR50 Appendix B. It is therefore highly unlikely that any further error, or significant inconsistency has gone undetected. Comed further believes that the risk and costs associated with the l

handling and shipping to ORNL of these irradiated materials in order to verify the i

results of ANL is not compensated by an increase in the margin of safety to the j

public. It is also Comed's desire to retain the tested ABB/CE 1P3571 weld metal j

specimens in long term storage for possible use at some future time (e.g., to be I

reconstituted for reannealing and reirradiation studies). This is in keeping with l

1

USNRC (7)

December 20,1995 the guidance provided by the Staffin Information Notice 90-52: " Retention of Broken Charpy Specimens."

In conclusion, Comed understands and appreciates the NRC's concern over the error in the chemistry results for the LaSalle Unit 1 RPV specimen capsule.

Comed also believes that, as the licensee, we have already taken all appropriate actions necessary to document, evaluate, correct, report, and prevent recurrence of this unfortunate error, including independent assessment of specimen chemistries l

by ANL.

Please direct any questions you may have concerning this matter to this office.

i Very truly yours, 6/3W Ga G. Benes 4

Nuclear Licensing Administrator Attachments cc:

H. J. Miller, Regional Administrator - RIII P. G. Brochman, Senior Resident Inspector - LSCS M. D. Lynch, Project Manager - NRR Office of Nuclear Facility Safety - IDNS 1

i

REFERENCES 1.

Letter from Mr. G. G. Benes (Comed) to the USNRC, dated March 23, 1995.

2.

Letter from Mr. G. G. Benes (Comed) to the USNRC, dated June 21, 1995.

3.

Letter from Mr. R. M. Latta (USNRC) to Mr. D. L. Farrar (Comed)

Request for Additional Information (RAI), dated October 25,1995.

4.

Letter from Mr. T. A. Caine (GE) to Mr. T. D. Spry (Comed), dated April 25,1995 (attached).

5.

Letter from Mr. T. D. Spry (Comed', to Mr. T. A. Caine (GE), dated May 23,1995, Chron. # 214035 (attached).

6.

Letter from Mr. T. A. Caine (GE), to Mr. T. D. Spry (Comed), dated September 26,1995 (attached).

7.

Letter from Ms. E. W. Sleight (GE), to Mr. T. D. Spry (Comed), dated October 30,1995 (attached).

8.

Letter from Mr. T. A. Caine (GE), to Mr. T. D. Spry (Comed), dated December 15,1995 (attached).

9.

Letter from Mr. D. G. Graczyk (ANL), to Mr. J. M. Chynoweth (Comed),

dated November 22,1995 (attached).

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I April 25,1995 Mr. Tom Spry CommonwealthEdison Company i

1400 Opus Place,' Suite 390 l

Downers Grove,IL 60515 I

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Subject:

Re-evaluation of LaSalle 1 SurymiBamce Specimen Chemistry Tests i

[.

Reference:

(1) Carey, RG, "LaSalle Unit 1 RPV Surveillance Materials Testing and l

Anal sis," GE-NE-523-A166-1294, March 1995, j

The NRC has recently been scrutinizing data on weld IP3571, thersame weld as is in the LaSalle 1 surveillance program, so you asked us to double check the information we have on the' surveillance weld to make sure there were no " surprises". At my suggestion, Vallecitos doubleAae9 the *=t=rf test results, and found a systamatic error which l

caused the cWintry values reported in Table 3-3 of[1] to be generally high, and therefore inaccurate and overly conservative. The cause of the error, its correction and l

the corrected resuits are provided below.

l Root Cause As described in Section 3.2.3 of the surveillance report, the ewimy test is done with a plasma spectrometer, which determines the concentration of selected elements in a solution. The solution for the test is made by dissolving about a one gram piece of a i

specimen in nitric and hydrochloric acid and then diluting in water so that a dilution factor

?

of about 625 is achieved: This means that the concentration ofa given element, like Cu, in Jl the solution is about 1/625th what it would be in the metal specimen. This dilution factor range has been determined in the past to provide element concentrations in solution with i

optimum spectrometer detectability for low alloy steels. In addition to testing the j'

surveillance spMmane, i set of five NIST reference matenals of known composition are tested using the same procedure.

i l

L' In order for the spectrometer to print out the right metal weight percents, the dilution l

factor for each specimen:is input to the computer that interfaces with the spectrometer.

I When the dilution factors for the surveillance spedmans were input to the spectrometer

]

for evaluation ofMn, Nil Cu, Mo and Cr, all of which are done at one time, incorrect i

values were input. The same error was not made for the reference murials, so the error j

was not caught d6 ring the testing or during review of the test results. Purthermore, l

Vallecitos did not have any input on expected chemistry resuhs fkom San Jose with which l

l to compare their results. The P evaluation, which is done separately, was donc correctly, j

so those values are not re-evaluated.

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j APR 25 '95 20:10 408 925 4175 PAGE.002 l

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9 When the chemistry testing report was received in San Jose, it was reviewed during incorpm.Gon into the surveillance report, and the presence of some==m! values was j

noted. lHowever, no detailed veri 6 cation of the calculations which were part of the test was peiformed at either Vallecitos or San Jose.

Correbtive Action A meeting was held between the San Jose personnel responsible for the surveillance report and tha, Vallecitos personnel responsible for the chemistry testing. The purpose was to review.the testing process.to find steps where errors could occair and where detailed verification would be useful in catching operator errors. The Vallecitos personnel I

explained the process ofidentifying, weighing, dissolving and M*ing the samples for the l

spectrometer evaluation. There is a good process in place, which is adequately d ed by preparing the reference materials in the same way. On process improvements, the j

following conclusions were reached:

l

)

The calculations involved in deterrnining the dilution factors should be verified.

The inputs to the spectrometer should be verified, namely specimen identification and i

i dihition factor.

I The chemistry values in the final report should be verified assinst the outputs from the

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spectrometer.

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The cosrective steps above were taken, using the raw data from the previous tests, such as sample; weights and spectrometer readings. The results are shownin Table 1. The results 4

for the six elements evaluated are reported for every specimen, except for P, which is j

shown for the same six spMm-as in [1].

i I

l Comparison with CMTR data in [1] and a recently discovered letter from CE, attached, shows that the revised chernistries are consistent:

l j'

soured of ChemistryData MMn

%Hi MCu %Ma %.Ct

%E l

l Plate-l Surveelance Specimen Sample Average 1.29 0.53 0.13 0.50 0.256 0.015 0.011 VesselPlate CMTR[1].

