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ADDENDUM TO THE DATA VALIDATION REPORT

FOR

PINE STREET SUPERFUND SITE SOT T H T<TT1?T TNCTON VFPATONT

INORGANIC ANALYSIS DAT Metals In Soil Samples

Laboratory Sample Delivery Group No. Z12'

Chemical Analyses Perform

By:

lEA Monroe, Connecticut

For:

The Johnson Company Montpelier, Vermont

By:

Trillium, Inc. RR5 Box 670 Upper North Street

Montpelier, Vermont 05602 (802) 223-6445

(802)223-6452 FAX

August 7,1996

96454/KB\V/CAE ADZ 12651

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EXEC! TFVE SUMMARV

Validation of the inorganics analysis data (metals) prepared by lEA for a single duplicate samplefiom the Pine Street Superfund site in South Burlington, Vermont, has been completed by T n l l i n m |pn Thp Hntn v r r p rpnoi'tpH IT^' tVi" loT-inrntoTr iipH.-^r "s'li-t^nlp r i '^ l i i 'prv nrmnA ^ ^ n n ^ Xin

Z1265 in a single data package which was received for review on May 22, 1996, and includes sample J_T25-82D.

This report is an addendum to the report previously submitted (6/13/96) for SDG No. Z1265 and is applicable to only the duplicate sample listed above. The chain of custody record indicated that sample J_T25-82D was to be analyzed in duplicate by the laboratory. Although laboratory quality control analyses are not generally reported as site samples and a separate Form I was not issued for the duplicate by the laboratory, at the request of USEPA, Region I and the client the validation of the duplicates (suffix "D") has been performed. Results for the duplicate only are presented on the Data Summar>' Form in Attachment A. In lieu of a Form I for the duplicate, the Duplicate Summary Form (Form VI) was included in Attachment B. For validation purposes and for the purpose of this addendum, these samples were considered to befield duplicates.

Based on the validation effort, results for inorganic analjtes were determined to be valid as reported with the following exceptions:

• Results for antimony and thallium in J_T25-82D were qualified as estimated (UJ).

• The result for potassium in J_T25-82D was qualified as less than the reported value (U).

• The result for lead in J_T25-82D was qualified as estimated (J).

All laboratory-applied "*" and "B" qualifiers were removed by the validator from the sample Form VI.

Problems with the chain of custody records in the data package for SDG No. Z1265 were previously discussed in the validation report submitted on 6/13/96, and are not repeated here.

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Brief explanations of the reasons for application of the qualifiers listed above may be found in the Overall Assessment (Section XIII). Details of the validation findings and conclusions based on review of the results for each quality control requirement are provided in the remaining sections of this report.

This validation report addendum should be considered part of the data package for all future HKtrihiitinn'; of the ir!rironnir<; Hstri

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INTRODUCTION

Analyses were performed according to SW-846 methods for the metals. The quality control and reporting format for all analytes was consistent with the U.S. EPA CLP protocols to the extent

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cadmium, calcium, chromium, cobah, copper, iron, lead, magnesium, manganese, mercury, nickel, potassium, selenium, silver, sodium, thallium, vanadium, zinc, and amenable cyanide (for selected samples). Results of sample analyses are reported by the laboratory as either qualified or unqualified; various qualifier codes are used by the laboratory to denote specific information regarding the analytical results.

Trillium's validation was performed in conformance with the EPA Region I Laboratory Data Validation Functional Guidelines for Evaluating Inorganics Analyses (2/89 modification), as well as EPA's National Functional Guidelines for Inorganic Data Review, EPA 540/R-94/013 (2/94). Professional judgment was applied as necessary and appropriate.

The data validation process is intended to evaluate data on a technical basis rather than a contract compliance basis for chemical analyses conducted under the CLP. An initial assumption is that the data package is presented in accordance with the CLP requirements (or CLP-like, as in this case). It is also assumed that the data package represents the best efforts of the laboratory and has already been subjected to adequate and sufficient quality review prior to submission for validation.

During the validation process, laboratory data are verified against all available supporting documentation. Based on thefindings of the evaluation, qualifier codes may be added, deleted, or modified by the data validator. Validated results are, therefore, either qualified or unqualified. Unqualified results mean that the reported values may be used without reservation. Final validated resuhs are annotated with the following codes as defined by the Region I guidelines:

U - The material was analyzed for, but was not detected above the level of the associated value. The associated value is either the sample quantitation limit or the sample detection limit.

J - The associated numerical value is an estimated quantity.

R - The data are unusable. (Note: Analyte may or may not be present).

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UJ - The material was analyzed for, but was not detected. The associated value is an estimate and may be inaccurate or imprecise.

