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February 1997
{&)
%>. r<^
PRO^
For
U.S. Environmental Protection Agency
Region II
and
U.S. Army Corps of Engineers
Kansas Citv District
V
Volume 2C
Book 3 of 3
TAMS Consultants, Inc.
The CADMUS Group, Inc.
Gradient Corporation
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February 1997
*1 pro^
For
U.S. Environmental Protection Agency
Region II
and
U.S. Army Corps of Engineers
Kansas City District
Volume 2C
Book 3 of 3
TAMS Consultants, Inc.
The CADMUS Group, Inc.
Gradient Corporation
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Table of Contents
Page
Volume 2C (Book 1 of 3)
Table of Contents i
LIST OF TABLES v
LIST OF FIGURES viii
LIST OF PLATES xv
Executive Summary E-l
Chapter 1
INTRODUCTION 1-1
1.1 Purpose of Report 1-1
1.2 Report Format and Organization 1-2
1.3 Technical Approach of the Data Evaluation and Interpretation Report 1-2
1.4 Review of the Phase 2 Investigations 1-5
1.4.1 Review of PCB Sources 1-5
1.4.2 Water Column Transport Investigation 1-6
1.4.3 Assessment of Sediment PCB Inventory and Fate 1-9
1.4.4 Analytical Chemistry Program 1-14
Chapter 2
PCB SOURCES TO THE UPPER AND LOWER HUDSON RIVER 2-1
2.1 Background 2-1
2.2 Upper Hudson River Sources . 2-2
2.2.1 NYSDEC Registered Inactive Hazardous Waste Disposal Sites ... 2-2
2.2.2 Remnant Deposits 2-18
2.2.3 Dredge Spoil Sites 2-21
2.2.4 Other Upper Hudson Sources 2-22
2.3 Lower Hudson River Sources 2-22
2.3.1 Review of Phase 1 Analysis 2-23
2.3.2 Sampling of Point Sources in New York/New Jersey (NY/NJ)
Harbor 2-23
2.3.3 Other Downstream External Sources 2-28
Chapter 3
WATER COLUMN PCB FATE AND TRANSPORT IN THE HUDSON RIVER 3-1
3.1 PCB Equilibrium Partitioning 3-3
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Table of Contents (cont 'd)
3.1.1 Two-Phase Models of Equilibrium Partitioning 3-4
3.1.2 Three-Phase Models of Equilibrium Partitioning 3-24
3.1.3 Sediment Equilibrium Partition Coefficients 3-31
3.1.4 Summary 3-38
3.2 Water Column Mass Loading 3-39
3.2.1 Phase 2 Water and Sediment Characterization 3-40
3.2.2 Flow Estimation 3-41
3.2.3 Fate Mechanisms 3-46
3.2.4 Conceptual Model of PCB Transport in the Upper Hudson 3-58
3.2.5 River Characterization 3-60
3.2.6 Mass Load Assessment 3-68
3.2.7 Source Loading Quantitation 3-86
3.3 Historical Water Column Transport of PCBs 3-91
3.3.1 Establishing Sediment Core Chronologies 3-92
3.3.2 Surface Sediment Characterization 3-105
3.3.3 Water Column Transport of PCBs Shown by Sediment Deposited
After 1975 3-107
3.3.4 Estimation of the PCB Load and Concentration across the
Thompson Island Pool based on GE Capillary Column Data . . . . 3-124
3.3.5 Estimated Historical Water Column Loadings Based on USGS
Measurements 3-131
3.3.6 Conclusions Concerning Historical Water Column Transport .. 3-136
3.4 Integration of Water Column Monitoring Results 3-140
3.4.1 Monitoring Techniques and PCB Equilibrium 3-141
3.4.2 Loadings Upstream of the Thompson Island Pool 3-143
3.4.3 Loading from the Thompson Island Pool during 1993 3-146
3.4.4 Loading at the Thompson Island Dam - 1991 to 1996 3-150
3.4.5 PCB Loadings to Waterford 3-155
3.4.6 PCB Loadings to the Lower Hudson 3-160
3.5 Integration of PCB Loadings to Lower Hudson River and New York/New
Jersey Harbor 3-164
3.5.1 Review of Lower Hudson PCB Mathematical Model 3-164
3.5.2 Estimate of 1993 PCB Loading from the Upper Hudson River 3-166
3.5.3 Revised PCB Loading Estimates 3-167
3.6 Water Column Conclusion Summary 3-170
Chapter 4
INVENTORY AND FATE OF PCBs IN THE SEDIMENT OF THE HUDSON
RIVER 4-1
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Table of Contents (cont'd)
4.1 Characterization of Upper Hudson Sediments by Acoustic Techniques ... 4-2
4.1.1 Geophysical Data Collection and Interpretation Techniques 4-6
4.1.2 Correlation of Sonar Image Data and Sediment Characteristics .. 4-15
4.1.3 Delineation of PCB-Bearing and Erodible Sediments 4-21
4.2 Geostatistical Analysis of PCB Mass in the Thompson Island Pool, 1984 4-25
4.2.1 Data Preparation for PCB Mass Estimation 4-26
4.2.2 Geostatistical Techniques for PCB Mass Estimation 4-32
4.2.3 Polygonal Declustering Estimate of Total PCB Mass 4-33
4.2.4 Geostatistical Analysis of Total PCB Mass 4-34
4.2.5 Kriging Total PCB Mass 4-38
4.2.6 Kriged Total Mass Estimate 4-41
4.2.7 Surface Sediment PCB Concentrations 4-42
4.2.8 Summary 4-48
4.3 PCB Fate in Sediments of the Hudson River 4-49
4.3.1 Anaerobic Dechlorination and Aerobic Degradation 4-50
4.3.2 Anaerobic Dechlorination as Documented in Phase 2 High-
Resolution Sediment Cores 4-52
4.4 Implication of the PCB Fate in the Sediments for Water Column Transport 4-71
4.5 Summary and Conclusions 4-83
REFERENCES R-l
Volume 2C (Book 2 of 3)
Tables
Figures
Plates
Volume 2C (Book 3 of 3)
Appendix A
DATA USABILITY REPORT FOR PCB CONGENERS HIGH RESOLUTION
SEDIMENT CORING STUDY
A.l Introduction A-l
A.2 Field Sampling Program A-2
A.3 Analytical Chemistry Program A-3
A.3.1 Laboratory Selection and Oversight A-3
A.3.2 Analytical Protocols for PCB Congeners A-4
A.4 Data Validation A-7
A.5 Data Usability A-10
A.5.1 Approach A-10
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Table of Contents (cont'd)
A.5.2 Usability - General Issues A-11
A.5.3 Usability - Accuracy, Precision, Representativeness and Sensitivity A-16
A.5.4 Usability - Principal Congeners A-25
Appendix B
DATA USABILITY REPORT FOR PCB CONGENERS WATER COLUMN
MONITORING PROGRAM
B.l Introduction B-l
B.2 Field Sampling Program B-2
B.3 Analytical Chemistry Program B-3
B.3.1 Laboratory Selection and Oversight B-3
B.3.2 Analytical Protocols for PCB Congeners B-4
B.4 Data Validation B-8
B.5 Data Usability B-10
B.5.1 Approach B-10
B.5.2 Usability - General Issues B-ll
B.5.3 Usability - Accuracy, Precision. Representativeness and Sensitivity B-16
B.5.4 Usability - Principal Congeners B-25
B.6 Conclusions B-28
Appendix C
DATA USABILITY REPORT FOR NON-PCB CHEMICAL AND PHYSICAL DATA
C.l Introduction C-l
C.2 High Resolution Coring Study and Confirmatory Sediment Sample Data .. C-4
C.2.1 Grain Size Distribution Data C-5
C.2.2 Total Organic Nitrogen (TON) Data C-10
C.2.3 Total Carbon/Total Nitrogen (TC/TN) Data C-13
C.2.4 Total Inorganic Carbon (TIC) Data C-l6
C.2.5 Calculated Total Organic Carbon (TOC) Data C-l8
C.2.6 Weight-Loss-on-Ignition Data C-18
C.2.7 Radionuclide Data C-19
C.2.8 Percent Solids C-22
C.2.9 Field Measurements C-22
C.3 Water Column Monitoring Program and Flow-Averaged Sampling Programs
7. . C-23
C.3.1 Dissolved Organic Carbon (DOC) Data C-24
C.3.2 Total Suspended Solids and Weight-Loss-on-Ignition (TSS/WLOI) Data
r 7 C-27
C.3.3 Chlorophyll-a C-33
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List of Tables
Tables Title
1-1 Water Column Transect and Flow-Averaged Sampling Stations
1 -2 Water Column Transect and Flow-Averaged Sampling Events
1-3 High-Resolution Sediment Core Sample Locations
1 -4 Phase 2 Target and Non-target PCB Congeners Used in Analyses (3 Pages)
2-1 Summary of Niagara Mohawk Power Corp. RI Data - Queensbury Site
2-2 Phase 1 Estimates of PCB Loads to the Lower Hudson
2-3 Summary of Results of L'SEPA Study of PCBs in NY/NJ Point Sources
2-4 Estimates of PCB Loading from Treated Sewage Effluent
3-1 Stepwise Multiple Regression for log(KPa) of Key PCB Congeners Showing Sign of
Regression Coefficients Determined to be Significant at the 95 Percent Level
3-2 Stepwise Multiple Regression for log(KPOCa) of Key PCB Congeners Showing Sign of
Regression Coefficients Determined to be Significant at the 95 Percent Level
3-3 Correlation Coefficient Matrix for Explanatory Variables Evaluated for Analysis of PCB
Partition Coefficients (KP0C a)
3-4 Temperature Slope Factors for Capillary Column Gas Chromatogram Peaks Associated with
Key PCB Congeners
3-5 Relative Performance of Distribution Coefficient Formulations: Squared Error in Predicting
Particulate-Phase PCB Congener Concentration from Dissolved-Phased Concentration
3-6a In Situ KPOCa Estimates for Hudson River PCB Congeners Corrected to 20°C (3 pages)
3-6b In Situ log (KPOCa) Estimates for Hudson River PCB Congeners Corrected to 20°C (3 pages)
3-7 Three-Phase PCB Partition Coefficient Estimates Using Regression Mehtod
3-8 Three-Phase PCB Partition Coefficient Estimates Using Optimization with Temperature
Correction to 20°C
3-9 A Comparison of Two-Phase Sediment log (KOC a) and log (KPOC a) Estimates for Hudson
River PCB Congeners
3-10a Three-Phase Partition Coefficient Estimates for PCBs in Sediment of the Freshwater
Portion of the Hudson River
3-10b Predicted Relative Concentration of PCB Congeners in Sediment Porewater for Various
Assumptions Regarding Three-Phase PCB Congener Partition Coefficients
3-11 Models for Predicting Flow at Stillwater and Waterford
3-12 Calculated Flows at Stillwater and Waterford for January 1993 to September 1993 (7
pages)
3-13 Summary of Prediction Uncertainty for Stillwater Flow Models
3-14 Summary of Prediction Uncertainty for Waterford Flow Models
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List of Tables (cont'd)
3-15 Summary of River Segment Characteristics
3-16 Comparison of Water Column Mass Transport at Rogers Island, Thompson Island Dam
and Waterford
3-17 Application of Dating Criteria to High Resolution Cores (2 pages)
3-18 Estimated Sedimentation Rates for Dated Cores
3-19 Comparison of Total PCB Concentrations of Suspended Matter and Surficial Sediment
Deposited after 1990
3-20 Dated Sediment Cores Selected for Historical Water Column PCB Transport Analysis
3-21 Cumulative Loading Across the Thompson Island Pool by Homologue Group from GE
Data April 1991 through February 1996
3-22 Breakpoint of Flow Strata (cfs) Used for Total PCB Load Estimation in the Upper Hudson
River
3-23 Estimated Yearly Total PCB Loads (kg/yr) in the Upper Hudson Based on USGS
Monitoring
3-24 Comparison of Calculated Water Column Loads at Rogers Island and Thompson Island
Dam for Phase 2, GE and USGS Data
3-25 Total PCB Loading Contribution Relative to River Mile 143.5 Near Albany Based on
Dated Sediment Cores for 1991 to 1992
4-1 Results of Linear Regression Study - Grain Size Parameter vs Image DN
4-2 GC-Mass Spectrometer Split-Sample Results for Total PCB Concentrations and Point
Values Selected to Represent Reported Ranges for the 1984 Thompson Island Pool
Sediment Survey
4-3 Sample Statistics for Thompson Island Pool PCB Mass Concentration Estimates, 1984
Sediment Survey
4-4 Subreach Variogram Models3 for Natural Log of PCB Mass Concentration, 1984
Thompson Island Pool Sediment Survey
4-5 Total PCB Mass Concentration in the Thompson Island Pool, 1984: Cross Validation
Comparison of Lognormal Kriging Results and Observed Values
4-6 Exponential Variogram Models for Natural Log of Surface Concentrations in the 1984
Sediment Survey of the Thompson Island Pool
4-7 Summary Results for Kriged Surface Layer Concentration of Total PCBs by Subreach,
1984 Sediment Survey of the Thompson Island Pool
4-8 Dechlorination of Aroclor 1242 (3 pages)
vi
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List of Tables (cont'd)
4-9 Molar Dechlorination Product Ratio and Mean Molecular Weight of Various Aroclor
Mixtures
4-10 Representation of Three Aroclor Mixtures by the Phase 2 Analytical Procedure
4-11 Statistics for High Resolution Sediment Core Results Molar Dechlorination Product and
Change in Molecular Weight
vii
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List of Figures
Figures Title
1-1 PCB Structure
2-1 Fish PCB Results - Niagara Mohawk Queensbury RI Report
2-2 General Electric Company - Hudson Falls Plant and Vicinity
2-3 GE Fort Edward Outfall Discharge Monitoring Report Data
2-4 NY/NJ POTW Influent PCB Data - Congener Basis
2-5 NY/NJ POTW Influent PCB Data - Homologue Basis
2-6 NY/NJ POTW Effluent PCB Data - Congener Basis
2-7 NY/NJ POTW Effluent PCB Data - Homologue Basis
2-8 NY/NJ River Water PCB Data - Congener Basis
2-9 NY/NJ River Water PCB Data - Homologue Basis
3-1 Total Suspended Solids Concentration [TSS] Upper Hudson River Water Column
T ransects
3-2 Particulate Organic Carbon Concentration [POC], Upper Hudson River Water Column
Transects
3-3 Two-Phase Partition Coefficients to Particulate Matter (KPa) for Water Column Transects
3-4 Two-Phase Partition Coefficients to Particulate Organic Carbon (KpoCa) for Water Column
Transects
3-5 Observed vs. Theoretical Partitioning to Organic Carbon for PCB Congeners in the
Freshwater Hudson
3-6 KPOC a Estimates vs. Water Temperature for BZ#52, Hudson River Water Column Transect
Samples
3-7 Variation in log KP a by Transect for BZ#44
3-8 Variation in log KP0C a by Transect for BZ#44
3-9 Variation in log KP a by River Mile for BZ#44
3-10 Variation in log KP0C a by River Mile for BZ#44
3-11 Temperature Correction Slope Estimates for PCB Capillary Column Peaks
3-12 Equilibration KPa Estimates for PCB Partitioning in Hudson River Transect Samples
3-13 KPa Estimates for Hudson River Transect 1
3-14 KPa Estimates for Hudson River Transect 4
3-15 KPa Estimates for Hudson River Transect 6
3-16 Percent Deviations in log KP0C.a Estimates for PCB Congeners by River Mile
3-17 Prediction of Particulate-Phase PCB Congener Concentration Using KPa with Temperature
Correction
3-18 Prediction of Particulate-Phase PCB Congener Concentration Using KP0Ca with
Temperature Correction
3-19 Median Values of log KPOC 2 Corrected to 20°C
viii
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List of Figures (cont'd)
3-20 PCB Congener KP0Ca Estimates for Hudson River Flow-Averaged vs. Transect Samples
3-21 Relationship of Dissolved and Particulate Organic Carbon Concentrations in Upper
Hudson Transect Samples
3-22 Estimated Average Percent Distribution of PCB Congeners Among Dissolved, POC and
DOC Phases in Hudson River Water Column Transect Data
3-23 Comparison of USGS Measured Flows at Fort Edward, Stillwater, and Waterford for
Water Year 1992
3-24 Stillwater Low-Flow Model C Prediction Uncertainty as a Function of Stillwater Flow
3-25 Comparison of Flows Predicted by Stillwater Low-Flow Models (Fort Edward Flow<
8,000 cfs)
3-26 Comparison of Flows Predicted by Stillwater High-Flow (Fort Edward Flow> 8,000 cfs)
Models
3-27 Comparison of Flows Predicted by Stillwater Low-Flow (Fort Edward Flow< 8,000 cfs)
and Stillwater High-Flow (Fort Edward > 8,000 cfs) Models
3-28 Comparison of Flows Predicted by Waterford Low-Flow (Fort Edward Flow< 8,000 cfs)
Models
3-29 Comparison of Flows Predicted by Waterford High-Flow (Fort Edward Flow > 8,000 cfs)
Models
3-30 Comparison of Flows Predicted by Waterford Low-Flow (Fort Edward Flow^ 8,000 cfs)
Models and Waterford High-Flow (Fort Edward > 8,000 cfs) Models
3-31 Homologue Distribution of the GE Hudson Falls Facility Source as Characterized by the
Transect 1 Remnant Deposit Area (RM 195.8) Sample
3-32 Suspended-Matter Loading in the Upper Hudson River - Transect 1 Low-Flow Conditions
3-33 Suspended-Matter Loading in the Upper Hudson River Transect 3 - Transition between
Low-Flow and High-Flow Conditions
3-34 Suspended-Matter Loading in the Upper Hudson River - Transect 4 High-Flow Conditions
3-35 Suspended-Matter Loading in the Upper Hudson River - Transect 6 Low-Flow Conditions
3-36 Sediment Homologue Distributions in the Thompson Island Pool
3-37 Estimated Porewater Homologue Distributions in Sediments from the Thompson Island
Pool
3-38 Upper River Water Column Instantaneous PCB Loading for Transect 1 Low-Flow
Conditions
3-39 Typical Homologue Distributions of the Batten Kill and Hoosic River PCB Water Column
Loads
3-40 Upper River Water Column Instantaneous PCB Loading for Transect 3 Transition from
Low-Flow to High-Flow Conditions
3-41 Homologue Distributions of Surficial Sediments (0 to 2 cm) in the Batten Kill and the
Hoosic River
3-42 Sediment Homologue Distributions in the Upper River Reaches below the Thompson
Island Dam
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List of Figures (cont'd)
3-43 Upper River Water Column Instantaneous PCB Loading for Transect 4 High-Flow
Conditions
3-44 Upper River Water Column PCB Loading for Flow-Averaged Event 1 High-Flow
Conditions
3-45 Upper River Water Column PCB Loading for Flow-Averaged Event 2 Low-Flow
Conditions
3-46 Upper River Water Column PCB Loading for Flow-Averaged Event 3 Low-Flow
Conditions
3-47 Upper River Water Column Instantaneous PCB Loading for Transect 6 Low-Flow
Conditions
3-48 Upper River Water Column PCB Loading for Flow-Averaged Event 5 Low-Flow
Conditions
3-49 Upper River Water Column PCB Loading for Flow-Averaged Event 6 Low-Flow
Conditions
3-50 The Coincidence of the U7Cs and ^Co Maxima at River Mile 43.2 (Core 6)
3-51 137Cs Concentrations in High Resolution Sediment Core 11 and Core 19
3-52 Comparison of 137Cs Profiles between a Phase 2 High-Resolution Sediment Core and a
Historical Core at River Mile 188.5
3-53 Upper River High-Resolution Sediment Cores Depth vs. 137Cs Concentration and PCB
Concentration
3-54 Lower River High-Resolution Sediment Cores Depth vs. 137Cs Concentration and PCB
Concentration
3-55 Tributaries and Background High Resolution Sediment Cores Depth vs. 137Cs
Concentration and PCB Concentration
3-56 Comparison of the Surficial Sediment Congener Distribution with the Corresponding
Transect 4 High-Flow Suspended-Matter Congener Distribution
3-57 Comparison of the Thompson Island Pool Surficial Sediment Congener Distribution with
the Thompson Island Dam Suspended-Matter Congener Distributions associated with Low-
Flow Winter and Summer Conditions
3-58 Comparison of the Albany Turning Basin Surficial Sediment Congener Distribution with
the Green Island Bridge Suspended-Matter Congener Distributions associated with Low-
Flow Winter and Summer Conditions
3-59 Total PCBs in Sediment vs. Approximate Year of Deposition at River Mile 188.5 Near
the Thompson Island Dam: High Resolution Sediment Core 19
3-60 Total PCB Content in Sediment Deposited Between 1991 and 1992 vs. River Mile
3-61 Total PCBs in Post-1975 Sediment vs. Approximate Year of Deposition in the Hudson
River
3-62 Total PCB Content in Sediment vs. River Mile
3-63 137Cs Levels in Surface Sediments in the Hudson River Based on High-Resolution
Sediment Coring Results
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List of Figures (cont'd)
3-64 Total PCBs/13Cs Content in Sediment vs. River Mile
3-65 Time Interval Comparison for Total PCBs/137Cs Ratios: 1975 through 1992
3-66 Comparison of Measured and Calculated Total PCBs/137Cs Ratios for Sediment Deposited
between 1991 and 1992
3-67 Comparison of Measured and Calculated Total PCBs/137Cs Ratios for Sediment Deposited
between 1982 and 1986
3-68 Total PCBs/137Cs Ratios in Dated Sediment vs. River Mile: A Comparison of Calculated
and Measured Results
3-69 Comparison of the Duplicate Core Results on a Congener Basis for RM 177.8 near
Stillwater for 1991 to 1992
3-70 A Comparison between the Post-1990 Sediment PCB Congener Pattern for Core 21 at
River Mile 177.8 near Stillwater and Three Aroclor Mixtures
3-71 Normalized PCB Congener Concentrations in Stillwater 1991 to 1992 Sediments and
Rogers Island Suspended Matter vs. Aroclors 1254 and 1260
3-72 Comparison of PCB Congener Patterns: Suspended Matter from River Mile 194.6 at
Rogers Island for Transect 4. April 12 to 14, 1993 and a Mixture of 94% Aroclor 1242
+ 5% Aroclor 1254 + 1% Aroclor 1260
3-73 A Comparison between the 1991 to 1992 PCB Congener Pattern at River Mile 177.8 near
Stillwater with the Period 1975 to 1990
3-74 A Comparison of the PCB Congener Pattern Chronology between River Mile 143.5 near
Albany and River Mile 177.8 near Stillwater for 1975 to 1992
3-75 A Comparison of the Combined Thompson Island Dam PCB Load Congener Pattern
Recorded at Stillwater with Downstream Congener Patterns in Sediments Dated Post-1990
3-76 A Comparison of the Combined Thompson Island Dam PCB Load Congener Pattern
Recorded at Stillwater with Downstream Congener Patterns in Sediments Dated 1987 to
1990
3-77 A Comparison of the Combined Thompson Island Dam PCB Load Congener Pattern
Recorded at Stillwater with Downstream Congener Patterns in Sediments Dated 1982 to
1986
3-78 A Comparison of the Combined Thompson Island Dam PCB Load Congener Pattern
Recorded at Stillwater with Downstream Congener Patterns in Sediments Dated 1975 to
1981
3-79 Comparison of PCB Congener Patterns at River Mile 143.5
3-80 Comparison of PCB Congener Patterns at River Mile -1.9
3-81 Monthly PCB Load, River Mile 194.6 at Rogers Island and River Mile 188.5 at Thompson
Island Pool Averaging Estimate on GE Data
3-82 Total PCB Concentrations at River Mile 194.6 GE Data, with Moving Average
3-83 Load across the Thompson Island Pool Total PCBs, GE Data
3-84 Load across the Thompson Island Pool Mono-Chlorinated PCB Homologues, GE Data
3-85 Load across the Thompson Island Pool Di-Chlorinated PCB Homologues. GE Data
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List of Figures (cont'd)
3-86 Load across the Thompson Island Pool Tri-Chlorinated PCB Homologues, GE Data
3-87 Load across the Thompson Island Pool Tetra-Chlorinated PCB Homologues, GE Data
3-88 Average Daily PCB Homologue Load at Rogers Island (River Mile 194.6) and Thompson
Island Dam (River Mile 188.5) April 1991 through February 1996, Averaging Estimate
on GE Data
3-89 Gain across the Thompson Island Pool Total PCBs, GE Data
3-90 Gain across the Thompson Island Pool Mono-Chlorinated PCB Homologues, GE Data
3-91 Gain across the Thompson Island Pool Di-Chlorinated PCB Homologues, GE Data
3-92 Gain across the Thompson Island Pool Tri-Chlorinated PCB Homologues, GE Data
3-93 Gain across the Thompson Island Pool Tetra-Chlorinated PCB Homologues, GE Data
3-94 PCB Homologue Composition Change across the Thompson Island Pool April 1991
through February 1995, GE Data
3-95 Summer PCB Homologue Concentrations June through August 1991, GE Data
Summer PCB Homologue Concentrations June through August 1992, GE Data
3-97 Summer PCB Homologue Concentrations June through August 1993, GE Data
3-98 Summer PCB Homologue Concentrations June through August 1994, GE Data
3-99 Summer PCB Homologue Concentrations June through August 1995, GE Data
3-100 Total PCB Load from USGS Data: Ratio Estimator
3-101 Total PCB Load from USGS Data: Averaging Estimator
3-102 Water Column PCB Homologue Composition at River Mile 194.6 at Rogers Island
3-103 Water Column PCB Homologue Composition of the Net Thompson Island Pool Load
3-104 Comparison of 1993 Upper Hudson River PCB Loadings at Waterford based on Phase 2
Data
3-105 Comparison of Transect Results, Flow-Averaged Event Results, and Monthly Mean Based
on GE Data
3-106 Mean PCB Loadings at the Thompson Island Dam from April 1991 through October 1995,
GE Data
3-107 Water Column Total PCB Concentrations at the Thompson Island Dam: June 1993 to May
1996 - GE Data
3-108 PCB Homologue Composition of the Net Thompson Island Pool Load, GE Data
3-109 Total PCB Load at Rogers Island and the Thompson Island Dam - May 27, 1996, GE Data
3-110 PCB Load vs. River Mile for Three Phase 2 Water Column Transects
3-111 PCB Loadings to the Hudson River at River Mile 153.9 near Albany based on the Water
Column Transect Sampling
3-112 Fractional PCB Loads at Albany for 1991 to 1992 Based on Dated High-Resolution
Sediment Core Results
3-113 Model-Projected PCB Loadings to Lower Hudson River and Harbor for 1993
3-114 Estimated PCB Loadings to Lower Hudson and Harbor for 1993
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List of Figures (cont'd)
4-1 A Comparison Between River Flow Velocity and Maximum Sediment PCB Inventory by
River Mile in the Thompson Island Pool
4-2 Hudson River Cross-Sectional Area for 8400 cfs Flow at Fort Edward
4-3 Comparison of the DN Value for 10 ft and 50 ft Circles at Confirmatory Sampling Sites
4-4 Calibration Plots of DN vs. Grain-Size
4-5 Three-Dimensional Correlation Plot of Digital Number vs. Grain Size
4-6 Two-Dimensional Correlation Plot of Digital Number vs. Grain Size
4-7 Comparison of 500 kHz Acoustic Signal and 1984 NYSDEC PCB Levels in Surface
Sediments
4-8 Examples Semivariogram with Labels
4-9 Variogram of Natural Log of PCB Mass Thompson Island Pool, 1984 Sediment Survey
Subreaches 1 and 2, Isotropic Variogram
4-10 Variogram of Natural Log of PCB Mass Thompson Island Pool, 1984 Sediment Survey
Subreach 3, Major Axis N 35 W
4-11 Variogram of Natural Log of PCB Mass Thompson Island Pool, 1984 Sediment Survey
Subreach 4, Major Axis N 10 W
4-12 Variogram of Natural Log of PCB Mass Thompson Island Pool, 1984 Sediment Survey
Subreach 5, Isotropic Variogram
4-13 Typical Arrangement of the Point Estimates Used in Generating Block Kriging Values
4-14 Variogram of Natural Log of Surface PCB Concentration GC/MS Screening Data
Thompson Island Pool, 1984 Sediment Survey
4-15 Variogram of Natural Log of Surface PCB Concentration GC/ECD Analytical Data
Thompson Island Pool, 1984 Sediment Survey
4-16 Variogram of Natural Log of Surface PCB Concentration Cross-Variogram between
GC/ECD and GC/MS Data Thompson Island Pool, 1984 Sediment Survey
4-17 Locations of Potential Chlorine Sites on a PCB Molecule
4-18 Congener Content of Four Aroclor Mixtures
4-19 Histogram of the Molar Dechlorination Product Ratio
4-20 Histogram of the Fractional Molecular Weight Difference Relative to Aroclor 1242
4-21 Comparison Between the Molar Dechlorination Product Ratio and the Fractional Change
in Molecular Weight for All Post-1954 Freshwater Sediments
4-22 Molar Dechlorination Product Ratio vs. Total PCB Concentration in Post-1954 Sediments
from the Freshwater Hudson River
4-23 Molar Dechlorination Product Ratio vs. Total PCB Concentration with Depth (Age) in
Core 18 at River Mile 185.8
4-24 Molar Dechlorination Product Ratio vs. Total PCB Concentration with Depth (Age) in
Core 19 at River Mile 188.5
4-25 Fractional Mass Loss as Measured by the Change in Mean Molecular Weight
4-26 Fractional Mass Loss as Measured by the Change in Mean Molecular Weight - Expanded
Scale
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FURTHER SITE CHARACTERIZATION AND ANALYSIS
VOLUME 2C - DATA EVALUATION AND INTERPRETATION REPORT
HUDSON RIVER PCBs REASSESSMENT RI/FS
List of Figures (cont'd)
4-27 Molar Dechlorination Ratio and Total PCB Concentration vs. Depth for Phase 2 Sediment
Core Samples
4-28a Histogram of the Change in Molecular Weight as a Function of Time of Deposition in
Post-1954 Dated Sediments from the Hudson River
4-28b Fractional Mass Loss as Measured by the Change in Mean Molecular Weight in Post-1954
Dated Sediments from the Hudson River
4-29 A Comparison Between Sediment and Water Column Samples from Rogers Island and
Thompson Island Dam
4-30 A Comparison of the Net Thompson Island Pool Contribution to the Water Column with
the Sediments of the Upper Hudson
4-31 Relationship Between Phase 2 Hudson River Water Column Samples and the Sediment
Regression Line - Molar Dechlorination Product Ratio vs. Change in Molecular Weight
4-32 Molar Dechlorination Product Ratio vs. Change in Molecular Weight for Water Column
Transects Showing Trend with Station
4-33 Trend of High Resolution Core Top Molar Dechlorination Ratio and Total PCB
Concentration with River Mile
4-34 A Comparison Among Various Water Column and Sediment Samples on a Homologue
Basis
4-35 Comparison Between Various Water Column and Estimated Porewater Distributions on
a Homologue Basis
4-36 Estimation of the Age of the Sediments Responsible for the Thompson Island Pool Source
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FURTHER SITE CHARACTERIZATION AND ANALYSIS
VOLUME 2C - DATA EVALUATION AND INTERPRETATION REPORT
HUDSON RIVER PCBs REASSESSMENT RI/FS
List of Plates
Plates Title
1-1 Hudson River Drainage Basin and Site Location Map
1-2 Phase 2 Water Column Sampling Locations in Hudson River
1-3 Phase 2 High-Resolution Sediment Core Sampling Locations in Hudson River
1-4 NYSDEC Hot Spot Locations in Upper Hudson River
1-5 Sheet 1 of 2 - Geophysical and Confirmatory Sediment Sampling Locations in Upper
Hudson River (2 Sheets)
2-1 PCB Contaminated Sites in the Upper Hudson Watershed
2-2 General Electric Hudson Falls, NY - Site Plan and Shore Profile
2-3 USEPA Point Source Sampling Locations in NY/NJ Harbor
3-1 NYS Thruway Authority, Office of Canals, Staffing Gauge Locations in the Upper Hudson
River
3-2 Dated High-Resolution Sediment Core Locations in Hudson River
4-1 Side-Scan Sonar Mosaic of the Hudson River Sediments in the Vicinty of Hotspot 14
4-2 X-Radiograph of Confirmatory Core 88 Collected at Approximately RM 187.6, South of
Thompson Island Near Hotspot 24
4-3 Interpretation of the 500 kHz Side-Scan Sonar Mosaic (A) and Comparison of Fine-
Grained Sediments & NYSDEC Hot Spot Areas (B) in the vicinity of Hot Spot 14
4-4 Zones of Potentially High Sediment PCB Contamination in the Upper Hudson River (2
Sheets)
4-5 Polygonal Declustering Results for Sediment Total PCB Inventory in the Thompson Island
Pool - Subreach 1
4-6 Polygonal Declustering Results for Sediment Total PCB Inventory in the Thompson Island
Pool - Subreach 2
4-7 Polygonal Declustering Results for Sediment Total PCB Inventory in the Thompson Island
Pool - Subreach 3
4-8 Polygonal Declustering Results for Sediment Total PCB Inventory in the Thompson Island
Pool - Subreach 4
4-9 Polygonal Declustering Results for Sediment Total PCB Inventory in the Thompson Island
Pool - Subreach 5
4-10 Segmentation of the Thompson Island Pool for Semivariogram Analysis
4-11 Block Kriging Results for Sediment Total PCB Inventory in the Thompson Island Pool -
Subreach 1
4-12 Block Kriging Results for Sediment Total PCB Inventory in the Thompson Island Pool -
Subreach 2
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VOLUME 2C - DATA EVALUATION AND INTERPRETATION REPORT
HUDSON RIVER PCBs REASSESSMENT RI/FS
List of Plates (cont'd)
4-13 Block Kriging Results for Sediment Total PCB Inventory in the Thompson Island Pool -
Subreach 3
4-14 Block Kriging Results for Sediment Total PCB Inventory in the Thompson Island Pool -
Subreach 4
4-15 Block Kriging Results for Sediment Total PCB Inventory in the Thompson Island Pool -
Subreach 5
4-16 Contoured Surface Sediment Total PCB Concentrations for The Thompson Island Pool
Based on Kriging Analysis - Subreach 1
4-17 Contoured Surface Sediment Total PCB Concentrations for The Thompson Island Pool
Based on Kriging Analysis - Subreach 2
4-18 Contoured Surface Sediment Total PCB Concentrations for The Thompson Island Pool
Based on Kriging Analysis - Subreach 3
. Contoured Surface Sediment Total PCB Concentrations for The Thompson Island Pool
Based on Kriging Analysis - Subreach 4
4-20 Contoured Surface Sediment Total PCB Concentrations for The Thompson Island Pool
Based on Kriging Analysis - Subreach 5
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Appendix A
Data Usability Report for PCB Congeners
High Resolution Sediment Coring Study
A.l Introduction
The usability of data relates directly to the data quality objectives of the environmental
investigation (Maney and Wait, 1991; USEPA, 1993. 1994). The Hudson River PCB congener
chemistry program required sophisticated, high resolution gas chromatography analyses with
stringent quality control criteria. In addition, various inorganic and physical parameters were
analyzed to define the chemical context within which the PCB congeners exist. This approach was
necessary to delineate the concentration of PCB congeners within the context of geochemical and
biological processes occurring in the river.
TAMS/Gradient selected a total of 90 PCB congeners as target congeners based on their
significance in environmental samples and the availability of calibration standards at the start of the
program. In addition, Aquatec obtained qualitative and quantitative information for an additional
36 PCB congeners (non-target congeners) from each sediment sample analysis using relative
retention time information detailed in the literature, and more recently verified with actual standards.
Certain target congeners are of particular importance in evaluating geochemical and biological
processes within the Hudson River sediments. These are the 12 "principal" target congeners, which
consist of BZ#1, 4, 8, 10. 18, 19,28,52, 101, 118, 138, and 180. The focus of this report will be on
the usability of the analytical data for these 12 principal congeners.
This report serves as an overall evaluation of the PCB congener analyses performed for the
Hudson River high resolution sediment coring study. The evaluation is based on the assessment of
data quality relative to the objectives of the study. The report will first provide a synopsis and
assessment of the field sampling, analytical chemistry and data validation programs, and then
evaluate data usability for all 126 congeners analyzed, with particular emphasis on the 12 principal
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target congeners. A data usability report assessing the non-PCB chemical and physical analyses for
the high resolution sediment samples is provided in Appendix C.
A.2 Field Sampling Program
TAMS/Gradient designed the high resolution sediment coring study to examine long-term
trends in PCB transport, release and degradation by an examination of the sediment record.
TAMS/Gradient describe the high resolution sediment collection program, sampling procedures,
analytical protocols, and quality control/quality assurance requirements in the "Phase 2A Sampling
and Analysis Plan/Quality Assurance Project Plan - Hudson River PCB Reassessment RI/FS"
(TAMS/Gradient, May 1992, referred to in this report as the Phase 2A SAP/QAPP).
TAMS/Gradient collected cores over a 200-mile length of the Hudson River using either hand
coring, gravity coring, or piston coring techniques. Co-located cores at each site were required to
provide sufficient sediment for all chemical and physical testing. Once the cores were returned to
shore, the sampling team extruded and aliquoted sediments from the cores in a manner described in
the Phase 2A SAP/QAPP. For most samples, this procedure involved taking 2 centimeter (cm) slices
from the top of the core for four intervals, and then removing 4 cm slices from the remainder of each
core. The sampling team aliquoted each slice into appropriate containers and submitted the samples
to a contract laboratory for analysis. A summary of the subsampling and analysis scheme is
provided in Figure A-l.
During the process of defining data quality objectives for the high resolution sediment coring
sampling study, TAMS/Gradient acknowledged that only a limited amount of sediment could be
obtained from 2 cm and 4 cm core slices. This affects the number of analyses that can be performed
per slice, as well as the detection limits for each analysis. TAMS/Gradient determined that
increasing the length of the core slices would cause valuable sediment dating information to be lost.
TAMS/Gradient considered this approach to be unacceptable because one of the main purposes for
conducting the high resolution sediment coring study was sediment dating. Consequently,
TAMS/Gradient decided to collect four cores at each site rather than two cores to obtain sufficient
sediment mass. The problem with collecting co-located samples, particularly for sediments, is the
potential lack of representativeness (homogeneity) between each core. TAMS/Gradient decided to
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collect multiple co-located cores in order to obtain all desired analyses at acceptable detection limits,
with the belief that co-located core homogeneity would be acceptable. A discussion on field
sampling precision and representativeness is provided in the data usability section of this report.
Scientists from TAMS, Lamont Doherty Earth Observatory (formerly Lamont Doherty
Geological Observatory), and Rensselaer Polytechnic Institute (RPI) performed sampling for the
high resolution sediment coring program from August 23, 1992 to November 6, 1992. The sampling
team collected a total of 495 sediment samples from 28 primary sampling stations in areas of
relatively continuous sedimentation of fine-grained material. Aquatec allocated these samples into
30 sample delivery groups (SDGs). In addition, the sampling team collected core tops from several
additional locations throughout the Hudson River in May and August to October of 1992. RPI dried
and archived core tops (0-2 cm) from these cores for eventual PCB congener analysis. Aquatec
analyzed a small subset of the archived core tops (A-cores) for PCBs. The TAMS/Gradient Program
Quality Assurance Officer (QAO) conducted a field sampling audit on September 9 and 10, 1992
to assess compliance of the sampling procedures with the Phase 2A SAP/QAPP. The audit findings
indicate that the sampling program was being conducted in a technically acceptable manner
consistent with the Phase 2A SAP/QAPP (Wait, 1992).