1.24 0.49 0.15 0.46 P

CE Letter on Surveillance Welded Plate 1.26 0.55 0.14 0.55 0.27 0.011 i

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s Weld:

3 Surveulance Specimen Sample Average 1.50 0.77 0.21 0.51 0.078 0.016 CE Letter on Surveillance Welded Plate 1.38 0.78 0.21 0.55 0.07 0.015 4

l 1

for con l discussed, we will ship five each of the plate and weld Charpy hal As we firmatory testing. The shipment, which is expected to be in a Type A cardboard l

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box by Federal Express, *ill be ready to leave Vallecitos by May 2. We will need the i

j shippig address fbr Argonne, f

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l APR 25 '95 20:11 400 925 4175 PAGE.003

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Once allissues sre resolve'd (Argonne data, appropriate CF, etc.), and you give us final I

instruc6ons for revision of the report [1], it should take about a week to revise and issue.

j L8 Weld Metal Chemistry Factor i j The IP3571 weld metal chemistry factor (CF) reported in Appendix B of(1) is 261. There are several possible ways to recalculate the CF, as shown below. The CF documented in Revision 1 of(1) will be determined by GE and Comed later.

ii Specimens Only 0.21% Cu,0.77% Ni CF = 192 I

j Average of Specimen 0.21% Cu,0.775%Ni CF = 193 i

i and Letter Data 1

l i

4

l Average of Specimen, 0.26% Cu,0.77% Ni CF=207 j'

Letter and Wald Qual.

Data (0.37% Cu,0;75% Ni) d I

As part of the report revision, an appropriate CF will be documented for the sutvailknce i

4 plate materialas well

2 I

This letter, and the supporting analyses, will be added to the surveillance capsule test design' record file, DRP B13-01746. Let me know if there is anything else you need to i

resolve this issue with the,WRC. I am disappointed that this happened, and I will be personally involved in thel aSalle 2 work to make sure, as best I can, that it is right the l

l first time.

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Regards, i

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TA Caine, PrincipalEngmeer l

l Reactor Internals Management Projects (408) 925-4047, Fax-4175 q

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APR 25 '95 20:11 408 925 4175 PAGE 004

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i Table 1. LaSalle I Surveillance Sample Chemical Analysis bl

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Metal Sample Metal Sample U

ID T

Mn(wt%)

Ni(wt%)

Cu (wt%)

Mo (wt%)

Cr(wt%)

P (wt%)

J hj _

..ype__

g 411 Base 1.41 0.56 0.15 0.53

,,, _ V; 0.278 g

4Il Base 1.24 0.51 0.13 0.48 0.253 l.

436 Base 1.36 0.57 0.15 0.54 0.287

[

437 Base 1.40 0.57 0.15 0.55 0.278 g

4J5 Base 1.20 0.50 0.13 0.45 0.228

.. 4JC -

... B ase...

1.13 0.50 0.13 0.44..

_ 0.224

~

~ ' 5I 416 Base 1.42 0.58 0.15 0.55 0.282 I

43B Base 1.35 0.56 0.14 0.54 0.273 413 Base 1.24 0.51 0.13 0.48 0.247 417 Base 1.28 0.56 0.14 0.54 0.283 0.015 433 Base 1.21 0.49 0.i2 0.46 0.239 0.015 435 Base L26 0.50 0_J.1 0.44 0.203 0.016 1.29 0.53 0.13 0.50 0.256 0.015 Data Avg.

0.09 0.04 0.01 0.05 0.028 0.001 Std. Dev.

l 444 Weld 1.47 0.75 0.22 0.49 0.077 44M Weld 1.41 0.73 0.22 0.48 0.073 i

g 45K Wdd 1.62 0.80 0.21 0.52 0.080 bl 45M Weld 1.57 0.80 0.21 0.53 0.081 45D Weld 1.55 0.80 0.22 0.54 0.079 447 Weld 1.47 0.79 0.22 0.53 0.082 44F Weld 1.60 0.83 0.22 0.55 0.082

~

44U Weld 1.44 0.73 0.20 0.48 0.072 4LD Weld 1.50 0.74 0.20 0.49 0.073 g

443 Weld 1.47 0.75 0.20 0.47 0.081 0.017 M

44A

~ Weld 1.41 0.76 0.20 0.52 0.079 0.016 7

45E Weld 1.47 O_82 0.23 0.55 0.082 0.014

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1.50 0.77 0.21 0.51 0.078 0.016 _

Data Avg.

l 0.07 0.04 0.01 0.03 0.004 0.002 Std. Dev.

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surveillance To:st Program

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G.E. P.O. 9205-H0401 Our Re:2:

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.hf C.E. Purchlasa Order #205-H.0401, Revision No. 1, dated 11/11/71.

. /. ' i Sin #1.ca' for cnnlysis of both pistes and the wald j{oining the placas utre obtcined at the 1/4T. level.

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COMBUSTION ENCIEERINC., INC.

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APR 25 '95 20:12 408 925 4175 PAGE.007

m a ), L C. - sos,s pwwcr 5~

214035 Commonwrith Edison

.a' v

May 23,1995 1

Thomas A, Caine Reactor Internals Management Projects General Electric Company i

175 Curtner Avenue San Jose CA 95125 E

Subject:

T. A. Caine to T.D. Spry, "Re-evaluation of LaSalle 1 Surveillance Specimen Chemistry Tests," 4 25-95 Jim Chynoweth and I have reviewed your letter, which was intended to explain the cause of the LaSalle 1 surveillance capsule specimen chemistry error and the corrective actions nnplemented by GE to prevent recurrence.

We understand your explanation of the chemical analysis process and the way in which the error occurred. But for corrective action and process improvement, we ask that you respond in the following areas:

0 Describe the corrective action options considered before arriving at the final conclusions. Are the corrective actions identified truly the best solutions to the problem?

1 O

Explain the degree of independence which the additional verifications referred to in Corrective Action will have from the process itself.

O Was benchmarking the GE chemical analysis process to the practices of independent laboratories considered? If so, was it pursued? If not, why not?

Additional layers of review may have the effect of " correcting" a process problem which should be designed out of the process in the first place. Benchmarking may be a way to identify an alternative to adding more reviews to the existing process. For example, Com Ed analytical chemistry personnel pointed out that simply having the raw data and dilution calculations for the test specimens as well as the NIST control specimens on the same sheet, instead of separate sheets, could be enough to flag a systematic error or inconsistency. However, analytical chemistry personnel from Argonne National Laboratory stated that their standard practice for reactor programs work is to have an inoependent verification of all calculations performed by a second analyst.

J l

/

We now recognize that requesting a chemical reanalysis should be an integral part of the approach to dealing with chemistry data which is unusual in any respect. In retrospect.

rather than take the conservative, bounding approach to data which we believed to represent weld metal variability, we should have obtained a deadline extension and had the chemical analyses redone. Reactor safety would not have been compromised with either approach, but verification by reanalysis would have eliminated any question of the identity of the surveillance specimens, and would have prevented subsequent damage to our credibility with the NRC in being forced to docket a revised version of the report.

