URS collected 603 incremental sediment samples between September 28, 2009 and October 22, 2009 at the Boise St. Helens Pulp and Paper Mill site in St. Helens, Oregon as part of the Remedial Investigation (RI). Incremental samples were composited into 24 primary sediment samples and two duplicate sediment samples. One rinsate sample was also submitted for laboratory analysis. Samples were collected and composited according to the URS Field Sampling Plan (FSP) for the Remedial Investigation, Ecological Risk Assessment, and Human Health Risk Assessment (URS, 2009a). Samples were submitted to Columbia Analytical Services, Inc. (CAS) located in Kelso, Washington and analyzed for one or more of the following parameters in general accordance with the methods indicated. The polychlorinated Dibenzo-p-dioxins (PCDDs)/Polychlorinated Dibenzofurans (PCDF) analysis was performed by Axys Analytical of Sidney, BC, Canada. In addition, sediment bioassays (10-day amphipod (Hyalella azteca) survival test and midge (Chironomus dilutus) survival and growth tests) were performed on seven sediment samples by Newfield Northwest Laboratory of Port Gamble, Washington. Data review was not required for these tests.

¹Total metals list: As, Sb, Cd, Hg, Pb, Se, and Zn

The analytical results for all samples were subjected to a limited data validation. This validation includes review of the data for compliance with the analytical methods and the project-specific PARCC (precision, accuracy, representativeness, completeness, and comparability) parameters. Specifically, the following items were reviewed in each laboratory report submitted: chain-of-custody records, proper sample preservation and handling procedures, laboratory case narratives, holding times, quantitation limits, field/method blank analyses, surrogate recoveries (labeled internal standards), laboratory control sample recoveries (ongoing precision and recovery), matrix spike (MS) recoveries, laboratory duplicate results, field duplicate results, data completeness and format, data qualifiers assigned by the laboratory, and verification of reported data in electronic data deliverable with the hard copy deliverable. For dioxin laboratory reports additional items reviewed included instrument performance checks (mass calibration and mass spectrometer resolution; chromatographic resolution and instrument stability), cleanup standard recoveries, identification criteria, and second column confirmation (2,3,7,8-TCDF only). The data review process followed the procedures in the URS Quality Assurance Project Plan (QAPP) for the Remedial Investigation, Ecological Risk Assessment, and Human Health Risk Assessment (URS, 2009b) and guidance from the EPA’s Contract Laboratory Program National Functional Guidelines (EPA NFGs) for Organic Data Review (USEPA, June 2008), EPA NFGs for Inorganic Data Review (USEPA, October 2004), EPA NFGs for Chlorinated Dibenz-p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDFs) (USEPA, September 2005).

A summary of qualifiers assigned to results in this investigation is included in Table 1. For ease of reference between the data review and other Remedial Investigation documents the samples are represented in Table 1 by their URS and laboratory IDs. Qualifiers that may be assigned to the results of this investigation include the following:

•  U - The analyte was analyzed for, but was not detected above the reported sample quantitation limit.

•  J - The analyte was positively identified; the associated numerical value is the approximate concentration of the analyte in the sample.

•  UJ - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approximate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample.

•  R - The sample results are rejected due to serious deficiencies in the ability to analyze the sample and meet quality control criteria. The presence or absence of the analyte cannot be verified.

•  DNR – Do Not Report. Multiple results from different analytical dates and/or dilutions. Value from another analysis should be used.

Final sample results and qualifiers are presented in the analytical tables in the Remedial Investigation Report.

REPRESENTATIVENESS

Chain-of-Custody and Holding Times

The chain-of-custody (COC) forms indicate that samples were maintained under COC and forms were signed upon release and receipt. All coolers were received by the laboratory at temperatures below 6°C. Some minor discrepancies between sample labels and the COC were noted upon sample receipt at the laboratories. In a few instances CAS noted sample containers on the COC were not included in a cooler shipment, these containers were received in subsequent shipments.

All samples were analyzed within the technical and contracted holding time, with the following exceptions:

•  The total sulfide analysis of sample M-2-D2 was performed past the recommended hold time. The total sulfide sample result for M-2-D2 was qualified as estimated and flagged ‘J’.

Case Narrative

CAS

All items discussed in the CAS case narratives are discussed in the following sections.