These codes are recorded on the Data Summary Form contained in Attachment A, as well as on the Duplicate Summary Fomi (Form VI) in Attachment B of this validation report to indicate qualilitaiions piaceu ua mc uaiti as a icsuii uFuic vaiiuitLioii ciiuii.

Two facts should be noted by all data users. First, the "R" qualifier means that the laboratory-reported value is unusable. In other words, due to significant quality control problems, the analysis is invalid and provides no information as to whether the analyte is present or not. Rejected values should not appear on data tables because they cannot be relied upon, even as a last resort. Second, no analyte concentration is guaranteed to be accurate even if all associated quality control is acceptable. Strict quality control conformance serves only to increase confidence in reported results; any analytical result will always contain some error.

The user is also cautioned that the validation effort is based on the raw data printouts as provided by the laboratory. Software manipulation cannot be routinely detected during validation; unless otherwise stated in the report, these kinds of issues are outside the scope of this review.

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I. Holding Times, Preservation and Sample Integrity

The duplicate soil sample was collected on October 25, 1994. All metals analyses were performed within the established holding times.

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data package; the measurements were correctly calculated and accurately reported.

H. Calibration

Initial and continuing calibration verification (ICV/CCV) standards were run at the required frequencies. Results for all ICV/CCV standards were correctly reported on the summary forms, and recoveries of all target analytes were within the applicable acceptance limits.

The raw data for the initial calibration blank and thefirst two standards for lead in the run sequence associated with all of the samples in this data set except J_MW-9B DUP were not included in the data package received for review; therefore, the acceptability of the cortelation coefficient could not be evaluated. It was assumed for validation purposes that the correlation coefficient was acceptable for lead in this analytical sequence, but the supporting data should be provided by the laboratory to confirm this assumption and to ensure that complete and accurate information is available for future reference.

Except as noted above, correlation coefficients of the initial calibrations for arsenic, lead, mercuiy, thalliimi, and selenium were greater than the 0.995 minimum acceptance limit with the exception of thallium (0.994) in the run sequence associated with J_H3-05, J_Tl-54, J_T2-57, J_T7­83, and J_T27-85. Lead determination for J_T25-82D was obtained from analysis by inductively coupled plasma (ICP).

Contract required detection limit (CRDL) standards were analyzed at the required frequencies and concentrations for all applicable analytes. However, the summary form (Form n Part 2), did not include the data for the CRDL standards for lead by ICP. The ICP raw data indicated that the CRDL standards for lead failed, but the laboratory did not report a true value for lead by ICP on the summary form, and the recovery could not be calculated by the validator. Due to the absence of the true value of the CRDL standard for lead and the ICP data indicating the standard was recovered at less than 80% of two times the CRDL (which would be the typical true value of the standard), the result for lead in J_T25-82D was qualified as estimated (J). Percent recoveries for all other CRDL standards were correctly calculated, accurately reported, and within acceptance limits.

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m . Blanks

Initial and continuing calibration blanks were prepared and analyzed at the proper frequency r M , , 1 . I i 1 1 1 ; 1 1 1 1 . , ' ' , • • ' ' ' • ' "

(Form ni) included in the data package.

No target analytes were detected in the calibration blanks at concentrations above the applicable CRDLs or below the negative CRDLs. However, response at concentrations greater than the applicable instrument detection limits (IDL) were observed in associated calibration blanks for aluminum (29.6 ug/L), iron (43.8 ^g/L), magnesium (21.8 ^g/L), and potassium (641.9 |ig/'L). Arsenic (-1.4 Mg/L), copper (-5.3 Mg/L), and thallium (-1.1 ^g/L) were detected in associated calibration blanks at values below the respective negative IDL. The results reported in parentheses reflect the highest absolute value reported for the respective analytes. Sample results were greater than two times the absolute value of the calibration blanks and no qualification was necessary.

Two soil-matrix preparation blanks (PB) were digested and analyzed with the soil samples in this data set. Calcium (4.8 mg'Kg), silver (1.246 mg/Kg), and zinc (0.914 mg/Kg) were detected in one or the other of the PBs. All sample results were greater than five times the concentration in the associated blank and no qualification was necessary.