Also, we understand that a review of the LaSalle 1 surveillance chemistry error for Part 21 applicability will be documented by GE, and that at this time it is your conclusion that the error is not Part 21 applicable.

If there are any questions, please call me at 708.663.7268 (FAX.7171) i Sincerely, 4

i htfM44o I

Thomas D. Spry Steam Generator and Reactor Vessel Projects cc:

J.C. Blomgren J.M. Chynoweth A.L. Kochis G.G. Benes P.J. Zurawski

)

GENuclearEn:rgy y

g Gever.o i ectnc Comcm 115 Cc:,er Avenue Se Jbse. CA 95125 September 26,1995 Mr. Tom Spry Commonwealth Edison Company 1400 Opus Place, Suite 300 Downers Grove,IL 60515

Subject:

Closure ofIssues Related to Surveillance Specimen Chemistry Testing

References:

[1] Letter dated 4/25/95, TA Caine to TD Spry,"Re-evaluation ofLaSalle 1 Surveillance Specimen Chemistry Tests."

(2) Letter dated 5/23/95, TD Spry to TA Caine, same subject.

In [1], I described the cause of chemistry testing errors on the LaSalle I surveillance capsule specimens, and the corrective action GE has established to prevent similar i

occurrences in the future. In (2), you requested responses to several issues, in order to close the subject. The issues and our responses are below.

" Describe the corrective action options considered before arriving at the final conclusions. Are the corrective actions identified truly the best solutions to the j

problem?"

j The root cause of the problem was human error in performing calculations with the raw data. Since standard reference materials (SRMs) are tested with each set of specimens, which checks both the method of obtaining raw data and performing calculations, it was agreed that the best process improvement was independent calculations from the raw data and independent review of the spectrometer results. The option ofverification at Vallecitos (by test personnel) vs. at San Jose (by personnel responsible for the surveillance report) was discussed, and it wa s concluded that San Jose verification was preferred for j

several reasons:

It would improve the surveillance report author's understanding of the chemistry testing process, The surveillance report author knows better the chemistry values that are expected, and Being less knowledgeable of the process, San Jose personnel are likely to do a more meticulous verification.

i

l While more elaborate means of verification could be considered, they could become cost prohibitive, so overall I think the corrective action in [1] is the best solution. It is also consistent with our QA process for verification to comply with 10CFR50 Appendix B requirements for safety-related work. One enhancement to the independent nature of the 2

testing and verification, not mentioned in [1], is our intent to retain in San Jose any advance information on the expected chemistries of the specimens, to assure that the Vallecitos testing is unbiased.

" Explain the degree ofindependence which the additional verifications referred to in Corrective Action will have from the process itself" The results reported by Vallecitos, weight percent of each element, is calculated by the spectrometer, based on raw data of pg/g concentration and the input value of dilution factor. The dilution factor is calculated from several raw data values related to sample weight, sample dissolution and dilution. In the corrective process, every calculation made with raw data at Vallecitos is independently duplicated at San Jose. Thus, once Vallecitos generates the raw data, using methods verified by SRM results, the calculation steps are performed twice by independent sources and discrepancies, if any, are resolved between the two sources.

"Was benchmarking the GE chemical analysis process to the practices of independent laboratories considered? If so, was it pursued? If not, why not?"

The GE chemical analysis process has been benchmarked, in a sense, by comparing results of numerous tests of surveillance specimens with past analyses done by test labs of vessel fabricators like CE and CB&I. In addition, the SRM specimens allow the GE process to be benchmarked against an absolute chemistry. Since the error on the LaSalle I specimens related to calculations and not to testing processes per se, benchmarking the practices of other laboratories was not considered. We are, however, always interested in cost effective improvements, and appreciate the information provided in [2].

The 10CFR21 review of this issue is complete. GE has concluded that there is no safety concern connected with the possibility of a past error in chemistry test results. I was contacted by Barry Elliot of the NRC on this subject, and provided him an informal explanation by phone of the issue, and why it is not a safety concern. He inquired about receiving documentation on the issue, so I referred him to our person with administrative responsibility for Part 21 issues. We have received no formal request from the NRC on the subject, so I believe the informal discussions with Barry were sufficient.

If you have any questions on the responses above, please call me.

Regards, l

TA Caine, Principal Engineer Reactor Internals Management Projects (408) 925-4047, Fax -4175 i

cc:

R Willems

~

BJ Branlund 4

I l

1 4

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q REfcecucE 7

GE Nuclear Energy Structural Mechanics Projects 175 Curtner Avenue M/C 747 San Jose, CA 95125 (408)925 1472 EWS-954 cc:

B.J. Branlund T. A. Caine P. S. Wall October 30,1995 Tom Spry Commonwealth Edison 1400 Opus Place, Suite 400 Downers Grove,IL 60515

SUBJECT:

Response to inquiry regarding selection of SRMs for spectrometer calibration e

Reference:

Conve~rsation with Tom Caine on 9/28/95

Dear Tom,

In response to your inquiry regarding the selection of Standard Reference Materials (SRMs)

I am including brief de.scriptions of the basis for calibration and system control. In summary, it has been determined that NIST standard solutions are used for spectrometer calibration and SRMs are used for system control.

CALIBRATION:

The DCP Spectrometer is calibrated with National Institute of Standards and Technology (NIST) standards meeting the criteria ofINPO. When the spectrometer is calibrated for determination of multiple elements, standards of each element under consideration (Fe, Mn, Cu, Ni, Mo, etc.) must be used in the calibration procedure. In addition, the chemical compositions of the standards are selected to be similar to the composition expected in the test specimens such that the spectrometer results are valid for the expected concentration of 1

a typical surveillance sample.

SYSTEM CONTROL:

The use of an appropriate SRM provides suflicient periodic monitoring of the system's measurement and performance capabilities. SRMs are' issued by the NIST and are selected i

on the basis of the closest possible simulation of the actual test sample material. The degree 1

EWS 954 10/30/95 of compatibility is based upon the similarity of both the matrix and level of analyte in the material. It is recommended that several SRMs be used to ensure the absence of bias and/or to identify the nature of any existing bias throughout the measurement range. In the procedure used at the Vallecitos Nuclear Center, five different SRMs are utilized.

We hope that the descriptions of calibration and system control answer your questions regarding our monitoring and calibration procedures. Ifyou should have any further questions or concerns, please feel free to call us.

Sincerely, Ericka W. Sleight Engineer RPV Surveillance Program i

I 3..

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G guenwcc 8' GENucle:r Energy GeneralBectnc Ccenoany 115 Curtner Avenue. San Jose. CA 9512$

December 15,1995 Mr. TD Spry Commonwealth Edison Company 1400 Opus Place, Suite 300 Downers Grove, IL 60515

Subject:

NRC RAI on LaSalle 1 Surveillance Chemistry Testing

Dear Tom,

Here are the responses on requests 2 and 3 of the subject RAI.