A.3 Analytical Chemistry Program
A.3.1 Laboratory Selection and Oversight
TAMS/Gradient retained a number of analytical laboratories to perform the analyses required
for this program. To verify that the selected laboratories had the capacity, capabilities, and expertise
to perform sample analyses in strict accordance with the specified methodologies, each qualifying
laboratory underwent an extensive audit by TAMS/Gradient's senior chemists. TAMS/Gradient
retained the following three laboratories to perform high resolution sediment sample analyses for the
Hudson River RI/FS program: Aquatec Laboratories, a division of Inchcape Testing Service located
in Colchester, Vermont; Lamont Doherty Earth Observatory (LDEO) located in Palisades, New York;
and Rensselaer Polytechnic Institute Department of Earth and Environmental Science located in Troy,
New York. USEPA Special Analytical Services (SAS) contract laboratories, ATEC Associates, Inc.
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located in Indianapolis. Indiana: GeoSea Consulting, Ltd. located in Vancouver, British Columbia: and
Chemtec Consulting Group Inc.. located in Englevvood, New Jersey, were also retained through the
USEPA SAS procurement process. Aquatec was the sole analytical laboratory which conducted the
PCB congener analyses for the entire program.
TAMS/Gradient conducted routine laboratory audits during the high resolution sediment coring
study to verify compliance of the laboratories contracted by TAMS/Gradient (Aquatec, LDEO, and
RPI) with the Phase 2A SAP/QAPP requirements. TAMS/Gradient did not perform audits of the
USEPA SAS laboratories.
Unique requirements of the PCB congener method necessitated refinements of previously
published methods. In conjunction with these changes, Aquatec conducted Method Detection Limit
(MDL) studies and Extraction Efficiency (EE) studies for the sediments to evaluate the adequacy of
uic methods. To conduct these studies, TAMS/Gradient collected seven replicate Hudson River
sediment samples. For the MDL studies, TAMS/Gradient collected the samples upstream from the
zone of major PCB contamination. TAMS/Gradient collected samples used for the EE study from
within the zone of major PCB contamination. A synopsis of the MDL/EE studies is provided in a
TAMS/Gradient memorandum dated December 29,1993 (Cook, 1993). The TAMS/Gradient Program
Quality Assurance Officer oversaw and approved the method refinements through out the process.
A.3.2 Analytical Protocols for PCB Congeners
The method used by TAMS/Gradient for the determination of PCB congeners in Phase 2A is
a program-specific method based on NYSDEC's Analytical Services Protocol Method 91-11
(NYSDEC, 1989) for PCB congeners. Appendix A4 of the Phase 2A SAP/QAPP describes procedures
for the calibration, analysis, and quantitation of PCB congeners by fused silica capillary column gas
chromatography with electron capture detection (GC/ECD). The method is applicable to samples
containing PCBs as single congeners or as complex mixtures, such as commercial Aroclors. Aquatec
extracted sediment samples with hexane, and performed applicable cleanup procedures prior to analysis
by GC/ECD, as detailed in Appendix A3 of the Phase 2A SAP/QAPP. Aquatec analyzed hexane
extracts for PCB congeners on a dual capillary-column GC/ECD, as detailed in Appendix A4 of the
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Phase 2A SAP/QAPP and identified PCB congeners using comparative retention times on two
independent capillar}' columns of different polarity. Aquatec used calibration standards for each target
congener to define retention times. In addition. Aquatec routinely analyzed Aroclor standards and
mixtures of Aroclor standards to verify identification and quantification of the primary calibration
standards. Due to the non-linear nature of the ECD over any significant calibration range (for this
project 1 to 100 ppb in extract), Aquatec generated the calibration curves used for quantitation from
a quadratic weighted least squares regression model where the correlation coefficient is greater than
0.99 (McCarty, 1995; USEPA, 1986 - Method 8000B, proposed 1995 update). For each PCB congener
which elutes as a single congener on each GC column, Aquatec reported the result as the lower of the
two values. Although this quantification scheme is compliant with USEPA CLP guidelines for dual-
column analyses (USEPA, 1991), it may introduce a slight low bias when calculating homologue and
total PCB sums. TAMS/Gradient compared data in the database relative to absolute results on both
columns and found the bias was usually negligible, and on a worst-case basis, may be 2% to 10% low.
For situations where coelution occurred on one column, Aquatec quantitated the result from the column
not displaying coelution. If only coelution results were available, Aquaiec performed a calculation to
decipher concentrations using response factors derived by Mullen (1984). For the 12 principal
congeners, BZ#19, 28, 52, and 118 eluted as a single congener peak on both GC columns. BZ#1, 4,
8, 10, 18, 138, and 180 eluted as a single congener peak on one column and coeluted on the other
column. BZ#101 coeluted on both columns and was always reported with BZ#90.
Approximately 10% of all samples analyzed by GC/ECD also underwent additional analysis
using a GC-ion trap detector (ITD) as an additional means of confirming PCB congener identifications,
as detailed in Appendix A5 of the Phase 2A SAP/QAPP. When possible, Aquatec selected samples
with the highest concentrations of PCB congeners for confirmation analysis by GC/ITD. Usually,
Aquatec performed two GC/ITD analyses per SDG, even if congener concentrations were minimal
throughout the SDG.
At the start of the Phase 2A sampling and analysis program, TAMS/Gradient and Aquatec
selected 90 target PCB congeners. These target congeners are listed in Table A-l and identified by BZ
number (Ballschmiter and Zell, 1980). TAMS/Gradient and Aquatec based the selection of these 90
PCB congeners on their significance in environmental samples and the commercial availability of
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calibration standards. TAMS/Gradient referred to PCB congeners for which calibration standards were
available as "target congeners". To verify that congener response for these calibration standards were
reproducible over time, TAMS/Gradient examined calibration data from November 1992 and October
1993. TAMS/Gradient found temporal consistency to be acceptable on both GC columns (Bonvell,
1994a).
The high resolution column chromatography techniques employed by Aquatec produced
acceptable PCB resolution for numerous congeners not contained in the target congener calibration
standards. Thus, TAMS/Gradient decided during method refinement to report approximately 50
additional PCB congeners. The laboratory identified these additional PCB congeners based upon the
relative retention times reported in the published literature (Mullen, 1984; Schulz, 1989; Fischer and
Ballschmiter, 1988, 1989). Aquatec calibrated these additional "non-target" congeners using the
calibration curve for target congener BZ#52. Aquatec chose BZ#52 because it elutes as a single
congener peak in the middle region of the chromatogram for both GC columns and is a major
component of Aroclor 1242, the Aroclor anticipated in Hudson River samples. Using additional
congener calibration standards which became commercially available by August 1993, Aquatec
performed analyses to verify and refine the historical relative retention times, and to determine
individual congener calibration parameters. These analyses confirmed a majority (36) of the historical
non-target congener relative retention times. For all analyses performed prior to August 1993, the
results for 14 non-target compounds not confirmed by this analysis, TAMS/Gradient considered
unusable and deleted from the database. A review of project data indicated that the 36 confirmed non-
target congeners represent a significant percentage, up to 25%, of the total PCB mass. Therefore,
TAMS/Gradient decided to include the non-target congener results to calculate homologue and total
PCB masses in the Hudson River. Omission of these non-target congener results would have resulted
in a significant low bias in the resulting calculations for homologue and total PCBs. Thus, 36 non-
target congeners are included in this report, as shown in Table A-l. Since the non-target congener
results were to be included in the calculations of homologue and total PCB mass, TAMS/Gradient
applied an individual correction factor to each congener's results based on the analysis of the additional
congener standards. The application of these correction factors served to minimize the uncertainty
associated with quantitation of non-target congeners. A series of TAMS/Gradient memoranda describe
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the method for deriving these calibration correction factors (Bonvell. 1993a,b.c). A listing of the
derived calibration correction factors is provided in a TAMS/'Gradient memorandum (Bonvell, 1994b).
To establisn a method of quantitating total Aroclor concentrations from PCB congener data,
Aquatec performed duplicate analyses of seven Aroclor standards (1016, 1221, 1232, 1242, 1248,
1254, 1260). TAMS/Gradient defined the quantitation of an Aroclor for this program as the sum of
all congeners present in the standard Aroclor mixture at a concentration greater that 0.1 % of the total
Aroclor mass. In this manner, TAMS/Gradient then compared the percentage of the total mass
represented by the detected target and non-target congeners greater than 0.1% of the Aroclor mass was
then compared to the actual concentrations of each Aroclor standard. The results produced the
following mass yields for the seven Aroclor standards: Aroclor 1016=93.3%, Aroclor 1221=86.8%,
Aroclor 1232=91.0%, Aroclor 1242=90.6%, Aroclor 1248=89.2%, Aroclor 1254=95.8%, and Aroclor
1260=87.0%. Thus, in each case, the 90 target and 36 non-target congeners represented more than 87%
of the original Aroclor mass. For those Aroclors most important to the Hudson River based on General
Electric's reported usage (Brown et ai, 1984) these congeners represented better than 90% of the
Aroclor mass (i.e., Aroclors 1242, 1254, and 1016). A further discussion of the results of the .Aroclor
standards analyses is presented in Section 4.3 of the main body of this report.
A.4 Data Validation
An essential aspect of understanding the uncertainties of the Phase 2 sediment data is
understanding the significance of the qualifiers associated with the results. Each result has an
associated qualifier. Qualifiers denote certain limitations or conditions that apply to the associated
result. Initially, the analytical laboratories applied qualifiers to the results, and then the data validators
modified the qualifiers, as necessary, based on the established validation protocols. Data reporting and
validation qualifiers direct the data users concerning the use of each analytical result. TAMS/Gradient
used two sets of qualifiers in the database, one set for PCB congener data, and a second set for non-
PCB chemical and physical data. Aquatec developed an extensive list of data reporting qualifiers to
be applied to the PCB congener data. The list is based on standard USEPA qualifiers used for organic
analyses, with additional qualifiers provided to note unique issues concerning PCB congener analysis,
e.g., the quantitation scheme. The data reporting qualifiers for PCB congener data, as applied by
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Aquatec. are defined in detail in Table A-2. Qualifiers for non-PCB data are discussed in Appendix
C.
During validation, the validators made modifications to the data qualifiers which are reflected
in the database. CDM Federal Programs Corporation and their subcontractors, under a separate
USEPA contract, performed data validation for the high resolution sediment coring study. Validation
procedures employed by CDM for GC/ECD analyses are detailed in Appendix A6 of the Phase 2A
SAP/QAPP, and validation guidelines for GC/ITD analyses are provided in Appendix A7 of the Phase
2A SAP/QAPP. TAMS/Gradient devised the validation procedures to reflect the data quality
objectives of the program, as well as to conform with USEPA (1988, 1992a) standards as appropriate.
USEPA Region II concurred with these method-specific validation protocols. In addition.
TAMS/Gradient designed comprehensive data validation templates to facilitate consistency of
approach and actions during validation. Prior to validation of the PCB data, Gradient conducted a
training workshop to aid CDM in properly performing the validation. Gradient reviewed and
commented on the initial CDM validation reports and provided real-time QA oversight. USEPA
Region II (Lockheed ESAT) revalidated data for 13 high resolution sediment coring samples to verify
that CDM had performed the validations properly. Lockheed ESAT noted no significant problems.
The initial data validation efforts for the high resolution sediment core samples and water
column samples were completed in December 1994. The results were subsequently incorporated into
the TAMS/Gradient database and available for review in March 1995. However, by April 1995, it
became clear that the validation results differed markedly but randomly from the unvalidated data.
Upon further investigation, the project staff at TAMS identified the source of some of these differences
as the result of incorrect data validation procedures largely pertaining to blank corrections.
Specifically, it was found that blank samples were sometimes incorrectly associated with
environmental samples and blank values were transcribed incorrectly among validation records, among
other concerns. These problems were found to be extensive enough that USEPA, in agreement with
TAMS/Gradient, decided to have both the entire high resolution sediment coring and the water-column
monitoring PCB analysis data validation program redone to minimize manual data manipulation and
transcription (e.g., Garvey, 1995). TAMS developed a computer spreadsheet macro for data validation
in July 1995. This macro electronically applied blank qualification criteria (i.e.. the "B" qualifier) to
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the electronic data files using an algorithm developed from the data validation procedures. These files
were then used to generate the standard data validation forms incorporated in the validation packages.
Subsequent to the electronic validation, CDM reviewed all data for blank qualifier assignment before
approving the data validation packages. As a result of this review, minor changes in the macro had to
be made to handle unusual data packages (e.g., extra congeners reported). Using the data validation
macro, CDM completed the revalidation of the high resolution sediment coring and water column PCB
samples in September 1995.
As an overall assessment of data quality, the TAMS/Gradient Program QAO reviewed
pertinent aspects of the sampling and analysis program (e.g., historical data, implementation of
sampling protocols, laboratory performance) relative to the data quality objectives. Decisions on data
usability sometimes overrode data qualification codes, as justified in this report. All qualifier changes
made by the TAMS/Gradient Program QAO, as reflected in this data usability report, are noted in the
final database (code Y in QA Comment field of database). For the high resolution sediment coring
study, TAMS/Gradient Program QAO modified 3033 qualifiers out of 62,426 PCB congener data
records as a result of data usability issues, representing 4.9% of the data. Specifically, TAMS/Gradient
Program QAO unrejected data for two reasons: 1) octachloronaphthalene (OCN) was deemed to be
an unacceptable surrogate standard (see Section A.5.2); as such, TAMS/Gradient Program QAO
unrejected any sample results rejected solely due to poor OCN recoveries, and 2) CDM rejected certain
positive BZ#18 detects due to poor dual column precision. The TAMS/Gradient Program QAO
changed the rejection qualifier (R) to presumptively present (N). The TAMS/Gradient Program QAO
based this decision on the routine presence of BZ#18 in historical sediment samples containing PCBs,
and the consistent PCB congener pattern distribution present throughout the Hudson River sediments.
Both the preponderance of BZ#18 retention time data and BZ#18 identification verification by GC/ITD
for most ITD-confirmed samples warrants inclusion of this principal congener in the database.
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A.5 Data Usability
A.5.1 Approach
Most previous studies of PCB chemistry in Hudson River sediments have focused on the
concentration of specific Aroclors, total PCBs and/or the distribution of PCB homologues. The current
assessment of PCB fate and distribution in the Hudson River required TAMS/Gradient scientists to
implement sophisticated equilibrium chemistry and transport modeling studies requiring concentration
ratios of certain PCB congeners. Of the 90 target and 36 non-target congeners. 12 target congeners are
of particular importance. The usability of these "principal" congeners is key to the high resolution
sediment coring study.
Principal congeners will be employed in the following studies by the data users:
• Molar dechlorination product ratio - The molar sum of BZ#1, 4, 8, 10, and 19 are
compared to the molar sum of all 126 congeners analyzed. This ratio is then compared
to a similar index for Aroclor 1242 to assess, calculate, and evaluate the extent of
dechlorination.
• Transport modeling - BZ#4, 28, 52, 101, and 138 are considered independently as
compounds modeling PCB transport.
• Aroclor 1016 and 1242 - BZ#18 is used to estimate the potential contribution of
Aroclor 1016 and 1242 to Hudson River sediments.
• Aroclor 1254 - BZ#118 is used to estimate the potential contribution of Aroclor 1254
to Hudson River sediments.
• Aroclor 1260 - BZp180 is used to estimate the potential contribution of Aroclor 1260
to Hudson River sediments.
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Thus, 12 principal congeners (BZ#1, 4, 8, 10, 18, 19, 28. 52, 101, 118, 138, and 180) are the
focus of this usability report. However, the remaining target and non-target congeners have important
implications to the high resolution sediment coring study. TAMS/Gradient used these congeners to
calculate the concentrations of total PCBs, PCB homologues. and Aroclor mixtures, as well as for
congener pattern analysis.
A.5.2 Usability - General Issues
The data quality objectives for the Hudson River high resolution sediment coring study-
required the development of a sensitive program-specific gas chromatography method. Available
standard agency methods were not adequate to achieve the congener-specific identifications and
detection limits needed for the project. TAMS/Gradient based the method utilized on a modified
NYSDEC ASP Method 91-11 (1989) protocol encompassing information published in the literature,
as well as in-house research conducted by Aquatec. This research included Method Detection Limit
(MDL) studies and Extraction Efficiency (EE) studies conducted in accordance with USEPA (1984,
1986) guidance. During the course of these studies, and the inception of the high resolution sediment
coring analytical program, TAMS/Gradient and Aquatec noted various nuances to the methods that
required refinement. As such, TAMS/Gradient and Aquatec made modifications to some of the
original protocols. The remainder of this section discusses some of the more significant changes, and
their ramifications.
A.5.2.1 Identification of Non-Target Congeners
At the beginning of this program, Aquatec identified non-target congeners based on historical
relative retention times reported in the literature. In August 1993, Aquatec analyzed calibration
standards for each of the non-target congeners. Using these additional calibration standards, Aquatec
performed analyses to confirm historical relative retention times. Though these analyses verified a
majority of the historical non-target congener relative retention times, some of the historical relative
retention times used to identify non-target congeners did not match the relative retention times
determined by the analyses of the non-target congener standards. TAMS/Gradient deleted fourteen
non-target congeners from the database for all analyses performed prior to August 1993 due to these
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unconfirmed identifications. The 14 non-target congeners deleted were: BZ#35. 39, 46, 100, 104. 130.
131, 132, 134, 162, 165, 173. 176, and 179. Aquatec identified and confirmed these 14 congeners
based on the current laboratory-derived relative retention times for samples analyzed during and after
August 1993. Therefore, the results for these 14 non-target congeners will remain in the database for
all samples analyzed during and after August 1993. Use of these non-target congener data should be
limited since they are not consistently available for all data sets. If a situation arises where information
for the deleted non-target congeners is critical to a data user, an in-depth review of the chromatograms
and re-calculation of the concentrations could potentially produce usable results for some of these
congeners.
A.5.2.2 Quantitation of Non-Target Congeners
The laboratory originally quantitated non-target congeners using the calibration curve
determined for BZ#52. Since the non-target congener results were to be included in the calculations
ofhomologue and total PCB mass, TAMS/Gradient desired a more accurate method of quantifying the
non-target congeners. Aquatec analyzed calibration standards for the non-target congeners in
September 1993, and again in April 1994, for the determination of congener-specific response factors.
Based on this information, TAMS/Gradient calculated correction factors for each non-target congener
and applied these to the laboratory data within the database (Bonvell, 1994b).
A.5.2.3 Re-calculation of Some PCB Congener Results
From August 1992 to July 1993, Aquatec observed that the relative retention times of congener
compounds were changing on the SB-octyl-50 GC column. The shifts in relative retention times did
not effect the target compound identification except for BZ#187 and 128. This specific identification
problem became apparent from the results of a blind performance evaluation sample. In the case of
BZ#187 and 128, their original identification on the SB-octyl-50 analytical column showed BZ#128
eluting before BZ#187. Over the course of eight months, the two congeners merged together as one
peak, then became resolved again, only BZ#187 now eluted before BZ#128. When the two congeners
resolved, Aquatec assumed that each congener eluted in the same order as previously indicated, which
was incorrect. To determine the effects of the shifts on the non-target congeners, Aquatec analyzed
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individual non-target congener standards. From these data, Aquatec discovered that the initial
identification of non-target PCB congener compounds obtained from Ballschmiter's research was
inconsistent with this study's SB-octyl-50 analytical column results. During the review of the elution
order of PCB congeners on the SB-octyl-50 column. Aquatec also discovered that BZ#91 was
misidentified. TAMS/Gradient and Aquatec corrected the misidentification of BZ#91 and the other
affected congeners.
Aquatec finalized the proper identification of non-target PCB congeners in November 1993.
In March 1994, TAMS/Gradient instructed Aquatec to review all PCB congener data analyzed from
September 1992 to July 1993 to rectify possible misidentifications. These corrections also necessitated
changes in the PCB congener database. All data initially entered into the database have been validated
without consideration to the changes discussed herein. Due to the GC column problem, Aquatec
changed some records and TAMS/Gradient flagged those records with a "K" to facilitate comparison
of original and changed records. A secondary validation of the changes has not been performed.
However, the identification changes made are not expected to adversely effect the overall validity of
the data. Some possible problems to be aware of include the analytical status of calibration curves and
check standards for BZ#91 for the entire time period, and BZ#187 and 128 from March 17, 1993
through July 1993. Another possible problem was 'B' flags. The 'B' flag was used to indicate method
blank contamination. Requantitation of results has changed the 'B' qualifier status in some cases.
A.5.2.4 GC Column Change
Initially, Aquatec used a HP-5 (or RTx-5) column and a SB-octyl-50 GC column for PCB
congener analyses. In November 1993, Aquatec obtained new SB-octyl-50 columns for pending
analyses of Phase 2 biological samples. Each of the new SB-octyl-50 columns showed signs of column
degradation resulting in severe peak retention time shifts. Due to the concern that an acceptable SB-
octyl-50 column would not be obtainable, TAMS/Gradient solicited approval from USEPA Region II
for a replacement column, Apiezon_L. TAMS/Gradient was concerned about data comparability for
the overall program, but had no alternative. USEPA Region II concurred with the replacement of the
SB-octyl-50 column with the Apiezon_L column in December 1993. The Apiezon L column was
selected for the following reasons:
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• The Apiezon_L column phase is similar to the SB-octyl-50 column phase.
• The Apiezon_L column provides PCB congener separations similar to the SB-octyl-50
column.
• The PCB congener retention times on the ApiezonJL column are more stable than on
the SB-octyl-50 column.
• The NYSDEC analytical laboratory performing Hudson River PCB congener analyses
was using the Apiezon_L column successfully for fish samples.
In February 1994, Aquatec performed a comparison study for the two column sets, HP-5/SB-
octyl-50 and HP-5/Apiezon_L (Cook, 1994). Aquatec analyzed four Phase 2 pilot fish samples on both
the HP-5/SB-octyl-50 column combination and also the RTx-5/Apiezon_L column combination. The
PCB congener results compared well qualitatively and quantitatively with few exceptions. The results
for BZ#15 and 37 were consistently 2 to 10 times higher on the SB-octyl-50 column pair. Data users
are cautioned that the results for BZ#15 and 37 reported through March 1994 and the same congeners
reported after March 1994 are not comparable due to differences in the method of quantitation. For
example, comparisons of sediment data between the high resolution sediment coring study and the low
resolution sediment coring study are not appropriate for BZ#15 and 37.
A.5.2.5 Lower Column Concentration Bias
The USEPA CLP protocol requires that for dual column GC analyses, the lower of the two
values from each column will be reported (USEPA, 1991). TAMS/Gradient incorporated this same
quantitation scheme into this program. This quantitative method may introduce a slight low bias when
calculating homologue and total PCB sums. TAMS/Gradient determined that this bias was usually
negligible, and on a worst-case basis, may be as much as 2% to 10% low. Therefore, the data user
should consider these totals as usable, but estimated values, due to the uncertainties of the individual
results which are summed to form these values.
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A.5.2.6 Surrogate Spike Compound
At the inception of the high resolution sediment coring study, TAMS/Gradient and Aquatec
employed two surrogates, tetrachloro-m-xylene (TCMX) and octachloronaphthalene (OCN). Aquatec
noted soon after the program began that OCN recoveries were a problem. For many of the sediment
samples, recoveries were less than 10% and sometimes 0%. although the TCMX and matrix
spike/matrix spike duplicate results for these same samples were usually acceptable. Reextraction and
reanalysis of the same samples produced similar results. The purpose of surrogate spike analyses is
to evaluate the performance of the extraction procedure. TAMS/Gradient and Aquatec determined that
OCN was an inappropriate surrogate for this program. Research by Aquatec suggests that OCN was
breaking down to heptachloronaphthalene and hexachloronaphthalene. During the validation process,
CDM rejected data that had OCN recoveries below 10%. During this data usability assessment, the
TAMS/Gradient Program QAO considered these results to be usable and changed the R qualifier to
a J qualifier (estimated results) for any result solely rejected due to poor OCN recoveries.
A.5.2.7 Confirmation by GC/ITD
Aquatec analyzed approximately 10% of all samples analyzed by GC/ECD by GC/ITD to
provide an additional mechanism to verify congener identification and. as a secondary objective,
quantitation of congeners. The ITD is not as sensitive as the ECD (approximately an order of
magnitude less sensitive); therefore, when possible, samples with the highest concentration of PCBs
were selected for GC/ITD confirmation. Although this may result in a program bias for only
confirming high concentration samples, the overall effect does not impair data usability.
In addition, there is the potential for some quantitative bias associated with the GC/ITD results
relative to the GE/ECD results. Aquatec quantified each congener detected in the GC/ITD analysis
using an average response factor per level of chlorination rather than using response factors determined
specifically for each individual congener. As such, potential bias, which will vary for each congener
within a chlorination homologue group, is present with the GC/ITD results. Since the ITD method was
not designed to be a primary quantitative tool, some variations in quantitative results were expected.
TAMS/Gradient considered quantitative differences between the GC/ITD and GC/ECD results less
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than a factor of five acceptable, while differences greater than five times were considered unacceptable
and associated results rejected,
A.5.3 Usability - Accuracy, Precision, Representativeness, and Sensitivity
TAMS/Gradient established a quality assurance system for this program to monitor and
evaluate the accuracy, precision, representativeness, and sensitivity of the results relative to the data
quality objectives. These are all important elements in evaluating data usability (e.g., USEPA. 1992b.
1993). Accuracy is a measure of how a result compares to a true value. Precision indicates the
reproducibility of generating a value. Representativeness is the degree to which a measurement(s) is
indicative of the characteristics of a larger population. Sensitivity is the limit of detection of the
analytical method.
This section will evaluate each of these parameters for the high resolution sediment coring
study. TAMS/Gradient assessed accuracy using holding times, instrument performance and
calibrations for both the GC/ECD and GC/ITD, internal standard performance for the GC/ITD,
surrogate criteria for both the GC/ECD and GC/ITD, spike recoveries, matrix spike/matrix spike
duplicate recovery results, and compared identification results. TAMS/Gradient assessed precision by
comparing matrix spike and matrix spike duplicate results. (A performance evaluation [PE] sample
was submitted with the water column samples. The results of the PE sample are discussed in Appendix
B.) TAMS/Gradient evaluated representativeness by comparing field duplicate results, and assessed
sensitivity using blank results and the sample-specific quantitation limits achieved.
Comparability and completeness are two other important data quality attributes. Comparability
expresses the confidence with which data are considered to be equivalent (USEPA, 1992b).
Comparable data allowed for the ability to combine the analytical results obtained from this study with
previous Hudson River studies. An in-depth discussion of data comparability is provided in Chapter
3 of the main body of this report. In addition, Gauthier (1994) has provided Aroclor translation
procedures for Hudson River capillary column GC data relative to previous packed column GC studies.
Completeness is a measure of the amount of usable data resulting from a data collection activity
(USEPA, 1992b). For this program, a 95% completeness goal was established. A discussion of
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completeness for the high resolution sediment coring study is provided in the conclusions section of
this report.
A.5.3.1 Accuracy
Accuracy was evaluated based on a number of factors, including holding times; instrument
performance; calibration; internal standard performance; surrogate spike recoveries; matrix
spike/matrix spike duplicate recoveries; and congener identification. These factors are discussed
below:
• Holding Times
Exceedance of holding times may indicate a possible loss of PCB congeners due to
volatilization, chemical reactions, and/or biological alterations. Due to the persistent nature of PCBs,
only severe exceedance should be considered deleterious to quantitative accuracy. For the sediment
samples, TAMS/Gradient established an extraction holding time of 7 days from sampling, followed
by an analysis holding time of 40 days from extraction.
Aquatec missed initial extraction holding times for only one sediment sample. However,
Aquatic reextracted 26 sediments sample past holding times. TAMS/Gradient considered data for all
these samples estimated. However, there were a significant number of sample extracts that Aquatec
analyzed outside of holding times. A summary of holding time exceedances are provided in Table A-3.
CDM appropriately qualified all data affected by missed holding times as estimated (G). CDM
qualified few samples for missed extraction holding times (5.9% of samples); and for those few
samples, the exceedances were not excessive. CDM noted significant analytical holding time
violations for many samples (16.7% of samples). In most cases, this was a direct result of Aquatec
encountering preparation and/or analytical problems requiring reextracticn and reanalysis of the
samples, or dilution of extracts with congener concentrations above the calibration range. As large as
some of these exceedances were, there should be no deleterious consequences to data quality. Aquatec
has routinely demonstrated the stability of all PCB congener standards in solvent is at least six months.
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Therefore, the TAMS/Gradient Program QAO considered all data qualified as estimated due to both
extraction and analytical holding time violations to be usable.
• GC/ECD Instrument Performance
Adequate chromatographic resolution and retention time stability throughout an analytical
sequence are essential attributes for qualitative identification of congeners on a GC. TAMS/Gradient
defined criteria for congener resolution and retention time windows in the Phase 2A SAP/QAPP. For
the SB-octyl-50 column, resolution must be greater than 50% between BZ#5 and 8,40 and 41,183 and
185, and BZ#209 and OCN. On the HP-5 column, resolution must be greater than 25% between BZ#4,
10 and TCMX, and between BZ#31 and 28. Resolution must be greater than 50% between BZ#84 and
101/90, and between BZ#206 and OCN. Aquatec initially established retention time windows for both
columns to be ±0.3% relative to the average initial calibration retention times for all target congeners
and surrogates.
CDM noted the only congener calibration standard coelution problems for BZ#5 with BZ#8
were on the HP-5 column. This occurred for five SDGs (171158, 172467, 172592, 170805, and
172624), with resolution ranging from 30% to 49%. The 50% resolution criteria established by
TAMS/Gradient for BZ#5/8 for this program was optimistic. Since 25% resolution was acceptable for
other congeners on the HP-5 column, the TAMS/Gradient Program QAO did not consider these
exceedances to be serious and they do not affect data usability. Only one SDG (167440) had any
significant number of exceedances for retention time criteria. However, all retention times were within
an expanded retention time window of ±0.4% (as agreed to by EPA Region II), and therefore, did not
affect identification.
Regarding sensitivity, for SDG 169803 Aquatec obtained no response for BZ#1 (a principal
congener) on the SB-octyl 50 column during the entire analytical sequence, hence CDM estimated (G)
and considered presumptively present the positive results for BZ#1 in all samples for this SDG. This
data is usable as a result of the documentation of its historical presence in Hudson River sediments.
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GC/ITD Instrument Performance
Verifying proper GC/ITD performance required evaluating GC column resolution, ion trap
detector sensitivity, and ion trap calibration. The GC resolution criteria required baseline separation
of BZ#87 from BZ#154 and BZ#77. The ion trap sensitivity requires the signal/noise ratio for m/z 499
for BZ#209 and m/z 241 for chrysene-d)2 to be greater than 5. For ion trap calibration, the abundance
of m/z 500 relative to m/z 498 for BZ#209 must be * 70% but ^95%. TAMS/Gradient noted no
significant ITD performance problems for samples analyzed during the high resolution sediment coring
study.
• GC/ECD Calibration
Instrument calibration requirements were established to verify the production of acceptable
quantitative data. Initial calibrations using 5-level standard concentration curves demonstrate an
instrument is capable of acceptable performance prior to sample analysis. The IC criteria is 20%
relative standard concentration error (%RSCE) for monochlorobiphenyl and 15% RSCE for all
remaining PCB congeners, and a correlation coefficient s 0.995. Continuing calibration standards
document maintenance of satisfactory performance over time. The only initial calibration problem of
any significance was with BZ#2. For six SDGs (171177, 172592, 172148, 170805, 172624, and
166425), BZ#2 was not detected in the low-level standard (5 ppb in extract), which required raising
the detection limit to the next lowest standard concentration (15 ppb in extract). For three SDGs
(167188,169031, and 167188), the correlation coefficient for BZ#2 was slightly below the requirement
of 0.995, thus requiring all related BZ#2 data for those SDGs to be qualified as estimated (G).
TAMS/Gradient noted no significant continuing calibration problems.
• GC/ITD Calibration
The initial calibration criteria for acceptable quantitative data for GC/ITD analyses required
percent relative standard deviations (% RSD) of the congener relative response factor (RRF) to be less
than 20%. For continuing calibration, the RRF for each congener must be within 20% of the mean
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calibration factor from the 5-level calibration at the beginning and end of each calibration sequence.
For the high resolution sediment coring study, TAMS/Gradient noted no significant GC/ITD
calibration problems.
• GC/ITD Internal Standard Performance
To demonstrate the stability of the ITD, internal standard performance criteria were monitored.
Internal standard area counts must not vary by more than 30% from the most recent calibration or by
more than 50% from the initial calibration. In addition, the absolute retention time of the internal
standard must be within 10 seconds of the retention time in the most recent calibration, and ion
abundance criteria must be met for chrysene-d12 and phenanthrene-ck . For the high resolution
sediment coring study, TAMS/Gradient noted no significant internal standard problems.
• Surrogate Spike Recoveries
Aquatec spiked surrogate compounds into all sediment samples prior to extraction to monitor
recoveries. Recoveries may be indicative of either laboratory performance or sample matrix effects.
For the high resolution sediment coring study, Aquatec used TCMX and OCN as surrogates. As
previously discussed, OCN did not perform properly as a representative surrogate, therefore, only
TCMX recoveries provide useful information. Therefore, the TAMS/Gradient Program QAO
considered data rejected solely because of poor OCN recoveries to be usable as estimated values.
These sequences are found in the QA comment field of the database. Affected samples are
summarized in Table A-4.
CDM qualified as estimated (G,UG) any data associated with samples that had TCMX
recoveries outside of a range of 60%-150%. For SDG 170825, five field samples and the matrix
spike/matrix spike duplicate sample associated with one of the five samples had no recovery of TCMX;
two field samples in SDG 172776 had no TCMX recoveries and one sample in SDG 172132 had a
TCMX recovery below 10%. CDM properly rejected (R) the results for these eight field samples.
These results were considered to be not usable.
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• Matrix Spike/Matrix Spike Duplicate Recoveries
Within each SDG, two aliquots of a representative sediment sample were spiked with a suite
of 20 congeners (BZ#8,18,28,44, 52,66, 77,101, 105,118,126, 128, 138,153,170,180,187,195,
206, and 209). The purpose of the spikes was, in part, to evaluate the accuracy of the analytical method
relative to laboratory performance and specific sample matrix. The advisory limits for spiked congener
recoveries are 60%-150%. TAMS/Gradient noted no significant spike recovery problems for any of
the high resolution sediment cores. Matrix spike/matrix spike duplicate analyses were analyzed for 30
high resolution sediment core samples. This represents a frequency of 6.1%, which exceeds the 5%
requirement stipulated in Phase 2A SAP/QAPP.
• Congener Identification
TAMS/Gradient established qualitative criteria to minimize erroneous identification of
s congeners. An erroneous identification can be either a false positive (reporting a compound present
when it is not) or a false negative (not reporting a compound that is present). The calculated
concentrations for congeners detected in both columns should not differ by more than 25% between
columns (%D s 25%). This criterion applies to only those congeners which can be resolved as
individual congeners on both columns. If the %D for the results between the two columns is > 25%
but j£ 50% the results were estimated. If the %D was > 50% but ^ 90%, the results were estimated and
presumptively present (GN). If the %D between columns was > 90%, the results were unusable (R).
TAMS/Gradient noted extensive problems with congener identifications as a result of dual
column imprecision for numerous SDGs, including 166783, 172897, 171177, 172592, 170805,
172624, and 169787. In fact, the majority of the estimated and rejected data for the high resolution
sediment coring study was a result of dual GC column imprecision. Of particular note was SDG
169787, for which 78 congener results were rejected, including BZ#18 (a principal congener) for one
sample. The greatest impact to the high resolution sediment coring study was to BZ#19, a principal
congener, which was rejected for 78 samples With the level of background organic material present
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in Hudson sediments, resultant interferences, particularly for congeners with low concentrations, likely
caused these differences between the dual GC column results.
A.5.3.2 Precision
• Matrix Spike/Matrix Spike Duplicate Comparison
The analysis of matrix spike (MS) and matrix spike duplicate (MSD) samples can also provide
valuable information regarding method precision relative to laboratory performance and specific
sample matrix. The advisory limit for relative percent difference (RPD) of spiked congeners in a
MS/MSD pair is 40%, and for nonspiked congeners, the precision criterion is 40% Relative Standard
Deviation (RSD).
TAMS/Gradient noted MS/MSD precision exceedances for only 4 SDGs (170825, 168494,
172897, and 172148). Regarding principal congeners, BZ#28 had a 57% RPD for SDG 168494 and
the %RPD ranged from 43% to 63% for BZ#8,18, 28, and 52 for SDG 172148. Overall, MS/MSD
performance for the high resolution sediment coring study was good.
A.5.3.3 Representativeness
• Field Duplicate Results
Analysis of field duplicate samples provides an indication of the overall precision of the
sampling and analysis program. These analyses measure both field and laboratory precision; therefore,
the results will likely have more variability than laboratory duplicates and MS/MSD samples, which
only measure laboratory precision. Data validators used a 50% RPD criteria for evaluating field
duplicate precision. Any congener precision greater than 50% RPD was qualified as estimated (G).
A total of 28 field duplicate samples were analyzed for the high resolution sediment coring
study. This represents a frequency of 5.7%, which exceeds the 5% requirement stipulated in the Phase
2A SAP/QAPP. Overall, field duplicate precision was acceptable; especially in the context of river
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sediments, which are typically heterogeneous. Typically a few congeners were qualified for each pair
of co-located sediments. Four SDGs had significant numbers of congeners with RPDs greater than
50%. These include SDG 172592 (26 congeners greater than 50%), 170825 (29 congeners greater than
50%), 167188 (35 congeners greater than 50%), and 17C473 (42 congeners greater than 50%). Table
A-5 summarizes the duplicate precision results for the 12 principal congeners for each field co-located
sample. Only one SDG (172592-Core 23) had serious precision problems for the principal congeners,
and to a lesser extent SDG 170825-Core 18. TAMS/Gradient scrutinized the data in SDG 172592 for
errors, but found none. Based on the difference in percent moisture between the two co-located
samples (70% versus 47.8%), the differences are suspected to be a result of extreme sample
heterogeneity.
A.5.3.4 Sensitivity
• Blanks
An important data quality objective associated with the high resolution sediment coring study
was to obtain detection limits as low as the analytical method could produce. One effect of this
approach is to register low level blank contamination during the preparation and analysis of the
sediments. As such, numerous congeners in all samples in all SDGs required blank contamination
qualifications. TAMS/Gradient reviewed the distribution of blank contaminants and found most
contamination associated with the monochlorobiphenyls, particularly with BZ#2. Blank levels for
BZ#2 usually ranged from 20 ppb to 80 ppb in extract, with a maximum of209 ppb in extract for SDG
169011. Since BZ#2 is not a dechlorination product, a major Aroclor component, or a principal
congener, TAMS/Gradient did not consider this to be a serious data quality problem. BZ#1, a principal
congener, was usually significantly lower in concentration in blanks than was BZ#2; but was present
in an enormous concentration (308 ppb in extract) for SDG 166308. BZ#4, a principal congener, was
often present in blanks from 10 ppb to 20 ppb in extract for most SDGs.