Axys (PCDDs/PCDFs)

Sample results are reported by Axys on a dry-weight basis. Any modifications made to Method 1613B are summarized in Axys analytical reports. The Axys case narrative for sample group DPWG31470 indicates that the original ongoing precision and recovery extract analyzed with the samples in batch WG31264 went dry during the extraction procedure and was lost. A spiked blank was prepared from hexane after the extraction and analyzed with the sample batch. The method blank associated with sample group DPWG31309 required reanalysis to be analyzed alongside the sample RB-1, blank results are reported from the reanalysis and the sample ID was flagged with an ‘i’.

Review of Blanks

Method Blanks

Method blanks were used to check for laboratory contamination and instrument bias. The laboratory analyzed at least one method blank for each analysis and for each batch, per method requirements. Qualification of samples due to method blank contamination followed guidelines set forth in the EPA NFGs. Target compounds detected in the method blanks but reported as not detected in the associated samples were not qualified.

CAS

Target compounds were detected in the method blanks for PAH analyses as follows:

•  Naphthalene, fluoranthene, pyrene, chrysene, and benzo(b)fluoranthene were detected in the method blank associated with batch KWG0910535 at concentrations between the MDL and MRL. All associated sample results were greater than MRL, and all analytes were detected at concentrations significantly greater than that found in the method blank; therefore, qualification of the results was not necessary.

•  Benz(a)anthracene and benzo(b)fluoranthene were detected in the method blank associated with analysis of RB-1 at concentrations between the MDL and MRL. The associated detections, also between the MDL and MRL for RB-1 were qualified as non-detect at the MRL.

Axys (PCDDs/PCDFs)

For dioxin/furan analyses in this project, sample results less than 10x the method blank concentration and between the method detection limit (MDL) and method-reporting limit (MRL) were flagged as non-detect (U) at the reported concentration. Target compounds detected in the method blanks but reported as not detected in the associated samples were not qualified. Method blank results that were qualified as estimated maximum potential concentration and flagged ‘K’ were not considered appropriate for qualifying project samples. Target compounds were detected in the method blanks for dioxin/furan analyses as follows:

•  1,2,3,4,6,7,8-HPCDD was detected in the sediment method blank WG28997-101i associated with the analysis of RB-1. The associated sample result in RB-1 was qualified as non-detect and flagged ‘U’ at the reported concentration.

•  OCDD was detected in the dioxin and furan method blank at a concentration of 0.127 picograms per gram. This concentration is less than three times the detection limit which is allowed for OCDD and OCDF method blank detections. Additionally, the OCDD concentrations in all associated project samples were greater than ten times the method blank concentration. Therefore, no results were qualified based upon the blank detection.

Equipment Rinsate Blank

One equipment rinsate blank, RB-1, was collected on October 22, 2009 as part of the RI sampling event. The rinsate sample was analyzed for dioxin/furans, PAHs, PCBs, and total metals. Several target analytes were detected in the equipment rinsate; however, all associated sample detections were either previously qualified or the sample concentrations were significantly greater equipment rinsate concentrations. No data were qualified based on the equipment rinsate results.

ACCURACY

Instrument Calibration

CAS

CAS analyzed initial calibration samples (ICALs) and continuing calibration samples (CCALs) at the appropriate frequency and concentrations required by the analytical method. The ICAL and CCAL analyses met the acceptance criteria with the following exceptions.

The case narrative for CAS report K0909140 noted two exceptions for the PAH analyses, including:

•  The control criterion for pyrene in the Continuing Calibration Verification (CCV) sequence 1116F002.D was exceeded. The samples analyzed in this sequence were dilutions for analytes other than pyrene, therefore, data qualification was not necessary.

•  The upper laboratory control criterion for 2,3,5-Trimethylnaphthalene was exceeded in the CCV sequences 1116F002.D and 1116F033.D. An incorrect PAH list was assigned to this work order and this analyte was not included, therefore, the laboratory did not take any corrective action. The CCV was within the NFG criterion; therefore, no qualification of the data was necessary.

The case narrative for CAS report K0910296 noted three exceptions for the PAH analyses of the rinsate blank sample, RB-1, including:

•  The laboratory control criterion for 2,3,5-Trimenthylnaphthalene was exceeded during the CCV. This analyte was not detected in the samples; therefore, the potential high bias associated with this exceedance did not affect data quality.

Exceptions noted in the CAS report K0909140 case narrative noted one exception for the PCB analyses, including:

•  The primary column criterion for Aroclor 1260 was exceeded in the CCV sequence 1114F029. The laboratory used the alternative evaluation (using an average of all analytes in the verification standard) specified in section 7.6.2.3 of the method. The alternative evaluation met the method criteria, data qualification was not necessary.