2. GE has performed testing on numerous BWR surveillance capsules since its first in 1984. As part of most testing scopes, the surveillance plate and weld chemistries of the irradiated surveillance specimens have been determined, typically by testing 2-3 pieces from different specimens of each material.

The results of the gamma spectrometry testing by which copper and nickel content were determined are provided in Table 1. For most of those tests, CMTR (certified material test report) chemistry data are available as a check on the validity of the surveillance chemistry tests. Comparison of the GE test results and the CMTR results show agreement within expected values when considering the uncertainties:

The GE method has iS% relative uncertainty, The CMTR method had some uncertainty, The materials themselves have some chemistry variability In a few cases, there is no baseline chemistry data for surveillance weld materials, either because chemistries for the heat in the as-welded condition were unknown, or because the heat number used in the weld was unknown. In these cases, there is still good confidence in the validity of the chemistry results because the surveillance plate specimens were tested at the same time by the same process and performer. These plate specimen results agree well with the plate CMTR data, which are available for comparison.

4

3. When the issue of chemistry testing errors on the LaSalle 1 specimens was identi6ed, an internal process was started at GE to determme if the error created a Potential Safety Concern (PSC). Under the GE process, a PSC is evaluated to determine if a 10CFR21 reportable condition exists.

In accordance with the GE process, an evaluation of the PSC was made. The focus of the evaluation was on the potential use of past chemistry test results for safety-related purposes. For most past analyses, the plant beltline analyses continued to be based on CMTR data alone, even after surveillance test results were available, so the test results were not used for safety-related purposes. Two instances were identified where surveillance material results were used to supplement existing beltline CMTR data.

In one case, Hope Creek, the chemistry test results were averaged with existing beltline weld data to provide a best estimate chemistry for one of the beltline heats.

The test results had been independently verified and found to be correctly evaluated, using the new process established after the LaSalle 1 error.

!I

~ In the other case, Hatch 1, the test results were used to establish the copper value j

e for a beltline weld for which no value was available. The test results for elements that could be compared with the existing element values from CMTR data agreed well, providing a basis that the surveillance copper value would be representative of the beltline copper.

I Since there was no evidence ofincorrect test results having been generated in either of the two cases above, GE determined that the PSC was not a reportable condition under 10CFR21.

One aspect of the evaluation of the PSC that was not originally considered is that surveillance chemistry test results issued in GE reports might have been used by PWRs to develop best estimate chemistries for their beltline materials. Based on the validity l

of the past chemistry test results, as demonstrated in Table 1, and the fact that all plants with IP3571 weld material are aware of the correct test results from LaSalle 1, GE has determined that a 10CFR21 reportable condition related to surveillance material chemistry testing does not exist.

i I

_~_ -

~

If you have any questions or comments on the responses, please call me at the number below.

Regards, a

TA Caine, Principal Engineer Reactor Internals Management (408) 925-4047 cc:

BJ Branlund, GE D Kelly, GE 1

4 t

i e

I Table 1. Previous GE Surveillance Chemistry Test Results l

Plant Test Plate Material Heat No.

Chemistry Cu Ni Mn Mo Comments Date or Data Wt %

Wt %

Wt %

Wt %

I W eld Source l

Cofrentes 1993 P

E12761 GE 0.03 0.60 1.48 0.58 CMTR 0.03 0.62 1.46 0.57 W

D60468 GE 0.07 0.76 1.70 0.50 CMTR 0.06 0.72 1.63 0.49 Cooper 1993 P

C2307-2 GE 0.22 0.76 1.28 0.50 1987 CMTR 0.21 0.73 1.25 0.47 W

20291 GE 0.22 0.74 1.33 0.54 CMTR CMTR data not available Duane Amold 1986 P

B0673-1 GE 0.15 0.70 1.35 0.62 CMTR 0.15 0.61 1.37 0.55 W

(SMAW)

GE 0.02 1.95 1.25 0.49 CMTR CMTR data not available FitzPatrick 1987 P

C3278-2 GE 0.12 0.62 1.35 0.49 CMTR 0.13 0.60 1.26 0.48 W

GE 0.31 0.72 1.45 0.50 CMTR Weld heat # unknown Hatch 1 1985 P

C4114-2 GE 0.11 0.65 1.40 0.56 CMTR 0.13 0.70 1.43 0.54 W

1P3571 GE 0.28 0.76 1.40 0.50 Heat # determined during 9201.S1 work ind. avg.

0.31 0.77 1.31 0.51 Mn,Mo values from one CMTR Hatch 2 1991 P

C8554 GE 0.08 0.63 1.39 0.60 i

CMTR 0.08 0.58 1.32 0.52 i

W 51912 GE 0.12 0.10 1.18 0.56 CMTR 0.16 1.13 0.53 Hope Creek 1995 P

SK3238/1 GE 0.09 0.66 1.32 0.56 I

CMTR 0.09 0.62 1.42 0.54 i

W D53040 GE 0.06 0.46 1.28 0.32 CMTR 0.09 0.68 1.69 0.51 i

Millstone 1 1993 P

C1079-1 GE 0.22 0.49 1.32 0.47 1984 CMTR 0.19 0.51 1.31 0.49 l

l W

348009 GE 0.20

.59-1.09 1.29 0.55 Separate Ni wire added during welding CMTR 0.18 1.03 1.34 0.49 l

l GE = Surveillance chemistry test by GE CMTR = Fabrication test report ESW = Electroslag weld

}

N/A = Not available SAW = Sub-arc weld SMAW = Shielded metal arc weld l

l

.. ~ _

i.

Tabl@ 1. Previous GE Surveillance Chemistry TG;st Results l.

[

Plant Test Plate Material Heat No.

Chemistry Cu Ni Mn Mo Comments Date or Data Wt %

Wt %

Wt %

Wt %

Weld Source i

Peach Bottora 2 1991 P

C2761-2 GE 0.10 0.54 1.26 0.48 CMTR 0.11 0.54 1.30 0.47 W

(ESW)

GE 0.10 0.32 1.44 0.49 CMTR Weld heat # unknown Peach Bottom 3 1990 P

C3103-1 GE 0.13 0.63 1.46 0.51 CMTR 0.14 0.60 1.35 0.47 W

(ESW)

GE 0.11 0.40 1.56 0.50 CMTR 0.11 0.41 1.56 0.51 Santa Maria 1995 P

524720-4487 GE 0.08 0.73 0.59 0.60 i

De Garona CMTR 0.10 0.72 0.58 0.61 W

(SAW)

GE 0.33 0.09 1.43 0.50 Surv. Spec.

0.30 0.09 1.49 0.51 Data from a report provided by Nucienor Susquehanna 1 1993 P

C2433-1 GE 0.09 0.60 1.32 0.56 CMTR 0.10 0.63 1.30 0.57 W

411L3071, or GE 0.02 0.94 1.19 0.55 402K9171 CMTR Avg.