CDM qualified results during data validations with a "B", which indicated that the result was
within 5 times of the blank action level. TAMS/Gradient converted all "B" qualified results in the
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database to nondetect results due to uncertainty in this detection. Table A-6 summarizes the congener
detects changed to non-detects.
• Quantitation Limits
Evaluating dechlorination processes and modeling transport pathways of PCB congeners in
sediments necessitated obtaining low detection limits. TAMS/Gradient and Aquatec devised analytical
methods to enhance lower detection limits. This, in part, required employing sample/extract cleanup
methods to remove matrix interferences, and maximizing sample size when possible. For the high
resolution coring study, TAMS/Gradient defined optimum detection limits as 1 (ag/kg for
monochlorobiphenyls, 0.5 ng/kg for dichlorobiphenyls through hexachlorobiphenyls, and 0.5-1 (J.g/kg
for heptachlorobiphenyls through decachlorobiphenyl. Results of the MDL study necessitated raising
the detection limit for BZ#2 (a monochlorobiphenyl) significantly above these requirements
(approximately a factor of 3).
In general, achieving appropriate detection limits for the sediment samples was not a problem.
Whenever TAMS/Gradient noted raised detection limits, the affected samples contained high organic
content; specifically the presence of PCBs. The relative ratio of congeners detected within each high-
concentration sample remained reasonably consistent, therefore the elevated detection limit for
nondetected congeners did not affect data usability. Aquatec achieved adequate detection limits for
critical low level samples used for delineating the outer boundaries of sediment contamination, or other
PCB sources (e.g., tributaries).
A.5.4 Usability - Principal Congeners
The 12 principal target congeners employed in the high resolution sediment coring study are
key to delineating PCB geochemistry in the Hudson River. The following synopsis will provide data
users with the strengths and weaknesses of the principal target congener data within the context of this
study:
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BZ#1. The reported results for BZ#1 met the data quality objectives of the program. Results
for 14 sediment samples were rejected (out of 495 samples) due to dual GC column
imprecision. Analytically, BZ#1 eluted as a single peak on one GC column and coeluted on
the other GC column, which was acceptable for the purposes of this program. Regarding
sensitivity, for SDG 169803 no response was obtained for BZ#1 on the SB-octyl 50 column
during the entire analytical sequence, hence all BZ#1 data for this SDG was considered
presumptively present. This data is usable as a result of the documentation of its historical
presence in Hudson River sediments. With regard to detection limits, monochlorobiphenyls
were initially optimized to 1 ppb. In fact, detection limits for BZ#1, a monochlorobiphenyl,
were generally realized to be 1 to 6 ppb, which were acceptable, with one notable exception for
SDG 166308. The blank contamination for this SDG was 308 ppb in extract, which resulted
in significantly higher detection limits for all samples.
BZ#4. The reported results for BZ#4 met the data quality objectives of the program. Results
for 11 sediment samples were rejected due to dual GC column imprecision. Analytically,
BZ#4 eluted as a single peak on one GC column, and coeluted with BZ#10, another principal
congener, on the other GC column. Data for both BZ#4 and BZ#10 were considered usable.
With regard to detection limits, a goal of 0.5 ppb was established. In general, this goal was
met, however, there were many samples with associated blank levels of 10 ppb to 20 ppb in
extracts of BZ#4, which required raising the detection limit. This did not affect data usability.
BZ#8. The reported results for BZ#8 met the data quality objective of the program. Results
for nine sediments samples were rejected due to dual GC column imprecision. Analytically,
BZ#8 eluted as a single peak on one GC column and coeluted with BZ#5 on the other GC
column, which was acceptable for the purposes of this program. The detection limit goal of
0.5 ppb was met for nearly all samples. Matrix spike results for BZ#8 further indicated that the
method was successful.
BZ#10. The usability assessment for BZ#10 is similar to that for BZ#4. BZ#10 eluted as a
single peak on one GC column and coeluted with BZ#4 on the other GC column. Data for both
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BZ#4 and BZ#10 were considered usable. Results for 6 sediment samples were rejected due
to dual column imprecision. In general, the detection limit goal of 0.5 ppb was met.
BZ#18. Numerous results for BZ#18 were initially rejected by the data validator due to poor
dual column precision. The TAMS/Gradient Program QAO changed the rejection qualifier to
a presumptively present qualifier based on the presence of BZ#18 in historical sediment
samples containing PCBs, the consistent PCB congener pattern distribution present throughout
the Hudson River sediment, and GC/ITD confirmational analysis on about 10% of the data.
However, 12 sediment samples still remained rejected due to dual column imprecision.
Analytically, BZ#18 eluted as a single peak on one GC column and coeluted on the other GC
column. The detection limit goal of 0.5 ppb was met for nearly all samples. Matrix spike
results for BZ#8 further indicated that the method was successful. As such, the reported results
for BZ#18 met the data quality objectives of the program.
BZ#19. Results for 78 sediment samples were rejected due to dual GC column imprecision.
The results rendered 16% of all BZ#19 data unusable. This loss of data did not affect the
overall integrity of the program. The reported results for BZ#19 met the data quality objectives
of the program. Analytically, BZ# 19 eluted as a single congener on both GC columns. The
detection limit goal of 0.5 ppb was met for nearly all samples.
BZ#28. The reported results for BZ#28 met the data quality objectives of the program. Results
for seven sediment samples were rejected due to dual GC column imprecision. Analytically,
BZ#28 eluted an a single congener peak on both GC columns. The detection limit goal of 0.5
ppb was met for nearly all samples. Matrix spike results for BZ#28 further indicates the
method was successful.
BZ#52. The reported results for BZ#52 met the data quality objectives of the program. Results
for two sediment samples were rejected due to dual GC column imprecision. Analytically,
BZ#52 eluted as a single congener peak on both GC columns. The detection limit goal of 0.5
ppb was met for nearly all samples. Matrix spike recovery for BZ#52 further indicated that the
method was successful.
A-26
T AM S/Cadmus/Gradient
-------
BZ#101. Data users should be aware that BZ#101 always coeluted with BZ#90 (on both GC
columns), and therefore was always reported with BZ#90. For reported results, all other
QA'QC requirements were met, therefore should be considered usable. No sample results were
rejected. The detection limit goal of 0.5 ppb was met for nearly all samples. Matrix spike
results for BZ#101 further indicated that the method was successful.
BZ#118. The reported results for BZ#118 met the data quality objectives of the program.
Results for 12 sediment samples were rejected due to dual column imprecision. Analytically,
BZ#118 eluted as a single peak on both GC columns. The detection limit goal of 0.5 ppb was
met for nearly all samples. Matrix spike results for BZ#118 further indicated that the method
was successful.
BZ#138. The reported results for BZ#138 met the data quality objectives of the program.
Results for three sediment samples were rejected due to dual column imprecision.
Analytically, BZ#138 eluted as a single peak on one GC column and coeluted on the other GC
column. The detection limit goal of 0.5 ppb was met for nearly all samples. Matrix spike
results for BZ#138 further indicated that the method was successful.
BZ#180. The reported results for BZ#180 met the data quality objectives of the program.
Results for three sediment samples were rejected due to dual column imprecision.
Analytically, BZ#180 eluted as a single peak on one GC column and coeluted on the other GC
column. The detection limit goal of 0.5 ppb to 1 ppb was met for nearly all samples. Matrix
spike results for BZ#180 further indicated that the method was successful.
A.5 Conclusions
The PCB congener analytical chemistry program implemented by TAMS/Gradient for the
Hudson River high resolution sediment coring study required the development and use of program-
specific GC/ECD methodology in order to generate data meeting the data quality objectives of the
program. A total of 495 sediment samples were analyzed for 126 target and non-target congeners.
A-27
TAMS/Cadmus/Gradient
-------
NYSDEC. 1989. "Analytical Service Protocols." Issued September 1989. revised December 1991
and September 1993. Method 91-11. pp D-XXVIII, 5-59. New York State Department of
Environmental Conservation. Bureau of Technical Services and Research. Albany, New York.
Schulz, D. 1989. "Complete Characterization of Polvchlorinated Biphenyl Congeners in Commercial
Aroclor and Clophen Mixtures by Multidimensional Gas Chromatography-electron Capture Detection."
Environ. Sci. Technol., 23:852-859.
TAMS/Gradient. 1992. '"Phase 2A Sampling and Analysis Plan/Quality Assurance Project Plan -
Hudson River PCB Reassessment RI/FS." EPA Contract No. 68-S9-2001.
USEPA. 1984. '"Definition and Procedure for the Determination of the Method Detection Limit -
Revision 1.11." Federal Register, 49(209): 198-199.
USEPA. 1986. Test Methods for Evaluating Solid Waste. U.S. Environmental Protection Agency,
Office of Solid Waste and Emergency Response, Washington, DC, SW-846, Third Edition, Chapter
1.
USEPA. 1988. "Laboratory Data Validation. Functional Guidelines for Evaluating Organics
Analyses/' U.S. Environmental Protection Agency. Hazardous Site Evaluation Division, Contract
Laboratory Program. Washington, DC.
USEPA. 1991. "Statement of Work for Organic .Analysis, Multi-Media, Multi-Concentration."
Document Number OLM 01.0, including revisions through OLM 01.8, August 1991, pp 55. U.S.
Environmental Protection Agency, Washington, DC.
USEPA. 1992a. "CLP Organics Data Review and Preliminary Review." SOP No. HW-6, Rev No.
8, U.S. Environmental Protection Agency Region II, Edison, New Jersey, January.
USEPA. 1992b. "Guidance for Data Usability in Risk Assessment." U.S. Environmental Protection
Agency, Office of Emergency and Remedial Response, Washington, DC. EPA PB92-963356,
Publication 9285.7-09A.
USEPA. 1993. "Data Quality Objectives Process for Superfund." U.S. Environmental Protection
Agency, Office of Solid Wraste and Emergency Response, Washington, DC, EPA 540-R-93-071,
Publication 9355.9-01.
USEPA. 1994. "Guidance for the Data Quality Objectives Process."' U.S. Environmental Protection
Agency, Quality Assurance Management Staff. Washington, DC, EPA QA/G-4.
Wait, A.D. 1992. Field Quality Assurance Audit Report, dated October 8.
A-30
T AMS/Cadmus/Gradient
-------
Table A-l
Phase 2 Target and Non-Target PCB Congeners Used in Analyses
Congener Number Homologue Group Congener Name Target*
BZ #1
Mono
2-ChlorobiphenvI
Yes
BZ #2
Mono
3-Chlorobiphenyl
Yes
BZ #3
Mono
4-Chlorobiphenyl
Yes
BZ #4
Di
2,2'-Dichlorobiphenyl
Yes
BZ #5
Di
2,3-Dichlorobiphenyl
Yes
BZ # 6
Di
2,3'-Dichiorobiphenyl
Yes
BZ #7
Di
2,4-Diclilorobiphenyl
Yes
BZ £8
Di
2,4'-Dichlorobiphenyl
Yes
BZ #9
Di
2,5-Dichlorobiphenyl
Yes
BZ #10
Di
2,6-Dichlorobiphenyl
Yes
BZ*12
Di
3,4-Dichlorobiphenyl
Yes
BZ £15
Di
4.4'-Dichlorobiphenvl
Yes
BZ #16
Tri
2,2',3-Trichlorobiphenyi
Yes
BZ #17
Tri
2,2',4-Trichlorobiphenyl
No
BZ#18
Tri
2.2',5-Trichlorobiphenyl
Yes
BZ#19
Tri
2,2',6-Trichlorobiphenyl
Yes
BZ #20
Tri
2,3,3'-Trichlorobiphenyl
No
BZ #22
Tri
2:3,4'-Trichlorobiphenyl
Yes
BZ #23
Tri
2,3,5-Trichlorobiphenyl
No
BZ #24
Tri
2,3,6-TrichlorobiphenyI
No
BZ #25
Tri
2,3',4-Trichlorobiphenyl
Yes
BZ #26
Tri
2,3',5-Trichlorobiphenyl
Yes
BZ #27
Tri
23',6-Trichlorobiphenyl
Yes
BZ #28
Tri
2,4,4'-Trichlorobiphenyl
Yes
BZ #29
Tri
2,4,5-Trichlorobiphenyl
Yes
BZ #31
Tri
2,4',5-Trichlorobiphenyl
Yes
BZ #32
Tri
2,4',6-Trich lorobiphenyl
No
BZ #33
Tri
2'.3.4-Trichlorobiphenyl
No
BZ #34
Tri
2'.3,5-Trichlorobiphenyl
No
BZ #37
Tri
3,4,4'-Trichlorobiphenyl
Yes
TAMS/Cadmus/Gradient
-------
Table A-l
(Continued)
Phase 2 Target and Non-Target PCB Congeners Used in Analyses
Congener Number Homologue Group Congener Name Target3
BZ £40
Tetra
2,2',3.3'-Tetrachlorobiphenyl
Yes
BZ #41
Tetra
22'.3,4-Tetrachlorobiphenyl
Yes
BZ £42
Tetra
2,2',3,4'-T etrach lorobipheny 1
No
BZ £44
Tetra
2,2',3.5'-Tetrachlorobiphenyl
Yes
BZ£45
Tetra
2.2',3,6-Tetrachlorobiphenyl
No
BZ #47
Tetra
2,2',4.4'-Tetrach lorobipheny 1
Yes
BZ £48
Tetra
2,2',4,5-Tetrachlorobiphenyl
No
BZ £49
Tetra
2,2'.4.5'-Tetrachlorobiphenyl
Yes
BZ £51
Tetra
2.2\4.6'-Tetrachlorobipheny]
No
52
Tetra
2.2'.5.5' Tetrachlorobiphenyl
Yes
BZ £53
Tetra
2,2',5,6'-TetrachlorobiphenyI
Yes
BZ £56
Tetra
2,3.3'.4'-Tetrachlorobiphenyl
Yes
BZ £58
Tetra
2.3.3'.5'-Tetrachlorobiphenyl
No
BZ #60
Tetra
2,3,4,4'-Tetrachlorobiphenyl
No
BZ £63
Tetra
2.3,4',5-Tetrachlorobipheny!
No
BZ £64
Tetra
2.3,4',6-Tetrachlorobiphenyl
No
BZ £66
Tetra
2.3'.4,4'-Tetrachlorobiphenyl
Yes
BZ £67
Tetra
2.3'.4,5-Tetrachlorobiphenyl
No
BZ £69
Tetra
2.3\4,6-Tetrachlorobiphenyl
No
BZ £70
Tetra
2,3\4',5-Tetrachlorobiphenyl
Yes
BZ £74
Tetra
2.4,4',5-Tetrachlorobiphenyl
No
BZ £75
Tetra
2.4,4',6-Tetrachlorobiphenyl
Yes
BZ £77
Tetra
3,3'A4'-Tetrachlorobiphenyl
Yes
BZ £82
Penta
2,2\3,3'.4-Pentachlorobiphenyl
Yes
BZ £83
Penta
2.2'.3,3',5-Pentachlorobiphenyl
Yes
BZ £84
Penta
2.2'.3,3',6-Pentachlorobiphenyl
Yes
BZ £85
Penta
2,2'.3,4,4'-Pentachlorobiphenyl
Yes
BZ £87
Penta
2r2\3A5'-Pentachlorobiphenyl
Yes
BZ £88
Penta
2.2'.3.4,6-Pentachlorobiphenyl
No
BZ £90
Penta
2,2',3,4',5-Pentachlorobiphenyl
No
T AMS/Cadmus/Gradient
-------
Table A-l
(Continued)
Phase 2 Target and Non-Target PCB Congeners Used in Analyses
Congener Number Homologue Group Congener Name Target*
BZ #91
Penta
2.2',3.4'.6-Pentachlorobiphenyl
Yes
BZ £92
Penta
2?2',3,5,5'-Pentachlorobiphenyl
Yes
BZ #95
Penta
2.2',3,5'.6-Pentachlorobiphenyl
Yes
BZ #96
Penta
2,2',3.6,6'-Pentachlorobiphenyl
No
BZ #97
Penta
2,2',3',4.5-Pentachlorobiphenyl
Yes
BZ #99
Penta
2,2',4,4',5-Pentachlorobiphenyl
Yes
BZ #101
Penta
2,2',4,5,5'-Pentachlorobiphenyl
Yes
BZ #105
Penta
2,3,3',4.4'-Pentachlorobiphenyl
Yes
BZ #107
Penta
2.3,3'.4,5'-Pentachlorobiphenyl
Yes
BZ #110
Penta
2.3.3'.4\6-Pentachlorobiphenyl
No
BZ #114
Penta
2.3,4.4',5-Pentachlorobiphenyl
No
BZ #115
Penta
2,3,4.4'.6-Pentachlorobiphenyl
Yes
00
N
CO
Penta
2,3',4,4',5-Pentachlorobiphenyl
Yes
CD
N
£
Penta
2.3',4,4\6-Pentachlorobiphenyl
Yes
BZ #122
Penta
2',3,3',4,5-Pentachlorobiphenyl
Yes
BZ #123
Penta
2',3,4,4',5-Pentachlorobipheny 1
Yes
BZ #126
Penta
3,3',4,4',5-Pentachlorobiphenyl
Yes
BZ #128
Hexa
2,2'.3,3',4,4'-Hexachlorobiphenvl
Yes
BZ # 129
Hexa
2,2',3,3',4,5-Hexachlorobiphenyl
Yes
BZ #135
Hexa
2,2',3,3',5,6'-Hexachlorobiphenyl
No
BZ #136
Hexa
2,2'.3,3',6,6'-Hexachlorobiphenyl
Yes
BZ #137
Hexa
2,2',3,4,4',5-Hexachlorobiphenyl
Yes
BZ #138
Hexa
2,2',3,4,4',5'-Hexachlorobiphenyl
Yes
BZ #140
Hexa
2,2',3,4,4',6'-Hexachlorobiphenyl
No
BZ #141
Hexa
2,2',3,4,5,5'-Hexachlorobiphenyl
Yes
BZ #143
Hexa
2,2',3,4,5,6-Hexachlorobiphenyl
No
BZ # 144
Hexa
2.2',3.4?5',6-Hexachlorobiphenyl
No
BZ # 146
Hexa
2,2',3,4',5.5'-Hexachlorobiphenyi
No
BZ #149
Hexa
2,2'3.4',5'.6-Hexachlorobiphenyl
Yes
BZ #151
Hexa
2,2',3,5.5'.6-Hexachlorobiphenyl
Yes
T AMS/Cadmus/Gradient
-------
Table A-l
(Continued)
Phase 2 Target and Non-Target PCB Congeners Used in Analyses
Congener Number Homologue Group Congener Name Target3
BZ #153
Hexa
2,2',4.4'.5:5'-Hexachlorobiphenyl
Yes
BZ #156
Hexa
2,3,3'.4,4',5-Hexachlorobiphenyl
No
BZ #157
Hexa
2.3.3\4,4',5'-Hexachlorobiphenyl
Yes
BZ #158
Hexa
2J,3',4.4',6-Hexachlorobiphenyl
Yes
BZ # 160
Hexa
2.3,3',4.5,6-Hexachlorobiphenyl
No
BZ # 167
Hexa
2,3',4,4',5.5'-Hexachlorobiphenyl
Yes
BZ #168
Hexa
2,3',4.4'.5'.6-Hexachlorobiphenyl
No-
BZ # 169
Hexa
3,3',4.4'.5.5'-HexachlorobiphenyI
No
BZ #170
Hepta
2,2',3,3'.4.4'.5-Heptachlorobiphenyl
Yes
BZ #171
Hepta
2,2'.3,3'A4'.6-Heptachlorobiphenyl
Yes
BZ #172
Hepta
2,2',3.3'A5,5'-Heptachlorobiphenyl
No
BZ # 174
Hepta
2,2',3,3',4.5,6'-Heptachlorobiphenyl
No
BZ #175
Hepta
2,2',3,3',4.5\6-Heptachlorobiphenyl
No
BZ #177
Hepta
2,2'.3,3\4',5,6-Heptachlorobiphenyl
Yes
BZ £178
Hepta
2.2',3,3',5,5',6-Heptachlorobiphenyl
No
BZ #180
Hepta
2.2',3,4,4',5,5'-Heptachlorobiphenyl
Yes
BZ*?183
Hepta
2,2',3,4,4',5',6-Heptachlorobiphenyl
Yes
BZ # 184
Hepta
2,2',3.4,4',6,6'-Heptachlorobiphenyl
No
BZ #185
Hepta
2,2',3,4.5,5',6-Heptachlorobiphenyl
Yes
BZ # 187
Hepta
2:2\3,4',5,5'.6-Heptachlorobiphenyl
Yes
CD
N
00
o
Hepta
2,3,3',4,4',5.5'-Heptachlorobiphenyl
Yes
BZ #190
Hepta
2,3.3'.4,4',5,6-Heptachlorobiphenyl
Yes
BZ #191
Hepta
2,3,3'.4,4',5',6-Heptachlorobiphenyl
Yes
BZ # 192
Hepta
2,3,3',4.5,5',6-Heptachlorobiphenyl
No
BZ #193
Hepta
2.3,3',4',5,5'.6-Heptachlorobiphenyl
Yes
BZ # 194
Octa
2,2'.3.3',4,4',5.5'-Octachlorobiphenyl
Yes
BZ # 195
Octa
2,2',3.3'.4.4',5,6-Octachlorobiphenyl
Yes
BZ # 196
Octa
2,2'.3.3',4,4',5',6-Octachlorobiphenyl
Yes
BZ #197
Octa
2,2'.3,3\4,4'.6.6'-Octachlorobiphenyl
No
BZ #198
Octa
2.2'.3.3'.4,5,5',6-Octachlorobiphenyl
Yes
TAMS/Cadmus/Gradient
-------
Table A-l
(Continued)
Phase 2 Target and Non-Target PCB Congeners Used in Analyses
Congener Number Homologue Group Congener Name Target'
BZ#199
Octa
2.2',3.3',4,5,6,6'-Octachlorobiphenyl
Yes
BZ #200
Octa
2.2',3,3',4,5',6,6'-Octachlorobiphenyl
Yes
BZ #201
Octa
2,2'.3.3'.4'.5,5'.6-Octachlorobiphenvl
Yes
BZ #202
Octa
2,2'.3,3',5,5',6,6'-OctachIorobiphenyI
Yes
BZ #203
Octa
2,2',3,4,4'.5,5'.6-Octachlorobiphenyl
No
BZ #205
Octa
2,3,3',4.4',5J',6-Octachlorobiphenyl
Yes
BZ #206
Nona
2,2',3,3\4,4',5,5',6-Nonachlorobiphenyl
Yes
BZ #207
Nona
2.2'.3.3'A4',5,6,6'-Nonachlorobiphenyl
Yes
BZ #208
Nona
2.2'.3.3'.4,5,5',6,6'-Nonachlorobiphenyl
Yes
BZ #209
Deca
2,2',3,3'.4,4',5.5\6,6'-Decachlorobiphenyl
Yes
Homologue Group
Congener Ratio6
Mono
3:3
Di
9:12
Tri
18:24
Tetra
23:42
Penta
23:46
Hexa
19:42
Hepta
16:24
Octa
11:12
Nona
3:3
Deca
1:1
Sum
126:209
Notes
"Fes. Target, .Yo. Son-target; So - Cal: Calibrated non-target.
Ratio of number of congeners used to total number of congeners in homologue group.
TAMS/Cadmus/Gradient
-------
Table A-2
Data Qualification Codes
Source of
Qualifier
Definition of Qualifier Code
Data Validation/
Assessment
Qualifier Code
Database
Qualifier
Code
Laboratory
Compound not detected above reporting limit of 0.1 ppb in extract for
all PCB congeners (0.5 ppb in extract for the monochlorinated
biphenyls). The reported value is the quantitation limit (QL).
U
U
Laboratory
Compound detected above reporting limit, but below calibration range.
This qualifier is applied to any positive result that is less than the
lowest calibration standard. The reported lesult is an estimated value,
due to uncertainty in the reported value near the quantitation limit.
J
J
I .aboratory
Compound concentration exceeds the calibration range.
This qualifier is applied to any positive result that exceeds the
calibration range. The laboratory may report some congeners with
concentrations up to twice the concentration in the highest calibration
standard, in order to report some very low concentrations and low
quantitation limits. The reported result is an estimated value, due to
uncertainty in the quantitation above the calibrated range of the
instrument.
K
J
Laboratory
Specific column result used for quantitation due to confirmation
column coelution.
This qualifier designates congeners whose results are always
quantitated from a specific column due to coelution w ith congeners or
surrogates on the other column. The reported result should be
considered an estimated value, due to inability to confirm the
concentration of the result because of coelution on the other column.
The S qualifier precludes the P qualifier since a %Difference (%D)
between columns is excepted to be greater than 25% due to coelution
on one column.
S
J
TAMS/'Cadmus/Gradient
-------
Table A-2
(Continued)
Data Qualification Codes
Source of
Qualifier
Definition of Qualifier Code
Data Validation/
Assessment
Qualifier Code
Database
Qualifier
Code
Laboratory
Tentative identification, specific column result used with no
confirmation information.
This qualifier designates congeners which could not be confirmed due
to an interferant (or surrogate) peak, however, there is good reason to
believe its presence. The reported value should be considered an
estimated value, due to inability to confirm reported concentrations.
T
JN
Laboratory
Estimated concentration due to coelution on both columns.
This qualifier designates congeners which coelute with congeners or
surrogates on both analytical columns. In order to report a
concentration for the congener of interest, the concentrations of the
coeluting congeners are subtracted from it. Therefore, the reported
result is an estimated value.
X
J
Laboratory
Confirmation column result exceeds reported result by more than 25%.
This qualifier is applied to a congener result if the concentration on the
quantitation and confirmation columns exceed the percent difference
(%D) criteria of 25. The reported result is an estimated value, due to
poor precision of results between columns.
P
J
Laboratory-'
Specific column or estimated result exceeds confirmation result by-
more than 25% despite expected confirmation coelution.
This qualifier is applied to a congener result if the result from the
quantitation column exceeds the confirmation result by more than 25
%D, even though the confirmation column result was expected to be
greater due to coelution on the confirmation column. Therefore, the
reported result should be considered an estimated value, bias high.
H
J
Data
Validation
Estimated data due to exceeded quality control criteria.
This qualifier is applied to data if problems with data quality are noted
and estimation of the data is deemed necessaiy. Justification for
qualification are given in the data validation report.
G
J
T AMS/Cadmus/Gradient
-------
Table A-2
(Continued)
Data Qualification Codes
Source of
Qualifier
Definition of Qualifier Code
Data Validation/
Assessment
Qualifier Code
Database
Qualifier
Code
Data
Validation
Reject data due to exceeded quality control criteria.
This qualifier is applied to data if serious problems with data quality
are noted and rejection of the data is deemed necessary. Justification
for rejection of data are given in the data validation report. Rejected
data are not usable and do not meet the data quality objectives of the
program. No numerical value is reported.
R
R
Data
Validation
The compound was also detected in associated blank(s).
This qualifier is applied to GC/ECD results that are within five times
the concentration detected in the associated blanks. The reported
result may be considered not detected: a false positive is suspected due
to blank contamination.
B
U
Data
Validation
GC/F.CD result at concentration within GCTTD calibration range, but
not confirmed by GC/ITD analysis.
This qualifier is applied to GC/ECD results that are not confirmed by
GCTTD analysis, even though the results are at sufficient
concentration to be detected by GCTTD. The reported result is
suspect as it may be a false positive.
Q
JN
Data
Validation
Positive GC'ITD result was not detected by GC/ECD analysis or
greater than five times GC'ECD result.
This qualifier is applied to GC/ECD results if the concentration of the
GC/ITD results are greater than five times the GC/ECD results. Also
the nondetect GC/ECD result is qualified if a congener is detected by
GC/ITD and not detected by GC/ECD. The reported result is suspect
as it mav be a false neeative or a misidentification.
M
R
Data
Validation
Presumptive evidence for the presence of a material.
This qualifier is applied to GO'ECD results that exceeded the
compound identification criteria. The reported result is suspect as it
may be a false positive.
N
N
TAMS/Cadmus/Gradient
-------
Table A-2
(Continued)
Data Qualification Codes
Source of
Qualifier
Definition of Qualifier Code
Data Validation/
Assessment
Qualifier Code
Database
Qualifier
Code
Data
Management
Results generated by decoupling BZ 34 and 10 using regression
analysis.
L
J
Data
Management
Results updated by Aquatec due to revisions in GC column
performance.
K
—
Data
Management
Results requalified by QAO due to decisions made during data
usability assessment.
Y
J
TAMS/Cadmus/Gradient
-------
Table A-3
Holding Time Violations for High Resolution Coring Study
Core Number
SDG
Holding Time Exceeded
Problem
HR-021
172132
Extraction/Analytical
All samples (16) reextracted and reanalyzed 39
days past criteria.
HR-014
169803
Analytical-1TD
Two samples exceeded 1TD criteria by a few
days.
HR-019
171158
Analytical
All samples (19) exceeded holding times by
nearly two months. Surrogate recoveries were
good.
HR-027
172790
Analytical
Four samples exceeded bv five days, one sample
exceeded by two days.
HR-026
172776
Analytical
One sample exceeded by four days.
HR-028
172467
Extraction
Two samples exceeded by 11 days.
HR-020
171177
Analytical
Seven samples exceeded by 63 days.
HR-007
167188
Analytical
Four samples exceeded by a few days.
HR-011
169011
Analytical
One sample exceeded by a few days.
HR-024
172624
Extraction/Analytical
Six samples reextracted 56 days past holding
times. One of those samples analyzed 35 days
past holding times. Original problem involved
method blank contamination. Both sets of data
submitted.
HR-002
166425
Extraction
One sample exceeded by a few days.
Analytical
Three samples exceeded by a few days.
HR-001
166308
Extraction
Three reextracts exceeded by a few days. One
reextract exceeded by 40 days.
HR-009
167474
Analytical
All samples (24) exceeded by 1-2 days.
HR-008
167440
Analytical
Seven samples exceeded by a few days.
T AMS/Cadmus/Gradient
-------
Table A-4
Sediment Data Unrejected Due to Poor OCN Recoveries
Core Number
SDG
Sample IDs
HR-018
170825
SB2976, 2968, 2979
HR-026
172776
SB 1225, 1226, 1227, 1231
HR-010
168494
SB2126, 2128, 2129, 2132
HR-005
166783
SB0687, 0688, 0689, 0690, 2008, 2010
HR-027
172763
SB 1211
HR-020
171177
SB3009, 3012,3027
HR-023/024
172592
SB3079
HR-022
172148
SB3053, 3054, 3055. 3056, 3060. 3062
HR-011
169011
SB2147, 2150, 2158,2160
HR-017
170805
SB2945, S946, 2947, 2959, 2964
HR-022
166425
SB0639
HR-011
169031
SB2164, 2166,2172
HR-001
166308
SB0618, 0629
HR-015/016
170473
SB2896
HR-009
167474
SB2086,2088,2096,2097, 2098, 2099, 2101, 2103
HR-006
167171
SB2014, 2015, 2016, 2017, 2018
HR-008
167440
SB2061, 2062,2063,2064,2067,2069, 2070, 2076,
2077, 2079, 2080, 2081, 2082, 2110
HR-013
169787
SB2851, 2854,2856, 2857,2860, 2862, 2865, 2867,
2868, 2870
HR-021
172132
SB3032, 2038, 3040, 3041, 3044
HR-012
169625
SB0614,2183, 2184,2187,2189, 2191,2193, 2195,
2196,2198,2199
HR-015/016
170310
SB2891, 2912,2914, 2915, 2927,2929,2930. 2931,
2932, 2934.2935, 2936
HR-014
169803
SB2871. 2872, 2874, 2876, 2883, 2884, 2887
HR-019
171158
SB2986
TAMS/Cadmus/Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-005-0812
1 BZtfl
ug/Kg D\V
7.88 U
7 91 U
NC
HR-005-0812
4 BZ#4
ug/Kg DVV
6.99 U
3.5 U
NC
HR-005-0812
8 BZ#8
ug/Kg DW
11.1 J
9.18 JN
19
HR-005-0812
10 BZ#10
ug/Kg DW
0.476 U
1.73 U
NC
HR-005-0812
18 BZ#18
ug/Kg DW
1 58 U
1.58 U
NC
HR-005-0812
19 BZ#19
ug/Kg DW
6.56 U
7 U
NC
HR-005-0812
28 BZ#28
ug/Kg DW
47.1 J
40.6 JN
15
HR-005-0812
52 BZ#52
ug/Kg DW
33.2 J
27.3 JN
20
HR-005-0812
101 BZ#101& BZ#[90]
ug/Kg DW
30.8 J
27.4 JN
12
HR-005-0812
118 BZ#118
ug/Kg DW
25.9 J
20.8 JN
22
HR-005-0812
138 BZ#138
ug/Kg DW
41.4 J
34.1 JN
19
HR-005-0812
180 BZ#180
ug/Kg DW
28.8 J
23.6 JN
20
HR-005-2024
1 BZ#1
ug/Kg DW
7.19 U
7.62 U
NC
HR-005-2024
4 BZ#4
ug/Kg DW
2.09 U
2.24 U
NC
HR-005-2024
8 BZ#8
ug/Kg DW
8.97 J
9 91 J
-10
HR-005-2024
10 BZ#10
ug/Kg DW
0.721 U
2.67 U
NC
HR-005-2024
18 BZ#18
ug/Kg DW
1.44 U
1.52 U
NC
HR-005-2024
19 BZ#19
ug/Kg DW
R
R
NC
HR-005-2024
28 BZ#28
ug/Kg DW
37 J
45.8 J
-21
HR-005-2024
52 BZ#52
ug/Kg DW
38.3 J
34.7 J
10
HR-005-2024
101 BZ#101 & BZ#[90]
ug/Kg DW
21.7 J
31.2 J
-36
HR-005-2024
118 BZ#118
ug/Kg DW
19.8 J
26.7 J
-30
HR-005-2024
138 BZ#138
ug/Kg DW
31.1 J
40.7 J
-27
HR-005-2024
180 BZ#180
ug/Kg DW
18.2 J
23.6 J
-26
HR-005-3236
1 BZ#1
ug/Kg DW
5.24 U
5.15 U
NC
HR-005-3236
4 BZ#4
ug/Kg DW
0.848 U
1.03 U
NC
HR-005-3236
8 BZ#8
ug/Kg DW
1.05 U
1.03 U
NC
HR-005-3236
10 BZ#10
ug/Kg DW
0.327 U
1.03 U
NC
HR-005-3236
18 BZ#18
ug/Kg DW
1.05 U
2.85 U
NC
HR-005-3236
19 BZ#19
ug/Kg DW
R
R
NC
HR-005-3236
28 BZ#28
ug/Kg DW
1.05 U
1.03 U
NC
HR-005-3236
52 BZ#52
ug/Kg DW
1.05 U
6.54 J
NC
HR-005-3236
101 BZ#101 & BZ#[90]
ug/Kg DW
1.05 U
1.03 U
NC
HR-005-3236
118 BZ#118
ug/Kg DW
1.05 U
1.03 U
NC
HR-005-3236
138 BZ#138
ug/Kg DW
0.483 U
' 0.147 U
NC
HR-005-3236
180 BZ#180
ug/Kg DW
R
1.03 U
NC
HR-005-4044
1 BZ#1
ug/Kg DW
R
R
NC
HR-005-4044
4 BZ#4
ug/Kg DW
4.95 U
1.18 U
NC
HR-005-4044
8 BZ#8
ug/Kg DW
1.11 U
1.18 U
NC
HR-005-4044
10 BZ#10
ug/Kg DW
1.44 U
1.42 U
NC
HR-005-4044
18 BZ#18
ug/Kg DW
111 U
4.21 U
NC
HR-005-4044
19 BZ#19
ug/Kg DW
R
R
NC
HR-005-4044
28 BZ#28
ug/'Kg DW
111 U
1.18 U
NC
HR-005-4044
52 BZ#52
ug/Kg DW
6.24 J
12.7 J
-68
Note: Congeners in [ ] are co-eluting non-target congeners.
1
TAMS/Cadmus/Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-005-4044
101 BZ#101 & BZif[90]
ug/Kg DW
1 11 U
1.18 U
NC
HR-005-4044
118 BZ#118
ug/Kg DW
0.17 U
R
NC
HR-005-4044
138 BZ#138
ug/Kg DW
1.11 U
0 398 U
NC
HR-005-4044
180 BZ#180
ug/Kg D VV
1.11 U
1.18 U
N'C
HR-007-3640
1 BZ#1
ug/Kg DW
24 U
26.9 U
NC
HR-007-3640
4 BZ#4
ug/Kg DW
53.6 JN
98.7 J
-59
HR-007-3640
8 BZ#8
ug/Kg DW
18.8 J
46.3 J
-84
HR-007-3640
10 BZ#10
ug/Kg DW
3.55 JN
10.9 J
-102
HR-007-3640
18 BZ#18
ug/Kg DW
184 J
375 J
-68
HR-007-3640
19 BZ#19
ug/Kg DW
22.7 U
43.3 U
NC
HR-007-3640
28 BZ#28
ug/Kg DW
280 J
667 J
-82
HR-007-3640
52 BZ#52
ug/Kg DW
132 J
345 J
-89
HR-007-3640
101 BZ310I & BZ£[90]
ug/Kg DW
42.3 J
125 J
-99
HR-007-3640
118 BZ#118
ug/Kg DW
30.4 J
96.2 J
-104
HR-007-3640
138 BZ#138
ug/Kg DW
20.9 J
63.1 J
-100
HR-007-3640
180 BZ#180
ug/Kg DW
9.22 U
21.4 JN
NC
HR-007-4852
1 BZ#1
ug/Kg DW
20.9 U
3.31 JN
NC
HR-007-4852
4 BZ#4
ug/Kg DW
156 J
257 J
-49
HR-007-4852
8 BZ#8
ug/Kg DW
76.4 J
124 J
-48
HR-007-4852
10 BZ#10
ug/Kg DW
15.3 J
16.8 J
-9
HR-007-4852
18 BZ#18
ug/Kg DW
350 JN
717 J
-69
HR-007-4852
19 BZ#19
ug/Kg DW
45 U
75.4 U
NC
HR-007-4852
28 BZ#28
ug/Kg DW
276 J
614 J
-76
HR-007-4852
52 BZ#52
ug/Kg DW
106 J
218 J
-69
HR-007-4852
101 BZ#101 & BZ#[90]
ug/Kg DW
34.2 J
55.8 J
-48
HR-007-4852
118 BZ#118
ug/Kg DW
25.7 J
42 J
-48
HR-007-4852
138 BZ#138
ug/Kg DW
19.4 J
28.7 J
-39
HR-007-4852
180 BZ#180
ug/Kg DW
6.6 U
9.36 U
NC
HR-008-4044
1 BZ#1
ug/Kg DW
30.9 U
R
NC
HR-008-4044
4 BZ#4
ug/Kg DW
449 J
268 U
NC
HR-008-4044
8 BZ#8
ug/Kg DW
368 J
245 J
40
HR-008-4044
10 BZ#10
ug/Kg DW
28.6 U
21.9 J
NC
HR-008-4044
18 BZ#18
ug/Kg DW
1830 J
780 J
80
HR-008-4044
19 BZ#19
ug/Kg DW
157
122 U
NC
HR-008-4044
28 BZ#28
ug/Kg DW
1960 J
936 J
71
HR-008-4044
52 BZ#52
ug/Kg DW
1020 J
524 J
64
HR-008-4044
101 BZ#101 & BZff[90]
ug/Kg DW
187 J
134 J
33
HR-008-4044
118 BZ#118
ug/Kg DW
157
110 J
35
HR-008-4044
138 BZ#138
ug/Kg DW
85.9 J
66.7 J
25
HR-008-4044
180 BZ#180
ug/Kg DW
31.3
24.3 J
25
HR-009-1012
1 BZ#1
ug/Kg DW
4.78 U
9.6 U
NC
HR-009-1012
4 BZ#4
ug/Kg DW
212 U
18.1 U
NC
HR-009-1012
8 BZ#8
ug/Kg DW
16.3 JN
18.9 J
-15
HR-009-1012
10 BZ#10
ug/Kg DW
17.2 U
11.4 U
NC
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 2 of 8
T AM S /Cadmus/ G radient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
TAMS ID
BZ Parameter
Units
Field Co-
Locate 1 Qualifier
Field Co-
Locate 2 Qualifier
RPD (%)
HR-009-1012
18 BZ#18
ug/Kg DW
R
105 JN
NC
HR-009-1012
19 BZ#19
ug/Kg DW
R
9.65 U
NC
HR-009-1012
28 BZ#28
ug/Kg DW
169 J
201 J
-17
HR-009-1012
52 BZ#52
ug/Kg DW
108 J
107 J
1
HR-009-1012
101 BZ#101& BZ#[90]
ug/Kg DW
76.1 J
76.5 J
-1
HR-009-1012
118 BZ#118
ug/Kg DW
54.2 J
54 J
0
HR-009-1012
138 BZ#138
ug/Kg DW
64 J
61.7 J
4
HR-009-1012
180 BZ#180
ug/Kg DW
17.8 J
18.7 J
-5
HR-010-2024
1 BZ#1
ug/Kg DW
27.9 JN
23.5 JN
17
HR-010-2024
4 BZ#4
ug/Kg DW
52 J
3v.l J
28
HR-010-2024
8 BZ#8
ug/Kg DW
93 J
53.2 J
54
HR-010-2024
10 BZ#10
ug/Kg DW
7.76 J
7 26 J
*?