The case narrative for CAS report K0910296 noted three exceptions for the PCB Aroclor analyses of the rinsate blank sample, RB-1, including:

•  The primary column evaluation criteria for Aroclor 1016 in the analysis of CAL 9019 were not met during the initial calibration verification, results were reported from the acceptable column. As the all results for Aroclor 1016 were reported from the confirmation column and with the exceptions described in this data review report met the QAPP acceptance crtiaria, data quality was not affected.

•  The primary column evaluation criteria were not met on the confirmation column (DB-35MS) for the CCV, results were reported from the column with the acceptable CCV (DB-XLB). As the all results were reported from the confirmation column and with the expcetions described in this data review report met the QAPP acceptance criteria, data quality was not affected.

Axys (PCDDs/PCDFs)

Axys analyzed ICALs and CCALs at the appropriate frequency and concentrations required by the analytical method. The ICAL and CCAL analyses met the acceptance criteria defined in Method 1613B.

Surrogate Recovery Review

Each sample analyzed for organic compounds was spiked with surrogates (system monitoring compounds) or labeled compounds (dioxin/furan analyses only). Surrogate recoveries are a measure of accuracy for the overall analysis of each individual sample.

CAS

Surrogate recoveries were acceptable for PAH analyses with the following exceptions:

•  The laboratory control criterion was exceeded for surrogate Terphenyl-d14 in sample M-2-C. The laboratory attributed this to matrix interference, non-target background analytes prevented adequate resolution of the surrogate and accurate quantitation of the analyte was not possible. The remaining surrogate recoveries were within the laboratory control criteria, no data were qualified on the basis of surrogate recoveries.

•  The laboratory control criteria were exceeded for surrogates Fluorene-d10 and Fluoranthene-d10 in the analysis of sample RB-1. Target analytes were not detected in the sample at concentrations greater than the MRL; therefore, the associated sample detections were already qualified as estimated and flagged ‘J’. Further qualification of the data was not necessary.

Axys (PCDDs/PCDFs)

All labeled compounds recoveries were acceptable.

Laboratory Control Samples and Ongoing Precision and Recovery

Laboratory control samples (LCS) are used to monitor the laboratory’s day-to-day performance of routine analytical methods, independent of matrix effects and to assess accuracy for the target compounds.

CAS

CAS analyzed at least one LCS for each applicable analysis and for each batch per method requirements. LCS analyses were within laboratory control limits.

Axys (PCDDs/PCDFs)

Axys analyzed ongoing precision and recovery samples (OPRs) at the appropriate frequency and concentrations required by the analytical method. The OPR analyses met the acceptance criteria defined in Method 1613B.

Matrix Spike/Matrix Spike Duplicate Review

Matrix spike/matrix spike duplicate (MS/MSD) samples are analyzed to assess the ability of the laboratory to recover the target compounds from the sample matrix.

CAS

CAS analyzed at least one MS/MSD (or one MS and one sample duplicate for metals analyses) for each applicable analysis and for each batch per method requirements. Additional volume from samples M-2-A and M-1-D was used for MS/MSD analyses as requested. Volume from samples M2-D-2, M-3-A and B-1-C was also used to perform additional MS/MSD analyses in some methods.

MS/MSD recoveries were acceptable for PAH analyses with the following exceptions:

•  Fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene, dibenzo(a,h)anthracene, and benzo(g,h,i)perylene recoveries in the MS/MSD analysis performed on sample M-2-A (batch KWG0910535) were outside the laboratory control limits. The LCS/LCSD was in control indicating acceptable accuracy was attained with respect to the analytical method; associated results in the parent sample were qualified as estimated and flagged ‘J’.

MS/MSD recoveries were acceptable for PCB analyses with the following exceptions:

•  The MS recoveries for Aroclor 1016 exceeded the laboratory control criteria. The chromatogram indicated the presence of Aroclor 1242, preventing accurate quantitation. Complete resolution of the two Aroclors was not possible and the Aroclor 1016 result is biased high. Aroclor 1016 was not detected in the associated rinsate blank sample; therefore, qualification of the data was not necessary.

MS/MSD recoveries were acceptable for ammonia analyses with the following exceptions:

•  The relative percent difference (RPD) of the MS/MSD recoveries in the analysis of duplicate sample M-2-D2 exceeded the QAPP limit of 32% at 78%. The ammonia sample results for M-2-D2 and the associated parent sample M-2-D were qualified as estimated and flagged ‘J’.