0.03 0.96 1.18 0.52 I

Susquehanna 2 1994 P

C2929-1 GE 0.12 0.63 1.32 0.58

}

CMTR 0.13 0.64 1.27 0.56

[

W 411L3071 or GE 0.02 0.94 1.16 0.54 401S0371 CMTR Avg.

0.03 0.98 1.19 0.53 l

GE = Surveillance chemistry test by GE CMTR = Fabrication test report ESW = Electroslag weld N/A = Not available SAW = Sub-arc weld SMAW = Shielded metal arc weld

'ARCONNE NATIONAL LABORATORY 1<iepi40~<: <7083252 3489 Giosc4 Tedwology DwisiON, ANMyliCM CIEMISTRy (AbORATony fax: (708)252,3146 9700 Sous Ces Awnue, AnqpNNE, Illros 604I9 4831 E Mail: GnAczyk@cMr.ANI.qov REFGRENCC

/

November 22,1995 Mr. James Chynoweth Commonwealth Edison Co.

Systems Materials Analysis Department 555 South Joliet Road Bolingbrook,IL 60440

Dear Mr. Chynoweth:

This letter is in response to your request for information regarding chemical analyses performed during May of 1995 by Argonne's Analytical Chemistry Laboratory (ACL) on a set of reactor surveillance capsule specimens submitted by Commonwealth Edison Co.

Areas addressed here include (1) chronology of analysis; (2) description of the analytical methodology applied; and (3) summary of the ACL's Quality Assurance program. We trust this response will satisfy your needs for information related to these aspects of the analytical work performed on Commonwealth Edison's behalf. If, however, you have questions on any of the items presented, please feel free to contact me at the above phone number.

_ Chronology: Attachment I to this letter contains a tabular presentation of events that took place during the processing of the surveillance specimens at Argonne. The samples were received by our Special Materials Group (SPM) on May 4,1995 and were transferred the same day to Argonne's Energy Technology Division where, under the direction of Dwight R. Diercks, each specimen was machined to produce chips of the steel. Portions of the chips from each specimen were subsequently analyzed to determine carbon, sulfur, and selected metal concentrations (including Cr, Cu, Fe, Mn, Mo, Ni, and Si).

Results of the individual determinations were reported by the ACL to D. Diercks, who transmitted the reports to Commonwealth Edison. Results for carbon and sulfur were transmitted on May 18,1995, and the report for metals was sent on May 31. One sample (Specimen No. 417) was subsequently reanalyzed to follow up on a high recovery for iron observed in the first measurements. Results of this reanalysis were reported on October 27,1995. Copies of the Reports of Analytical results for the carbon and sulfur determinations and a summary report of the final results for metals are provided in Attachment 2.

Methodolonv: Carbon in each steel specimen was determined with a LECO Corporation Model WR-12 Carbon Determinator, which conforms to the test method described in ASTM Designation E 1019-94 (Total Carbon by the Combustion Instrumental Measurement Method). For these analyses, the instrument was calibrated and calibration verified with Carbon-in-Steel standards obtained from either LECO Corporation or Alpha Resources, Inc.; both of these suppliers reference traceability of their standards to NIST Reference Materials, including NIST 8j,12h, I5g,15h, and 335.

Sulfur was determined with a LECO Corporation Model 518 Determinator, which conforms to the test method described in ASTM Designation E 1473-94a (Sulfur by the Combustion-lodate Titration Method). The instrument was calibrated with ACS Reagent Grade Potassium Sulfate according to manufacturer's instructions and the calibration was verified by analysis of the NBS Reference Material SRM 32d.

OpcnATEd by %E Univtasily of Cl4icAgo fon EE UNITED STATES DEPARTMENT of ENEnqy

1

]

Mr. James Chynoweth November 22,1995

)

4.

Metallic elements were determined by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) analysis of solutions prepared by dissolving weighed portions of the chips from each specimen in i

hydrochloric acid containing a small amount (few drops) of hydrofluoric acid. Although not yet an i

ASTM designated method, plasma spectrometry is a well recognized and widely used technique for the determination of metallic elements in solution. De system used for the Commonwealth Edison d

surveillance specimens is an ARL Model 3520 Spectrometer equipped with glovebox containment for analysis of radioactive samples (a brief description of the ICP-AES capabilities in the ACL is provided in Attachment 3). The ICP-AES system was calibrated immediately before the samples were analyzed, i

using spectrometric standard solutions procured from either SPEX Industries Inc. of Edison, NJ, or Fisher Scientific of Fair Lawn, NJ. The SPEX industries standard is a multielement calibration standard that includes all the elements that were measured, except Mo and Si. For these latter two elements, Reference 1

Standard Solutions from Fisher were used. Copies of the certification provided by the suppliers for both

{

the SPEX and Fisher solutions are enclosed in Attachment 4. The certificate for the SPEX solution j

includes references that establish traceability of individual components of the standard to NIST.

j Certificates for these components are available for review if needed.

Both the dissolution procedure and ICP-AES measurements applied for the surveillance specimens were verified by carrying a sample of NBS 32d Steel through the analysis process along with the samples.

Ouality Assurance: Activities in the ACL are carried out under an organizational Quality Assurance Plan (Analytical Chemistry Laboratory Quality Assurance Plan, Document No. C0030-0221, Revision 06, June 1994) structured in accordance with U.S. Department of Energy (DOE) Order 5700.6C, Quality Assurance. His plan incorporates the Quality Assurance (QA) requirements of ASME NQA-1 (Quality J

Assurance Program Requirements for Nuclear Facilities) as well as the DOE required elements of Training, Quality Improvement, and Independent and Management Assessments. By virtue of our QA program's conformance with the requirements of ASME NQA-1, ACL activities satisfy 10CFR50, Appendix B (Quality Assurance Criteria for Nuclear Power Plants and Fuel Reprocessing Plants). A copy of the Cover Page and Table of Contents of the ACL QA Plan is provided as Attachment 4. If you should want a copy of the entire document, please contact Fred Martino, ACL QA/QC Coordinator, at (708) 252-4474.

Sincerely, i

Donald G. Graczyk Group Leader, Chemical Analysis Analytical Chemistry Laboratory Chemical Technology Division DGG:amb Attachments cc:

w/ attach.

J. Laidler (2)

D. Green D. Bowers F. Martino D. Diercks (ET)

Subject:

Information on Analysis of Steels

List of Attachments to Letter: J. Chynoweth, Commonwealth Edison Co. : Table, Chronology of Analysis for Commonwealth Edison Steel Samples (1 page) : Reports of Analytical Results for Carbon, Sulfur, and Metals in Commonwealth Edison Steel Samples.