HR-010-2024
18 BZ#18
ug/Kg DW
52.2 JN
36.4 JN
36
.„. . 24
19 BZ#19
ug/Kg DW
13.7 U
8.65 U
NC
HR-010-2024
28 BZ#28
ug/Kg DW
131 J
112 J
16
HR-010-2024
52 BZ#52
ug/Kg DW
48 J
34.9 J
32
HR-010-2024
101 BZ#101& BZf?[90]
ug/Kg DW
20.1 J
14.1 J
35
HR-010-2024
118 BZ#118
ug/Kg DW
15.5 J
11.9 J
26
HR-010-2024
138 BZ#138
ug/Kg DW
15.7 J
9.86 J
46
HR-010-2024
180 BZ#180
ug/Kg DW
6.25 J
4.77 J
27
HR-011-1216
1 BZ#1
ug/Kg DW
25.7 JN
22.2 JN
15
HR-011-1216
4 BZ#4
ug/Kg DW
41.4 U
39.7 U
NC
HR-011-1216
8 BZ#8
ug/Kg DW
30 J
30.1 J
0
HR-011-1216
10 BZ#10
ug/Kg DW
8.46 J
7.35 J
14
HR-011-1216
18 bZ#18
ug/Kg DW
27.9 JN
28.3 JN
-1
HR-011-1216
19 BZ#19
ug/Kg DW
15.2 U
13.4 U
NC
HR-011-1216
28 BZ#28
ug/Kg DW
52.9 J
53.2
-1
HR-011-1216
52 BZ#52
ug/Kg DW
33.9 J
33.4
1
HR-011-1216
101 BZ#101& BZ#[90]
ug/Kg DW
22.9 J
23.6 J
HR-011-1216
118 BZ#118
ug/Kg DW
17.1 J
16.7
2
HR-011-1216
138 BZ#138
ug/Kg DW
17.9 J
17.7 J
1
HR-011-1216
180 BZ#180
ug/Kg DW
6.53 JN
6.28 JN
4
HR-011-6064
1 BZ#1
ug/Kg DW
73.8 JN
112 JN
-41
HR-011-6064
4 BZ#4
ug/Kg DW
218 U
311 J
NC
HR-011-6064
8 BZ#8
ug/Kg DW
219 J
315 J
-36
HR-011-6064
10 BZ#10
ug/Kg DW
38.9 J
35.7 J
9
HR-011-6064
18 BZ#18
ug/Kg DW
163 JN
160 JN
2
HR-011-6064
19 BZ#19
ug/Kg DW
83 U
87.4 J
NC
HR-011-6064
28 BZ#28
ug/Kg DW
375
339 J
10
HR-011-6064
52 BZ#52
ug/Kg DW
223
211 J
6
HR-011-6064
101 BZ#101& BZ#1901
ug/Kg DW
106 J
139 J
-27
HR-011-6064
118 BZ#118
ug/Kg DW
54.1
50.1 J
8
HR-011-6064
138 BZ#138
ug/Kg DW
117 J
151 J
-25
HR-011-6064
180 BZ#180
ug/Kg DW
116 JN
157 JN
-30
Note: Congeners in [ ] are co-eluting non-target
congeners.
Page 3 of8
TAMS/Cadmus/Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-012-1216
1 BZ#1
ug/Kg DW
5.2 U
4 95 U
NC
HR-012-1216
4 BZ#4
ug/Kg DW
3.11 U
2.35 U
NC
HR-012-1216
8 BZ#8
ug/Kg DW
1.37 U
0.957 U
NC
HR-012-1216
10 BZ#10
ug/Kg DW
5.39 U
4.71 U
NC
HR-012-1216
18 BZ#18
ug/Kg DW
7.93 JN
7.12 JN
11
HR-012-1216
19 BZ#19
ug/Kg DW
R
R
NC
HR-012-1216
- 28 BZ#28
ug/Kg DW
7.28 J
5.64 J
25
HR-012-1216
52 BZ#52
ug/Kg DW
9.18 J
7.41 J
21
HR-012-1216
101 BZ#101 & BZ?[90]
ug/Kg DW
12.6 J
10.3 J
20
HR-012-1216
118 BZ#118
ug/Kg DW
10.5 J
8.72 J
19
HR-012-1216
138 BZ#138
ug/Kg DW
16.3 J
13.4 J
20
HR-012-1216
180 BZ#180
ug/Kg DW
5.56 JN
4.77 JN
15
HR-013-1216
1 BZ#1
ug/Kg DW
9.62 U
18.1 U
\C
HR-013-1216
4 BZ#4
ug/Kg DW
22.9 J
36.7 J
-46
HR-013-1216
8 BZ#8
ug/Kg DW
31.9 J
33.5 J
-5
HR-013-1216
10 BZ#10
ug/Kg DW
11.6 J
14.6 J
-23
HR-013-1216
18 BZ#18
ug/Kg DW
52 JN
48.2 JN
8
HR-013-1216
19 BZ#19
ug/Kg DW
9.49 U
11.3 U
NC
HR-013-1216
28 BZ#28
ug/Kg DW
121 J
124 J
-2
HR-013-1216
52 BZ#52
ug/Kg DW
39.6 J
40.7 J
-3
HR-013-1216
101 BZ#101& BZ#[90]
ug/Kg DW
17.9 J
17.7 J
I
HR-013-1216
118 BZ#118
ug/Kg DW
16 1 J
16.4 J
-2
HR-013-1216
138 BZ#138
ug/Kg DW
12.7 J
13.3 J
-5
HR-013-1216
180 BZ#180
ug/Kg DW
5.32 J
5.65 J
-6
HR-014-3236
1 BZ#1
ug/Kg DW
3.45 U
3.54 U
NC
HR-014-3236
4 BZ#4
ug/Kg DW
3.21 U
2.88 U
NC
HR-014-3236
8 BZ#8
ug/Kg DW
R
0.102 U
NC
HR-014-3236
10 BZ#10
ug/Kg DW
2.19 J
6.45 U
NC
HR-014-3236
18 BZ#18
ug/Kg DW
0.689 U
0.707 U
NC
HR-014-3236
19 BZ#19
ug/Kg DW
0.689 U
0.707 U
NC
HR-014-3236
28 BZ#28
ug/Kg DW
0.825 U
0.283 U
NC
HR-014-3236
52 BZ#52
ug/Kg DW
0.153 U
0.707 U
NC
HR-014-3236
101 BZ#101& BZ#[90]
ug/Kg DW
0.689 U
0.707 U
NC
HR-014-3236
118 BZ#l18
ug/Kg DW
0.689 U
0.707 U
NC
HR-014-3236
138 BZ#138
ug/Kg DW
0.0896 U
0.707 U
NC
HR-014-3236
180 BZ#180
ug/Kg DW
0.689 U
0.707 U
NC
HR-015-2832
1 BZ#1
ug/Kg DW
R
R
NC
HR-015-2832
4 BZ#4
ug/Kg DW
894 J
355 J
86
HR-015-2832
8 BZ#8
ug/Kg DW
745 J
396 J
61
HR-015-2832
10 BZ#10
ug/Kg DW
36.4 J
21.8 J
50
HR-015-2832
18 BZ#18
ug/Kg DW
444 J
200 JN
76
HR-015-2832
19 BZ#19
ug/Kg DW
220 J
92 U
NC
HR-015-2832
28 BZ#28
ug/Kg DW
440 J
245 J
57
HR-015-2832
52 BZ#52
ug/Kg DW
327 J
141 J
79
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 4 of 8 TAMS/Cadmus/Gradient
-------
Table A-S
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-015-2832
101 BZ#101& BZ~[90]
ug/Kg DW
37.1 J
18 J
69
HR-015-2832
118 BZ#118
ug/Kg DW
30.7 J
16.6 J
60
HR-015-2832
138 BZ-138
ug/Kg DW
26 J
12.7 J
69
HR-015-2832
180 BZ#180
ug/Kg DW
8,72 J
4.09 J
72
HR-016-1216
1 BZ#1
ug/Kg DW
95.4 U
82.8 JN
NC
HR-016-1216
4 BZ#4
ug/Kg DW
321 U
330 J
NC
HR-016-1216
8 BZ#8
ug/Kg DW
358 U
298 JN
NC
HR-016-1216
10 BZfflO
ug/Kg DW
16.2 J
13,7 J
17
HR-016-1216
18 BZ#18
ug/Kg DW
208 JN
182 J
13
HR-016-1216
19 BZ#19
ug/Kg DW
112 U
106 J
HR-016-1216
28 BZ«28
ug/Kg DW
268 J
192 J
33
HR-016-1216
52 BZ#52
ug/Kg DW
204 J
159 J
25
HR-016-1216
101 BZ#101 & BZsf90]
ug/Kg DW
40.1 I
29.6 J
30
HR-016-1216
118 BZ#118
ug/Kg DW
28.3 J
20.8 J
31
HR-016-1216
138 BZ? 138
ug/Kg DW
26.4 j
18.3 J
36
HR-016-1216
180 BZ#180
ug/Kg DW
8.99 J
5.76 J
44
HR-016-6872
1 BZ#1
ug/Kg DW
3.53 U
3.63 U
NC
HR-016-6872
4 BZ#4
ug/Kg DW
3.43 U
6.26 U
NC
HR-016-6872
8 BZ#8
ug/Kg DW
0.771 U
1.79 U
NC
HR-016-6872
10 BZ#10
ug/Kg DW
4,42 U
3.71 U
NC
HR-016-6872
18 BZ#18
ug/Kg DW
5.94 JN
7.28 JN
-20
HR-016-6872
19 BZ#19
ug/Kg DW
R
R
NC
HR-016-6872
28 BZ#28
ug/Kg DW
• 0,379 U
1,69 J
NC
HR-016-6872
52 BZ#52
ug/Kg DW
0.449 U
1,71 J
NC
HR-016-6872
101 BZ#101& BZ?{90]
ug/Kg DW
0.258 U
0.599 U
NC
HR-016-6872
118 BZif 118
ug/Kg DW
0.277 U
0.399 U
NC
HR-016-6872
138 BZ#138
ug/Kg DW
0.505 U
0.659 J
NC
HR-016-6872
180 BZ#180
ug/Kg DW
0.719 J
0.675 J
6
HR-017-1216
1 BZ#1
ug/Kg DW
5.81 U
5.83 U
NC
HR-017-1216
4 BZ#4
ug/Kg DW
4,51 U
2.05 U
NC
HR-017-1216
8 BZ#8
ug/Kg DW
0.559 R
0.794 U
NC
HR-017-1216
10 BZ#10
ug/Kg DW
3,74 U
3.32 U
NC
HR-017-1216
18 BZ#18
ug/Kg DW
3.86 U
5.81 U
NC
HR-017-1216
19 BZ#19
ug/Kg DW
1,16 U
1.17 U
NC
HR-017-1216
28 BZ#28
ug/Kg DW
2.5 U
3.03 U
NC
HR-017-1216
52 BZ#52
ug/Kg DW
1.67 U
2.07 U
NC
HR-017-1216
101 BZS101& BZf[901
ug/Kg DW
0,758 U
0.895 U
NC
HR-017-1216
118 BZ#118
ug/Kg DW
0.681 U
0.811 U
NC
HR-017-1216.
138 BZ#138
ug/Kg DW
1.22 J
1.14 J
7
HR-017-1216
180 BZ#180
ug/Kg DW
1.72 U
2.23 J
NC
HR-018-0812
1 BZ#1
ug/Kg DW
58300 JN
19600 JN
99
HR-018-0812
4 BZ#4
ug/Kg DW
63200 J
13700 J
129
HR-018-0812
8 BZ#8
ug/Kg DW
10800 J
5420 J
66
HR-018-0812
10 BZ#10
ug/Kg DW
13600 J
2830 J
131
Note: Congeners in [) are co-eluting non-target congeners.
TAMS/Cadmus/Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-018-0812
18 BZ#18
ug/Kg DW
4630 J
1400 J
107
HR-018-0812
19 BZ#19
ug/Kg DW
12800 J
2340 J
138
HR-018-0812
28 BZ#28
ug/Kg DW
1270 J
1350
-6
HR-018-0812
52 BZ#52
ug/Kg DW
6660 J
1940 J
110
HR-018-0812
101 BZ#101& BZ#[90]
ug/Kg DW
986 J
251 J
119
HR-018-0812
118 BZ#118
ug/Kg DW
269 J
55.7 JN
131
HR-018-0812
138 BZ#138
ug/Kg DW
404 J
1370 J
-109
HR-018-0812
180 BZ#180
ug/Kg DW
130 J
360 U
NC
HR-019-2024
1 Bzn
ug/Kg DW
648000 JN
863000 JN
-28
HR-019-2024
4 BZ#4
ug/Kg DW
673000 J
1020000 J
-41
HR-019-2024
8 BZ*8
ug/Kg DW
40500 J
68500 J
-51
HR-019-2024
10 BZ#10
ug/Kg DW
93100 J
138000 J
-39
HR-019-2024
18 BZ#18
ug/Kg DW
9810 U
11900 U
NC
HR-019-2024
19 BZ#19
ug/Kg DW
74800 U
114000 J
NC
HR-019-2024
28 Bzm
ug/Kg DW
2580 U
3120 U
\rC
HR-019-2024
52 BZ»52
ug/Kg DW
18200 J
23500 J
-25
HR-019-2024
101 BZ#101& BZ#[90]
ug/Kg DW
2420 J
3020 J
-22
HR-019-2024
118 BZ#118
ug/Kg DW
3650 U
389 J
NC
HR-019-2024
138 BZ#138
ug/Kg DW
1460 J
1580 J
-8
HR-019-2024
180 BZ#180
ug/Kg DW
624 U
673 U
NC
HR-020-2832
1 BZ#1
ug/Kg DW
141000 JN
58200 JN
83
HR-020-2832
4 BZ#4
ug/Kg DW
215000 J
78100 J
93
HR-020-2832
8 BZ#8
ug/Kg DW
14500 J
10200 J
35
HR-020-2832
10 BZ#10
ug/Kg DW
31000 J
11000 J
95
HR-020-2832
18 BZ#18
ug/Kg DW
2270 J
1530 J
39
HR-020-2832
19 BZ#19
ug/Kg DW
36700 J
11300 U
NC
HR-020-2832
28 BZ#28
ug/Kg DW
2540 J
1940 J
27
HR-020-2832
52 BZ#52
ug/Kg DW
4000 J
1620 J
85
HR-020-2832
101 BZ#101& BZ#[90]
ug/Kg DW
145 J
467 U
NC
HR-020-2832
118 BZ#118
ug/Kg DW
701 U
467 U
NC
HR-020-2832
138 BZ#138
ug/Kg DW
1390 J
387 U
NC
HR-020-2832
180 BZ#180
ug/Kg DW
104 J
65 J
46
HR-021-2024
1 BZ#1
ug/Kg DW
6940 U
2180 JN
NC
HR-021-2024
4 BZ#4
ug/Kg DW
11900 U
3310 U
NC
HR-021-2024
8 Bzn
ug/Kg DW
5140 J
1710 J
100
HR-021-2024
10 BZ#10
ug/Kg DW
2010 U
466 U
NC
HR-021-2024
18 BZ#18
ug/Kg DW
1560 J
791 J
65
HR-021-2024
19 BZ#19
ug/Kg DW
3570 U
897 U
NC
HR-021-2024
28 BZ#28
ug/Kg DW
1100 J
593 J
60
HR-021-2024
52 BZ#52
ug/Kg DW
1400 U
643 J
NC
HR-021-2024
101 BZ#101& BZ#[90]
ug/Kg DW
103 U
85.9 J
NC
HR-021-2024
118 BZ#118
ug/Kg DW
65 U
51 J
NC
HR-021-2024
138 BZ#138
ug/Kg DW
97.5 U
55.4 J
NC
HR-021-2024
180 BZ#180
ug/Kg DW
29.7 U
19.6 J
NC
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 6 of 8 TAMS/Cadmus'Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-022-2024
1 BZ21
ug/Kg D\V
321 U
359 U
NC
HR-022-2024
4 BZ#4
ug/Kg DW
543 J
588 J
-8
HR-022-2024
8 BZ#8
ug/Kg DW
348 JN
314 JN
10
HR-022-2024
10 BZ#10
ug/Kg DW
125 U
137 U
NC
HR-022-2024
18 BZ#18
ug/Kg DW
151 JN
156 JN
*•»
HR-022-2024
19 BZ#19
ug/Kg DW
170 J
177
-4
HR-022-2024
28 BZ#28
ug/Kg DW
351 J
361 J
-3
HR-022-2024
52 BZ#52
ug/Kg DW
216 J
221
-2
HR-022-2024
101 BZ#101& BZ=[90]
ug/Kg DW
71 7 J
72.3 J
-1
HR-022-2024
118 BZ#118
ug/Kg DW
55.7 J
53.6
4
HR-022-2024
138 BZ#138
ug/Kg DW
46.5 J
41.5 J
11
HR-022-2024
180 BZ#180
ug/Kg DW
14.6 J
12 J
20
HR-073-2024
1 BZ#1
ug/Kg DW
367000 JN
31000 JN
169
2024
4 BZU
ug/Kg DW
260000 J
29300 J
159
HR-023-2024
8 BZ#8
ug/Kg DW
21600 JN
11300 JN
63
HR-023-2024
10 BZ#10
ug/Kg DW
70100 J
7720 J
160
HR-023-2024
18 BZ#18
ug/Kg DW
8990 J
1390 J
146
HR-023-2024
19 BZ#19
ug/Kg DW
52800 J
9350 J
140
HR-023-2024
28 BZ#28
ug/Kg DW
835 U
1050 J
NC
HR-023-2024
52 BZ#52
ug/Kg DW
8640 J
1920 J
127
HR-023-2024
101 BZ#101& BZf>[90]
ug/Kg DW
2450 J
251 J
163
HR-023-2024
118 BZ#118
ug/Kg DW
686 J
39.1 U
NC
HR-023-2024
138 BZ#138
ug/Kg DW
1130 J
123 J
161
HR-023-2024
180 BZ#180
ug/Kg DW
316 J
34.2 J
161
HR-026-0812
i BZ#1
ug/Kg DW
22500 JN
29400 JN
-27
HR-026-0812
4 BZ#4
ug/Kg DW
42700 J
51600 J
-19
HR-026-0812
8 BZ#8
ug/Kg DW
18800 J
17900 J
5
HR-026-0812
10 BZ#10
ug/Kg DW
8830 J
10400 J
-16
HR-026-0812
18 BZ#18
ug/Kg DW
3740
2980
23
HR-026-0812
19 BZ#19
ug/Kg DW
14800 J
16100 J
-8
HR-026-0812
28 BZ#28
ug/Kg DW
1870
1840
2
HR-026-0812
52 BZ#52
ug/Kg DW
3890
3500
11
HR-026-0812
101 BZ#101 & BZ#[90]
ug/Kg DW
497 J
523 J
-5
HR-026-0812
118 BZ#118
ug/Kg DW
230
322
-33
HR-026-0812
138 BZ#138
ug/Kg DW
374 J
394 J
HR-026-0812
180 BZ# 180
ug/Kg DW
141 L"
138 U
NC
HR-027-1216
1 BZ#1
ug/Kg DW
11.8 U
8 U
NC
HR-027-1216
4 BZ#4
ug/Kg DW
12.3 U
1.6 U
NC
HR-027-1216
8 BZ#8
ug/Kg DW
13.1 U
4.19 J
NC
HR-027-1216
10 BZ#10
ug/Kg DW
2.36 i;
1.6 U
NC
HR-027-1216
18 BZ#18
ug/Kg DW
9 15 JN
8.63 JN
6
HR-027-1216
19 BZ# 19
ug/Kg DW
R
1.6 U
NC
HR-027-1216
28 BZ#28
ug/Kg DW
20.5
17.6
15
HR-027-1216
52 BZ#52
ug/Kg DW
8.64
8.54
1
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 7 of 8 TAMS/Cadmus/Gradient
-------
Table A-5
High Resolution Cores PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ
Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
HR-027-1216
101
BZ#101 & BZf[90]
ug/Kg DW
9.08 J
16.6 J
-59
HR-027-1216
118
BZ#118
ug/Kg DW
6.58
8.95
-31
HR-027-1216
138
BZ#138
ug/Kg DW
8.61 J
16.8 J
-64
HR-027-1216
180
BZ#180
ug/Kg DW
8.32 J
24 J
-97
HR-028-1620
1
BZ#1
ug/Kg DW
9830 JN
6470 JN
41
HR-028-1620
4
BZ#4
ug/Kg DW
30600 J
17700 J
53
HR-028-1620
8
BZ#8
ug/Kg DW
24700 JN
17300 JN
35
HR-028-1620
10
BZ#10
ug/Kg DW
1670 J
858 J
64
HR-028-1620
18
BZ#18
ug/Kg DW
1360 U
1520 U
NC
HR-028-1620
19
BZ#19
ug/Kg DW
7820 U
3990 U
NC
HR-028-1620
28
BZ#28
ug/Kg DW
3120 J
7260 J
-80
HR-028-1620
52
BZ#52
ug/Kg DW
1490
2240
-40
HR-028-1620
101
BZ#101 & BZ*[90]
ug/Kg DW
697 J
1100 J
-45
HR-028-1620
118
BZ#118
ug/Kg DW
449 U
830
NC
HR-028-1620
138
BZ#138
ug/Kg DW
465 U
411 U
NC
HR-028-1620
180
BZ#180
ug/Kg DW
173 U
134 U
NC
HR-029-0002
1
BZ#1
ug/Kg DW
27.7 JN
33.6 JN
-19
HR-029-0002
4
BZ#4
ug/Kg DW
227 J
500 J
-75
HR-029-0002
8
BZ#8
ug/Kg DW
5.3 J
6.12 J
-14
HR-029-0002
10
BZ#10
ug/Kg DW
5.65 J
6.55 J
-15
HR-029-0002
18
BZ#18
ug/Kg DW
2.44 J
2.37 JN
3
HR-029-0002
19
BZ#19
ug/Kg DW
4.7 J
5.59 J
-17
HR-029-0002
28
BZ#28
ug/Kg DW
4.44 J
5.37 J
-19
HR-029-0002
52
BZ#52
ug/Kg DW
4 51 J
5.59 J
-21
HR-029-0002
101
BZ#101& BZ?[90]
ug/Kg DW
5.82 J
7 J
-18
HR-029-0002
118
BZ#118
ug/Kg DW
5.74 J
6.94 J
-19
HR-029-0002
138
BZ#138
ug/Kg DW
7.04 J
8.55 J
-19
HR-029-0002
180
BZ#180
ug/Kg DW
2.36 J
2.92 J
-21
NC - Not calculated because PCB congener was not detected or rejected in one or both samples.
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 8 of 8
TAMS/Cadmus/Gradient
-------
Table A-6
PCB Detects Changed to Non-detects
High Resolution Sediment Core Study
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#1
53
495
11
BZU2
93
495
19
BZ#3
110
495
22
BZ#4
93
495
19
BZ#5
32
495
6
BZ#6
56
495
11
BZ#7
110
495
22
BZ#8
77
495
16
BZ#9
82
495
17
BZ#10
80
495
16
BZ#12
116
495
23
BZ#15
68
495
14
BZ#16
89
495
18
BZ#18
57
495
12
BZ#19
212
495
43
BZ#22
74
495
15
BZ#25
61
495
12
BZ#26
38
495
8
BZ#27
85
495
17
BZ#28
43
495
9
BZ#29
128
495
26
BZ«1
75
495
15
BZ#37
60
495
12
BZ#40
31
495
6
BZ#41
67
495
14
BZ#44
63
495
13
BZ#47
43
495
9
BZ#49
91
495
18
BZ#52
39
495
8
BZ#53
34
495
7
BZ#56
40
495
8
BZ#66
54
495
11
BZ#70
20
495
4
BZ#75
25
495
5
BZ#77
76
495
15
BZ#82
55
495
11
BZ#83
95
495
19
BZ#84
77
495
16
BZ#85
45
495
9
Page 1 of 3
TAMS/Cadmus/Gradient
-------
Table A-6
PCB Detects Changed to \on-detects
High Resolution Sediment Core Study
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#87
54
495
11
BZ#91
67
495
14
BZ#92
45
495
9
BZ#95
27
495
5
BZ#97
34
495
7
BZ#99
33
495
7
BZ#105
76
495
15
BZ#107
108
495
22
BZ#115
3
495
1
BZ#118
38
495
8
BZ#119
99
495
20
BZ#122
145
495
29
BZ#123
64
495
13
BZ#126
155
495
31
BZ#128
226
495
46
BZ#129
39
495
8
BZ#136
36
495
7
BZ#137
104
495
21
BZ#138
29
495
6
BZ#141
91
495
18
BZ#149
11
495
2
BZ#151
15
495
3
BZ#153
62
495
13
BZ#157
117
495
24
BZ#158
114
495
23
BZ#167
77
495
16
BZ#170
96
495
19
BZ#171
97
495
20
BZ#177
44
495
9
BZ#180
68
495
14
BZ#I83
74
495
15
BZ#185
150
495
30
BZ#187
103
495
21
BZ#189
72
495
15
BZ#190
147
495
30
BZ#191
52
495
11
BZ#193
113
495
23
BZ#194
154
495
31
BZ#195
128
495
26
Page 2 of 3
T AMS/Cadmus/Gradient
-------
Table A-6
PCB Detects Changed to Non-deteets
High Resolution Sediment Core Study
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#196
75
495
15
BZ#198
23
495
5
BZ#199
70
495
14
BZ#200
98
495
20
BZ#201
103
495
21
BZ#202
26
495
5
Bzms
18
495
4
BZ#206
114
495
23
BZ#207
51
495
10
BZ#2Q8
106
495
21
BZ#209
111
495
22
Note * - Results were considered nondetect due to suspected false positive as indicated by blank
contamination
Page 3 of 3
TAMS/Cadmus/Gradient
-------
Table A-7
High-Resolution Coring Sample Summary
Hudson River RI/FS PCB Reassessment
Values
_ Total Number Unqualified Estimated Unqualified Estimated _ , Rejected
Congener Name , _ .. , , „ .. . , . ,7 . , . Qualified * . % Rejected
or Results Nondetccts Nondetects Detects Detects . , Results J
with K
BZttl
495
67
189
1
224
6
14
3%
BZ#2
495
115
288
0
0
10
92
19%
BZ#3
495
74
209
7
74
6
131
26%
BZ#4
495
12
208
0
264
88
11
2%
BZ#5
495
147
206
0
115
5
27
5%
Bzm
495
36
92
121
232
2
14
3%
BZ#7
495
116
252
0
112
3
15
3%
BZ#8
495
12
99
8
367
2
9
2%
BZ#9
495
56
172
0
253
3
14
3%,
BZ#1(>
495
24
193
0
272
84
6
1%
BZ#12
495
39
180
0
256
2
20
4%
BZ# 15
495
35
128
0
310
5
22
4%
BZ816
495
46
161
0
276
5
12
2%
BZJI7 Non-Target
495
68
3
0
424
6
0
0%
BZ#18
495
25
99
48
311
0
12
2%
BZ# 19
495
65
227
35
90
2
78
16%
BZ#2() Non-Target
495
9
125
0
361
474
0
0%
BZR21 Non-Target
14
14
0
0
0
0
0
0%
BZ#22
495
24
104
125
234
2
8
2%
B7J23 Non-Target
495
406
15
0
74
15
0
0%
BZ#24 Non-Target
495
158
3
0
334
3
0
0%
BZ#25
495
21
102
94
257
1
21
4%
BZ#26
495
16
87
0
381
136
11
2%
BZ#27
495
34
140
0
316
2
5
1%
BZ#28
495
11
71
104
302
2
7
1%
BZ#29
495
60
203
0
191
3
41
8%
Noic: Congeners in | J are co-eluO'ng non-target congeners.
I'agc I of 6
CAM S/C admus'C; rati tent
-------
Table A-7
High-Resolution Coring Sample Summary
Hudson River RI/FS PCB Reassessment
Values
Total Number Unqualified Estimated Unqualified Estimated Rejected
Congener Name Nondetects Nondetects Detects Delects ^."l'r"d Result,. %
with K
BZJ31
495
19
98
106
260
2
12
2%
BZ#32
Non-Target
495
44
3
0
448
5
0
0%
BZ#33
N on-Target
495
17
105
0
373
474
0
0%
BZ#34
Non-Target
495
281
13
13
188
13
0
0%
BZ#37
495
13
92
0
388
446
2
0%
BZ#4()
495
49
91
59
243
2
53
11%
BZ#4I
495
55
138
0
249
2
53
11%
BZ#42
Non-Target
495
51
7
0
437
22
0
0%
BZ#44
495
12
95
0
383
2
5
1%
BZ#45
Non-Target
495
84
3
0
408
3
0
0%
BZJ47
495
13
77
0
385
2
20
4%
BZ#48
Non-Target
495
199
12
116
168
107
0
0%
BZ#49
495
16
114
104
225
2
36
7%
BZ#51
Non-Target
495
0
45
27
423
447
0
0%
BZ#52
495
19
54
156
264
2
2
0%
BZ#53
495
23
150
60
246
111
16
3%
BZ#54
Non-Target
14
14
0
0
0
0
0
0%
BZ#56
495
29
84
0
377
2
5
!%
BZ#58
Non-Target
495
254
3
0
238
3
0
0%
BZ#60
Non-Target
495
113
3
0
379
3
0
0%
BZJ63
Non-Target
495
1
286
0
208
474
0
<1%
BZ#64
N on-Target
495
61
3
0
431
3
0
0%
BZ#66
495
12
103
0
379
450
1
0%
BZ#67
Non-Target
495
161
0
0
334
0
0
0%
BZJ69
Non-Target
495
412
15
1
67
15
0
0%
BZ#70
495
20
54
0
421
16
0
0%
Note: Congeners in ( ] are eo-eluting non-target congeners.
Page 2 of 6
T A M S/Cadmus/G rad lent
-------
I able A-7
High-Resolution Coring Sample Summary
Hudson River RI/FS PCB Reassessment
V
-------
Table A-7
High-Resolution Coring Sample S imary
Hudson River RI/FS PCB Reassc inent
_ Total Number Unqualified Estimated Unqualified Estimated Rejected
Congener Name Noildc(ccts N„ndctccts DclccB Dc,„,s Q""'™ ^ , % Rejected
__ with K
BZ#I23
495
64
147
0
239
3
45
9%
BZ#126
495
96
292
0
40
2
67
14%
BZJ128
495
20
294
1
168
38
12
2%
BZ#129
495
161
262
0
56
16
16
3%
BZ#135 Non-Target
495
198
7
I
289
7
0
0%
BZ#136
495
41
162
2
254
130
36
7%
BZ#137
495
75
190
6
220
2
4
1%
BZ#138
495
14
64
0
414
454
3
1%
BZ*I40 Non-Target
495
485
0
0
10
0
0
0%
BZJ14I
495
53
161
0
279
288
2
0%
BZ#143 Non-Target
495
109
4
0
382
4
0
0%
BZ#144 Non-Target
495
183
4
0
708
4
0
0%
BZ#146 Non-Target
495
312
13
0
170
13
0
0%
BZ#149
495
22
52
0
420
2
1
0%
BZ#151
495
31
71
100
292
2
I
0%
BZ# 153
495
20
118
0
357
402
0
0%
BZ# 156 Non-Target
495
173
4
93
225
59
0
(}%
BZ#157
495
112
254
0
122
6
7
1%
BZ#158
495
58
194
0
231
2
12
2%
BZ#160 Non-Target
14
14
0
0
0
0
0
0%
BZ#167
495
90
177
13
179
2
36
7%
BZ# 169 Non-Target
495
479
15
0
I
15
0
0%
BZ#170
495
57
132
61
239
2
6
1%
BZ#171
495
77
189
12
208
- 71
9
2%
BZ# 172 Non-Target
495
21
159
0
315
474
0
0%
BZ# 174 Non-Target
495
78
4
141
272
150
0
0%
Note: Congeners in [ ) are co-eluting non-target congeners.
Page 4 ot 6
TAMS/Cadmus/Gradient
-------
Table A-7
High-Resolution Coring Sample Summary
Hudson River RI/FS PCB Reassessment
Vulucs
Total Number Unqualified Estimated Unqualified Estimated Rejected „ .
Congener Name ofRes|||ts Nondctccts Nondctcc(s Detects Detects Results /o Rcjcc,cd
BZ#175 Non- Target
495
429
15
1
50
18
0
0%
wmn
495
58
112
42
270
2
13
3%
BZ#178 Non-Target
495
490
0
0
5
0
0
0%
BZ#180
495
27
114
6
345
39
3
1%
BZ#183
495
62
139
54
235
2
5
1%
BZ#184 Non-Target
495
447
15
0
33
15
0
0%
BZ#185
495
113
297
1
42
3
42
8%,
BZ#187
495
26
165
5
297
21
2
0%
BZ#189
495
147
254
0
66
4
28
6%
BZ#190
495
98
2S8
1
82
2
56
1 1%
BZ#191
495
174
272
0
20
5
29
6%
BZ# 192 Non-Target
495
1
280
0
214
474
0
0%
BZ#I93
495
74
304
0
66
123
51
10%
BZ#194
495
49
222
33
163
2
28
6%
BZ#195
495
100
248
4
99
3 '
44
9%
BZ#196
495
60
151
0
271
2
13
3%
B7J 197 Non-Target
495
449
15
0
31
22
0
0%
BZ#198
495
121
352
0
1
238
21
4%
BZ#199
495
142
240
4
81
5
28
6%
BZ#200
495
119
251
0
119
4
6
1%
BZJ201
495
47
159
34
243
2
12
2%
BZ#202
495
145
200
9
117
3
24
5%
BZ#203 Non-Target
495
80
3
0
412
3
0
0%
BZ#205
495
185
272
0
18
5
20
4%
BZ#206
495
74
169
30
193
2
29
6%
B7J207
495
141
221
5
89
4
39
8%
Note: Congeners in | ] are co-eluting non-target congeneis.
Page 5 ot 6
TAMS/Cadmus/Grad u!
-------
Table A-7
High-Resolution Coring Sample Summary
Hudson River RI/FS PCB Reassessment
Values
. vaiucs .
Total Number Unqualified Estimated Unqualified Estimated 0uaHficd Rejected Rejected
— ¦ «• • - - ' - —«-»•—Results
Congener Name 0f Results Nondetects Nondeteets Detects Detects
with K
BZ#208
BZ#209
495
495
108
109
208
202
14
34
130
135
35
15
7%
3%
Totals
62426
12206
16242
2356
29704
8808
1918
3%
Note: Congeners in | j are co-eluting non-target congeners.
I'agc 6 of 6
TAMS/Oadmus/Gradu'iH
-------
Figure A-1
Subsampling and Analysis Scheme for High Resolution Coring
Co-Located Cores
Core P
Core A
Core G
CoreX
Intended for
X-ray
Photography
Analysis.
Work Never
Performed
Redox Potential
Contract Labs
Contract Labs
Contract Labs
Subsampled
Subsampled
Subsampled
Lamont Doherty Lab
High Resolution Coring
PCB Congeners
otal Organic Nitrogen
Laser Grain Size
(small volume)
for 4 cm Slices
Total Carbon
Total Nitrogen
Total Inorganic Carbon
Radionuclides
Weight Loss on Ignition
Laser Grain Size PCB QC Samples
(small volume)
for 2 cm Slices
Archived Samples
Selected Samples
for PCB,
Radionuclides
Laser Grain Size
(large volume)
TAMS/Cadmus/Gradient
-------
Appendix B
Data Usability Report for PCB Congeners
Water-Column Monitoring Program
B.l Introduction
The usability of data relates directly to the data quality objectives of the environmental
investigation (Maney and Wait, 1991; USEPA, 1993, 1994). The Hudson River PCB congener
chemistry program required sophisticated, high resolution gas chromatography analyses with
stringent quality control criteria. In addition, various inorganic and physical parameters were
analyzed to define the chemical context within which the PCB congeners exist. This approach was
necessary to delineate the concentration of PCB congeners within the context of geochemical and
biological processes occurring in the river.
Initially, TAMS/Gradient selected 90 PCB congeners as target congeners based on their
significance in environmental samples and the availability of calibration standards. In addition,
qualitative and quantitative information for an additional 36 PCB congeners (non-target congeners)
was obtained from each water sample analysis using relative retention time information detailed in
the literature, and more recently verified with actual standards. In addition to these 126 PCB
congeners, for certain sampling episodes (Transect 6 and flow-averaged events 4, 5, and 6) Aquatec
analyzed an additional 17 PCB congeners.
Certain target congeners are of particular importance in evaluating geochemical and
biological processes within the Hudson River water-column. These are the 12 "principal" target
congeners, which consist of BZ# 1, 4, 8, 10, 18, 19, 28, 52, 101, 118, 138, and 180. The focus of
this report will be on the usability of the analytical data for these principal congeners. However, the
importance of accurately measuring all individual congeners is greater for the water-column samples
than the high resolution sediment coring samples because all individual congeners were employed
to determine congener-specific water/particulate partition coefficients.