Two water-matrix field-generated equipment blanks were submitted with the soil samples in this data set. Aluminum (34.5 \iglL), calcium (329 Mg/L), copper (13.8 \iglL), iron (66.0 ME-^),

magnesium (73.3 Mg/L), sodium (256 Mg/L), and zinc (42.5 Mg/L) were reported in Equipment Blank (11/03/94) and calcium (1410 Mg/L), copper (2.3 Mg/L), iron (30.7 Mg/L), magnesium (969 Mg/'L), potassium (3340 Mg/L), sodium (278 M&^), and zinc (17.4 Mg/L) were reported in Equipment Blank (J_MW-17). On the basis of equipment blank contamination, the result for potassium in J_T25-82D was qualified as less than the reported value (U).

rV. ICP Interference Check Sample

Percent recoveries (%R) for the interference check samples were correctly calculated and accurately reported. All recoveries were within the acceptance limits of 80 to 120 percent.

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V. Matrix Spike Sample Analysis

Sample J_T25-82 was prepared as a soil matrix spike. Percent recoveries of all spiked analytes were correctly calculated, accurately reported, and acceptable (75-125%) with the exceptions of antimony (69.4%) and thallium (61.6%), A post-digestion spike analysis was pciiumicu oa laib iuaipic iui a.auiauiiy, bui lac iccuvcij VMii duuvc lac aiaAunuia aci^cpianv^c iianl

(147%). On the basis of the unacceptably low recoveries in the matrix spike analysis, results for antimony and thallium in J_T25-82D were qualified as estimated (UJ).

VI. Duplicate Sample Analysis

A. Laboratory and Field Duplicates

Sample J_T25-82 was prepared as a soil-matrix laboratory duplicate and is being considered as afield duplicate in association with the samples in this data package. Paired results for all target analytes were within the applicable validation acceptance criteria (± 35% or + 2xCRDL). The "*" qualifiers appropriately applied by the laboratory to the lead results determined by GFAA to indicate unacceptable method-specified agreement between reported results were removed by the validator; the acceptance limits provided in the validation guidelines were applied.

VH. Laboratory Control Sample Analyses

Percent recoveries for the soil-matrix and water-matrix laboratory control samples were correctly calculated and accurately reported. Concentrations of all target analytes in the soil-matrix laboratory control samples were within the laboratoiy-established acceptance limits, as documented on Form VII,

Vin. Furnace Atomic Absorption QC

Post-digestion spike recoveries for the metals analyzed by graphite furnace atomic absorption (GFAA) spectrometry were within the quality control limits of 85 to 115 percent with the exceptions of arsenic in J_T25-82 (69% in the original analysis and 47.4% in the second analysis).

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Result for arsenic in J_T25-82 was determined by method of standard additions (MSA) and were not affected by the low post-digestion spike recoveries. The correlation coefficients for the MSA analyses were acceptable (greater than 0.995 in both cases).

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ICP serial dilution analyses was performed on J_T25-82. Percent difference (%D) values were less than the maximum acceptance limit of 15 percent for all target analytes in which the original concentration (in the undiluted sample) was greater than 50 times the instrument detection limit (IDL).

X. Detection Limits

Sample-specific IDLs were correctly calculated and reported for the duplicate sample, including necessary adjustments for sample size and percent solids content.

XI. Sample Result Verification

Sample results were cortectly calculated and reported, including necessary adjustments for sample size and percent solids content.

The validation guidelines specify that results for arsenic, thallium, selenium, and lead be qualified when these analytes are analyzed by ICP and the reported results are less thanfive times the IDL. Arsenic, thallium, selenium, and lead are t}'pically analyzed by graphite furnace atomic absorption so that lower IDLs can be achieved In this data set, arsenic, thallium, selenium, and lead in all samples except J_T25-82D were analyzed by GFAA. Lead determinations in J_T25-82D was performed by ICP and the reported result was greater than five times the ICP IDL (were > 5 x 17 = 85); therefore, no data were qualified on this basis.

Target analyte results for the duplicate sample were reported to four decimal places on Form VI; these values were rounded to reflect two decimal places, for the sake of consistency with the original sample analysis results and in accordance with the Statement of Work.

"B" qualifiers were appropriately applied by the laboratory to sample Form I results when concentrations of target analytes were less than the CRDL. As concentrations approach the IDL, the accuracy of the measurement decreases; values closer to the CRDL, however, are probably quite

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accurate. Since all results less than the CRDL and not otherwise qualified were also greater than two times the IDL, no additional qualifiers were applied on this basis and all laboratory-applied "B" qualifiers were removed by the validator.

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The COC record provided for review was accurately completed and included reference to the duplicate sample. Problems observed with the COC record and with the overall data presentation are discussed in the previously submitted validation report for SDG No. Z1265.

Xni. Overall Assessment

Based on the validation effort, results for inorganic analytes were qualified as follows:

• Due to the absence of the true value of the CRDL standard for lead and the ICP data indicating the standard was recovered at less than 80% of two times the CRDL (which would be the typical true value of the standard), the result for lead in J_T25­82D was qualified as estimated (J).