(3 pages) : Summaries of ACL Capabilities forICP-AES (2 pages) : Certificates of Analysis for ICP Reference Standard Solutions (3 pages) : Cover Page and Table of Contents, Analytical Chemistry Laboratory Quality Assurance Plan (3 pages) i 4

I e

l Chronology of Analysis for Commonwealth Edison Steel Samples Analyzed by Argonne i

l National Laboratory Analytical Chemistry Laboratory l

Chemical Technology Division i

Event Date Remarks Specimens Received at ANL May 4,1995 Delivery to Special Materials (Specid Materials Group)

Group Specimens Transferred to Building May 4,1995 212 for Preparation (Machining)

Samples Transferred to Analytical May 9,1995 SPM Doc. No. E3259 l

Chemistry Laboratory (Building 200) for Carbon / Sulfur Determinations Analyzed for Carbon May 16,1995 ACL Logbook 769, p. 51 Analynd for Sulfur May 18,1995 ACL Logbook 769, pp. 52,53 Sulfur and Carbon Results Reported May 18,1995 ACL Job No. 95-0240 i

to D. Diercks Sulf u and Carbon Data Transmitted May 18,1995 Date of transmittal is not by D. Diercks to Comed.

certain; on-or-about.

i Samples Transferred to Analytical May 22,1995 SPM Doc. No. C7002 l

Chemistry Laboratory (Building 205) for Metals Determinations Portions Dissolved in Mineral Acids May 22,1995 ACL Logbook 1174, pp. 67-70 Solutions Analyzed by ICP-AES May 23,1995 ACL Logbook 1174, pp. 67-70 (ARL 3520 Instrument)

Metals Data Reported to D. Diercks May 25,1995 ACL Job No. 95-2062 Revised Metals Report Issued May 31,1995 ACL Job No. 95-2062 (Missing Decim4 Point in One Fe Value) 1 Metals Data Transmitted by D.

May 31,1995 Date of transmittalis not Diercks to Comed.

certain; on-or-about.

Specimen 417 k[omalyzed Oct. 22-23,1995 ACL Logbook 1174, p.170 Reanalysis l$sNts Reported to D.

Oct. 27,1995 ACL Job No. 95-2062, Diercks continued.

Metals Data Compiled into Summary Nov.22,1995 See Attachment 2.

Reportand Transmitted to Comed

.=

l Reports of Analytical Results for Carbon, Sulfur, and Metals in Commonwealth Edison Steel Samples.

i 1

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t 5

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i l

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l L

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a ANALYTICAL CHEMISTRY LABORATORY Argonne National Laboratory Argonne, IL 60439 REPORT OF ANALYTICAL RESULTS Sample Material:

Steel Samples Date Received:

5/9/95

@ubmitted by:

D. Diercks Date Reported:

5/18/95 Submitter's ACL Sample Wt., g Sample Wt., g Sample No.

Sample No.

Carbon. Wt. %

(for Carbon)

Sulfur, Wt. %

(for Sulfur) 417 95-0240-01 0.182 0.4822 0.024 0.5406

-01 Duplicate 0.016 0.9597 433

-02 0.185 0.3402 0.015 0.9468 435

-03 0.192 0.2955 0.014 1.1772 443

-04 0.150 0.6596 0.012 0.9407

-04 Duplicate 0.146 0.4027 44A

-05 0.174 0.2611 0.011 0.9893 44F

-06 0.193 0.2789 0.013 1.1380 44M

-07 0.170 0.3822 0.010 1.2739 45E

-08 0.16S 0.3804 0.012 1.2740 4JC

-09 0.192 0.3303 0.017 0.9624 4J6

-10 0.199 0.2393 0.016 0.9839

-10 Duplicate 0.188 0.3486 0.016 1.0231 K SO Known: 18.40 % S Found: 18.28 % S 2

4 NBS Known: 0.027% S Found: 0.028% S Standard:

SRM 32d i

LOTE: Unused sample material will be retumed to the Customer. Prepared samples will be discarded one (1) mont ftir tha d;te of this report unless other arrangements are made. When making future inquiries regarding this report, Insa r:firence the ACL sample number (s) above. For further information about the results reported here, please call

,Ross at 2-3492

firince(s)

L. Ross Notebook No. 769, pp. 51-53.

opits To:

D. Diercks Analyst (s):

L Ross D. Green D. Graczyk

(., M +

mb L Ross

'19/95 ACL 200 File um Page 1 of 2 Pages

.~

~.

ANALYTICAL CHEMISTRY LABORATORY Argonne National Laboratory Argonne, IL 60439 REPORT OF ANALYTICAL RESULTS Sample Material:

Steel Samples Date Received:

5/9/95 Submitted by:

D. Diercks Date Reportei 5/18/95 Submitter's ACL Sample Wt., g S a m ple W t., g Sample No.

Sample No.

Carbon, Wt. %

(for Carbon)

Sulfur, Wt. %

(for Sulfur) l 95-0240 Carbon Quality Control Standard.s.

% Recovery

% Recovery Standard. Wt. % C Before Samoles Run After Samoles Run 0.0072 94.4 102.8 0.021 99.0 101.4 0.059 95.6 98.3 0.172 99.5 Carbon determined using the LECO WR-12 Analyzer.

Combustion is at -1500*C in pure oxygen.

Instrument detection limit (IDL) is 25 pg C.

Carbon results: iS%.

NOTES: Sulfur determined using the LECO Model 518 Determinator.

Sulfur results on samples: 110 %.

NOTE: Unused sample material will be retumed to the Customer. Prepared samples will be discarded one (1) month aft:r the date of this report unless other arrangements are made. When making future inquiries regarding this report, pleas 2 reference the ACL sample number (s) above. For further information about the results reported here, please call L.Ross at 2-3492 R;f;r:nce(s):

L. Ross Notebook No. 769, pp. 51-53.

Copi:s To:

D. Diercks Analyst (s):

L.Ross D. Green D. Graczyk lamb L.Ross 5/19/95 ACL 200 File um m Page 2 of 2 Pages

- i

.4s-ANALYTICAL CHEMISTRY tABORATORY I

Argonne National Laboratory Argonne, IL 60439 REPORT OF ANALYTICAL RESULTS Sample Material:

Machined Steel Chips Date Received:

5/23/95 Submitted by:

D. Diercks Date Reported:

5/25'95,10/27/95 Submitter's ACL Wt. %

Sample No.

Sample No.