B-l
TAMS/Cadmus/Gradient
-------
This report serves as an overall evaluation of the PCB congener analyses performed for the
Hudson River water-column monitoring program. The evaluation is based on the assessment of data
quality relative to the objectives of the study. The report will first provide a synopsis and assessment
of the field sampling, analytical chemistry and data validation programs, and then evaluate data
usability for all the 126 congeners with particular emphasis on the principal target congeners. A data
usability report assessing the non-PCB chemical and physical analyses for the water column samples
is provided in Appendix C.
B.2 Field Sampling Program
TAMS/Gradient designed the water-column monitoring program to investigate water-column
PCB levels, transport, sources, and dissolved phase to suspended matter partitioning of PCB
congeners. This was accomplished by sequential sampling along transects for whole water, filtered
water and particulates (water-column transect study); and collecting flow-averaged composite
samples (flow-averaged water-column sampling study) to provide a measure of mean total PCB
transport in the Upper Hudson from Baker Falls to Waterford. The flow-averaged water-column
sampling study provides a perspective on river conditions midway between the instantaneous
conditions determined by the water-column transect study and the long-term average water-column
conditions determined by the high resolution sediment coring program. The water-column
monitoring collection program, sampling procedures, analytical protocols, and quality control/quality
assurance requirements are described in the "Phase 2A Sampling and Analysis Plan/Quality
Assurance Project Plan - Hudson River PCB Reassessment RI/FS" (TAMS/Gradient, May 1992,
referred to in this report as the Phase 2A SAP/QAPP). A summary of the subsampling and analysis
scheme is provided in Figure B-I.
The water-column transect study consisted of six sampling events (transects) occurring
approximately monthly at 13 stations in the Upper Hudson River and spanning the high-flow spring-
runoff event. In addition, monitoring at four stations in the Lower Hudson coincided with three
Upper Hudson events. The timing of sampling at sequential stations in the Upper Hudson was
designed to monitor the same parcel of water moving downstream. One exception to this scheme
was Transect 8, which occurred on April 23, 1993. Samples were not sequentially collected during
B-2
TAMS'Cadmus/Gradient
-------
this transect. Instead, sample collection at this transect was conducted near the annual peak flow.
A subset of samples from the transect program representative of the main-stem Hudson River (not
tributaries or sources) were used for an equilibration study. Samples from Saratoga Springs were
used for blanks. The study consisted of samples being stored for four days, with occasional stirring,
prior to being submitted to the analytical laboratory for analysis.
The flow-averaged water-column sampling study consisted of a series of six 15-day sampling
events conducted over a period of six months overlapping the water-column transect study.
Sampling occurred at four Upper Hudson stations coinciding with water-column transect stations,
and involved compositing of samples collected every other day at each station over a 15-day period.
This resulted in eight individual samples per a 15-day period. For flow-average event 7, four
separate temporal composites were collected from Waterford. These samples were collected daily
over a two to four week period and then composited into - 'e_
TAMS/Gradient initiated sampling for the water-column monitoring program on January 29,
1993 and concluded on September 23, 1993. Scientists from TAMS and Rensselaer Polytechnic
Institute (RPI) performed the sampling. The sampling team collected a total of 135 pairs of filtered
water and particulate samples (on filters). Aquatec allocated these samples into 14 Sample Delivery
Groups (SDGs). In addition, the sampling team collected 14 whole water (i.e., unfiltered) samples.
The TAMS/Gradient Program Quality Assurance Officer (QAO) conducted a field sampling audit
on March 26, 1993 to assess compliance of the sampling procedures with the Phase 2A SAP/QAPP.
The audit findings indicate that the sampling program was being conducted in a technically
acceptable manner consistent with the Phase 2A SAP/QAPP (Wait, 1993b).
B.3 Analytical Chemistry Program
B.3.1 Laboratory Selection and Oversight
TAMS/Gradient retained a number of analytical laboratories to perform the analyses required
for this program. To verily that the selected laboratories had the capacity, capabilities, and expertise
to perform sample analyses in strict accordance with the specified methodologies; each qualifying
B-3 TAMS/'Cadmus/Gradient
-------
laboratory underwent an extensive audit by TAMS/Gradient's senior chemists. TAMS/Gradient
retained the following two laboratories to perform water-column sample analyses for the Hudson River
RI/FS program: Aquatec Laboratories, a division of Inchcape Testing Service located in Colchester,
Vermont; and Rensselaer Polytechnic Institute located in Troy, New York. A USEPA Special
Analytical Services (SAS) contract laboratory, Chemtec Consulting Group Inc., located in Englewood,
New Jersey, was also retained through the SAS procurement process. Aquatec was the sole analytical
laboratory which conducted the PCB congener analyses for the entire program.
TAMS/Gradient conducted routine laboratory audits of RPI and Aquatec during the water-
column monitoring program to verify compliance of each laboratory with the Phase 2A SAP/QAPP
requirements. TAMS/Gradient did not perform audits of the USEPA SAS laboratories.
Unique requirements of the PCB congener method necessitated refinements of previously
published methods. In conjunction with these changes, Aquatec conducted Method Detection Limit
(MDL) studies and Extraction Efficiency (EE) studies for river water to verify the adequacy of the
methods. The TAMS/Gradient Program Quality Assurance Officer oversaw and approved the method
refinements throughout the program.
B.3.2 Analytical Protocols for PCB Congeners
The method used by TAMS/Gradient for the determination of PCB congeners in Phase 2A is
a program-specific method based on NYSDEC's Analytical Services Protocol Method 91-11
(NYSDEC, 1989) for PCB congeners. Appendix A4 of the Phase 2A SAP/QAPP describes procedures
for the calibration, analysis, and quantitation of PCB congeners by fused silica capillary column gas
chromatography with electron capture detection (GC/ECD). The method is applicable to samples
containing PCBs as single congeners or as complex mixtures, such as commercial Aroclors. Aquatec
extracted water and filter samples with hexane, and performed applicable cleanup procedures prior to
analysis by GC/ECD, as detailed in Appendix A3 of the Phase 2A SAP/QAPP. Aquatec analyzed
hexane extracts for PCB congeners on a dual capillary-column GC/ECD, as detailed in Appendix A4
of the Phase 2A SAP/QAPP. Aquatec identified PCB congeners using comparative retention times on
two independent capillary columns of different polarity. Aquatec used calibration standards for each
B-4
TAMS/Cadmus/Gradient
-------
congener to define retention times. In addition, Aquatec routinely analyzed Aroclor standards and
mixtures of Aroclor standards to verify identification and quantification of the primary calibration
standards. Due to the non-linear nature of the ECD over any significant calibration range (for this
project 1 to 100 ppb in extract), Aquatec generated the calibration curves used for quantitation from
a quadratic weighted least squares regression model where the correlation coefficient is greater than
0.99 (McCarty, 1995; EPA, 1986 - Method 8000B, proposed 1995 update). For each PCB congener
which elutes as a single congener on each GC column, Aquatec reported the result as the lower of the
two values. Although this quantitation scheme is compliant with USEPA CLP guidelines for dual-
column analyses (USEPA, 1991), it may introduce a slight low bias when calculating homologue and
total PCB sums. TAMS/Gradient compared data in the database relative to absolute results on both
columns and found the bias was usually negligible, and on a worse-case basis, may be 2% to 10% low.
For situations where coelution occurred on one column, Aquatec quantitated the result from the column
not displaying coelution. If only coelution results were available, Aquatec performed a calculation to
decipher concentrations using response factors derived by Mullen (1984). For the 12 principal
congeners, BZ#19, 28, 52, and 118 eluted as a single congener peak on both GC columns. BZ#1, 4,
8, 10, 18, 138, and 180 eluted as a single congener peak on one column and coeluted on the other.,
column. BZ#101 coeluted on both columns and was always reported with BZ#90.
Approximately 10% of all samples analyzed by GC/ECD also underwent additional analysis
using a GC-ion trap detector (ITD) as an additional means of confirming PCB congener identifications,
as detailed in Appendix 5A of the Phase 2A SAP/QAPP. Where possible, Aquatec selected samples
with the highest concentrations of PCB congeners for confirmation analysis by GC/ITD. Aquatec
usually performed two GC/ITD analyses per SDG, even if congener concentrations were minimal
throughout the SDG.
MDL and EE studies were conducted in accordance with USEPA (1984) guidance to ensure
that the methods adequately addressed the program data quality objectives. For the water-column
samples, this included studies for nominally 16-liter filtered water samples and the associated
suspended matter filters (particulates), and 1-liter whole (unfiltered) water collected from the Hudson
River. With regard to the MDL studies, acceptable results were found for the 16-liter filtered water
samples and suspended matter filters. For the 1-liter whole water samples, some congener detection
B-5
TAMS/Cadmus/Gradient
-------
limits were significantly higher than the objectives specified in the Phase 2A SAP/QAPP, especially
for the monochlorobiphenyls. No acceptable technical alternatives were available; therefore, the
elevated detection limits were adopted for the program. For this reason, 1 -liter samples were collected
and analyzed for only Transect 1. PCB congeners were not present in high enough concentrations to
provide meaningful results on the first set of Hudson River water samples for the EE study. Therefore,
the study was reconducted with new river water samples containing higher concentrations of PCBs and
found to be acceptable. A synopsis of the MDL/EE studies is provided in a TAMS/Gradient
memorandum dated July 1, 1993 (Cook, 1993). At the start of the Phase 2A sampling and analysis
program, TAMS/Gradient and Aquatec selected 90 target PCB congeners. These target congeners are
listed in Table A-l and identified by BZ number (Ballschmiter and Zell, 1980). TAMS/Gradient and
Aquatec based the selection of these 90 PCB congeners on their significance in environmental samples
and the commercial availability of calibration standards. TAMS/Gradient referred to PCB congeners
for which calibration standards were available as "target congeners". To verify that congener response
for these calibration standards was reproducible over time, TAMS/Gradient examined calibration data
from November 1992 and October 1993. TAMS/Gradient found temporal consistency to be acceptable
on both GC columns (Bonvell, 1994a).
The high resolution column chromatography techniques employed by Aquatec produced
acceptable PCB resolution for numerous congeners not contained in the target congener calibration
standards. Thus, TAMS/Gradient decided during method refinement to report approximately 50
additional PCB congeners. The laboratory identified these additional PCB congeners based upon the
relative retention times reported in the published literature (Mullen, 1984; Schulz, 1989; Fischer and
Ballschmiter, 1988, 1989). Aquatec calibrated these additional "non-target" congeners using the
calibration curve for target congener BZ#52. Aquatec chose BZ#52 because it elutes as a single
congener peak in the middle region of the chromatogram for both GC columns and is a major
component of Aroclor 1242, the Aroclor anticipated in Hudson River samples. Using additional
congener calibration standards which became commercially available by August 1993, Aquatec
performed analyses to verify and refine the historical relative retention times, and to determine
individual congener calibration parameters. These analyses confirmed a majority (36) of the historical
non-target congener relative retention times. For all analyses performed prior to August 1993, the
results for 14 non-target compounds not confirmed by this analysis TAMS/Gradient considered
B-6
TAMS/Cadmus/Gradient
-------
unusable and deleted from the database. A review of project data indicated that the 36 confirmed non-
target congeners represent a significant percentage, up to 25%, of the total PCB mass. Therefore,
TAMS/Gradient decided to include the non-target congener results to calculate homologue and total
PCB masses in the Hudson River. Omission of these non-target congener results would have resulted
in a significant low bias in the resulting calculations for homologue and total PCBs. Thus, 36 non-
target congeners are included in this report, as shown in Table A-l. Since the non-target congener
results were to be included in the calculations of homologue and total PCB mass, TAMS/Gradient
applied an individual correction factor to each congener's results based on the analysis of the additional
congener standards. The application of these correction factors served to minimize the uncertainty
associated with quantitation of non-target congeners. A series of TAMS/Gradient memoranda describe
the method for deriving these calibration correction factors (Bonvell, 1993a,b,c). A listing of the
derived calibration correction factors is provided in a TAMS/Gradient memorandum (Bonvell, 1994b).
To establish a method of quantitating total Aroclor concentrations from PCB congener data,
Aquatec performed duplicate analyses of seven Aroclor standards (1016, 1221, 1232, 1242, 1248,
1254, 1260). TAMS/Gradient defined the quantitation of an Aroclor for this program as the sum of
all congeners present in the standard Aroclor mixture at a concentration greater than 0.1 % of the total
Aroclor mass. In this manner, TAMS/Gradient then compared the percentage of the total mass
represented by the detected target and non-target congeners greater than 0.1 % of the Aroclor mass to
the actual concentrations of each Aroclor standard. The results produced the following mass yields for
the seven Aroclor standards: Aroclor 1016=93.3%, Aroclor 1221=86.6%, Aroclor 1232=91.0%,
Aroclor 1242=90.6%, Aroclor 1248=89.2%. Aroclor 1254=95.8%, and Aroclor 1260=87.0%. Thus,
in each case, the 90 target and 36 non-target congeners represented more than 87% of the original
Aroclor mass. For those Aroclors most important to the Hudson River based on General Electric's
reported usage (Brown et al., 1984), these congeners represented better than 90% of the Aroclor mass
(i.e., Aroclors 1242, 1254, and 1016). A further discussion of the results of the Aroclor standards
analyses is presented in Section 4.3 of the main body of the report.
As a part of the TAMS/Gradient monitoring of Aquatec's method performance, a blind spiked
water sample (i.e., performance evaluation [PE] sample) was supplied to the laboratory (Sample
TW-003-0020, SDG 181370). For the most part, the PE results were reasonable (Wait, 1993b).
B-7
TAMS/Cadmus/Gradient
-------
TAMS/Gradient noted no significant false positives. Recoveries were fairly consistent, but rather low,
ranging from 62 to 76%. These values are all within the acceptable range for matrix spike sample
recoveries (60%-150%). However, for most congeners these values are typically lower than what was
experienced in the actual water column sample analyses (generally greater than 90% recovery). This
difference may be due to losses in the field during preparation of the sample (e.g., spilling, weighing
and dilution). One significant false negative was discovered (i.e., laboratory failure to report a
detection of BZ#187), which required a revaluation of one of the GC columns used for analysis. This
situation is discussed in more detail in the data usability section of this report.
B.4 Data Validation
An essential aspect of understanding the uncertainties of the Phase 2 water-column data is
understanding the significance of the qualifiers associated with the results. Each result has an
associated qualifier. Qualifiers denote certain limitations or conditions that apply to the associated
result. Initially, the analytical laboratories applied qualifiers to the results, and then the data validators
modified the qualifiers, as necessary, based on the established validation protocols. Data reporting and
validation qualifiers direct the data users concerning the use of each analytical result. TAMS/Gradient
used two sets of qualifiers in the database, one set for PCB congener data, and a second set for non-
PCB chemical and physical data. Aquatec developed an extensive list of data reporting qualifiers to
be applied to the PCB congener data. The list is based on standard USEPA qualifiers used for organic
analyses, with additional qualifiers provided to note unique issues concerning PCB congener analysis,
e.g., the quantitation scheme. The data reporting qualifiers for PCB congener data, as applied by
Aquatec, are defined in detail in Table A-2 of Appendix A. Qualifiers for non-PCB data are discussed
in Appendix C.
During validation, the validators made modifications to the data qualifiers which are reflected
in the database. CDM Federal Programs Corporation and their subcontractors, under a separate
USEPA contract, performed data validation for the water-column monitoring program. Validation
procedures employed by CDM for GC/ECD analyses are detailed in Appendix A6 of the Phase 2A
SAP/QAPP, and validation guidelines for GC/ITD analyses are provided in Appendix A7 of the Phase
2A SAP/QAPP. TAMS/Gradient devised the validation procedures to reflect the data quality
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objectives of the program, as well as to conform with USEPA (1988,1992a) standards as appropriate.
USEPA Region II concurred with these method-specific validation protocols. In addition,
TAMS/Gradient designed comprehensive data validation templates to facilitate consistency of
approach and actions during validation. Prior to validation of the PCB data, Gradient conducted a
training workshop to aid CDM in properly performing the validation. Gradient reviewed and
commented on the initial CDM validation reports and provided real-time QA oversight. All validation
reports were inspected by the Program QAO, with only minor errors readily apparent. USEPA Region
II (Lockheed ESAT) revalidated data for 16 water-column samples. Lockheed ESAT noted no
significant problems.
The initial data validation efforts for the high resolution sediment core samples and water
column samples were completed in December 1994. The results were subsequently incorporated into
the TAMS/Gradient database and available for review in March 1995. However, by April 1995, it
became clear that the validation results differed markedly but randomly from the unvalidated data.
Upon further investigation, the project staff at TAMS identified the source of some of these differences
as the result of incorrect data validation procedures largely pertaining to blank corrections.
Specifically, it was found that blank samples were sometimes incorrectly associated with
environmental samples and blank values were transcribed incorrectly among validation records, among
other concerns. These problems were found to be extensive enough that USEPA, in agreement with
TAMS/Gradient, decided to have both the entire high resolution sediment coring and the water-column
monitoring PCB analysis data validation program redone to minimize manual data manipulation and
transcription (e.g., Garvey, 1995). TAMS developed a computer spreadsheet macro for data validation
in July 1995. This macro electronically applied blank qualification criteria (i.e., the "B" qualifier) to
the electronic data files using an algorithm developed from the data validation procedures. These files
were then used to generate the standard data validation forms incorporated in the validation packages.
Subsequent to the electronic validation, CDM reviewed all data for blank qualifier assignment before
approving the data validation packages. As a result of this review, minor changes in the macro had to
be made to handle unusual data packages (e.g., extra congeners reported). Using the data validation
macro, CDM completed the revalidation of the high resolution sediment coring and water column PCB
samples in September 1995.
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As an overall assessment of data quality, the TAMS/Gradient Program QAO reviewed
pertinent aspects of the sampling and analysis program {e.g., historical data, implementation of
sampling protocols, laboratory performance) relative to the data quality objectives. Decisions on data
usability sometimes overrode data qualification codes, as justified in this report. All qualifier changes
made by the TAMS/Gradient Program QAO, as reflected in this data usability report, are noted in the
final database (code Y in QA Comment field of database). For the water-column monitoring program,
the TAMS/Gradient Program QAO modified 115 qualifiers out of 20,448 PCB congener data records
as a result of data usability issues, representing 0.56% of the data. The only qualifier change involved
unrejecting results for three samples (TS0040017, F2-001 -0000[TS], and TS-001 -0009) associated with
poor octachloronaphthalene (OCN) surrogate recoveries.
B.5 Data Usability
B.5.1 Approach
Most previous studies of PCB chemistry in Hudson River waters have focused on the
concentration of specific Aroclors, total PCBs and/or the distribution of PCB homologues. The current
assessment of PCB fate and distribution in the Hudson River required TAMS/Gradient scientists to
implement sophisticated equilibrium chemistry and transport modeling studies requiring concentration
ratios of certain PCB congeners. Of the 90 target and 36 non-target congeners, 12 target congeners are
of particular importance. The usability of these "principal" congeners is key to the water-column
monitoring program.
Principal congeners will be employed in the following studies by the data users:
• Molar dechlorination product ratio - The molar sum of BZ#1, 4, 8, 10, and 19 are
compared to the molar sum of all 126 congeners analyzed. This ratio is then compared
to a similar index for Aroclor 1242 to assess, calculate, and evaluate the extent of
dechlorination.
• Transport modeling - BZ#4, 28, 52, 101, and 138 are considered independently as
compounds modeling PCB transport.
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• Aroclor 1016 and 1242 - BZ#18 is used to estimate the potential contribution of
Aroclor 1016 and 1242 to Hudson River waters.
• Aroclor 1254 - BZ#118 is used to estimate the potential contribution of Aroclor 1254
to Hudson River waters.
• Aroclor 1260 - BZ#180 is used to estimate the potential contribution of Aroclor 1260
to Hudson River waters.
Thus, 12 principal congeners (BZ#1, 4, 8, 10, 18, 19, 28, 52, 101, 118,138, and 180) are the
focus of this usability report. However, the remaining target and non-target congeners have important
implications to the water-column monitoring program. TAMS/Gradient used these congeners to
calculate the concentrations of total PCBs, PCB homologues, and Aroclor mixtures. Homologue group
information was more relevant for the water-column monitoring program than for the high resolution
sediment coring study. In addition, partition coefficients ~ 1 calculated for each congener for
the purpose of trend analysis. Each of the 126 congeners is employed to evaluate partition coefficients.
In this regard, the accuracy of the individual congener concentrations in the water-column monitoring
program is more important than in the high resolution sediment coring study.
B.5.2 Usability - General Issues
The data quality objectives for the Hudson River water-column monitoring program required
that the development of a sensitive program-specific gas chromatography method. Available standard
agency methods were not adequate to achieve the convener-specific identifications and detection limits
needed for the project. TAMS/Gradient based the method utilized on a modified NYSDEC ASP
Method 91-11 (1989) protocol encompassing information published in the literature, as well as in-
house research conducted by Aquatec. This research included conducting Method Detection Limit
(MDL) studies and Extraction Efficiency (EE) studies in accordance with USEPA (1984, 1986)
guidance. During the course of these studies, and the inception of the water-column monitoring
program, TAMS/Gradient and Aquatec noted various nuances to the methods that required refinement.
As such, TAMS/Gradient and Aquatec made modifications to some of the original protocols. The
remainder of this section discusses some of the more significant changes and their ramifications.
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• Identification of Non-Target Congeners
At the beginning of this program, Aquatec identified non-target congeners based on historical
relative retention times reported in the literature. In August 1993, Aquatec analyzed calibration
standards for each of the non-target congeners. Using these additional calibration standards, Aquatec
performed analyses to confirm historical relative retention times. Though these analyses verified a
majority of the historical non-target congener relative retention times, some of the historical relative
retention times used to identify non-target congeners did not match the relative retention times
determined by the analyses of the non-target congener standards. TAMS/Gradient deleted fourteen
non-target congeners from the database for all analyses performed prior to August 1993 due to these
unconfirmed identifications. The 14 non-target congeners deleted were: BZ#35, 39,46,100,104,130,
131, 132, 134, 162, 165, 173, 176, and 179. Aquatec identified and confirmed these 14 congeners
based on the current laboratory-derived relative retention times for samples analyzed during and after
August 1993. Therefore, the results for these 14 non-target congeners will remain in the database for
all samples analyzed during and after August 1993. Use of these non-target congener data should be
limited since they are not consistently available for all data sets. If a situation arises where information
for the deleted non-target congeners is critical to a data user, an in-depth review of the chromatograms
and re-calculation of the concentrations could potentially produce usable results for some of these
congeners.
• Quantitation of Non-Target Congeners
The laboratory originally quantitated non-target congeners using the calibration curve
determined for BZ#52. Since the non-target congener results were to be included in the calculations
of homologue and total PCB mass, TAMS/Gradient desired a more accurate method of quantifying the
non-target congeners. Aquatec analyzed calibration standards for the non-target congeners in
September 1993, and again in April 1994, for the determination of congener-specific response factors.
Based on this information, TAMS/Gradient calculated correction factors for each non-target congener
and applied these to the laboratory data within the database (Bonvell, 1994b).
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• Re-calculation of Some PCB Congener Results
From August 1992 to July 1993, Aquatec observed that the relative retention times of congener
compounds were changing on the SB-octyl-50 GC column. The shifts in relative retention times did
not effect the target compound identification except for BZ#187 and 128. This specific identification
problem became apparent from the results of a blind performance evaluation sample. In the case of
BZ#187 and 128, their original identification on the SB-octyl-50 analytical column showed BZ#128
eluting before BZ#187. Over the course of eight months, the two congeners merged together as one
peak, then became resolved again, only BZ#187 now eluted before BZ#128. When the two congeners
resolved, Aquatec assumed that each congener eluted in the same order as previously indicated, which
was incorrect. To determine the effects of the shifts on the "non-target" compounds, Aquatec analyzed
individual "non-target" standards. From these data, Aquatec discovered that the initial identification
of non-target PCB congener compounds obtained from Ballschmiter's research was inconsistent with
this study's SB-octyl-50 analytical column results. During the review of the elution order of PCB
congeners on the SB-octyl-50 column, Aquatec also discovered that BZ#91 was misidentified.
TAMS/Gradient and Aquatec corrected the misidentification of BZ#91 and the other affected
congeners.
Aquatec finalized the proper identification of non-target PCB congeners in November 1993.
In March 1994, TAMS/Gradient instructed Aquatec to review all PCB congener data analyzed from
September 1992 to July 1993 to rectify possible misidentifications. These corrections also necessitated
changes in the PCB congener database. All data initially entered into the database have been validated
without consideration to the changes discussed herein. Due to the GC column problem, Aquatec
changed some records and TAMS/Gradient flagged those records with a "K" to facilitate comparison
of original and changed records. A secondary validation of the changes has not been performed.
However, the identification changes made are not expected to adversely effect the overall validity of
the data. Some possible problems to be aware of include the analytical status of calibration curves and
check standards for BZ#91 for the entire time period, and BZ#187 and 128 from March 17, 1993
through July 1993. Another possible problem was 'B' flags. The 'B' flag was used to indicate method
blank contamination. Requantitation of results has changed the 'B' qualifier sfatus in some cases.
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• GC Column Change
Initially, Aquatec used a HP-5 (or RTx-5) column and a SB-octyl-50 GC column for PCB
congener analyses. In November 1993. Aquatec obtained new SB-octyl-50 columns for pending
analyses of Phase 2 biological samples. Each of the new SB-octyl-50 columns showed signs of column
degradation resulting in severe peak retention time shifts. Due to the concern that an acceptable SB-
octyl-50 column would not be obtainable, TAMS/Gradient solicited approval from USEPA Region II
for a replacement column, ApiezonL. TAMS/Gradient was concerned about data comparability for
the overall program, but had no alternative. USEPA Region II concurred with the replacement of the
SB-octyl-50 column with the Apiezon L column in December 1993. The Apiezon L column was
selected for the following reasons:
• The Apiezon_L column phase is similar to the SB-octyl-50 column phase.
• The ApiezonJL column provides PCB congener separations similar to the SB-octyl-50
column.
• The PCB congener retention times on the Apiezon_L column are more stable than on
the SB-octyl-50 column.
• The NYSDEC analytical laboratory performing Hudson River PCB congener analyses
was using the Apiezon L column successfully for fish samples.
In February 1994, Aquatec performed a comparison study for the two column sets, HP-5/SB-
octyl-50 and HP-5/Apiezon_L (Cook, 1994). Aquatec analyzed four Phase 2 pilot fish samples on both
the HP-5/SB-octyl-50 column combination and also the RTx-5/Apiezon_L column combination. The
PCB congener results compared well qualitatively ahd quantitatively with few exceptions. The results
for BZ#15 and 37 were consistently 2 to 10 times higher on the SB-octyl-50 column pair. Data users
are cautioned that the results for BZ#15 and 37 reported through March 1994 and the same congeners
reported after March 1994 are not comparable due to differences in the method of quantitation.
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• Lower Column Concentration Bias .
The USEPA CLP protocol requires that for dual column GC analyses, the lower of the two
values from each column will be reported (USEPA, 1991). TAMS/Gradient incorporated this same
quantitation scheme into this program. This quantitative method may introduce a slight low bias when
calculating homologue and total PCB sums. TAMS/Gradient determined that this bias was usually
negligible, and on a worst-case basis, may be as much as 2% to 10% low. Therefore, the data user
should consider these totals as usable, but estimated values, due to the uncertainties of the individual
results which are summed to form these values.
• Surrogate Spike Compound
At the inception of the water-column monitoring pro an m TAMS/Gradient and Aquatec
employed two surrogates: tetrachloro-m-xylene (TCMX) and octachloronaphthalene (OCN). Aquatec
noted soon after the program began that OCN recoveries were a problem. For many of the water-
column samples, recoveries were less than 10% and sometimes 0%, although the TCMX and matrix
spike/matrix spike duplicate results for these same samples were usually acceptable. Reextraction and
reanalysis of the same samples produced similar results. The purpose of surrogate spike analyses is
to evaluate the performance of the extraction procedure. TAMS/Gradient and Aquatec determined
OCN was an inappropriate surrogate for this program. Research by Aquatec suggests that OCN was
breaking down to heptachloronaphthalene and hexachloronaphthalene. During the validation process,
CDM rejected data that had OCN recoveries below 10%. During this data usability assessment, the
TAMS/Gradient Program QAO considered these results to be usable and changed the R qualifier to
a J qualifier (estimated results) for any result solely rejected due to poor OCN recoveries.
• Confirmation by GC/ITD
Aquatec analyzed approximately 10% of all samples analyzed by GC/ECD by GC/ITD to
provide an additional mechanism to verify congener identification and, as a secondary objective,
quantitation of congeners. The ITD is not as sensitive as the ECD (approximately an order of
magnitude less sensitive); therefore, when possible, samples with the highest concentration of PCBs
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were selected for GC/ITD confirmation. Although this may result in a program bias for only
confirming high concentration samples, the overall effect does not impair data usability.
In addition, there is the potential for some quantitative bias associated with the GC/ITD results
relative to the GC/ECD results. Aquatec quantified each congener detected in the GC/ITD analysis
using an average response factor per level of chlorination rather than using response factors determined
specifically for each individual congener. As such, potential bias, which will vary for each congener
within a chlorination homologue group, is present with the GC/ITD results. Since the ITD method was
not designed to be a primary quantitative tool, some variations in quantitative results were expected.
TAMS/Gradient considered quantitative differences between the GC/ITD and GC/ECD results less
than a factor of five acceptable, while differences greater than five times are rejected, were considered
unacceptable and associated results rejected.
B.5.3 Usability - Accuracy, Precision, Representativeness, and Sensitivity
TAMS/Gradient established a quality assurance system for this program to monitor and
evaluate the accuracy, precision, representativeness, and sensitivity of the results relative to the data
quality objectives. These are all important elements in evaluating data usability {e.g., USEPA, 1992b,
1993). Accuracy is a measure of how a result compares to a true value. Precision indicates the
reproducibility of generating a value. Representativeness is the degree to which a measurement(s) is
indicative of the characteristics of a larger population. Sensitivity is the limit of detection of the
analytical method.
This section will evaluate each of these parameters for the water-column monitoring program.
TAMS/Gradient assessed accuracy using holding times, instrument performance and calibrations for
both the GC/ECD and GC/ITD, internal standard performance for the GC/ITD, surrogate criteria for
both the GC/ECD and GC/ITD, spike recoveries, matrix spike/matrix spike duplicate recoveries,
compound identification results, and PE sample results (previously discussed in Section B.3).
TAMS/Gradient assessed precision by comparing matrix spike, and matrix spike duplicate results.
TAMS/Gradient evaluated representativeness by comparing field duplicate results, and assessed
sensitivity using blank results and the sample-specific quantitation limits achieved.
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Comparability and completeness are two other important data quality attributes. Comparability
expresses the confidence with which data are considered to be equivalent (USEPA, 1992b).
Comparable data allowed for the ability to combine the analytical results obtained from this study with
previous Hudson River studies. An in-depth discussion of data comparability is provided in Chapter
3 of the main body of this report. In addition, Gauthier (1994) has provided Aroclor translation
procedures for Hudson River capillary column GC data relative to previous packed column GC studies.
Completeness is a measure of the amount of usable data resulting from a data collection activity
(USEPA, 1992b). For this program, TAMS/Gradient established a 95% completeness goal. A
discussion of completeness for the water-column monitoring program is provided in the conclusions
section of this report.
B.5.3.1 Accuracy
Accuracy was evaluated based on a number of factors, including holding times; instrument
performance; calibration; internal standard performance; surrogate spike recoveries; matrix
spike/matrix spike duplicate recoveries; and congener identification. These factors are discussed
below:
• Holding Times
Exceedance of holding times may indicate a possible loss of PCB congeners due to
volatilization, chemical reactions, and/or biological alterations. Due to the persistent nature of PCBs,
only severe exceedance should be considered deleterious to quantitative accuracy. For water samples
and associated filters, TAMS/Gradient established an extraction holding time of 7 days from sampling,
followed by an analysis holding time of 40 days from extraction.
For the water-column transect study, Aquatec extracted 11 samples (5 samples in SDG 194193
and 6 samples in SDG 179191) passed holding times by a few days. One sample in SDG 178104
missed the analysis holding time by five days. CDM qualified all affected results as estimated (G).
TAMS/Gradient considered these results usable. For the flow-averaged water-column sampling study,
only one SDG (183681) had any exceedances for holding times. Aquatec extracted seven water
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samples 11 days past holding times and one water sample extracted three days past holding time. This
situation was not a result of poor performance by Aquatec, since Aquatec received the samples past
holding times due to sample shipment problems. For this same SDG, the sampling team performed
water filtration two weeks after sampling. All filters were extracted within holding times based on
verified time of sample receipt (VTSR). CDM qualified all affected results as estimated (G).
TAMS/Gradient considered these results usable.
• GC/ECD Instrument Performance
Adequate chromatographic resolution and retention time stability throughout an analytical
sequence are essential attributes for qualitative identification of congeners on a GC. TAMS/Gradient
defined criteria for congener resolution and retention time windows in the Phase 2A SAP/QAPP. For
the SB-octyl-50 column, resolution must be greater than 50% between BZ#5 and 8,40 and 41,183 and
185, and BZ#209 and OCN. On the HP-5 column, resolution must be greater than 25% between BZ#4,
10 and TCMX, and between BZ#31 and 28. Resolution must be greater than 50% between BZ#84 and
101/90, and between BZ#206 and OCN. Aquatec initially established retention time windows for both
columns to be ±0.3% relative to the average initial calibration retention times for all target congeners
and surrogates.
For the water-column transect study, CDM noted congener calibration standard coelution
problems for BZ#5 with BZ#8 on the HP-5 column for four SDGs (#194193, 179191, 179067, and
178104). Resolution ranged from 23% to 45%. The 50% resolution criteria established by
TAMS/Gradient for BZ#5/8 for this program was optimistic. Since 25% resolution was acceptable for
other congeners on the HP-5 column, the TAMS/Gradient Program QAO did not consider these
exceedances to be serious and they do not affect data usability. Concentrations of BZ#8 were much
higher than BZ#5 in SDG 179191; therefore, CDM considered and qualified BZ#5 results
presumptively present (N). CDM did not qualify BZ#8 results for SDG 179191. In addition, CDM
noted coelution problems for BZ#206 and OCN on the HP-5 column for three SDGs (194193,179191
and 179045). Aquatec did not detect BZ#206 in any samples associated with these three SDGs;
therefore, no action was taken.
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For the flow-averaged water-column sampling study, Aquatec encountered similar instrument
performance problems. CDM noted coelution problems for BZ#5 with BZ#8, for three SDGs (190020,
194059, and 187042). In addition, BZ#206 and OCN did not resolve on the HP-5 column for SDG
194059.
• GC/ITD Instrument Performance
Verifying proper GC/ITD performance required evaluating GC column resolution, ion trap
detector sensitivity, and ion trap calibration. The GC resolution criteria required baseline separation
of BZ#87 from BZ#154 and BZ#77. The ion trap sensitivity requires the signal/noise ratio for m/z 499
for BZ#209 and m/z 241 for chrysene-d12 to be greater than 5. For ion trap calibration, the abundance
of m/z 500 relative to m/z 498 for BZ#209 must be ^ 70% but rs 95%. CDM noted no significant ITD
-^nce problems for samples analyzed during the water-column monitoring program.
GC/ECD Calibration
Instrument calibration requirements were established to verify the production of acceptable
quantitative data. Initial calibrations (IC) using 5-level standard concentration curves demonstrate an
instrument is capable of acceptable performance prior to sample analysis. The IC criteria is 20%
relative standard concentration error (% RSCE) for monochlorobiphenyl and 15% RSCE for all
remaining PCB congeners and a correlation coefficient ^ 0.995. Continuing calibration standards
document maintenance of satisfactory performance over time. CDM noted some problems obtaining
appropriate sensitivity for the low-level standards for BZ#2, 3, and 4. Typically, detection limits for
these congeners were raised to 15 ppb in extract. Affected SDGs and congeners include 187749 (for
BZ#2), 182249 (for BZ#4), 179045 (for BZ#2), 179191 (for BZ#2,3, and 4), 179067 (for BZ#2,3, and
4), 178104 (for BZ#2, 3, and 4), and 187042 (for BZ#2). In addition, the correlation coefficient for
BZ#4 for SDG 182249 was slightly below the requirement of 0.995, thus requiring all related BZ#4
data for that SDG to be qualified as estimated (G). Finally, the % RSCE for the five point calibration
curve was greater than 50% (exceeding the criteria of less than 15%) for BZ#4 for SDG 181370, thus
requiring all positive results to be estimated. The TAMS/Gradient Program QAO considered the
estimated results to be usable for project decisions.
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GC/ITD Calibration
The initial calibration criteria for acceptable quantitative data for GC/ITD analyses required
percent relative standard deviations (% RSD) of the congener relative response factor (RRF) to be less
than 20%. For continuing calibration, the RRF for each congener must be within 20% of the mean
calibration factor from the 5-level calibration at the beginning and end of each calibration sequence.
For the water-column monitoring program. TAMS/Gradient noted no significant GC/ITD calibration
problems.
• GC/ITD Internal Standard Performance
To demonstrate the stability of the ITD, internal standard performance criteria were monitored.
Internal standard area counts must not vary by more than 30% from the most recent calibration or by
more than 50% from the initial calibration. In addition, the absolute retention time of the internal
standard must be within 10 seconds of the retention time in the most recent calibration, and ion
abundance criteria must be met for chrysene-d,2 and phenanthrene-d 10 For the water-column
monitoring program, TAMS/Gradient noted no significant internal standard problems.
• Surrogate Spike Recoveries
Aquatec spiked surrogate compounds into all water samples prior to extraction to monitor
recoveries. Recoveries may be indicative of either laboratory performance or sample matrix effects.
For the water-column monitoring program, Aquatec used TCMX and OCN as surrogates. As
previously discussed, OCN did not perform properly as a representative surrogate, therefore, only
TCMX recoveries provide useful information for most samples. In addition to TCMX, BZ#I92 was
used as a surrogate for Transect 6 and Flow-Averaged Events 4, 5, and 6.
Surrogate recoveries for both the water-column transect and flow-averaged water-column
sampling studies were much improved relative to the high resolution sediment coring study. Although
OCN surrogate recovery performance was also better than for the high resolution sediments, OCN is
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still deemed an unacceptable surrogate. Therefore, three water-column transect samples which CDM
qualified as rejected due to poor OCN recoveries have been unrejected to be qualified as estimated
results (G or UG, as appropriate). These samples were F2-001-0000 (TS) and TS-001-0009 in SDG
178104, and TS-004-0017 in SDG 182249.
• Matrix Spike/Matrix Spike Duplicate Recoveries
Within each SDG, Aquatec spiked two aliquots of a representative water sample with a suite
of 20 congeners (BZ#8, 18,28,44, 52,66, 77,101, 105, 118, 126, 128, 138, 153,170, 180, 187, 195,
206, and 209). The purpose of the spikes were, in part, to evaluate the accuracy of the analytical
method relative to laboratory performance and specific sample matrix. The advisory limits for spiked
congener recoveries are 60%-150%. TAMS/Gradient noted no spike recovery problems for any of the
water-column monitoring samples.