• Due to unacceptable matrix spike recoveries, results for antimony and thallium in J_T25-82D were qualified as estimated (UJ, J).

• Due to equipment blank contamination the result for potassium in J_T25-82D was qualified as less than the reported value (U).

All laboratory-applied "*" and "B" quahfiers were removed by the validator from the sample Form VI.

Problems with the chain of custody records and data presentation were discussed in the previously submitted validation report (6/13/96) for SDG No. Z1265 and are not repeated here.

This validation report addendum should be considered part of the data package for all fiiture distributions of the inorganics data.

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ATTACHMENT A

DATA SUMMARY FORM Laboratory Sample Delivery Group No. Z1265 (Addendum)

Metals and Amenable Cyanide in Water and Soil

DATA SUMMARY FORM: INORGANICS (ADDENDUM 8/7/96) SOIL SAMPLES

(mg/Kg)

Site Name: Pine Strcit Superfund Site Sampling Dates: October 25, 1994

Laboratory SDG No. .CI265 (Addendum) Trillium Project No. 96454 (ADZ 12651)

J_T25- ;2D

12650 4D

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Sample Ideniificalion

Sample No.

% Solids

cmn.

Aluminum

Antimony

Arsenic

Barium

Beryllium

Cadmium

Calcium

Chromium

Cobalt

Copper

Iron

Lead

Magnesium

Manganese

Mercju-y

Nickel

Potassium

Selenium

Silver

Sodium

Thallium

Vanadium

Zinc

Cyanide, amen.

SW-846 Methods Pi ige 1

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ATTACHMENT B

DUPLICATE SUMMARY FORM (Form VI) Laboratory Sample Delivery Group No. Z1265 (Addendum)

Metals and Amenable Cyanide in Water and Soil

li U.S. EPA CLP 578 EPA SAMPLE NO.

DUPLICATES

J T25 -82D Lab Name: TEA Contract

Lab Code: TEA Case No. SAS N o . : SDG N o . : Z1265

Matrix: SOIL Level (low/med): LOW

Solids for Sample: 42.6 Solids for Duplicate: 42.6

Concentration Units (ug/L or mg/kg dry weight): MG/KG

C o n t r o l A n a l y t e L i m i t S a m p l e (S) . C D u p l i c a t e (D) C RPD Q M

Aluminum A n t i m o n y

1 1 4 5 5 . 8 6 8 5 1 7 . 8 4 0 4 U

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5 . 4 P P

A r s e n i c 4 . 6 1 3 . 8 0 2 8 12 .1? t^^ 1 3 . 0 F B a r i u m 9 3 . 8 1 5 1 . 9 2 4 9 140.^-^44 7 . 9 P B e r y l l i u m 0 . 4 6 9 5 U -fr 2 0 0 . 0 P Cadmium 2 . 3 6 . 5 5 8 7 6.73r89 2 . 4 P C a l c i u m Chromium

2 0 4 6 2 . 4 4 1 3 9 2 . 3 5 2 1

/ t^OO ± ' J u l U . J z U u 4 . 2 6 . 4

P P

C o b a l t 1 3 . 2 1 6 0 B /3.*^ 3 r 3 . 3 D ^ B- 1 .3 P C o p p e r 2 4 3 . 5 5 4 0 2 3 5 . 4 ^ ± 5 3 . 4 P I r o n L e a d

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P F

Magnes ium M a n g a n e s e

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5 . 0 5 . 7

P P

M e r c u r y 0 . 0 0 . 7 5 6 3 0 . 7 0 ̂ 7 . 3 CV N i c k e l 1 8 . 7 4 2 . 4 3 1 9 4 2 . 2 0 ^ ^ 0 . 5 P P o t a s s i u m 1 0 1 4 . 2 7 2 3 B 9 0 5 . 2 ^ e i ^ /7 1 1 . 4 P S e l e n i u m 0 . 9 8 5 9 B 0.75ar2 -«- 2 7 . 0 F S i l v e r 9 0 . 6 5 2 6 0 . 7 P Sodium 7 6 5 . 7 7 4 6 B 7 5 e 1D7.7AG-5 -B- 1 .0 P T h a l l i u m 0 .5634 B ^p.V7 0 . 4696 U >r 2 0 0 . 0 F Vanad ium 2 3 . 4 4 5 . 4 4 1 3 V .̂̂ U 42.S96-2 6 . 5 P Z i n c 8 6 0 . 9 8 5 9 2 . 9 P C y a n i d e ^R

FORM VI IN ILM03.0