1

.G.E

.QM En Mn Ma fit E

417 95-2062-01 0.22 0.14 94.9 1.13 0.62 0.47 0.24 433

-02 0.24 0.14 97.4 1.27 0.51 0.57 0.21 i

435

-03 0.18 0.18 93.7 1.27 0.48 0.60 0.20 443

-04 0.091 0.19 94.8 1.37 0.50 0.69 0.42 1

44A

-05 0.086 0.18 92.0 1.33 0.46 0.70 0.39 j

44F

-06 0.089 0.19 93.1 1.35 0.47 0.71 0.39 1

44M

-07 0.097 0.18 91.3 1.32 0.49 0.64 0.39 45E

-08A 0.094 0.18 91.7 1.37 0.48 0.69 0.26 45E Dup

-08B 0.095 0.18 87.9 1.31 0.47 0.64 0.20 l

4JC

-09 0.24 0.14 90.1 1.21 0.49 0.54 0.26 4J6

-10 0.24 0.15 93.4 1.27 0.51 0.56 0.24 l

i 96 i

j NBS 32d Steel Found 0.64 0.090 92.8 0.76 0.026 1.20 0.31

)

(Known Value)

(0.71)

(0.096)

(96.4)

(0.80)

(0.038)

(1.19)

(0.30)

% Recovery 90.1 93.8 96.3 95.0 68.4 101 103 Estimated uncertainties: 10%

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l Summary report compiled from original report of 5/25/95 and followup analysis on Specimen 417 (ACL No. 95-2062-01), performed on 10/23/95.

I NOTE: Unused sainple material wil be retumed to the Customer. Prepared samples will be discarded one (1) month aft:r the date of this report unless other arrangements are made. When making future inquiries regarding this report, pielso reference the ACL sample number (s) above. For further information about the results reported he're, please call l

D. Bowers at 2-4354 R;ftr:nce(s):

Data record *ed in CMT Book No.1174, pp. 67-70,170.

l Copts To:

D.Diercks ACL 200 File Analyst (s):

D. Bowers C.Sabau h % 6 D. Green D. Graczyk

/lll/ mb F. Martino 11/22/95 D. Bower C. Sabau (2) cm. m

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Summaries of ICP-AES Capabilities

1. Inductively Coupled Plasma-Atomic Emission Spectrometry

2. " Hot" Inductively Coupled Plasma-Atomic Emission Spectrometry I

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Inductivelv Couoled Plasma-Atomic Emission Soectrometrv (ICP-AES)

Apolication: The technique of ICP-AES is used to characterize diverse analytical samples by the simultaneous measurement of multiple cations in solution. The sample solution is introduced into an argon plasma in which the cations are excited and emit light at discreet wavelengths; the intensity of the emission is related to the concentration ofions in the sample.

Any elemental constituent that, upon excitation, emits light in the 180-800 nm spectral region can be quantitatively determined by ICP-AES. Most metallic elements and common non-metals such as boron, silicon, and phosphorus can be measured.

Instrumentation: Measurements are performed by using an Instruments SA JY86 Spectrometer System, which incorporates a 48-channel polychromator (JY-48), capable of the simultaneous determination of 42 elements, and a scanning monochromator (JY-38) for the determination of additional analytes. Both instmments are focused on a single plasma excitation source. The polychromator system is controlled by, and data are stored on, a DEC PDP-11/23 computer. A Gateway 2000 PC is used with the monochromator system for operation and data storage.

Samole Reauirements: Samples for analysis must be in solution, and the concentration of total dissolved solids cannot exceed 20 mg/mL. Any mineral acid can be used for sample dissolution, but the acidity should be in the range 0.1 to 0.5N. Separation techniques (e.g., ion exchange, extraction) can be applied to improve detectability.

Detection Limits: Elements at concentrations from I to 500 ng/mL in aqueous solution can be detected, depending on the wavelength and sensitivity. Generally, results are reported if the measured concentration exceeds three times the detection limit; otherwise a "less than" value is provided.

Accuracy: Typically, measurements can be made with an estimated accuracy of 10% at analyte concentrations of 10 to 100 times the detection limit, and 3-5% if the concentration exceeds 100 times the detection limit.

Interferences: The method is reasonably free from chemical and ionization interferences. Spetral overlaps have to be evaluated on an individual basis and may require the use of attemative wavelengths and/or spectral interference corrections.

Time Reauired for Analysis: The following factors enter into time assessment:

1. Sample preparation (dissolutions, separation)

4. Matrix complexity

2. Number of samples of similar composition

5. Instrument calibration requirements

3. Number of elements determined

6. Analytical quality control Based on these considerations, analytical time may range from 0.5 to 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> per sample. Usually multiple samples can be analyzed with less time per sample.

Some information on this page is very general. Most analytical problems have unique characteristics that are not easily generalized. Please contact the ACL Office (2-4473) to obtain specific information about the application of this technique to your analytical problem.

Note: This summary is an updated version of one issued 3/28/84, and should replace it.

September 8,1995

ANALYTICAL CHEMISTRY LABORATORY

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" Hot" Inductively Coupled Plasma / Atomic Emission Socetrometry (ICP/AES)

Acolicability: The ICP/AES system is used to determine the concentration of elements that, upon excitation, emit light in the 180 to 800 nm spectral region. This instrument, with the excitation source (plasma torch) interfaced with a glove box,is primarily used for elemental analyses of materials that are radioactive. Solutions with high levels of alpha-emitting isotopes and moderate levels (<100 mR/hr) of g, y radionuclides can be safely analyzed with this instrument. This instrument can also be used to determine radioactive elements such as "Tc and heavy elements such as Th, U, Pu, Am, Np, and Om.

Instrument: The ACL has an Applied Research Laboratories (ARL) Model 3520 scanning spectrometer that is interfaced to a glove box facility. The spectrometeris controlled with a DEC PDP 11/23+ computer and associated equipment.

Samole Preparation: Samples that are not received as solutions must be dissolved and also may have to be chemically separated in special cases by such techniques as ion exchange.

Detection Limits: The detection limit varies from 1 to 500 ppb in solution.

Accuracy and Precision: Accuracy and precision are dependent on sample signal response, which depends on the amount of element in the sample. Uncertainties of 5 to 10% are typical.

Interferences: Interference levels are dependent on the sample matrix, which could cause background shifts and/or spectral overlap. Background or baseline shift corrections can be made and spectralinterference curves can be generated. Also, alternative wavelengths may be chosen for the particular element ofinterest.

Analysis Time: Analysis time varies with the sample preparation required and with the number of elements to be determined.

+++++

Some information on this page is very general. Most analytical problems have unique char-acteristics that are not easily generalized. Please contact the ACL Office (2 4473) to obtain specific information about the application of this technique to your analytical problem.

December 20,1988 1

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Certificates of Analysis for ICP Reference Standard Solutions l

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&$. )OY~~'hb S& #1 % E. N !

no-M %y ss L B&.n &q).68uw 26 so-L

%kwarf &> n5DS d&D lL CERTIFICATE QE. ANALYSIS SPEX PART #

XANL-2 DESCRIPTION:

100 ug/ml each of A1, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, Sr, T1, Zn, Zr and V MATRIX:

5% hcl in H O 2

LOT NO:

4-244MM The enclosed certi fi cates represent analyses of the starting material of all elements contained in your Custom Multi-Element Solution Standard.