• Congener Identification
TAMS/Gradient established qualitative criteria to minimize erroneous identification of
congeners. An erroneous identification can be either a false positive (reporting a compound present
when it is not) or a false negative (not reporting a compound that is present). The calculated
concentrations for congeners detected in both columns should not differ by more than 25% between
columns (%D ^ 25%). This criterion applies to only those congeners which can be resolved as
individual congeners on both columns. If the %D for the results between the two columns is > 25%
but s 50%, the results were estimated. If the %D was >50 but ^ 90%, the results were estimated and
considered presumptively present (GN). If the %D between columns was > 90%, the results were
unusable (R).
TAMS/Gradient noted sporadic problems with congener identification as a result of dual
column imprecision. Although the extent of the dual GC column imprecision was not as extensive as
for the high resolution sediment coring study, a majority of the estimated and rejected data for the
water-column monitoring program were still a result of dual GC column imprecision. TAMS/Gradient
often qualified Station 2, 3; and principal congeners 4, 8, 10, 18, and 118 were qualified for a few
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SDGs. For SDG 185277, CDM qualified as rejected the positive results for BZ#2 in all samples due
to the relative percent difference (RPD) between the results for both columns being greater than 90%.
These results are not usable for project decisions.
B.5.3.2 Precision
• Matrix Spike/Matrix Spike Duplicate Comparison
The analysis of matrix spike (MS) and matrix spike duplicate (MSD) samples can also provide
valuable information regarding method precision relative to laboratory performance and specific
sample matrix. The advisory limit for relative percent difference (RPD) of spiked congeners in a
MS/MSD pair is 40%, and for nonspiked congeners, the precision criterion is 40% Relative Standard
Deviation (RSD).
TAMS/Gradient noted MS/MSD exceedances for only 3 SDGs (190020,183681, and 182249).
Regarding principal congeners, the 40% RPD criterion was exceeded for BZ#8 for SDG 190020 and
BZ#8, 18, 52, 101, and 118 for SDG 182249. Overall, MS/MSD performance for the water-column
monitoring program was good.
Additional information on precision is also obtained from an evaluation of the field duplicate
results, discussed (Subsection B.5.3.3).
B.5.3.3 Representativeness
• Field Duplicate Results
Analysis of field duplicate samples provides an indication of the overall representativeness and
precision of the sampling and analysis program. These analyses measure both field and laboratory
precision; therefore, the results will likely have more variability than laboratory duplicates and
MS/MSD samples, which only measure laboratory precision. Data validators used a 50% RPD
criterion for evaluating field duplicate precision.
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Field duplicate results for the principal congener for the dissolved water column samples are
compared in Table B-l, and results for the principal congeners for the particulate water column
samples are presented in Table B-2. The precision for the principal congeners throughout the water
column program was good, except for SDG 187749 (Sample TS-005-0006), where all principal
congeners had %RPD above 50% (typically 60% to 70%). A total of 33 congeners for TS-005-0006
were estimated (G) due to this problem.
B.5.3.4 Sensitivity
• Blanks
An important data quality objective associated with the water-column monitoring program was
to obtain detection limits as low as the analytical method could produce. One effect of this approach
is to register low level blank contamination during the preparation and analysis of the water and
particulates. As such, numerous congeners in all samples in all the SDGs required blank
contamination qualifications. In general, TAMS/Gradient found blank levels lower for the water-
column monitoring program than for the high resolution sediment coring study. TAMS/Gradient
reviewed the distribution of blank contaminants and found most contamination associated with the
monochlorobiphenyls, particularly with BZ#2. Blank levels for BZ#2 typically ranged from 30 ppb
to 70 ppb in extract; however, very high concentration of BZ#2 (542 ppb in extract) was detected in
SDG 183681. The highest concentration of principal congener BZ#1 was 23 ppb in extract for SDG
185277, and for principal congener BZ#4 was 15 ppb in extract for SDG 182249.
CDM qualified results during data validations with a "B", which indicated that the result was
within 5 times of the blank action level. TAMS/Gradient converted all "B" qualified results in the
database to nondetect results due to uncertainty in this detection. Tables B-3 and B-4 summarizes the
congener detects changed to non-detects for particulate and dissolved congeners, respectively.
B-23
T AMS/Cadmus/Gradient
-------
• Quantitation Limits
Evaluating dechlorination processes and modeling transport pathways of PCB congeners within
the Hudson River water column necessitated obtaining low detection limits. TAMS/Gradient and
Aquatec devised analytical methods to enhance lower detection limits. This, in part, required
employing sample/extract cleanup methods to remove matrix interferences, and maximizing sample
size when possible. For the water-column monitoring program, TAMS/Gradient defined optimum
detection limits as follows:
Matrix
Homolog
Detection Limit
Particulates
Monoch lorobipheny 1
Dichlorobiphenyl through Hexachlorobiphenvl
Heptachlorobiphenyl through Decachlorobiphenyl
2 iig<;filter
1 ug/filter
1 -2 |ig/filter
Water (20 liters)
Monochlorobiphenyl
Dichlorobiphenyl through Hexachlorobiphenyl
Heptachlorobiphenyl through Decachlorobiphenyl
0.1 ng'L
0.05 ng'L
0.05-0.1 ng/L
Water (1 liter)
Monochlorobiphenyl
Dichlorobiphenyl through Hexachlorobiphenyl
Heptachlorobiphenyl through Decachlorobiphenyl
1.0 ng'L
0.5 ng/L
0.5-1 ng/L
Based on the results of the MDL study, TAMS/Gradient raised the detection limits for BZ#2
(a monochlorobiphenyl) significantly above these requirements (approximately a factor of 3). In
addition, CDM selectively raised detection limits for BZ#2, 3 and 4 for SDGs 187749, 182249,
179045,179191, 179067,178104, and 187042 due to a lack of sensitivity during initial calibration (see
Subsection B.5.3.1).
In general, achieving appropriate detection limits for the water column samples was not a
problem. Whenever TAMS/Gradient noted raised detection limits, the affected samples contained high
organic content; specifically the presence of PCBs. The relative ratio of congeners detected within each
high-concentration sample remained reasonably consistent, therefore the raised detection limits for
nondetect congeners did not affect data usability. For critical low level samples used for delineating
the outer extent of contamination, or other PCB sources (e.g., tributaries), Aquatec achieved adequate
detection limits.
B-24
TAMS/Cadmus/Gradient
-------
B.5.4 Usability - Principal Congeners
The 12 principal target congeners employed in the water-column monitoring program are key
to delineating PCB geochemistry in the Hudson River. The following synopsis will provide data users
with the strengths and weaknesses of the principal target congener data within the context of this study:
BZ#1. The reported results for BZ#1 met the data quality objectives of the program. Results
for 4 samples were rejected due to dual GC column imprecision. Analytically, BZ#1 eluted as
a single peak on one GC column and coeluted on the other GC column, which was acceptable
for the purposes of this program. The detection limit goal was met for nearly all samples.
BZ#4. The reported results for BZ#4 met the data quality objectives of the program. Results
for 12 samples were rejected due to dual GC column imprecision. Analytically, BZ#4 eluted
as a single peak on one GC column and coeluted with BZ#10, another principal congener, on
the other GC column. Data for both BZ#4 and BZ#10 were considered usable. The detection
limit objectives were generally met, although come blanks ranged up to 15 ppb in extract and
there were some sensitivity problems on occasion of the low-level standard. This did not affect
data usability.
BZ#8. The reported results for BZ#8 met the data quality objectives of the program. Results
for 38 samples were rejected due to dual GC column imprecision. The number of rejects for
BZ#8 was significantly higher than that experienced for the high resolution sediment coring
study. Analytically, BZ#8 eluted as a single peak on one GC column and coeluted with BZ#5
on the other GC column, which was acceptable for the purposes of this program. For some
samples, the initial resolution criteria between BZ#8 and BZ#5 was not met, requiring
associated data to be qualified presumptively present. This data should be considered usable.
The detection limit goal was met for nearly all samples. Matrix spike results for BZ#8 further
indicated that the method was successful.
B-25
TAMS/Cadmus/Gradient
-------
BZ#10. The usability assessment for BZ#10 is similar to that for BZ#4. BZ#10 eluted as a
single peak on one GC column and coeluted with BZ#4 on the other GC column. Data for both
BZ#4 and BZ#10 were considered usable. Results for 10 samples were rejected due to dual
column imprecision. In general, the detection limit objectives were met.
BZ#18. The reported results for BZ#18 met the data quality objectives of the program. Results
for 12 samples were rejected due to dual GC column imprecision. Analytically, BZ# 18 eluted
as a single peak on one GC column and coeluted on the other GC column. In general, the
detection limit objectives were met. Matrix spike results for BZ#18 further indicated that the
method was successful.
BZ#19. Results for 40 samples were rejected due to dual GC column imprecision. The
reported results for BZ#19 met the data quality objectives of the program. Analytically, BZ#19
eluted as a single congener on both GC columns. The detection limit objectives were met.
BZ#28. The reported results for BZ#28 met the data quality objectives of the program. Results
for 3 samples were rejected due to dual column imprecision. Analytically, BZ#28 eluted as a
single congener peak on both GC columns. In general, the detection limit objectives were met.
Matrix spike results for BZ#28 further indicated that the method was successful.
BZ#52. The reported results for BZ#52 met the data quality objectives of the program. Results
for 9 samples were rejected due to dual GC column imprecision. Analytically, BZ#52 eluted
as a single congener peak on both GC columns. The detection limit objectives were met for
nearly all samples. Matrix spike results for BZ#52 further indicated that the method was
successful.
BZ#101. Data users should be aware that BZ#101 always coeluted with BZ#90. For reported
results, all other QA/QC requirements were met. therefore should be considered usable. No
samples were rejected. The detection limit objectives were met for nearly all samples. Matrix
B-26
TAMS/Cadmus/'Gradient
-------
spike results for BZ#101 further indicated that the method was successful.
BZ#118. The reported results for BZ#118 met the data quality objectives of the program.
Results for 43 samples were rejected due to dual GC column imprecision. The number of
rejects for BZ#118 was significantly higher than expected for the high resolution sediment
coring study. Analytically, BZ#118 eluted as a single congener peak on both GC columns.
The detection limit objectives were met for nearly all samples. Matrix spike results for BZ#118
further indicated that the method was successful.
BZ#138. The reported results for BZ#138 met the data quality objectives of the program. No
results were rejected. Analytically, BZ#138 eluted as a single congener peak on one GC
column and coeluted on the other GC column. The detection limit objectives were met for
nearly all samples. Matrix spike results for BZ#138 further indicated that the method was
successful.
BZ#180. The reported results for BZ#180 met the data quality objectives of the program. No
results were rejected. Analytically, BZ#180 eluted as a single congener peak on one GC
column and coeluted on the other GC column. The detection limit objectives were met for
nearly all samples. Matrix spike results for BZ#180 further indicated that the method was
successful.
B.6 Conclusions
The PCB congener analytical chemistry program implemented by TAMS/Gradient for the
Hudson River high resolution sediment coring study required the development and use of program-
specific GC/ECD methodology in order to generate data meeting the data quality objectives of the
program. A total of 281 dissolved, particulate, and whole water samples were analyzed for 126 target
and non-target congeners. Considering the complexity of the program, TAMS/Gradient considers the
outcome of the analytical chemistry program to have been successful.
B-27 TAMS/Cadmus/Gradient
-------
A summary of the number of qualifiers applied to each PCB congener is tabulated in Tables
B-3 through B-8. For the water-column monitoring program 35,726 congener measurements were
recorded, of which 641 values were rejected. A 98.2% completeness rate was achieved for this
program, which exceeds the 95% completeness goal. A breakdown of the rejected data per study
follows:
Analysis
Data Points
Rejected Data
Completeness Ratio
Monitoring-dissolved
14,577
248
98.3%
Monitoring-particulate
14,663
288
98.0%
Equilibrium-dissolved
2,166
16
99.3%
Equilibrium-particulate
2,175
39
98.2%
Flow-averaged Event 7
381
6
98.4%
Whole water
1,764
44
97.5%
Total 35,726 641 98.2%
Although the completeness rate was higher for the water-column monitoring study than for the
high resolution sediment coring study, the imprecision between GC columns remained a problem. A
majority of the data that was either estimated or rejected was a result of dual GC column imprecision.
With regard to the principal congeners, data rejected due to this problem included BZ#1 (4 rejects),
BZ#4 (12 rejects), BZ#8 (38 rejects), BZ#10 (10 rejects), BZ#18 (12 rejects), BZ#19 (40 rejects),
BZ#28 (3 rejects), BZ#52 (9 rejects), and BZ#118 (43 rejects).
B-28
TAMS/Cadmus/Gradient
-------
References
Ballschmiter, K. and M. Zell. 1980. "Analysis of Poly chlorinated Biphenyls (PCB) by Glass Capillary
Gas Chromatography. Composition of Technical and Aroclor and Clophen PCB Mixtures."
Fresenius Z. Anal. Chem., 302:20-31.
Bonvell, S. 1993a,b,c. Congener Calibration. TAMS/Gradient memoranda, dated August 26,
September 17, and December 29.
Bonvell, S. 1994a. Congener Calibration - Temporal Consistency. TAMS/Gradient memorandum,
dated March 7.
Bonvell, S. 1994b. Calibration of Non-Target Congeners. TAMS/Gradient memorandum, dated
June 22.
Brown, J.F., R.E. Wagner, D.L. Bedard, M.J. Brennan, J.C. Carnahan, and R.J. May. 1984. "PCB
Transformations in Upper Hudson Sediments." Northeast Environ. Sci. 3:167-179.
Cook, L.L. 1993. Water Column Method Detection Limit/Extraction Efficiency Determination for
Hudson River PCB Congener Analysis. TAMS/Gradient memorandum, dated July 1.
Cook, L.L. 1994. Apiezon_L column study. TAMS/Gradient memorandum, dated August 4.
Fischer, R. and K. Ballschmiter. 1988. "Ortho-substituent Correlated Retention of Poly chlorinated
Biphenyls on a 50% n-octyl Methylpolysilixane Stationary Phase by HRGC/MSD." Fresenius Z.
Anal. Chem., 332:441-446.
Fischer, R. and K. Ballschmiter. 1989. "Congener-specific Identification of Technical PCB Mixtures
by Capillary Gas Chromatography on a n-octyl-methyl Silicon Phase (SB-octyl-50) with Electron
Capture and Mass-selective Detection." Fresenius Z. Anal. Chem., 335:457-463.
Gauthier, T. 1994. "Aroclor Translation Procedures." TAMS/Gradient memorandum, dated July 7.
Maney, J. and D. Wait. 1991. "The Importance of Measurement Integrity." Environ. Lab, 3(5):20-25.
McCarty, H. and B. Lesnik. 1995. "Approaches to Quality Control of Non-linear Calibration
Relationships for SW-846 Chromatographic Methods." In Proceeding of the Eleventh Annual Waste
Testing & Quality Assurance Symposium. American Chemical Society and U.S. Environmental
Protection Agency, Washington, DC, July 23-28, pp 203-208.
B-29
TAMS/Cadmus/Gradient
-------
Mullen, M. 1984. "High Resolution PCB Analysis: Synthesis and Chromatographic Properties of all
209 PCB Congeners." Environ. Sci. Technol., 18:468-475.
NYSDEC. 1989. "Analytical Service Protocols." Issued September 1989, revised December 1991
and September 1993, Method 91-11, pp D-XXVIII, 5-59, New York State Department of
Environmental Conservation, Bureau of Technical Services and Research, Albany, New York.
Schulz, D. 1989. "Complete Characterization of Polychlorinated Biphenyl Congeners in Commercial
Aroclor and Clophen Mixtures by Multidimensional Gas Chxomatography-Electron Capture
Detection." Environ. Sci. Technol., 23:852-859.
TAMS/Gradient. 1992. "Phase 2A Sampling and Analysis Plan/Quality Assurance Project Plan -
Hudson River PCB Reassessment RI/FS." EPA Contract No. 68-S9-2001.
USEPA. 1984. "Definition and Procedure for the Determination of the Method Detection Limit -
Revision 1.11." Federal Register, 49(209): 198-199.
USEPA. 1986. Test Methods for Evaluating Solid Waste. U.S. Environmental Protection Agency,
Office of Solid Waste and Emergency Response, Washington, DC, SW-846, Third Edition, Chapter
1.
USEPA. 1988. "Laboratory Data Validation. Functional Guidelines for Evaluating Organics
Analyses." U.S. Environmental Protection Agency, Hazardous Site Evaluation Division, Washington,
DC.
USEPA. 1991. "Statement of Work for Organic Analysis, Multi-Media, Multi-Concentration."
Document Number OLM 01.0, including revisions through OLM 01.8, August. U.S. Environmental
Protection Agency, Washington, DC.
USEPA. 1992a "CLP Organics Data Review and Preliminary Review." SOP No. HW-6, Rev. No.
8, U.S. Environmental Protection Agency Region II, Edison, New Jersey, January.
USEPA. 1992b. "Guidance for Data Usability in Risk Assessment." U.S. Environmental Protection
Agency, Office of Emergency and Remedial Response, Washington, DC, EPA PB92-963356,
Publication 9285.7-09A.
USEPA. 1993. "Data Quality Objectives Process for Superfund." U.S. Environmental Protection
Agency, Office of Solid Waste and Emergency Response, Washington, DC, EPA 540-R-93-071,
Publication 9355.9-01.
B-30
TAMS/Cadmus/Gradient
-------
USEPA. 1994. ''Guidance for the Data Quality Objectives Process." U.S. Environmental Protection
Agency, Quality Assurance Management Staff, Washington, DC EPA QA/G-4.
Wait, A.D. 1993a. Field Quality Assurance Audit Report, dated March 26.
Wait, A.D. 1993b. Letter from A.D. Wait to J. Comeau of Aquatec, Inc., dated December 14.
B-31
TAMS/Cadmus/Gradient
-------
Table B-l
Water Column Dissolved PCB Field Co-located Samples
Hudson River PCB Reassessment
TAMS ID
BZ Parameter
Units
Field Co-
Locate 1 Qualifier
Field Co-
Locate 2 Qualifier
RPD {%)
FW-209-0004
1 BZ#1
ng/L
1.99 U
1.89 U
NC
FW-209-0004
4 BZ#4
ng/L
5,19 I
5,15 J
I
FW-209-0004
8 BZ#8
ng/L
1.43 JN
1,51 JN
-5
FW-209-0004
10 BZ#10
ng/L
1.28 J
1.29 J
-1
FW-209-0004
18 BZ#18
ng/L
2.01
2.11
-5
FW-209-0004
19 BZ#19
ng/L
1.99
2.17
-9
FW-209-0004
28 BZ#28
ng/L
2.71
2.91
-7
FW-209-0004
52 BZ#52
ng/L
1.45
1.53
-5
FW-209-0004
101 BZ#101 & BZ#[90]
ng/L
0.27 J
0.312 J
-14
FW-209-0004
118 BZ#118
ng/L
R
0.181
NC
FW-209-0004
138 BZ#138
ng/L
0.0729 U
0.095 U
NC
FW-209-0004
180 BZ#180
ng/L
0,0213 U
0.0412 U
NC
FW-609-0005
1 BZ#1
ng/L
14.9
18
-19
FW-609-0005
4 BZ#4
ng/L
22.4 J
25.5 J
-13
FW-609-0005
8 BZ#8
ng/L
1.82 JN
2.12 JN
-15
FW-609-0005
10 BZ#10
ng/L
3.6 J
4.1 J
-13
FW-609-0005
18 BZ#18
ng/L
2.85
3.16
-10
FW-609-0005
19 BZ#19
ng/L
6.18 J
7.08 J
-14
FW-609-0005
28 BZ#28
ng/L
2.23
2.54
-13
FW-609-0005
52 BZ#52
ng/L
2.14 J
2.38 J
-11
FW-609-0005
101 BZ#101 & BZ#(90]
ng/L
0,54 U
0.501 U
NC
FW-609-0005
118 BZ#118
ng/L
0.199 U
0.205 U
NC
FW-609-0005
138 BZ#138
ng/L
0,1181 U
0.0275 U
NC
FW-609-0005
180 BZ#180
ng/L
0.13 U
0.0401 U
NC
TW-001-0014
1 BZ#1
ng/L
2.84 JN
2.92 JN
-3
TW-001-0014
4 BZ#4
ng/L
6.59 J
6.99 J
-6
TW-001-0014
8 BZ#8
ng/L
0.672 U
0.689 U
NC
TW-001-0014
10 BZ#10
ng/L
1.08 U
1.1 U
NC
TW-001-0014
18 BZ#18
ng/L
1.12 U
1.15 U
NC
TW-001-0014
19 BZ#19
ng/L
0.983 U
1.08 U
NC
TW-001-0014
28 BZ#28
ng/L
1.04
1.08
-4
TW-001-0014
52 BZ#52
ng/L
0.768 U
0.792 U
NC
TW-001-0014
101 BZ#101 & BZ#[90]
ng/L
0.142 U
0,15 J
NC
TW-001-0014
118 BZ#118
ng/L
R
R
NC
TW-001-0014
138 BZ#13S
ng/L
0.0454 U
0.0497 U
NC
TW-001-0014
180 BZ#180
ng/L
0.0095 U
0.0107 U
NC
TW-002-0004
1 BZ#1
ng/L
0.249 U
0.237 U
NC
TW-002-0004
4 BZ#4
ng/L
0.875 U
1.09 U
NC
TW-002-0004
8 Bzm
ng/L
0.406 U
0.379 U
NC
TW-002-0004
10 BZ#10
ng/L
0.118 J
0.1 J
17
TW-002-0004
18 BZ#18
ng/L
0.671 U
0.671 U
NC
TW-002-0004
19 BZ#19
ng/L
0.297 U
R
NC
TW-002-0004
28 BZ#28
ng/L
0.711 U
0.684 U
NC
TW-002-0004
52 BZ#52
ng/L
0.368 J
0.352
4
Note: Congeners in [ ] are co-eluting non-target congeners.
Page i of 3 TAMS/Cadmus/Gradient
-------
Table B-l
Water Column Dissolved PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
TW-002-0004
101 BZ#101 & BZ#[90]
ng/L
0.0521 U
0.0521 U
NC
TW-002-0004
118 BZ#118
ng/L
0.0238 R
0.0324 U
NC
TW-002-0004
138 BZ#138
ng/L
0.0276 U
0.0189 U
NC
TW-002-0004
180 BZ#180
ng/L
0.0469 U
0.0451 U
NC
TW-003-0008
1 BZ#1
ng/L
1.57 JN
1.59 JN
-1
TW-003-0008
4 BZ#4
ng/L
4.68 J
2.12 U
NC
TW-003-0008
8 BZ#8
ng/L
0.463 J
0.459 J
1
TW-003-0008
10 BZ#10
ng/L
0.806 U
0.443 U
NC
TW-003-0008
18 BZ#18
ng/L
0.947
0.963
-2
TW-003-0008
19 BZ#19
ng/L
0.923
0.953
-3
TW-003-0008
28 BZ#28
ng/L
0.835
0.856
-2
TW-003-0008
52 BZ#52
ng/L
0.713
0.721
-1
TW-003-0008
101 BZ#101 & BZ#[90]
ng/L
0.169 U
0.169 U
NC
TW-003-0008
118 BZ#118
ng/L
R
0.0801 U
NC
TW-003-0008
138 BZ#138
ng/L
0.061 U
0.0592 U
NC
TW-003-0008
180 BZ#180
ng/L
0.0106 U
0.0097 U
NC
TW-004-0005
I BZ#1
ng/L
4.05 JN
4.82 JN
-17
TW-004-0005
4 BZ#4
ng/L
R
0.478 U
NC
TW-004-0005
8 BZ#8
ng/L
3.59 JN
5.66 JN
-45
TW-004-0005
10 BZ#10
ng/L
1.93 J
2.13 J
-10
TW-004-0005
18 BZ#18
ng/L
5.96 J
8.37 J
-34
TW-004-0005
19 BZ#19
ng/L
2.47
3.16
-25
TW-004-0005
28 BZ#28
ng/L
4.91 J
6.65 J
-30
TW-004-0005
52 BZ#52
ng/L
2.03
2.64
-26
TW-004-0005
101 BZ#101& BZ#[90]
ng/L
0.309 J
0.388 J
-23
TW-004-0005
118 BZ#118
ng/L
0.15
0.18
-18
TW-004-0005
138 BZ#138
ng/L
0.0622 U
0.0681 U
NC
TW-004-0005
180 BZ#180
ng/L
0.0157 U
0.0151 U
NC
TW-005-0006
1 BZ#1
ng/L
27.4 JN
29.2 JN
-6
TW-005-0006
4 BZ#4
ng/L
40.2 J
42 7 J
-6
TW-005-0006
8 BZ#8
ng/L
2.57 JN
2.71 JN
-5
TW-005-0006
10 BZ#10
ng/L
8.39 J
9.02 J
-7
TW-005-0006
18 BZ#18
ng/L
4.24
4.55
-7
TW-005-0006
19 BZ#19
ng/L
7.08
7.49
-6
TW-005-0006
28 BZ#28
ng/L
4.58
4.88
-6
TW-005-0006
52 BZ#52
ng/L
3.23
3.45
-7
TW-005-0006
101 BZ# 101 & BZ#[901
ng/L
0.609 J
0.644 J
-6
TW-005-0006
118 BZ#118
ng/L
0.329
0.351
-6
TW-005-0006
138 BZ#I38
ng/L
0.19 J
0.207 J
-9
TW-005-0006
180 BZ#180
ng/L
0.0411 U
0.0573 U
NC
TW-006-0006
1 BZ#1
ng/L
8.38
8.02
4
TW-006-0006
4 BZ#4
ng/L
20.0 J
19.1 J
5
TW-006-0006
8 BZ#8
ng/L
1.56 JN
1.51 J
3
T'V-906-0006
10 BZ#10
ng/L
3.198 J
3.0545 J
5
Note: Congeners in [ ] are co-e!uling non-target congeners.
Page 2 of 3
T AM S/Cadmus/Gradient
-------
Table B-l
Water Column Dissolved PCB Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
TW-006-0006
18 BZ#18
ng/L
3.31
3.19
4
TW-006-0006
19 BZ#19
ng/L
6.47 J
6.26 JN
3
TW-006-0006
28 BZ#28
ng/L
3.31
3.21
3
TW-006-0006
52 BZ#52
ng/L
2.69 J
2.57 JN
5
TW-006-0006
101 BZ#101& BZ#[90]
ng/L
0.494 J
0.493 J
0
TW-006-0006
118 BZ#118
ng/L
0.29
0.295
-2
TW-006-0006
138 BZ#138
ng/L
0.155 J
0.176 J
-13
TW-006-0006
180 BZ#180
ng/L
0.0188 U
0.0323 J
NC
TW-E02-0005
1 BZ#1
ng/L
15.3 JN
10.5 JN
37
TW-E02-0005
4 BZ#4
ng/L
0.482 U
0.626 U
NC
TW-E02-0005
8 BZ#8
ng/L
1.83 JN
1.47 JN
22
TW-E02-0005
10 BZ#10
ng/L
3.86 J
2.59 J
39
TW-E02-0005
18 BZ#18
ng/L
1.98 J
1.8 J
10
TW-E02-0005
19 BZ#19
ng/L
3.17 J
2.38 U
NC
TW-E02-0005
28 BZ#28
ng/L
1.58 J
1.52 J
4
TW-E02-0005
52 BZ#52
ng/L
1.16 J
1.04 J
11
TW-E02-0005
101 BZ#101& BZ#[90]
ng/L
0.162 U
0.16 U
NC
TW-E02-0005
118 BZ#118
ng/L
0.0482 U
0.0626 U
NC
TW-E02-0005
138 BZ#138
ng/L
0.0482 U
0.0505 J
NC
TW-E02-0005
180 BZ#180
ng/L
0.0081 U
0.0113 U
NC
TW-E06-0003
1 BZ#1
ng/L
0.195 J
0.21 J
-7
TW-E06-0003
4 BZ#4
ng/L
0.593 U
0.661 U
' NC
TW-E06-0003
8 BZ#8
ng/L
0.511 U
0.52 U
NC
TW-E06-0003
10 BZ#10
ng/L
0.593 U
0.661 U
NC
TW-E06-0003
18 BZ#18
ng/L
0.884
0.887
0
TW-E06-0003
19 BZ#19
ng/L
0.374 J
0.383 J
-2
TW-E06-0003
28 BZ#28
ng/L
0.92
0.912
1
TW-E06-0003
52 BZ#52
ng/L
0.498 J
0.496 J
0
TW-EO6-O0O3
101 BZ#101&BZ#190]
ng/L
0.18 U
0.141 U
NC
TW-E06-0003
118 BZ#118
ng/L
0.0705
0.0631
11
TW-E06-0003
138 BZ#138
ng/L
0.0494 J
0.0306 J
47
TW-E06-0003
180 BZ#180
ng/L
0.0116 U
0.0477 U
NC
NC - Not calculated because PCB congener was not detected or rejected in one or both samples.
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 3 of3
TAMS/Cadmus/Gradient
-------
Table B-2
Water Column Particulate Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
FS-209-0004
1 BZ#1
ug/Kg
70.58 U
134.35 U
\'C
FS-209-0004
4 BZ#4
Mg/Kg
416.70 U
455.13 U
NC
FS-209-0004
8 BZ#8
ug/Kg
143.78
206.21 JN
-36
FS-209-0004
10 BZ#10
ug/Kg
79.99 U
115.08 U
NC
FS-209-0004
18 BZ#18
ug/Kg
111.36 U
141.64
NC
FS-209-0004
19 BZ#19
ug/Kg
141.69 J
223.40 J
-45
FS-209-0004
28 Bzns
ug/Kg
425.07 U
598.85 U
NC
FS-209-0004
52 BZ#52
ug/Kg
262.99 U
405.66 U
NC
FS-209-0004
101 BZ#10l & BZ#f90]
ug/Kg
138.03 U
191.63 U
NC
FS-209-0004
118 BZ#118
ug/Kg
129.14 U
175.49 U
NC
FS-209-0004
138 BZ#138
ug/Kg
76.86 U
92.69 U
NC
FS-209-0004
180 BZ#180
ug/Kg
26.87 U
31.92 U
NC
FS-609-0005
1 BZ#1
ug/Kg
160.48 J
113.88 J
34
FS-609-0005
4 BZU
ug/Kg
297.26 J
243.12 J
20
FS-609-0005
8 BZ#8
ug/Kg
235.16 U
231.07 U
NC
FS-609-0005
10 BZ#10
ug/Kg
47.57 J
38.91 J
20
FS-609-0005
18 BZ#18
ug/Kg
106.24
130.01
-20
FS-609-0005
19 BZ#19
ug/Kg
135.58 J
140.45 J
-4
FS-609-0005
28 BZ#28
ug/Kg
277.39
305.09
-10
FS-609-0005
52 BZ#52
ug/Kg
289.40 J
337.36 J
-15
FS-609-0005
101 BZ#101& BZ#[90]
ug/Kg
195.60 J
182.68 J
7
FS-609-0005
118 BZ#118
ug/Kg
108.91 J
116.72
-7
FS-609-0005
138 BZ#138
ug/Kg
84.46 J
78.76 J
7
FS-609-0005
180 BZ#180
ug/Kg
16.09 U
27.76 U
NC
TS-001-0014
1 BZ#1
ug/Kg
84.46 m
48.04 JN
55
TS-001-00I4
4 BZ#4
ug/Kg
91.08 U
115.64 U
NC
TS-001-0014
8 BZ#8
ug/Kg
4
-------
Table B-2
Water Column Particulate Field Co-located Samples
Hudson River PCB Reassessment
TAMS ID
BZ Parameter
Units
Field Co-
Locate 1 Qualifier
Field Co-
Locate 2 Qualifier
RPD (%)
TS-002-G004
101 BZ#101& BZ#[90]
ug/Kg
421.30 J
182.34 J
79
TS-002-0004
118 BZ#118
ug/Kg
481.72 J
170.84 J
95
TS-002-0004
138 BZ#138
ug/Kg
172.16 J
93.63 J
59
TS-002-0004
180 BZ#I80
ug/Kg
53.30 U
43.04 U
NC
TS-003-0008
1 BZ#1
ug/Kg
9.05 JN
7.90 JN
14
TS-003-0008
4 BZ#4
ug/Kg
12.39 J
7.26 J
52
TS-003-0008
8 BZ#8
ug/Kg
11.63 JN
8.35 JN
33
TS-003-0008
10 BZ#10
ug/Kg
2.62 U
1.54 U
NC
TS-003-0008
18 BZ#18
ug/Kg
10.28 J
8.83 J
15
TS-003-0008
19 BZ#19
ug/Kg
R
0.30 U
NC
TS-003-0008
28 BZ#28
ug/Kg
30.18 J
28.03 J
TS-003-0008
52 BZ#52
ug/Kg
14.51 J
13.46 J
8
TS-003-0008
101 BZ#101 & BZ#[90]
ug/Kg
7.5C
6.96 J
9
TS-003-0008
118 BZ#118
ug/Kg
7.49 J
6.81 J
10
TS-003-0008
138 BZ#138
ug/Kg
5.67 J
6.04 J
-6
TS-003-0008
180 BZ#180
ug/Kg
1.68 J
2.89 J
-53
TS-004-0005
1 BZ#1
ug/Kg
133.67 JN
163.03 JN
-20
TS-004-0005
4 BZH
ug/Kg
119.73 U
145.21 U
NC
TS-004-0005
8 BZ#8
ug/Kg
172.03 JN
140.61 J
20
TS-004-0005
10 BZ#10
ug/Kg
54.05 J
53.48 J
1
TS-004-0005
18 BZ#18
ug/Kg
305.13
231.47 J
27
TS-004-0005
19 BZ#19
ug/Kg
108.10
88.27 J
20
TS-004-0005
28 BZ#28
ug/Kg
656.75 J
494.56 J
28
TS-004-0005
52 BZ#52
ug/Kg
284.20
210.76 J
30
TS-004-0005
101 BZ#10L&BZ#[901
ug/Kg
100.84 J
70.73 J
35
TS-004-0005
118 BZ#118
ug/Kg
90.38
63.55 J
35
TS-004-0005
138 BZ#138
ug/Kg
40.68 J
28.75 J
34
TS-004-0005
180 BZ#180
ug/Kg
11.25 U
7.02 U
NC
TS-005-0006
1 BZ#1
ug/Kg
195.02 U
323.42 U
NC
TS-005-0006
4 BZ#4
ug/Kg
205.00 J
390.34 J
-62
TS-005-0006
8 BZm
ug/Kg
85.87 JN
171.53 JN
-67
TS-005-0006
10 BZ#10
ug/Kg
49.69 J
96.36 J
-64
TS-005-0006
18 BZ#18
ug/Kg
84,41 J
154.57 J
-59
TS-005-0006
19 BZ#19
ug/Kg
78.38 U
141.64 U
NC
TS-005-0006
28 BZ#28
ug/Kg
268.21 J
521.94 J
-64
TS-005-0006
52 BZ#52
ug/Kg
168.20 J
334.57 J
-66
TS-005-0006
101 BZ#101&BZ#[901
ug/Kg
86.91 J
175.54 J
-68
TS-005-0006
118 BZ#118
ug/Kg
80.26 J
168.63 J
-71
TS-005-0006
138 BZ#138
ug/Kg
55.51 J
115.32 J
-70
TS-005-0006
180 BZ#180
ug/Kg
17,44 U
36.36 U
NC
TS-006-0006
1 BZ#1
ug/Kg
71.65 JN
119.92 J
-50
TS-006-0006
4 BZ#4-
ug/Kg
140,47 U
119.92 U
NC
TS-006-0006
8 BZ#8
ug/Kg
195.15 U
168.35 U
NC
TS-006-0006
10 BZ#10
ug/Kg
140,47 U
119.92 U
NC
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 2 of 3 TAMS/Cadmus/Gradient
-------
Table B-2
Water Column Particulate Field Co-located Samples
Hudson River PCB Reassessment
Field Co- Field Co-
TAMS ID
BZ Parameter
Units
Locate 1 Qualifier
Locate 2 Qualifier
RPD (%)
TS-006-0006
18 BZ#18
ug/Kg
92.39
87.00
6
TS-006-0006
19 BZ#19
ug/Kg
60.34 JN
47.97 JN
23
TS-006-0006
28 BZ#28
ug/Kg
257.84 U
242.19 U
NC
TS-006-0006
52 BZ#52
ug/Kg
198.45 JN
191.87 JN
3
TS-006-0006
101 BZ#101 & BZ#[90]
ug/Kg
112.19 J
102.52 J
9
TS-006-0006
118 BZ#118
ug/Kg
98.04
97.34
1
TS-006-0006
138 BZ#I38
ug/Kg
73.53 J
68.66 J
7
TS-006-0006
180 BZ#180
ug/Kg
18.85 U
15.52 U
NC
TS-E02-0005
1 BZ#1
ug/Kg
479.18 JN
193.55 JN
85
TS-E02-0005
4 BZ#4
ug/Kg
R
392.64 U
NC
TS-E02-0005
8 BZ#8
ug/Kg
188.22 JN
173.39 U
NC
TS-E02-0005
10 BZ#10
ug/Kg
R
104.33 U
NC
TS-E02-0005
18 BZ#18
ug/Kg
145.29 U
140.12 U
NC
TS-E02-0005
19 BZ#19
ug/Kg
146.44 U
125.50 U
NC
TS-E02-0005
28 BZ#28
ug/Kg
287.51
357.86
-22
TS-E02-0005
52 BZ#52
ug/Kg
271.02
276.21 J
-2
TS-E02-0005
101 BZ#101 & BZ#[90]
ug/Kg
85.87 J
109.38 J
-24
TS-E02-0005
118 BZ#118
ug/Kg
72.45 JN
98.79 JN
-31
TS-E02-0005
138 BZ#138
ug/Kg
52.13 JN
66.53 J
-24
TS-E02-0005
180 BZ#180
ug/Kg
15.79 U
24.34 U
NC
TS-E06-0003
1 BZ#1
ug/Kg
220.58 U
217.94 U
NC
TS-E06-0003
4 BZ#4
ug/Kg
44.20 U
43.59 U
NC
TS-E06-0003
8 BZ#8
ug/Kg
R
R
NC
TS-E06-0003
10 BZ#10
ug/Kg
44.20 U
43.59 U
NC
TS-E06-0003
18 BZ#18
ug/Kg
49.25
39.78 J
21
TS-E06-0003
19 BZ#19
ug/Kg
44.20 U
43.59 U
NC
TS-E06-0003
28 BZ#28
ug/Kg
207.53 U
179.01 U
NC
TS-E06-0003
52 BZ#52
ug/Kg
82.93 J
72.79 J
13
TS-E06-0003
101 BZ#101&BZ#[90]
ug/Kg
80.82 J
60.52 J
29
TS-E06-0003
118 BZ#118
ug/Kg
53.04
41.30 J
25
TS-E06-0003
138 BZ#138
ug/Kg
32.41 J
27.63 J
16
TS-E06-0003
180 BZ#180
ug/Kg
6.95 J
5.37 J
26
NC - Not calculated because PCB congener was not detected or rejected in one or both samples.