Axys (PCDDs/PCDFs)

The dioxin/furans analytical method does not include MS/MSDs, a laboratory duplicate prepared from sample M-2-A was prepared and analyzed instead.

PRECISION

Second Column Confirmation

CAS

Second column confirmation was performed for all PCB analyses. The laboratory noted that the confirmation comparison criterion of 40% was exceeded for Aroclor 1254 in the analysis of samples M-1-C and M-3-C and flagged the sample results ‘P’. The laboratory reported the lower of the two values because of an apparent interference on the alternate column that produced the higher value. The Aroclor 1254 results for samples M-1-C and M-3-C were qualified as estimated and flagged ‘J’.

Axys (PCDDs/PCDFs)

Second column confirmation was performed on all samples when 2,3,7,8-Tetrachlorodibenzofuran was detected. The 2,3,7,8-TCDF result from the confirmation analysis is the more accurate result and should be selected for reporting for all samples. All 2,3,7,8-TCDF results from the initial DB-5 column analyses have been qualified do not report and flagged ‘DNR’ because a more accurate value is available. 2,3,7,8-TCDF results from the DB-225 confirmation column analyses are reported unqualified and used in the TEQ calculations by Axys.

Duplicate Review

Two sediment sample duplicates were generated from composite samples M-5-B and M-2-D, sample duplicates were identified as M-5-B2 and M-2-D2, respectively. The samples were analyzed to assess the precision of the homogenization technique and to provide checks on laboratory procedures. In addition, the laboratory performed in-house duplicate analyses for many samples. Laboratory duplicate precision was acceptable for all laboratory duplicates performed. The RPD for the sediment sample duplicate was calculated when sample results were greater than 5x the reporting limit. Sediment sample duplicate precision was within the QAPP limits.

COMPARABILITY

Compound Identification

Axys qualified several congener results “K”, which represent estimated maximum possible concentrations (EMPC). EMPCs represent congener peaks that were detected, but did not meet identification criteria. Therefore, the congener results associated with the EMPCs (i.e., lab flag “K”) should be considered false-positive values and were qualified “U” at the reported concentration. It should be noted that EMPC results were not included in Toxicity Equivalent (TEQ) calculations performed and reported by Axys.

Reporting Limits

The sensitivity (i.e., reporting limits) of the analytical methods is driven by the project specific DQOs. Occasionally analyte RLs were above levels specified in the QAPP. The laboratory reported all detections between the MDL and RL and qualified those results as estimated ‘J’.

Elevated reporting limits for Aroclor 1254 and 1260 exist for some samples due to the presence of non-target background components (i.e. matrix interference), which prevented adequate resolution of the target compounds at the RL. The laboratory flagged these results with an ‘i’.

CAS combines results for various dilutions on a single report form for each sample. Dilution factors for individual analytes are listed adjacent to the corresponding analyte and are designated “D”. The samples that required dilution due to elevated concentrations did not meet the requested reporting limits; however, data are not qualified based on high analyte concentrations that require dilution.

COMPLETENESS

The laboratory reported all requested analyses and the deliverable data reports were complete. Completeness is defined as the percentage of usable data out of the total amount of data generated. The project completeness goal is 100 percent. Some data were qualified as estimated (J) and some as non-detect (U). A summary of qualifiers can be found in Table 1. Completeness for the supplemental sediment investigation is 100%.

Table 1

SAMPLE QUALIFICATION SUMMARY

REFERENCES

USEPA, April 1998. Test Methods for Evaluation of Solid Waste, Physical/Chemical Methods, SW-846, 3rd Edition, Rev. 5, EPA, Office of Solid Waste, Washington, D.C.

USEPA, October 2004. EPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review.

USEPA, September 2005. EPA Contract Laboratory Program National Functional Guidelines for Organics Data Review.

USEPA, June 2008. EPA Analytical Services Branch National Functional Guidelines for Chlorinated Dibenzo-p-Dioxins (CDDs) and Chlorinated Dibenzofurans (CDF) Data Review.

URS, 2009a. Field Sampling Plan for the Remedial Investigation, Ecological Risk Assessment, and Human Health Risk Assessment. September 21.

URS, 2009b. Quality Assurance Project Plan for the Remedial Investigation, Ecological Risk Assessment, and Human Health Risk Assessment. September 21.