Each individual element in the solution has been referenced and en j

appropriate certificate is included.

l Custom Multi-Element solutions are prepared by pipetting and i

diluting stock single-element solutions and a final ICP check is performed.

Each solution is guaranteed stable and accurate to within +/-0.5% of labeled concentration for one year from date of l

shipment.

s Please keep these certificate on file.

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l FISHER SCIENTIFIC CHEMICAL DIVISION One Reagent Lane, Fair Lawn, NJ 07410 ANALYTICAL CONTROL LABORATORY ANALYSIS I

NIme & Grade:

SILICJN REFERENCE STANDARD SOLUTION 1ML = 1MG Si Cctolog Number: 88465 Lot Numbert 947038 Date of Testing / Mfg: 12/14/94 P.O./ Other Customer ID:

j Thio is to certify that units of the above mentioned lot number were tested and found to comply with the specifications of the grade listed.

Tho following are the actual analytical results obtained:

Tect Unit Result APPEARANCE PASS / FAIL PASS-CLEAR COLORLESS LIQUID CON-GRAVIMET.MTH-PPM PPM 1002.00 Approved by:

rederick H.

Turk, Robert Dowd Edgar E.

Hess, FL Liquid Supv.

FL Dry Supv.

BPF Lab Supv.-

Dato: 12/19/94 (Signed and dated original is on file) l NOTE: The data listed is valid for all package sizes of th,is lot of product, expressed as a extension of the catalog number listed above.

If there are any questions with this certificate, please call Ch02ical Services (option 5) at (800) 388-8355.

j Raf. No. S5465. 94703a.B1-Location: FL E Id

FICHER SCIENTIFIC CHEMICAL DIVISICN Cn3 RocgCnt Lan3, Fair Lawn, NJ 07410 ANALYTICAL CONTROL LABORATORY ANALYSIS Name & Grade:

MOLYBDENUM REFERENCE STANDARD SOLUTION, IML = IHC Mo C tclog Number: SM113 Lot Number: 936313 Date of Testing / Mfg: 11/04/93 P.O./ Other customer ID:

Thic is to certify that units of the above mentioned lot number were tested and found to comply with the specifications of the grade listed.

-Tha following are the actual analytical results obtained:

Tact Unit Result APPEARANCE PASS / FAIL PASS-CLEAR COLORLESS LIQUID CONCENTRATION IN PPM PPM 999.000 CONCENTRATION _,AA-P/F PASS / FAIL PASS ir l

MN j Approved by:

raderick H. Turk, or Edgar E.

Ness, FL Analytical QA Supv.

BPF Analytical QA Supv.

Data: 11/05/93 (Signed and dated original is on file)

! NOTE: The data listed is valid for all package sizes of this lot of product,. expressed as a extension of the catalog number listed above.

If there are any questions with this certificate, please call Stovcn P. Davis, Analytical QA Manager, at (201) 703-3149.

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! R3f. No. SM113.936313.81.

Location: FL i

d Cover Page and Table of Contents, Analytical Chemistry Laboratory Quality

~

Assurance Plan.

t

COP N l2 ARGONNE NATIONAL LABORATORY 9700 SOUTH CASS AVENUE i

ARGONNE, ILLINOIS 60439 ANALYTICAL CHEMISTRY LABORATORY CHEMICAL TECHNOLOGY DIVISION QUALITY ASSURANCE PLAN DOCUMENT NO. C0030-0221 REVISION 06 Reissued:

h S2 (Date of OriginalIssue: February 26,1982)

(See Page 1 for Revision Record) 1 For Date R7!9M Prepared by:

S,/dd4A b CMT/ACL ACL(dA/QC Coordinator Reviewed by: g Met CMT/ACL 6-78-fY 0!2 fY Approved by:

d/

CMT/ACL ACL Manager

I ARGONNE NATIONAL LABORATORY C0030-0221 1

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Title:

QUALITY ASSURANCE PLAN FOR THE Rev.

Approved Date g

O ANALYTICAL CHEMISTRY LABORATORY 06

% o, Page 2 of 31 TABLE OF CONTENTS Pace

.n Index of Page Revisions (Document Control Record)................................. 1 Elements of the ACL QA Plan:

1.

Purpose and Scope of the Analytical Chemistry Laboratory Quality Assurance Plan....... 4 1.1 Mission.......................................................4 1.2 Pu rpo s e....................................................... 4 1.3 Organization and Responsibility...................................... 5 1.4 Quality Assurance Requirements....................................

11 2.

Personnel Training and Qualification....................................... 12 3.

Quality Improvement......

................................12 3.1 Management

.... 12 3.2 Employee Development

. 13 3.3 Nonconformances/ Deficiencies 13 j

3.4 Correc ti ve Action............................................... 14 4.

Documents and Records............................

.... 14 4.1 Disposition..................

................................14 4.2 S t o ra g e......................

14 4.3 Co n t ro l.....................................

. 15 4.4 S ecurity....................

16 5.

Wo rk Proce s s e s......................................................

17 5.1 Signature List..........

. 17 5.2 Analytical Reports..............

17 5.3 Control of Analytical Processes (Quality Control)......................... I8 5.4 Scientific Investigation Control (Notebooks)............................

19 sN L.212 (3-83)

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_t ARGoNNE NATIONAL LA30RATORY i

g g

Title:

QUALITY ASSURANCE PLAN FOR THE Rev.

Approved Date j

b ANALYTICAL CHEMISTRY LABORATORY 06 1

• Y Page 3 of 31 2889.

5.5 Analytical Standards.............................................. 20 5.6 Computerized Data.............................................. 21 5.7 Handling. Storage, and Shipment (Samples)

...........................23 6.

De sign............................................................ 23 6.1 Procedures / Technical Plans / Work Plans............................... 23 7.

Procu rement........................................................ 24 7.1 Requireme n ts.................................................. 24 7.2 Control of Subcontracts (Procurements/ Service Work)..................... 25 l

i 7.3 Control of Materials and Equipment.................................. 25 8.

Inspection and Testing................................................. 26 j

8.1 Inspection, Test, and Operations Status.

..............................26 i

8.2 Measuring and Tcst Equipment..................................... 27 l

8.3 Safety Review of Analytical EquipmenVSystems.......................,,, 28 9.

Management Assess ment............................................... 28 10.

Indepe ndent Assessment................................................ 2 8 Appendix A: Reference Documents

...........................................30 Appendix B: De fi nitions................................................... 31 Appendix C: He ACL QA Plan and Its Relationship to ACL Jobs..................... 34 Appendix D: Retention of Documents by the ACL................................. 35 Distribution of ACL OA Plan ACL Staff J. E. Battles (CMT)

L. D. Chipman (OQA)

R. F. Malecha (CMT)

D. C. Parzyck (EQO)

J. R. Phillips (LANL)

N L.2s2 (3.c31

.