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 3 of 3
TAMS/Cadmus/Gradient
-------
Table B-3
PCB Detects Changed to .N'on-detects
Particulate Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Congener Name
Number of results
considered nondetect*
Total number of
results
Percentage of results
considered nondetect*
BZ#1
10
113
9
8Z#2
15
113
13
BZ#3
9
113
8
BZ#4
17
113
15
BZ#5
38
113
34
BZ#6
13
113
12
BZ#7
28
113
25
BZ#8
18
113
16
BZ#9
14
113
12
BZ#I0
11
113
10
BZ#12
12
113
11
BZ#15
13
113
12
BZ#16
12
113
11
BZ#17
2
30
7
BZ#18
15
113
13
BZ#19
8
113
7
BZ*22
15
113
13
BZ#25
24
113
21
BZ#26
15
113
13
BZ#27
11
83
13
BZ#28
23
113
20
BZ#29
9
113
8
BZ#31
14
113
12
BZ#37
5
113
4
BZ#40
5
113
4
BZ#41
9
113
8
BZ#44
7
113
6
BZ#45
4
30
13
BZ#47
12
113
11
BZ#49
13
113
12
BZ#52
12
113
11
BZ#53
6
113
5
BZ#56
28
113
25
BZ#59
1
30
3
BZ#66
9
113
8
BZ#70
6
113
5
BZ#75
1
113
1
BZ#77
37
113
33
BZ#82
19
113
17
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 1 of 3
T AMS/Cadmus/Gradtent
-------
Table B-3
PCB Detects Changed to Non-detects
Particulate Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#83
11
113
10
BZ#84
14
113
12
Bzms
12
113
11
BZ#87
17
113
15
BZ#9I
20
113
18
BZ#92
19
113
17
BZ#95
10
113
9
BZ#97
20
113
18
BZ#99
11
113
10
BZ#105
32
83
39
BZ#107
18
113
16
BZ#110
3
30
10
BZ#118
25
113
22
BZ#119
9
113
8
BZ#122
23
113
20
BZ#123
48
113
42
BZ#126
4
113
4
BZ#128
29
113
26
BZ#129
40
113
35
BZ#136
3
113
3
BZ#137
2
113
2
BZ#138
27
113
24
BZ#I41
34
113
30
BZ#149
43
113
38
BZ#151
11
113
10
BZ#153
35
113
31
BZ#157
6
113
5
BZ#158
48
113
42
BZ#165
7
30
23
BZ#167
12
113
11
BZ#170
55
113
49
BZ#171
8
113
7
BZ#174
4
30
13
BZ#176
1
30
3
BZ#177
11
113
10
BZ#179
1
30
3
BZ#180
61
113
54
BZ#183
11
113
10
BZ#185
8
113
7
Note:
Congeners in [ ] are co-eluting non-target congeners.
Page 2 of 3
TAMS/Cadmus/Gradient
-------
Table B-3
PCB Detects Changed to Non-detects
Particulate Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#187
25
113
22
BZ#I89
10
113
9
BZ#190
21
113
19
BZ#191
I
113
1
BZ#193
8
113
7
BZ#194
9
113
8
BZ#195
20
113
18
BZ#196
10
113
9
BZ#199
1
113
1
BZ#201
25
in
22
BZ#202
1
J, w
1
BZ#205
3
113
3
BZ#206
2
113
2
BZ#207
1
113
1
BZ#208
1
113
1
BZ#209
11
113
10
Note * - Results were considered nondetect due to suspected false positive as indicated by blank
contamination
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 3 of 3
TAMS/Cadmus/Gradient
-------
Table B-4
PCB Detects Changed to Non-detects
Dissolved Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#1
8
117
7
BZ#2
21
117
18
BZ#3
16
117
14
BZ#4
28
117
24
B Z#5
40
117
34
BZ#6
16
117
14
BZ#7
38
117
32
BZ#8
29
117
25
BZ#9
30
117
26
BZ#10
17
117
15
BZ#12
12
117
10
BZ#15
17
117
15
BZ#16
16
117
14
BZ#18
24
117
21
BZ#19
14
117
12
BZ#22
27
117
23
BZ#25
23
117
20
BZ#26
8
117
7
BZ#27
9
87
10
BZ#28
29
117
25
BZ#29
8
117
7
BZ#31
20
117
17
BZ#37
22
117
19
BZ#40
8
117
7
BZ#41
16
117
14
BZ#44
26
117
22
BZ#45
5
30
17
BZ#47
9
117
8
BZ#49
15
117
13
BZ#52
32
117
27
BZ#53
4
117
3
BZ#56
57
117
49
BZ#66
32
117
27
BZ#70
29
117
25
BZ#74
1
30
3
BZ#77
62
117
53
BZ#82
34
117
29
BZ#83
24
117
21
BZ#84
59 '
117
50
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 1 of 3
TAMS/Cadmus/Gradient
-------
Table B-4
PCB Detects Changed to Non-detects
Dissolved Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondeteet*
Bzms
44
117
38
BZ#87
63
117
54
BZ#91
45
117
38
BZ#92
37
117
32
BZ#95
58
117
50
BZ#97
36
117
31
BZ#99
32
117
27
BZ#105
49
87
56
BZ#107
30
117
26
BZ#ilO
12
30
40
BZ#118
49
117
42
BZ#119
18
117
15
BZ#122
9
117
8
BZ#123
45
117
38
BZ#126
1
117
1
BZ#128
21
117
18
BZ#129
16
117
14
BZ#135
1
3u
3
BZ#136
10
117
9
BZ#137
7
117
6
BZ#138
73
117
62
BZ#141
55
117
47
BZ3149
74
117
63
BZ#151
12
117
10
BZ#153
61
117
52
BZ#157
I
117
1
BZ#158
47
117
40
BZ# 167
1
117
1
BZ#170
51
117
44
BZ#171
1
117
1
BZ#174
8
30
27
BZ#180
72
117
62
BZ#183
3
117
3
BZ#187
32
117
27
BZ#189
1
117
1
BZ#190
6
117
5
BZ#194
4
117
3
BZ#195
9
117
8
BZ#196
3
117
3
Note: Congeners in [ 1 are co-eluting non-tr.rget congeners.
Page 2 of 3
TAMS/Cadmus/Gradient
-------
Table B-4
PCB Detects Changed to Non-detects
Dissolved Data
Water-column Monitoring Program
Hudson River RI/FS PCB Reassessment
Number of results Total number of Percentage of results
Congener Name considered nondetect* results considered nondetect*
BZ#2Q1 13 117 11
BZ#209 2 117 2
Note * - Results were considered nondetect due to suspected false positive as indicated by blank
contamination
Note; Congeners in [ ] are co-eluting non-target congeners.
Page 3 of 3
TAMS/Cadmus/Gradient
-------
Table B-5
Wafer Column Samples -- Dissolved
Hudson River RI/FS I'CB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejec
BZ#1
115
34
13
10
58
0
0
0%
BZ#2
115
32
50
0
0
9
33
29%
BZ#3
115
51
43
1
5
13
15
13%
BZM
115
4
64
0
45
18
2
2%
BZU5
115
57
54
0
3
0
1
1%
Bzm
115
50
12
38
14
0
1
1%
Bzm
115
40
51
0
24
0
0
0%
Bzm
115
10
33
1
57
0
14
12%
Bzm
115
42
40
0
33
0
0
0 %
BZ#I0
115
19
34
0
61
2
1
1%
BZ#12
115
59
22
0
28
0
6
5%
BZ#15
115
34
27
0
53
4
1
1%
BZ#16
115
28
22
0
63
1
2
2%
BZ#)7
29
6
0
0
23
0
0
0%
BZ#17
Non-Target
86
8
0
0
78
14
0
0%
BZ#18
115
16
19
50
27
0
3
3%
BZ#I9
115
39
11
31
29
0
5
4%
BZ#20
Non-Target
86
4
29
0
53
78
0
0%
BZ#20
29
13
2
0
13
0
1
3%
BZ021
Non-Target
0
0
0
0
BZ#22
115
15
25
49
22
2
4
3%
BZ#23
s Non-Target
115
33
12
0
70
14
0
0%
BZ#24
Non-Target
86
25
0
0
61
14
0
0%
BZ#25
115
39
19
28
19
0
10
9%
BZ#26
115
13
25
18
56
If.
3
3%
BZ#27&BZ#[24|
29
7
0
0
22
0
0
0%
Noie; Congeners in J ] arc co-eluting non-iargel congeners.
Page I «f6
TAMS/Oadmti.s/Grailii-nl
-------
Table B-5
Water Column Samples — Dissolved
Hudson River RI/FS PCB Reassessment
_ %t . , Unqualified Estimated Unqualified Estimated _ , Rejected
Congener Name Number of „ . . , „ . , _ «... « , Qualified „ % Rejected
6 „ , Nondctects Nondetects Detects Detects . . Results J
Results _ with K
BZ#27
86
26
15
0
45
0
0
0%
BZ#28
115
18
22
57
16
0
2
2%
BZ#29
115
46
13
0
56
0
0
0%
BZ#31
115
30
12
47
23
0
3
3%
BZ032 Noil-Target
115
16
5
0
94
14
0
0%
BZ#33
29
12
1
0
15
0
1
3%
BZ#33 Non-Target
86
4
11
0
71
78
0
0%
BZ#34 Non-Target
115
28
6
1
80
14
0
0%
BZ#37
115
25
24
0
63
77
3
3%
BZ#40
115
32
7
31
44
0
1
1%
BZ#41
115
28
22
0
65
1
0
0%
BZ#42
29
6
0
0
23
0
0
0%
BZ#42
Non-Target
86
6
0
0
80
14
0
0%
BZ#44
115
10
22
54
27
0
2
2%
BZ#45
29
10
4
11
3
0
1
3%
BZ#45
Non-Target
86
20
0
66
14
0
0%
BZ#47
115
29
11
0
75
0
0
0%
BZ#48
Non-Target
115
35
5
7
68
17
0
0%
BZ#49
115
30
16
39
22
1
8
7%
BZ#51
Non-Target
115
13
7
1
94
78
0
0%
BZ#52
115
14
23
40
33
2
5
4%
BZ#53
115
26
27
16
39
30
7
6%
BZ#54
Non-Target
0
0
0
0
0
BZ#56
115
8
66
0
40
0
1
1%
BZ#58 Non-Target
115
68
6
0
41
14
0
0%
BZ#59
29
8
1
16
4
0
0
0%
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 2 of6
TA M S/Cadmus/G radiant
-------
Table B-5
Water Column Samples — Dissolved
Hudson River RI/FS PCB Reassessment
_ .. .. . . Unqualified Estimated Unqualified Estimated Rejected
Congener Name Number of „ . A J Qualified 0/ r. .
„ .. Nondetects Nondetccts Detects Detects . , Results kljlucu
Results with K
BZU60 Non-Target
115
19
7
1
88
14
0
0%
BZ#63 Non-Target
115
21
36
0
58
78
0
0%
BZ#64 Non-Target
115
34
7
0
74
14
0
0%
BZ//66
115
9
41
0
65
76
0
0%
BZ#67 Non-Target
115
73
6
0
36
14
0
0%
BZ#69 Non-Target
115
99
13
0
3
14
0
0%
Bzm
115
5
35
14
60
4
1
1%
BZH72
29
14
3
1
11
0
0
0%
RZ#74
29
2
1
15
10
0
1
3%
BZ#74 Non-Target
86
3
5
0
78
78
0
0%
BZ#75
115
50
65
0
0
63
0
0%
BZ#77
115
23
85
0
7
0
0
0%
BZ#82
115
28
34
11
40
2
2
2%
BZ#83
115
41
29
2
43
0
0
0%
BZ#84
115
10
69
7
28
8
1
1%
BZ#85
115
17
46
19
32
4
1
1%
BZ#87
115
2
70
0
43
45
0
0%
BZ#88 Non-Target
0
0
0
BZ#90 Non-Target
0
0
0
BZ#91
115
19
66
13
17
18
0
0%
BZJ92
115
26
43
3
35
0
8
7%
Bzms
115
16
66
0
31
72
2
2%
BZ#96 Non-Target
115
76
10
0
29
14
0
0%
BZ#97
115
31
28
31
19
2
6
5%
BZ#99
115
26
35
12
42
0
0
0%
BZ#101& BZ#|90|
115
3
65
0
47
37
0
0%
Note: Congeners in 1 ) are co-eluling non-larget congeners.
Page 3 of6
TAMS/Cadmus/Gradieni
-------
Table B-5
Water Column Samples -- Dissolved
Hudson River Rl/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejec
BZ#105 & BZ#[68]
29
8
16
0
5
0
0
0%
BZ#I05
86
13
61
0
12
0
0
0%
BZ#107
115
43
41
0
31
0
0
0%
BZ#110
29
2
14
0
13
0
0
0%
BZ#110
Non-Targel
86
2
0
0
84
14
0
0%
BZ#114
Non-Target
115
97
14
0
4
14
0
0%
BZ#il5
115
103
12
0
0
0
0
0%
BZ#I 18
115
13
45
15
13
2
29
25%
BZ#119
115
67
29
0
9
6
10
9%
BZ#122
115
56
51
0
4
50
4
3%
BZ#123
115
53
59
0
3
2
0
0%
BZ#126
115
92
21
0
2
4
0
0%
BZ#128
115
17
83
0
12
62
3
3%
BZ#129
115
45
59
0
10
41
1
1%
BZ#135
29
16
4
0
9
0
0
0%
BZ#135 Non-Target
86
72
14
0
0
14
0
0%
BZ#136
115
46
46
0
23
36
0
0%
BZ#137
115
81
13
0
21
0
0
0%
BZ#138
115
8
85
0
22
84
0
0%
BZ#140 Non-Targcl
115
96
14
0
5
14
0
0%
BZ#141
115
28
67
0
20
59
0
0%
BZ#143
29
28
1
0
0
0
0
0%
BZ#143
Non-Target
86
71
12
0
3
14
0
0%
BZ#144
Non-Target
115
94
14
0
7
14
0
0%
BZ#146
Non-Target
115
83
14
2
16
14
0
0%
BZ#149
115
14
86
0
15
0
0
0%
Note: Congeners in ( J are co-eluting non-target congeners.
Page 4 of 6
TAMS/Catlmus/Grailient
-------
Table B-5
Water Column Samples -- Dissolved
Hudson River RI/FS PCB Reassessment
. Unqualified Estimalcd Unqualified Estimated ^Val"fS Rejected
Congener Name Number of Nom|ctem N(|ndctccts Dctec„ Detcc(s Q"al.r,e
-------
Table B-5
Water Column Samples -- Dissolved
Hudson River RI/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Values
Qualified
witli K
Rejected
Results
% Rejected
BZ#I89
115
102
13
0
0
0
0
0%
BZ#190
115
96
18
0
1
0
0
0%
BZ#191
115
101
12
0
2
0
0
0%
BZ#192 Non-Target
86
8
76
0
2
78
0
0%
BZ#193
115
70
45
0
0
35
0
0%
BZ#194
115
94
16
0
5
0
0
0%
BZ#195
115
91
21
0
1
0
2
2%
BZ#196
115
96
17
0
1
0
1
1%
BZ#197 Non-Target
115
101
14
0
0
14
0
0%
BZ#198
115
65
49
0
0
40
1
1%
BZ#199
115
101
13
0
1
0
0
0%
BZ#200
115
103
12
0
0
0
0
0%
BZ#201
115
80
27
0
7
0
1
1%
BZ#202
115
102
13
0
0
0
0
0%
BZ#203 Non-Target
115
93
14
1
7
14
0
0%
BZ#205
115
102
13
0
0
0
0
0%
BZ#206
115
104
11
0
0
0
0
0%
BZ#207
115
103
12
0
0
0
0
0%
BZ#208
115
104
11
0
0
0
0
0%
BZ#209
115
96
12
0
6
0
1
1%
14577 6401 3664 694 3570 1965 248 2%
Note: Congeners in 1 ] are co-eluting non-target congeners.
Page 6 of6
TAMS/Cadmus/Gradicnt
-------
Table B-6
Water Column Samples -- Particulate
Hudson River RF/FS PCB Reassessment
Total Values
„ .. m i <• Unqualified Estimated Unqualified Estimated ^ Rejected
Congener Name Number of . ' . ., , ' _ Qualified 0/ R - f ,
_ , Nondetects Nondetects Detects Detects Results KtjtUuI
Results with K s
BZ#1
115
23
30
1
58
3
3%
BZ#2
115
32
53
1
29
25%
BZ#3
115
46
45
3
5
16
14%
BZ#4
115
5
92
11
50
7
6%
BZJ5
115
42
66
5
2
2%
B Z#6
115
32
41
11
27
4
3%
BZ#7
115
50
62
3
0
0%
BZ#8
115
26
31
1
49
8
7%
BZ#9
115
49
49
17
0
0%
BZ#10
115
13
72
24
14
6
5%
BZ#12
115
32
41
35
7
6%
BZ#15
115
25
27
63
0
0%
BZ#16
115
25
37
51
2
2%
BZ#17
29
7
3
19
0
0%
BZ# 17 Non-Target
86
26
0
60
0
0%
BZ#18
115
20
23
33
32
7
6%
BZJ19
115
29
28
15
23
20
17%
BZ#20 Non-Target
86
0
38
48
86
0
0%
BZ#20
29
11
3
15
0
0%
BZ#21 Nun-Target
0
0
0
BZ#22
115
15
23
27
47
3
3%
BZ#23 Non-Target
115
40
0
75
0
0%
BZ#24 Non-Target
86
30
0
56
0
0%
BZ#25
115
20
34
14
32
15
13%
BZ#26
115
17
29
11
57
2
1
1%
BZ#27 & BZ#[24|
29
9
2
1
16
1
3%
Note: Congeners in [ | are co-eluting non-target congeners.
Page 1 of 6
TAMS/Oadmus/Gnulient
-------
Table B-6
Water Column Samples -- Particulate
Hudson River RI/FS PCB Reassessment
,, .. , Unqualified Estimated Unqualified Estimated _ , Rcicctcd
Congener Name Number of ' , Qualified ,/ , % Rejected
. _ Nondctects Nondetects Detects Detects . Results J 1
Results with K
BZ#27
86
16
33
37
0
0%
BZ#28
115
23
26
27
38
1
1%
BZ#29
115
41
39
34
1
1%
BZ#31
115
16
22
34
36
7
6%
BZ#32 Non-Targcl
115
30
0
85
0
0%
BZ#33
29
12
2
15
0
0%
BZ#33 Non-Target
86
0
40
46
86
0
0%
BZ#34 Non-Target
115
49
0
66
0
0%
BZ#37
115
17
15
83
74
0
0%
BZ#40
115
25
19
12
59
0
0%
BZ#41
115
18
23
73
1
1%
BZ#42
29
7
0
22
0
0%
BZ#42 Non-Target
86
46
0
40
0
0%
BZ#44
115
17
14
34
47
3
3%
BZ#45
29
6
7
2
8
6
21%
BZ#45 Non-Target
86
31
0
55
0
0%
BZ#47
115
18
23
74
0
0%
BZJ48 Non-'Target
115
55
0
60
5
0
0%
OZ#49
115
17
27
21
41
9
8%
BZ#51 Non-Targcl
115
15
20
80
86
0
0%
BZ#52
115
15
19
19
58
4
3%
BZ#53
115
25
29
14
44
14
3
3%
BZ#54 Non-Target
0
0
0
0
BZ#56
115
13
49
51
2
2%
BZ#58 Non-Target
115
78
0
37
0
0%
Noic: Congeners in | | are co-eluting non-iargci congeners.
Page 2 of 6
TAMS/Oadmus/Gradient
-------
Table B-6
Water Column Samples — Particulate
Hudson River RI/FS PCB Reassessment
„ T°*a' Unqualified Estimated Unqualified Estimated ,*Va!!!!S Rejected
Congener Name Number of Nonde,ccl! Non(lctects Dclcc|s Dclects Qmi hfieil ^ % Rejectal
Results with K
BZ#59
29
8
3
15
3
10%
BZ#60 Non-Target
115
25
0
90
0
0%
BZ#63 Non-Target
115
23
64
28
86
0
0%
BZ#64 Non-Target
115
49
0
66
0
0%
BZ#66
115
9
21
85
79
0
0%
BZ#67 Non-Target
115
84
0
31
0
0%
BZ#69 Non-Targe!
115
103
0
12
0
0%
BZ#70
115
8
20
18
69
10
0
0%
BZ#72
29
24
3
2
0
0%
BZ#74
29
5
0
15
9
0
0%
BZ#74 Non-Target
86
0
16
70
86
0
0%
BZ#75
115
43
70
2
47
0
0%
BZ#77
115
12
53
5
0
0%
BZ#82
115
19
33
12
4
3
3%
BZ#83
115
30
34
4
6
5%
BZ//84
115
16
30
6
6i
0
0%
BZ#85
115
10
23
16
64
2
2%
BZ#87
115
10
24
81
54
0
0%
BZ#88 Non-Target
0
0
0
0
BZ#90 Non-Target
86
64
0
22
0
BZ#91
115
19
35
1
60
0
0%
BZ#92
115
21
33
8
53
0
0%
BZ#95
115
23
31
58
68
3
3%
BZ#96 Non-Target
115
82
0
33
0
0%
BZ#97
115
23
27
20
44
1
1%
Note: Congeners in | ] are co-eluting non-target congeners.
I'agc 3 of 6
TA M X/Cad mus/( i radium
-------
Table B-6
Water Column Samples -- Particulate
Hudson River RI/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nomlctects
Estimated
Nomletccts
Unqualified
Detects
Estimated
Detects
Values
Qualfficd
with K
Rejected
Results
% Rejec
Bzm
115
16
26
13
58
2
2%
BZ#101 & BZ#{90|
115
8
21
86
38
0
0%
BZ#105 & BZ#[68]
29
8
14
7
0
0%
BZ#105
86
7
41
38
0
0%
BZ#107
115
35
37
42
1
1%
BZ#110
29
6
3
20
0
0%
BZ#110 Non-Target
86
13
0
73
0
0%
BZ#I 14 Non-Target
115
115
0
0
0
0%
BZ#115
115
68
47
0
0
0%
BZ# 118
115
12
3!
22
36
14
12%
BZ#119
115
42
39
1
32
1
1%
BZ#122
115
45
64
2
23
4
3%
BZ#I23
115
33
79
3
0
0%
BZ#126
115
65
43
5
2
2%
BZ#128
115
11
51
44
47
9
8%
BZ#129
115
29
71
12
20
3
3%
BZ#135
29
16
1
12
0
0%
BZ#135 Non-Targei
86
84
0
2
0
0%
BZ#136
115
34
34
2
45
19
0
0%
BZ#137
115
35
20
1
59
0
0%
BZ#138
115
4
35
76
78
0
0%
BZ#140 Non-Targei
115
114
0
1
0
0%
BZ#141
115
24
51
40
39
0
0%
BZ#143
29
26
3
0
0
0%
B7.fi 143 Non-Targei
86
47
0
39
0
0%
Note: Congeners in ( | are co-eluling noniarget congeners.
I'agc 4 of 6
I AMS/Cadinu,s/{JracJicnl
-------
Table B-6
Water Column Samples -- Particulate
Hudson River RI/FS PCB Reassessment
^ .. Unqualified Estimated Unqualified Estimated „ Re ected
Congener Name Number of x. . . , x Qualified * % Rejected
b . R it Nondeteets Nondetccts Detects Detects Results tJWIUI
BZ#144 Non-Target
115
85
0
30
0
0%
BZ#146 Non-Target
115
98
0
17
0
0%
BZ#149
115
13
56
46
0
0%
BZJ151
115
27
33
7
48
0
0%
BZ#I53
115
6
49
60
38
0
0%
BZ#156
29
19
1
9
0
0%
BZ#156 Non-Target
86
53
0
33
0
0%
BZ#157
115
53
38
24
0
0%
BZ#158
115
32
73
10
0
0%
BZ#160 Non-Target
0
0
0
0
0
BZ#165
29
13
14
0
2
7%
BZ#167
115
38
40
3
34
30%
BZ# 169 Non-Target
115
84
0
31
0
0%
BZ#170
115
16
78
5
15
1
1%
BZ#171
115
53
38
24
0
0%
BZ#172 Non-Target
115
28
63
24
86
0
0%
BZ#I74
29
16
5
8
0
0%
BZ#174 Non-Target
86
51
0
35
1
0
0%
BZ#175 Non-Target
115
114
0
1
0
0%
BZ#176
29
25
4
0
0
0%
BZ#177
115
41
39
35
0
0%
BZ#178
29
26
3
0
0
0%
BZ#178 Non-Target
86
85
0
1
0
0%
BZ#179
29
23
4
1
1
3%
BZ#180
115
6
83
26
0
0%
Note: Congeners in [ ] are eo-eluting non-target congeners.
Page 5 of6
I AMS/Cadmu.s/(itaificnt
-------
Table 11-6
Water Column Samples — Particulate
Hudson River RI/FS PCB Reassessment
„ .. - Unqualified Estimated Unqualified Estimated ^ Rejected
Congener Name Number of M . %, a . . n . . , Qualified . % Rejected
_ Nondetects Nondetects Detects Detects . Results J
Results with K
BZ#183
115
43
38
1
30
3
3%
BZ#184 Non-Target
115
112
0
3
0
0%
BZ#185
115
59
49
7
0
0%
BZ#187
115
21
49
4
38
22
3
3%
BZ#189
115
59
52
1
2
1
1%
BZ#190
115
53
54
7
1
1%
BZ#I91
115
60
37
17
1
1%
HZ# 192 Non-Target
86
0
62
24
86
0
0%
BZ#193
115
61
52
2
0
0%
BZ#194
115
47
42
1
22
3
3%
BZ#195
115
48
56
10
1
1%
BZ#196
115
47
42
25
1
1%
BZ#197 Non-Target
115
115
0
0
0
0%
BZ#198
115
68
46
0
1
1%
BZ#199
115
61
45
, 8
1
1%
BZ#200
115
62
45
8
0
0%
BZ#201
115
15
45
5
44
6
5%
BZ#202
115
62
37
16
0
0%
BZ#203 Non-Target
115
62
3
50
0
0%
BZ#205
115
61
52
2
0
0%
BZ#206
115
68
41
5
1
1%
BZ#207
115
65
46
4
0
0%
BZ#208
115
63
38
10
4
3%
BZ#209
115
58
48
8
1
1%
14663
5196
4067
439
4673
1344
288
2%
Note: Congeners in [ ] arc eo-eluting non-target congeners.
Page 6 of6
T A M S/Cadmus/G radicni
-------
Table B-7
Water Column Samples -- Flow-Averaged Event 7
Hudson River RI/FS PCB Reassessment
_ m, mI Unqualified Estimated Unqualified Estimated Estimated ,Va'UfS Refected
Congener Name Number of w M , n, » „ , , _ , Qualified . % Reiccted
„ Nondetects Nondeteets Detects Detects Detects Results
Results with K
BZ#1
3
0
1
0
2
2
0
0
0%
BZ#2
3
2
1
0
0
0
0
0
0%
BZ»3
3
2
1
0
0
0
0
0
0%
B7M
3
3
0
0
0
0
0
0
0%
BZ#3
3
0
3
0
0
0
0
0
0%
B7M
3
2
1
0
0
0
0
0
0%
BZ#7
3
1
2
0
0
0
0
0
0%
BZ#8
3
0
0
0
3
3
0
0
0%
BZ#9
3
1
2
0
0
0
0
0
0%
BZ#10
3
3
0
0
0
0
0
0
0%
BZ#12
3
0
0
0
3
3
0
0
0%
BZ#I5
3
0
3
0
0
0
0
0
0%
BZ#16
3
0
3
0
0
0
0
0
0%
BZ#17 Non-Target
3
0
0
0
3
3
0
0
0%
BZ# 18
3
0
0
3
0
0
0
0
0%
BZ#19
3
0
0
3
0
0
0
0
0%
BZ#20 Non-Target
3
1
0
0
2
2
0
0
0%
BZ#21 Non-Target
0
0
0
0
0
0
0
0
BZ#22
3
1
0
2
0
t!
0
(!
0%
BZ#23 Non-Target
3
0
1
0
2
2
0
0
0%
BZ#24 Non-Target
3
1
2
0
0
0
0
()
0%
BZ#25
3
0
i
0
0
0
0
2
67%
BZ#26
3
0
2
0
1
1
0
0
0%
BZ#27
3
0
2
0
1
1
0
0
0%
BZ#28
3
1
0
2
0
0
0
0
0%
BZ#29
3
1
2
0
0
0
0
0
0%
Note: Congeners in ( j arc eo-eluting non-target congeners.
Page I of 6
TAMS/Cadmus/Gradient
-------
Table B-7
Water Column Samples -- FIow-Averaj d Event 7
Hudson River RI/FS PCB Reasses lent
,, . Unqualified Estimated Unqualified Estimated Estimated Va,"cs Rejected
Congener Name Number of Qnalificd ^ % Rejeced
Results with K
BZ#31
3
0
0
3
0
0
0
0
0%
BZ#32 Non-Target
3
0
0
0
3
3
0
0
0%
BZ#33 Non-Target
3
0
0
0
3
3
0
0
0%
BZ#34 Non-Target
3
0
0
0
3
3
0
0
0%
BZ#37
3
0
0
0
3
3
0
0
0%
BZ#40
3
1
i
0
1
i
0
0
0%
BZ#41
3
0
3
0
0
0
0
0
0%
BZ#42 Non-Target
3
0
2
0
1
1
0
0
0%
BZ#44
3
1
0
2
0
0
0
0
0%
BZ#45 Non-Target
3
0
0
0
3
3
0
0
()%
BZW47
3
0
2
0
1
1
0
0
0%
BZ#48 Non-Target
3
0
2
0
1
)
0
0
0%
BZ#49
3
0
0
1
2
2
0
0
0%
BZ#51 Non-Target
3
0
I
0
2
2
0
0
0%
BZ#52
3
2
0
1
0
0
0
{}
()%
BZ#53
3
2
0
0
1
1
0
0
0%
BZ#54 Non-Target
0
0
0
0
0
0
0
0
BZ#56
3
0
1
0
2
2
0
0
0%
BZ#58 Non-Target
3
1
2
0
0
0
0
0
0%
BZ#60 Non-Target
3
0
0
0
3
3
0
0
0%
BZ#63 Non-Target
3
1
2
0
0
0
0
0
0%
BZ#64 Non-Target
3
0
1
0
2
2
0
0
0%
BZ#66
3
0
0
0
3
3
0
0
0%
BZ#67 Non-Targe!
3
1
1
0
1
1
0
0
0%
BZ#69 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#70
3
0
0
0
3
3
0
0
0%
Note: Congeners in [ | are co eluting non-target congeners.
Page 2 of6
T A M S/Cadmus/G radical
-------
Table B-7
Water Column Samples -- Flow-Averaged Event 7
Hudson River RI/FS PCB Reassessment
Tota' , Unqualified Estimated Unqualified Estimated Estimated , Rejected
Congener Name Number of NondctcctJ Nondelccls DelC[ls Delccts Dclccls Oual.ned % Rejected
Results with K
BZ#74 Non-Target
3
0
0
0
3
3
0
0
()%
BZ#75
3
3
0
0
0
0
0
0
0%
BZ#77
3
0
3
0
(}
0
0
0
0%
BZ#82
3
0
3
0
0
0
0
0
0%
BZ#83
3
0
3
0
0
0
0
0
0%
BZ#84
3
0
3
0
0
{)
0
0
0%
BZ#85
3
2
1
0
0
0
0
0
0%
BZ#87
3
0
3
0
0
0
0
0
0%
BZ#88 Non-Target
0
0
0
0
0
0
{)
0
BZ#90 Non-Target
3
0
3
0
0
0
0
0
0%
BZ#9I
3
0
3
0
0
0
0
0
0%
BZ#92
3
1
1
0
0
0
0
1
33%
BZ#95
3
0
3
0
0
0
0
0
0%
BZ#96 Non-Target
3
1
2
0
0
0
0
0
0%
Bzmi
3
1
0
2
0
0
0
0
0%
BZ#99
3
0
2
0
1
1
0
0
0%
BZ#101&BZ#[9D]
3
0
1
0
2
2
0
0
0%
BZ#1D5
3
0
3
0
0
0
0
0
0%
BZ#I05 & BZ#[68J
D
0
0
0
0
0
0
0
BZ#107
3
0
1
0
2
2
0
0
0%
BZ#110 Non-Target
3
0
I)
0
3
3
0
()
0%
BZ#114 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#115
3
3
0
()
0
0
0
0
0%
BZ#118
3
1
(}
0
2
2
0
0
0%
RZ#119
3
0
3
0
0
0
0
0
0%
BZ#122
3
0
3
0
0
0
{)
0
0%
Note: Congeners in [ 1 are eo-eluting non-target ojngtnen,.
Page 3 of6
T A M S/Cad mus/G rail ie nt
-------
Table B-7
Water Column Samples — Flow-Averaged Event 7
Hudson River RI/FS PCB Reassessment
Total Unqualified Estimated Unqualified Estimated Estimated , Rejected
Congener Name Number of Nondetecls Nondetccts Dctccts Dctccts Dclects Qualified Results % Rejected
Results with K
BZ#123
3
0
3
0
0
0
0
0
0%
BZ#126
3
3
0
0
0
0
0
0
0%
BZ#I28
3
0
3
0
0
0
0
0
0%
BZ#129
3
0
2
0
1
1
0
0
0%
BZ#135 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#136
3
0
0
0
3
3
0
0
0%
BZ#137
3
0
0
0
3
3
0
0
0%
BZ#138
3
0
1
0
2
2
0
0
0%
BZ#140 Non-Target
3
2
1
0
0
0
0
0
0%
BZ#141
3
0
3
0
0
0
0
0
0%
BZ#143 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#144 Non-Target
3
1
2
0
0
0
0
0
0%
BZ#146 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#149
3
0
3
0
0
0
0
0
0%
BZ#151
3
0
2
0
1
1
0
0
0%
BZ#153
3
0
1
0
2
2
0
0
0%
BZ#156 Non-Target
3
0
3
0
0
0
0
0
0%
BZ#157
3
1
0
0
2
2
0
0
0%
BZ#158
3
0
3
0
0
0
0
0
0%
BZ#J60 Non-Targci
0
0
0
0
0
0
0
0
BZ#167
3
2
0
0
0
()
0
1
33%
BZ# 169 Non-Target
3
1
0
0
2
2
0
0
0%
BZ#170
3
0
3
0
0
0
0
0
0%
BZ#171
3
0
0
0
3
3
0
0
0%
BZ#172 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#174 Non-Target
3
1
2
0
0
0
0
0
0%
Note: Congeners in | | are eo-eluting non-target congeners.
Page 4 of6
TAMS/Catlmus/( Madicnt
-------
Table B-7
Water Column Samples — Flow-Averaged Event 7
Hudson River RI/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondctects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejected
BZ#175 Non-Target
3
3
0
0
0
(S
0
0
0%
BZ#177
3
1
0
0
2
2
0
0
0%
BZ#178 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#180
3
0
3
0
0
0
0
0
0%
BZ#183
3
0
0
0
3
3
0
0
0%
BZ#184 Non-Target
3
3
0
0
0
0
0
0%
BZ#185
3
0
1
0
2
2
0
0
0%
BZ#187
3
0
2
0
1
1
0
0
0%
BZ#189
3
3
0
0
0
0
0
0
0%
BZ#190
3
2
0
0
I
1
0
0
0%
BZ#191
3
3
0
0
0
0
0
0
0%
BZ# 192 Non-Target
3
0
3
0
0
0
0
0
0%
BZS193
3
3
0
0
0
0
0
0
0%
BZ#194
3
D
2
0
1
1
0
0
0%
BZ# i 95
3
2
1
0
0
0
0
0
0%
BZ#196
3
1
1
0
1
1
0
()
0%
BZ#197 Non-Target
3
3
0
0
0
0
0
0
0%
BZ#198
3
3
0
0
0
0
0
0
0%
BZ#199
3
3
0
0
0
0
0
0%
BZ#200
3
3
0
0
0
0
0
0
0%
BZ#201
3
0
0
0
3
3
0
0
0%
BZ#202
3
1
0
0
2
2
0
0
0%
BZ#2()3 Non-Target
3
2
1
0
0
0
0
0
0%
BZ#205
3
3
0
0
0
0
0
0
0%
BZ#206
3
3
0
0
0
0
0
0
0%
BZ#207
3
3
0
0
0
0
0
0
0%
Nolo; Congeners in | | arc co-eluting non-target congeners.
Page 5 ol'6
i AMS/Cadmus/Gradicnt
-------
Table B-7
Water Column Samples — Flow-Avera d Event 7
Hudson River RI/FS PCB Reasse meat
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejected
BZ#208
BZ#209
3
3
1
0
0
2
0
0
0
1
0
1
0
0
2
0
67%
0%
381 118 134 19 104 104 0 6 2%
Nolo: Congeners in | | are co-eluting non-iargef congeners.
Page 6 of6
T A M S/CaUmus/( > i adieni
-------
Table B-8
1 Liter Whole Water Samples
Hudson River RI/FS PCB Reassessment
Total unqUa|i(ie(j Estimated Unqualified Estimated „Va',"iS. Rejected „ .
Congener N.mt Number Non<)etects Qu.l.lied Resu|ts % H,,.c..d
of Results With K
BZ#1
14
7
0
0
6
0
1
7%
BZ#2
14
8
5
0
0
0
1
7%
BZ#3
14
14
0
0
0
0
0
0%
BZ#4
14
I
11
0
0
13
2
14%
BZ#5
14
4
10
0
0
()
0
0%
BZ#6
14
13
0
1
0
0
0
0%
BZ#7
14
11
2
0
1
0
0
0%
BZ#8
14
5
4
0
1
1)
4
29%
BZJ9
14
13
1
0
0
0
0
0%
BZ#10
14
10
2
0
0
3
2
14%
BZ#I2
14
7
7
0
0
0
0
0%
BZ#15
14
10
1
0
2
0
1
7%
BZ#16
14
6
4
0
4
0
0
0%
UZttn Non-Target
14
4
0
0
10
(}
0
0'!;.
BZ# 18
14
7
6
1
0
0
0
()"/o
BZ#I9
14
1
2
0
0
0
11
79%
BZ#20 Non-Target
14
0
H)
0
4
14
0
()"/»
BZ#21 Non-Target
0
0
0
0
0
0
0
—
BZ#22
14
9
0
0
5
0
0
()"«
\iZU23 Non-Target
14
14
0
0
0
0
0
0%
BZ#24 Non-Target
14
3
0
0
11
0
0
0%
BZ#25
14
7
2
0
0
0
5
36%
BZ#26
14
0
13
0
1
6
0
0%
BZ#27
14
7
6
0
1
0
0
0%
BZ#28
14
8
5
1
0
0
0
0%
BZJ29
14
13
0
0
1
0
0
0%
BZ#31
14
6
5
0
1
0
2
14%
Nolo: Congeners in | ] are eo-eluting non-target congeners.
Page I oi' 5
TAMS/Cadmus/Gradicnt
-------
Table B-8
1 Liter Whole Water Samples
Hudson River RI/FS PCB Reassessment
Tota| V » , Qualified % Rejected
6 „ Nondetects Nondetects Detects Detects . , Results
of Results with K
UZU32 Non-Target
14
6
0
0
8
0
0
0%
BZ#33 Non-Targei
14
0
13
0
1
14
0
0%
BZ#34 Non-Target
14
8
0
0
6
0
0
0%
BZ#37
14
3
5
0
6
11
0
0%
BZ#40
14
10
0
1
3
0
0
0%
BZ#41
14
11
0
0
3
0
0
0%
BZ#42 Non-Target
14
8
0
0
6
0
0
0%
BZ#44
14
5
2
0
7
0
0
0%
BZ#45 Non-Target
14
8
0
0
6
0
0
0%
BZ#47
14
7
3
0
4
0
0
0%
BZ#48 Non-Target
14
8
0
0
6
0
0
0%
BZ#49
14
6
2
0
0
0
6
43%
BZ#51 Non-Target
14
0
9
0
5
14
0
0%
BZ#52
14
6
0
5
3
1)
0
0%
BZ#53
14
9
2
0
0
3
3
21%
BZ.#54 Non-Target
0
0
0
0
0
0
0
BZ#56
14
7
3
0
4
0
0
0%
BZ#58 Non-Target
14
13
0
0
1
0
0
()"/„
BZ#60 Non-Target
14
11
0
0
3
0
0
0%
BZ#63 Non-Target
14
0
14
0
0
14
0
0%
BZ.#64 Non-Target
14
11
0
0
3
0
0
0%
BZJ66
14
4
0
0
10
10
0
0%
BZ#67 Non-Target
14
13
0
0
1
0
0
0%
BZ#69 Non-Target
14
14
0
0
0
0
0
0%
BZ#70
14
4
2
0
8
2
0
0%
BZ#74 Non-Target
14
0
7
0
7
14
0
0%
BZ#75
14
11
3
0
0
3
0
0%
Nolo: Congeners in [ | are co-eluting non-target congeners.
Page 2 TAMS/Cadnm.s/(ira»lii.'iil
-------
Table B-8
I Liter Whole Water Samples
Hudson River RI/FS PCB Reassessment
Total ,, , ,, . , . „ . . Values
,, , Unqualified Estimated Unqualified Estimated „ , Rejected
Congener Name Number . ^ 4 w ^ ^ „ . „ Qualified ' , % Rejected
Nondctects Nondetects Detects Detects . , Results 1
of Results with K
BZ#77
14
13
0
0
1
0
()
0%
Rzmi
14
11
2
1
0
0
0
0%
BZ#83
14
13
1
0
0
0
0
0%
BZ#84
14
13
0
0
1
0
()
0%
BZ#85
14
It)
3
1
0
0
(!
0%
BZ#87
14
11
2
0
1
2
0
0%
BZ#88 Non-Target
0
0
0
0
0
0
0
—
BZ#90 Non-Targei
0
0
0
0
0
0
0
—
BZ#91
14
12
0
0
2
0
0
0%
BZ#92
14
13
0
0
1
0
0
0%
BZ#95
14
I
7
0
6
13
0
0%
BZ#96 Non-Targel
14
13
0
0
i
0
0
0%
BZ#97
14
13
0
1
0
0
0
0%
BZ#99
14
13
0
0
1
0
0
0%
BZftlOl & BZ#[90|
14
8
0
0
6
5
0
0%
BZ#105
14
6
7
0
1
0
0
0%
BZ#105 8c BZ#[68]
0
0
0
0
0
0
0
—
BZ#107
14
13
1
0
0
0
0
0%
BZif 110 Non-Targel
14
3
0
0
11
0
0
0%
BZ#114 Non-Target
14
14
0
0
0
0
0
0%
BZ#115
14
14
0
D
0
0
0
0%
BZ#118
14
6
3
0
5
0
0
0%
BZ#119
14
13
0
0
1
0
(1
0%
BZ#122
14
12
2
0
0
2
0
0%
BZ#123
14
13
0
0
1
0
0
0%
BZf/126
14
13
1
0
0
0
I)
()"«,
BZ#I28
14
5
9
0
0
7
0
0%
Nolo: Congeners in ) | are co-eluting non-iargel congeners.
Page* 3 ol' 5
1 AMS/Caiinms/Ciradient
-------
Table B-8
1 Liter Whole Water Samj s
Hudson River RI/FS PCB Reass. snient
Unqualified Estimated Unqualified Estimated „ Rejected
Congener Name Number ^ t , Qualified * , % Rejected
s u Nondetects Nondetects Detects Detects .. „ Results 1
of Results with K
BZ#129
14
13
1
0
0
1
0
0%
BZ#135 Non-Targe!
14
14
0
0
0
0
0
0%
BZ#136
14
13
1
0
0
1
0
0%
BZ#i37
14 .
13
0
0
1
0
0
0%
BZ#138
14
6
7
0
1
8
()
0%
BZ#140 Non-Target
14
14
0
0
0
0
0
0%
BZ#14f
14
13
1
0
0
1
0
0%
BZ#143 Non-Target
14
14
0
0
0
0
0
0%
BZ#I44 Non-Target
14
14
0
0
0
0
0
0%
BZ#146 Non-Target
14
14
0
0
0
0
0
0%
BZ#I49
14
13
0
0
1
. 0
0
0%
BZ#!5I
14
13
0
0
1
0
0
0%
BZ#153
14
12
1
0
1
2
0
0%
BZ#156 Non-Target
14
13
0
0
1
0
0
0%
BZ#157
14
13
0
0
ft
0
1
7%
BZ#158
14
13
1
0
0
0
t)
0%
BZ#160 Non-Target
0
0
0
0
0
0
0
—
BZ#167
14
14
0
0
0
0
0
0%
BZ#169 Non-Target
14
14
0
0
0
0
0
0%
BZ#I70
14
13
1
0
0
0
()
0%
BZ#171
14
13
0
0
I
0
0
0%
BZ#172 Non-Target
14
0
14
0
0
14
0
0%
BZ# 174 Non-Targe!
14
13
0
0
1
0
()
0%
HZ# 17 5 Non-Target
14
14
0
0
0
0
0
0%
BZ#177
14
14
0
0
0
(1
0
0%
BZ#178 Non-Target
14
14
0
0
0
0
0
0%
BZ#180
14
12
2
0
0
0
()
0%
Nuic: Congeners in [ | are eo-ciuting non-target congeners.
Pago -1 ol' 5
T AMS/Cadmus/Gradient
-------
Table B-8
I Liter Whole Water Samples
Hudson River RI/FS PCB Reassessment
Congener Name
Total
Number
of Results
Unqualified Estimated
Nondetects Nondeteets
Unqualified Estimated
Detects Detects
Values
Qualified
with K
Rejected
Results
% Rejected
BZ#183
14
14
0
0
0
()
0
0%
BZ#184
Non-Targei
14
14
0
0
0
0
0
0%
BZ#I85
14
11
1
(»
0
0
2
14%
BZ#187
14
14
0
0
0
0
0
0%
HZ#189
14
14
0
0
0
0
0
0%
BZ#190
14
14
0
0
0
0
0
0"„
BZ#191
14
14
0
()
0
0
0
0%
BZ#192
Non-Targei
14
0
14
0
0
14
0
0%
BZ#193
14
13
1
0
0
0
0
()"/»
BZ#194
14
14
0
()
0
f)
0
0%
BZ#195
14
13
0
0
{)
(1
1
7%
BZ#196
14
13
0
0
0
0
1
7%
BZ#19?
Non-Targei
14
14
0
0
0
0
0
0%
BZ#198
14
0
13
0
0
14
1
7%
BZ#199
14
14
0
0
0
0
0
0%
BZ#2()0
14
14
0
0
0
0
0
0%
BZ#201
14
13
0
0
I
0
0
0%
BZ#202
14
14
0
0
0
0
0
0%
BZ#2()3
Non-Targei
14
14
()
1)
0
0
0
0°/.
BZ#2()5
14
13
1
0
0
()
0
0%
BZ#206
14
14
0
0
0
()
0
0%
BZ#207
14
14
0
0
0
0
0
0%
BZ#208
14
14
0
0
0
0
0
0%
BZ#2!)9
14
14
0
0
0
0
0
0%
1764
1253
258
12
197
205
44
2%
Noic: Congeners in [ | are eo-eluting non-iargci congeners.
1JS'"5 ol 5 TAMS/Cailmus/Gnidic.ni
-------
Table B-9
Equilibration Study — Particulate Samples
Hudson River RI/FS PCB Reassessment
Total Unqualified Estimated Unqualified Estimated . Rejected n. „ .
Congener Name Number of Non<|electJ NondcttcB Dclcc,s DcIccts Ou« .fled % Recced
Results with K
BZ#1
17
8
1
1
7
0
0%
BZ#2
17
3
13
0
0
1
6%
BZ#3
17
12
3
0
0
2
12%
BZ#4
17
0
16
0
0
9
1
6%
BZ#5
17
13
4
0
0
0
0%
BZ#6
17
10
2
3
1
1
6%
BZ#7
17
12
5
0
0
0
0%
Bzm
17
3
4
0
2
8
47%
Bzrn
17
11
6
0
0
0
0%
BZ#10
17
2
14
0
0
5
1
6%
BZ#12
17
11
4
0
2
0
0%
BZ#I5
17
3
1
0
13
0
0%
BZ#16
17
6
2
0
9
0
0%
BZ#I7
8
2
0
0
6
0
0%
BZ# 17 Non-Target
9
2
0
0
7
0
0%
BZ#I8
17
3
6
3
4
1
6%
B7J19
17
7
3
0
3
4
24%
BZ#20 Non-Target
9
0
2
0
7
9
0
0%
BZ#20
8
6
1
0
1
0
0%
BZ#21 Non-Target
0
0
0
BZ#22
17
3
1
3
9
1
6%
BZ#23 Non-Target
17
10
0
0
7
0
0%
BZ#24 Non-Target
9
8
0
0
1
0
0%
BZ#25
17
5
6
2
4
0
0%
BZ#26
17
3
3
2
9
0
0%
BZ#27 & BZ#[24|
8
3
1
0
4
0
0%
Note: Congeners in 1 ] are co cluting non-target congeners.
Page I of6
TAMS/Cadmus/Clradk'tit
-------
Table B-9
Equilibration Study — Particulate Samples
Hudson River RI/FS PCB Reassessment
^ M M TTl r Unqualified Estimated Unqualified Estimated „Va!"~S, Rejected
Congeneric Nunbwof Nondc|cc|s N(IIldclcc„ Dctccts Dc|ccts Q^MIcd ^ % KejccM
BZ#27
9
1
8
0
0
0
0%
BZ#28
17
7
2
7
1
0
0%
BZ#29
17
12
2
0
3
0
0%
BZ#31
17
4
3
5
3
2
12%
BZ#32 Non-Target
17
4
0
0
13
0
0%
BZ#33
8
3
1
0
4
9
0
0%
BZ#33 Non-Target
9
0
7
0
2
0
0%
BZ#34 Non-Target
17
17
0
0
0
0
0%
BZ#37
17
3
1
0
13
7
0
0%
BZ#40
17
3
1
0
13
0
0%
BZ#4I
17
3
2
0
11
1
6%
BZ#42
8
2
0
0
W
0
0%
BZJ42 Non-Targel
9
2
0
0
7
0
0%
BZ#44
17
3
1
11
2
0
0%
BZ#45
8
2
3
0
0
3
38%
BZU45 Non-Target
9
2
0
0
7
D
0%
BZ#47
17
3
3
0
11
0
0%
BZ#48 Non-Target
17
5
0
0
12
2
0
0%
BZ#49
17
3
7
1
5
1
6%
BZJ51 Non-Target
17
4
1
0
12
9
0
0%
BZ#52
17
3
0
2
12
0
0%
BZ#53
17
5
3
1
8
1
0
()%
BZ#54 Non-Target
0
0
0
0
BZ#56
17
2
6
0
9
0
0%
BZ#58 Non-Target
17
9
0
0
8
0
0%
BZS59
8
3
3
0
2
0
0%
Note: Congeners in \ \ are co-eluting non-target congeners.
Page 2 of 6
T A M S / Cad mu s/G rail i ei 11
-------
Table B-9
Equilibration Study — Particulate amples
Hudson River RI/FS PCB Reassi iinent
^ .. . r Unqualified Estimated Unqualified Estimated ^ , Rciectcd
Congener Name Number of „ ^ „ Qualified i % Rejected
_ Nondetects Nondctects Detects Detects . Results J
Results with K
BZ#60 Non-Targei
17
2
0
0
15
0
0%
BZ#63 Non-Target
17
7
9
0
1
9
0
0%
BZ#64 Non-Target
17
10
0
0
7
0
0%
BZ#66
17
3
1
1
12
7
0
0%
BZ#67 Nun-Target
17
12
0
0
5
0
0%
BZH69 Non-Target
17
17
0
0
0
0
0%
BZ#70
17
2
2
4
9
1
0
0%
BZ#72
8
6
1
0
1
0
0%
BZ#74
8
2
0
4
2
0
0%
BZ#74 Non-Target
9
0
2
a
7
9
0
0%
BZ#75
17
14
3
0
0
1
0
0%
BZ#77
17
2
6
0
9
0
0%
BZ#82
17
3
3
0
11
0
0%
BZ#83
17
7
2
0
8
0
0%
BZ#M
1?
4
1
1
11
0
0%
BZ#85
17
3
1
2
11
0
0%
Bzmi
17
2
6
0
9
5
0
0%
BZ-/88 Non-Target
0
0
0
0
0
BZ#90 Non-Target
9
6
0
0
3
0
BZ#91
17
5
1
1
9
1
6%
BZ#92
17
6
7
0
4
0
0%
BZ#95
17
5
3
0
9
7
0
0%
BZ#96 Non-Target
17
17
0
0
0
0
0%
BZ#97
17
3
1
2
11
0
0%
BZ#99
17
3
6
3
5
0
{}%
BZJ101 &BZ#[90|
17
3
1
0
13
1
0
0%
Note: Congeners in ( 1 are co-eluting ncm-iarge! congeners.
I'agc 3 of 6
T AMS/Cadmus/Grnilient
-------
Table B-9
Equilibration Study -- Particulate Samples
Hudson River RI/FS PCB Reassessment
T°tal Unqualified Estimated Unqualified Estimated , Rejected
Congener Name Number of Nradclcc,s Dctrels Dclccls Q»»'fi«l Resul|s % Rejected
Results with K
BZ#105 & BZ#|68]
8
2
5
0
1
0
0%
BZ#105
9
1
3
0
5
0
0%
BZ#107
17
6
9
0
2
0
0%
BZJ110
8
2
1
0
5
0
0%
BZ#110 Non-Target
9
0
0
0
9
0
0%
BZ#l14 Non-Target
17
16
0
0
1
0
0%
BZ#115
17
15
2
0
0
0
0%
BZ#118
17
3
2
4
8
0
0%
BZ#119
17
14
2
0
1
0
0%
BZ#122
17
14
2
0
0
I
1
6%
BZ#123
17
13
4
0
0
0
0%
BZJ126
17
15
2
0
0
0
0%
BZ#128
17
4
10
0
2
9
1
6%
BZ#129
17
8
8
0
1
1
0
0%
BZ//135
8
6
1
0
1
0
0%
BZ#135 Non-Targe!
9
9
0
0
0
0
0%
BZ#136
17
10
5
t)
2
4
0
0%
BZ#137
17
8
1
0
8
0
0%
BZ#138
17
3
4
0
10
7
0
0%
BZ# 140 Non-Target
17
17
0
0
0
0
0%
BZ#141
17
7
2
0
8
5
0
0%
BZ#143
8
7
1
0
0
0
0%
BZ#I43 Non-Target
9
2
0
0
7
0
0%
BZ#144 Non Target
17
17
0
0
0
0
0%
BZ#146 Non-Target
17
14
0
0
3
0
0%
BZJ149
17
5
8
0
4
0
0%
Note: Congeners in [ 1 are co-cluting non-target congeners.
Page 4 of 6
TAMS/Cadmus/Gradient
-------
Table B-9
Equilibration Study — Particulate Samples
Hudson River RI/FS PCB Reassessment
,, .. . t Unqualified Estimated Unqualified Estimated ^ , Rejected
Congener Name Number of . . . .. . . , _ . _ , . Qualified * , % Rejected
. _ , Nondetects Nondetects Detects Detects , Results im-jixm-w
Results with K
BZ0I51
17
10
1
0
5
1
6%
BZ#153
17
3
6
0
8
6
0
0%
BZ#156
8
6
0
0
2
0
0%
BZ#156 Non-Target
9
7
0
0
2
0
0%
BZ#157
17
15
2
0
0
0
0%
BZ#158
17
7
10
0
0
0
0%
BZtt 160 Non-Target
0
0
0
0
0
0
BZ#165
8
2
6
0
0
0
0%
BZ#167
17
13
3
0
0
I
6%
BZ#169 Non-Target
17
9
0
0
8
0
0%
BZ#170
17
9
4
0
4
0
0%
BZ#17i
17
15
2
0
0
0
0%
BZJ172 Non-Target
17
8
9
0
0
9
0
0%
BZ#174
8
4
0
0
4
0
0%
BZ# 174 Non-Target
9
7
0
0
2
0
0%
BZ#175 Non-Target
17
17
0
0
0
0
0%
BZ#176
8
7
1
0
0
0
0%
BZ#)77
17
10
2
0
5
0
0%
BZ#178
8
7
1
0
0
0
0%
BZ#178 Non-Target
9
9
0
0
0
0
0%
BZ#179
8
7
1
0
0
0
0%
BZ#180
17
2
8
0
7
0
0%
BZ#I83
17
13
3
0
1
0
0%
BZ#184 Non-Target
17
17
0
0
0
0
0%
BZ#185
17
15
2
0
0
0
0%
BZ#187
17
6
1
0
8
5
2
12%
Nole: Congeners in ( J arc eo-eluting non-target congeners.
Page 5 of6
TAM S/Cadmus/( J radicnt
-------
Table B-9
Equilibration Study -- Particulate Samples
Hudson River RI/I S PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Values
Qualified
Willi K
Rejected
Results
% Rejected
BZ#189
17
15
2
0
0
0
0%
BZ#190
17
15
2
0
0
0
0%
BZ# 191
17
15
2
0
0
0
¦ 0%
BZ#192 Non-Target
9
0
9
0
0
9
0
0%
BZ#193
17
15
2
0
0
0
0%
BZ#194
17
14
2
0
1
0
0%
BZ#195
17
13
3
0
0
1
6%
BZ#196
17
14
2
0
1
0
0%
BZ# 197 Non-Targel
17
17
0
0
0
0
0%
BZ#198
17
15
2
0
0
0
0%
BZ#199
17
15
2
0
0
0
0%
BZ#200
17
15
2
0
0
0
0%
BZ#201
17
6
6
0
1
4
24%
BZ#202
17
15
2
0
0
0
0%
BZ#203 Non-Target
17
12
0
0
5
0
0%
BZ#205
17
13
4
0
0
0
0%
BZ#206
17
15
2
0
0
0
0%
BZ#207
17
15
2
0
0
0
0%
BZ#208
17
15
2
0
0
0
0%
BZ#2Q9
17
15
2
0
0
0
0%
2175
1107
392
63
574 '
147
39
2%
Note; Congeners in | | are co-eluting non-target congeners.
Page 6 of6
T A MS/Cadmus/Gradient
-------
Table B-10
Equilibration Study — Dissolved S;> pies
Hudson River Rl/FS PCB Reasses eiit
„ M Mir Unqualified Estimated Unqualified Estimated __ Rejected
Congener Name Number of n 1 Qualified „ % Rejected
„ Nondetccts Njndetccts Detects Detects Results J tl
Results with K
BZ#1
17
3
2
3
9
0
0%
BZ#2
17
0
15
0
0
2
12%
BZ#3
17
6
9
0
0
2
12%
BZ#4
17
0
10
0
7
1
0
0%
BZ#5
17
8
8
0
1
0
0%
BZ#6
17
6
5
5
I
0
0%
BZU1
17
2
9
0
6
0
0%
BZ#S
17
4
4
1
4
4
24%
BZ#9
17
3
8
0
6
0
0%
BZJ10
17
0
7
0
10
1
0
0%
BZ#J2
17
5
9
0
2
1
6%
BZ#15
17
2
4
0
11
0
0%
BZ#I6
17
2
3
0
12
0
0%
BZJ i 7
8
2
0
0
6
0
0%
BZ#I7 Non-Target
9
2
0
0
7
0
0%
BZ#18
17
1
3
9
3
1
6%
BZ# 19
17
3
4
2
8
0
0%
BZ#20 Non-Target
9
2
0
7
9
0
0%
BZ#20
8
4
0
0
4
0
0%
BZ#21 Non-Target
0
0
0
0
0
BZ#22
17
2
2
7
6
0
0%
BZ#23 Non-Target
17
8
0
0
9
0
0%
BZ#24 Non-Target
9
2
0
0
7
0
0%
BZ#25
17
2
3
9
3
0
0%
BZ#26
17
2
2
6
7
0
0%
BZ#27 & BZ#[24]
8
2
0
0
6
0
0%
Note: Congeners in | | arc co-cluiing non-target congeners.
Page 1 of6
TA MS/Cadmus/Gradient
-------
Table IMO
Equilibration Study -- Dissolved Samples
Hudson River RI/FS PCU Reassessment
Tnfa) Values
, Unqualified Estimated Unqualified Estimated Rejected
Congener Name Number of Nom|t(ecll N„ndclecls Dclcc|s nelcc,s Q»«-Bed % Rejected
Results with K
BZ#27
9
0
3
0
6
0
0%
B7J28
17
1
3
9
4
0
0%
BZ#29
17
4
3
0
10
0
0%
BZ#31
17
2
2
8
4
1
6%
BZ#32 Non-Target
17
1
0
0
16
0
()%
BZI33
8
4
0
0
4
0
0%
BZ#33 Non-Target
9
0
2
0
7
9
0
0%
BZ#34 Non-Target
17
11
0
0
6
0
0%
BZ#37
17
8
2
0
7
9
0
0%
BZ#40
17
2
3
3
9
0
0%
BZ#41
17
1
3
0
13
0
()%
BZ#42
8
2
0
0
6
0
0%
BZ#42 Non-Target
9
1
0
0
8
0
0%
BZ#44
17
0
4
8
5
0
0%
BZ#45
8
2
3
3
0
0
0%
BZ#45 Non-Targel
9
2
0
0
7
0
0%
BZ#47
17
2
3
0
12
0
0%
BZ#48 Non-Target
17
5
0
0
12
7
0
0%
BZ#49
17
3
2
5
7
0
0%
BZ#51 Non-Target
17
2
2
0
13
9
0
0%
BZ#52
17
0
5
2
ID
0
0%
BZ#53
17
4
4
0
9
4
0
0%
BZ#54 Non-Target
0
()
0
0
0
0
BZti5C>
17
2
9
0
6
0
0%
BZ#5Z Non-Target
17
9
0
0
8
0
0%
BZ#59
8
2
0
3
3
0
0%
Nolo: Congeners in | ) arc eo-eluting non-targel congeners.
Page 2 of 6
TAMS/Cadmus/GnuJietil
-------
Table B-10
Equilibration Study -- Dissolved Samples
Hudson River RJ/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetccts
Estimated
Nondetects
Unqualified
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejc<
B7.#60 Non-Target
17
2
0
0
15
0
0%
BZ#63 Non-Target
17
2
5
0
10
9
0
0%
BZM64 Non-Target
17
4
0
0
13
0
0%
BZ#66
17
2
3
1
11
9
0
0%
BZ#67 Non-Targci
17
8
0
0
9
0
0%
BZ#69 Non-Target
17
17
0
0
0
0
0%
BZ#70
17
0
4
5
8
0
0%
BZ#72
8
5
0
1
2
0
0%
BZ#74
8
1
2
5
0
0
0%
BZ#74 Non-Targci
9
0
2
0
7
9
0
0%
BZ#75
17
8
9
0
0
7
0
0%
BZ#77
17
3
14
0
0
0
0%
BZ#82
17
2
5
2
7
1
6%
BZ#83
17
4
5
0
8
0
0%
B2#84
17
5
9
3
0
2
0
0%
BZ#85
17
2
8
3
4
0
()%
BZ#87
17
0
14
0
3
3
0
0%
BZ#88 Non-Target
0
0
0
BZ#90 Non-Target
0
0
0
BZ#9I
17
2
9
3
2
1
6%
BZ#92
17
3
10
0
4
0
0%
BZ#95
17
6
11
0
0
9
0
0%
BZ#96 Non-Target
17
13
0
0
4 .
0
0%
BZ#97
17
3
4
7
3
0
0%
BZ#99
17
5
9
3
0
0
0%
BZ#I0I & BZ#(90]
17
0
15
0
2
0
0%
Nolo: Congeners in I 1 are co-eluling non-target congeners.
J*agc 3 of 6
TAMS/Cadmus/Gradient
-------
Table B-10
Equilibration Study -- Dissolved Samples
Hudson River RI/FS PCB Reassessment
„ .. m . » Unqualified Estimated Unqualified Estimated _ , Re ected
Congener Name Number of 11 Qualified J % Rejected
„ Nondetects Nondetects Detects Detects Results -ILLILH
Results with K
BZ#105 & BZ#|681
8
2
6
0
0
0
0%
BZ#105
9
0
9
0
0
0
0%
BZ#107
17
4
7
0
6
0
0%
BZ#110
8
0
0
0
8
0
0%
BZ#110 Non-Target
9
0
0
0
9
0
0%
BZ#114 Non-Target
17
16
0
0
1
0
0%
BZ#115
17
11
6
0
0
0
0%
BZ#118
17
0
7
6
4
0
0%
BZ#119
17
8
9
0
0
0
0%
BZJ122
17
10
7
0
0
4
0
0%
BZ#123
17
8
7
0
2
0
0%
BZ#126
17
11
6
0
0
0
0%
BZJ128
17
4
10
0
3
7
G
0%
BZ#129
17
7
8
0
2
0
0%
BZ#135
8
6
0
0
2
0
0%
BZ#135 Non-Target
9
9
0
0
0
0
0 %
BZ#136
17
5
0
0
5
7
1
6%
BZ#137
17
10
7
0
0
0
0%
BZ#138
17
0
9
0
8
5
0
0 %
BZ#140 Non-Target
17
16
0
0
1
0
0%
BZJ141
17
4
11
0
2
6
0
0%
BZ#I43
8
8
0
0
0
0
0%
BZJ143 Non-Target
9
8
0
0
1
0
0%
BZ#144 Non-Target
17
15
0
0
2
0
0%
BZ#146 Non-Target
17
14
0
0
3
0
0%
B7J149
17
3
11
0
3
0
0%
Note: Congeners in [ 1 are eo-cluting non-target congeners.
1'age 4 of 6
T A MS/Cad mus/Ciradicnt
-------
Table B-10
Equilibration Study — Dissolved S
Hudson River RI/FS PCB Reassc
nples
ment
^°ta' , Unqualified Estimated Unqualified Estimated ^a!!!-S. Rejected
Congener Name Number of Nflndcfccts lVondctccts De(ccts Dctccls Qualilied ^ «/„ Rejected
Results with K
BZ# 151
17
6
5
0
6
0
0%
BZ#153
17
0
16
0
1
8
0
0%
BZ#156
8
8
0
0
0
0
0%
BZ#156 Non-Target
9
9
0
0
0
0
0%
BZ#157
17
11
6
0
0
0
0%
BZ#158
17
8
9
0
0
0
0%
BZ#160 Non-Target
0
0
0
BZ#165
8
7
1
0
0
0
0%
BZ#167
17
10
7
0
0
0
0%
BZ#169 Non-Target
17
10
0
0
7
0
0%
BZ#170
17
10
5
0
1
1
6%
BZ#171
17
11
6
0
0
0
0%
BZ#172 Non-Target
17
8
5
0
4
9
0
0%
BZ#174
8
6
2
0
0
0
0%
BZ#174 Non-Target
9
9
0
0
0
0
0%
BZ#175 Non-Target
17
17
0
0
0
0
0%
BZ#176
8
8
0
0
0
0
0%
BZ#177
17
11
6
0
0
0
0%
BZ#178
8
8
0
0
0
0
0%
BZ#178 N on-Target
9
9
0
0
0
0
0%
BZ#179
8
8
0
0
0
0
0%
BZ#180
17
2
15
0
0
4
0
0%
BZ#183
17
11
6
0
0
0
0%
BZ# 184 Non-Target
17
17
0
0
0
0
0%
BZ#185
17
11
6
0
0
0
0°/,
BZ#187
17
6
10
0
1
5
0
0%
Note: Congeners in | ] are eo-eluting non-target congeners.
l'.iyc 5 uf'6
TAMS/Cadnius/Gradient
-------
Table B-10
Equilibration Study -- Dissolved Samples
Hudson River RI/FS PCB Reassessment
Congener Name
Total
Number of
Results
Unqualified
Nondetects
Estimated
N on detects
Unqualified
Detects
Estimated
Detects
Values
Qualified
with K
Rejected
Results
% Rejected
BZJ189
17
11
6
0
0
0
0%
BZ#190
17
11
6
0
0
0
0%
BZ# 191
17
11
6
0
0
0
0%
BZ#192 Non-Target
9
0
9
0
0
9
0
0%
BZ#193
17
10
7
0
0
4
0
0%
BZ»194
17
11
6
0
0
0
0%
BZJI95
17
11
5
0
0
1
6%
BZff 196
17
11
6
0
0
0
0%
BZft 197 Non-Target
17
17
0
0
0
0
0%
BZ#198
17
10
7
0
0
4
0
0%
BZ#199
17
11
6
0
0
0
()%
BZ#200
17
11
6
{)
0
0
0%
BZ#201
17
5
12
0
0
0
0%
BZ#2G2
17
11
6
0
0
0
0%
BZ//203 Non-Target
17
16
0
0
1
(}
0%
BZ#2()5
17
10
7
0
0
0
0%
BZ#206
17
11
6
0
0
0
0%
BZ#207
17
11
6
0
0
0
0%
BZ#208
17
11
6
0
0
0
0%
BZ#209
17
11
6
0
0
0
0%
2166 849 650 122 529 169 16
Note: Congeners in [ ] are co-eluting non-target congeners.
Page 6 of6
TA M S/Oa«J»ius/( i radicnt
-------
Figure d-1
Subsampling and Analysis Scheme for Water-Column Monitoring
j| Suspended Solids
Chlorophyll a*
(field filtered)
jived Organic Carbon
(field filtered)
Total Suspended Solids
Weight Loss on Ignition
Dissolved Organic Carbon
(field filtered)
Conductivity
1 liter
Aliquot
4 liter
Aliquot
4 x 4.25 liter
Aliquot**
or
FCB Congeners
(whole water)
for Transect 1 Only
Temperature
Dissolved O
Conductivity
SAS Lab
PCB Congeners
(particulates)
Subsampled In
the Field
Aquatec
RPI Lab
Filtered In the
Field
In-Situ Field
Measurement
Filtered at
RPI Lab
Aquatec
Water-Column Monitoring
PCB Congeners
(filtered water)
Transect sampling only
'For flow-averaged samples, approximately 1 liter was collected daily and then composited to 16 liter
TAMS/Cadinus/Gradicni
-------
Appendix C
Data Usability Report for Non-PCB Chemical and Physical Data
C.l Introduction
The usability discussion of the non-PCB chemical and physical data for the Phase 2A
sampling and analysis programs is presented in this appendix and sorted by program and matrix type.
The data usability reports assessing the PCB congeners for the high resolution sediment coring study
and the water-column monitoring programs are provided in Appendices A and B, respectively. The
high resolution sediment coring study and the confirmatory sediment sampling study data sets are
evaluated together in Section C.2, and the review of the water-column monitoring program (water-
column transects and flow-averaged sampling) results are presented in Section C.3. All chemical
data associated with the collected field samples for these Phase 2A sampling and analysis programs
have been validated (100% validation frequency) by CDM Federal Programs Corp. (CDM), TAMS,
and/or Gradient. These data include the parameters listed in Table C-l.
CDM, TAMS, and Gradient performed data validation for the non-PCB parameters based
upon the specific method criteria listed in the Appendices of the "Phase 2A Sampling and Analysis
Plan/Quality Assurance Project Plan Hudson River PCB Reassessment RI/FS" (TAMS/Gradient,
1992, referred to in this report as the Phase 2A SAP/QAPP), and the USEPA Region II validation
guidelines (USEPA, 1992), where applicable. TAMS/Gradient determined the usability of the data
based upon an evaluation of the data validation reports in conjunction with historical or expected
results, program data quality objectives (DQOs) as defined in the Phase 2A SAP/QAPP for the high
resolution sediment coring study, the confirmatory sediment sampling study, and the water-column
monitoring program. Additionally, TAMS/Gradient based the evaluation on usability on the
intended use(s) of the data, consistency with other data sets (both internal, i.e., from the Hudson
River PCB Reassessment RJ/FS and external, i.e., historical data or data gathered from the
literature), and professional judgment.
C-l
TAMS/Cadmus/Gradient
-------
During the data usability assessment, final qualification of the data presented in the Hudson
River project database were determined. In most cases, TAMS/Gradient maintained the
qualifications added during validation and interpreted these qualifications in terms of the usability
of the results for project objectives. In cases where the qualification of the data was changed from
the validation actions, details of the technical justification for these changes, and the resultant
usability of the data, are presented in this appendix for all non-PCB results generated in support of
the high resolution, confirmatory sediment, water-column monitoring, and flow-averaged sampling
programs.
An essential aspect of understanding the uncertainties of the Phase 2A chemical and physical
data is understanding the significance of the qualifiers associated with the results. Initially, the
analytical laboratories applied qualifiers to the results, then the data validators modified the
qualifiers, as necessary, using established validation protocols from the USEPA Region II standard
ig procedure (SOP) for data validation (USEPA, ! 992), where applicable, the specific DQOs
and quality control (QC) criteria established for the non-PCB tests in the Hudson River SAPs/QAPP
(TAMS/Gradient, 1992), and professional judgment. All the analytical data (100%) collected in the
Phase 2A programs were validated using validation protocols established by TAMS/Gradient and
performed by CDM and TAMS/Gradient. The validation qualifiers were further modified, as
necessary, during the usability assessment to direct the data users concerning the use of each result.
Specifically, data were evaluated to determine compliance with the SAS request or the Phase 2A
SAP/QAPP, adherence to the technical specifications of the analytical method prescribed, and
achievement of precision and accuracy objectives of the analysis as measured by specific QC
samples including laboratory control samples, matrix spike and duplicate samples, method and field
blanks, field duplicate (split and co-located) samples, and calibration QC samples. The definition
of the final qualification flags that appear in the database for non-PCB results are based upon
USEPA data validation guidance (USEPA, 1992) and are listed in Table C-2. A complete list of
result qualifiers, for both the PCB and non-PCB data, can be found in the "Qualify Table" of the
project database.
The quality assurance/quality control (QA/QC) program included establishment of project
DQOs, laboratory procurement and auditing and oversight, field sample auditing and oversight,
C-2
T AMS/Cadmus/Gradient
-------
method development and validation, and data validation. These QA/QC activities are described in
the Phase 2A SAP/QAPP (TAMS/Gradient, 1992) and briefly summarized in the data usability
reports for the PCB congeners, which are provided in Appendices A and B. The pro-active approach
to QA/QC, including on-site (field and laboratory) audits and implementation of corrective actions,
as necessary, was successful in achieving the completeness goal of 95% for the collection of usable
non-PCB data in support of these Phase 2A programs. In fact, for the results reported by
TAMS/Gradient from laboratories procured specifically for the Phase 2A programs by
TAMS/Gradient, less than 1% of the data were rejected, i.e., considered unusable for project
decisions. TAMS/Gradient considered several data sets generated by one of the SAS contract
laboratories (Chemtech) as unusable due to method bias, high detection limits, and/or contamination.
These unusable data include the SAS data for TON in the high resolution sediment coring study and
DOC, TSS, and chlorophyll-a in the water-column monitoring/flow-averaged sampling programs.
Nevertheless, data users have valid results for these parameters from the TAMS/Gradient contract
laboratories; therefore, no significant data gaps were created by the loss of these SAS data.
C.2 High Resolution Sediment Coring Study and Confirmatory
Sediment Sample Data
The high resolution sediment collection program, sampling procedures, analytical protocols
and qualitycontrol/quality assurance requirements are presented in the Phase 2A SAP/QAPP and
summarized in Appendix A of this report.
The non-PCB chemical and physical data for the confirmatory sediment sampling study
include grain size (particle size) distribution, percent solids, total carbon (TC), total nitrogen (TN),
total inorganic carbon (TIC), and reduction/oxidation potential (redox). In addition to these
parameters, the high resolution sediment coring study provided for the collection and analysis of
sediment samples for specific radionuclides (7Be, 60Co, l37Cs), total organic nitrogen (TON), and
weight-loss-on-ignition (WLOI).
C-3
TAMS/Cadmus/Gradient
-------
C.2.1 Grain Size Distribution Data
Grain size distribution was determined for all confirmatory and high resolution sediment core
sections to classify the type of sediment collected. These results are used in the interpretation of
sediment PCB chronologies and degradation, particularly where important geochemical features
correspond to changes in sediment texture. Due to the limited sample sizes for some of the high
resolution sediment coring samples collected and the need to classify the entire grain size
distribution on the same basis, a laser particle technique was used. Additionally, a subset of the
sediment samples from both the confirmatory sediment sampling study and high resolution sediment
coring study were measured using standard sieve/hydrometer methodologies for grain size
distribution to provide a basis for comparison between the laser based particle analysis and the
standard techniques.
Confirmatory sediment core and grab samples were collected and analyzed for grain size
distribution by ATEC Associates using a sieve and hydrometer method (ASTM Methods D-421-85
and D-422-63, reapproved 1990) and by GeoSea Consulting, Ltd. using a combined sieving method
(ASTM D-421-85 equivalent, to remove the particles greater than about 2 mm) and laser
methodology (for the particle size distribution under 2 millimeters [mm]). The combined laser
method was also used for the grain size analysis of the high resolution sediment coring samples. The
grain size distribution results were validated for data package completeness, calibration verification,
laboratory and field duplicate (co-located and split) results, and sample result verification. TAMS
developed validation criteria for grain size distribution based specific method requirements, the
project DQOs in the Phase 2A SAP/QAPP, and professional judgment.
Data were validated (by TAMS) and evaluated for usability by the TAMS/Gradient QA team.
QC samples results (field co-located and laboratory split/duplicate samples) to evaluate
representativeness and precision were obtained at a frequency of greater than or equal to the project
DQO of 5%. The interpretation of the QC results and the accuracy and representativeness of the
grain size data are evaluated in this section.
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Gravel particles are typically not represented accurately in the collection of a small sample.
This situation may result in a sample that is not representative of its general location and may cause
a skewing of the weight distribution. Therefore, some of the grain size distribution results for
confirmatory sediment samples and small volume high resolution sediment coring samples were
qualified, as described below.
C.2.1.1 Sieve/Hydrometer Grain Size Distribution Data
All of the confirmatory sample sieve/hydrometer data generated by ATEC is considered
estimated (qualified J) due to the possible skewing of the distributions based upon the small sample
sizes obtained for analysis. Note that for the initial distribution of the project database that five
results were not qualified "J" in the project database, due to transcription errors, and should be
considered estimated (qualified "J"). Limitations of the coring system used to obtain the samples,
along with the need to obtain adequate sample volume for other analyses, limited the mass available
for grain size analysis to about 250 grams (gm). The sieve/hydrometer method recommends
minimum sample weights for the particle size analysis which are dependent upon the largest
individual particle in the sample (e.g., if the largest particle is 3/4" [19 mm; this was the median
value for the 56 samples], a sample weight of 1000 gm is specified for determination of the greater
than 2 mm [No. 10 sieve] fraction; 65 gm to 115 gm are required for analysis of the portion passing
the No. 10 sieve). The laboratory was consistently able to generate adequate sample mass for the
minus No. 10 sieve fraction (except in isolated instances where splitting a sample for QC analysis
reduced the available sample quantity for each of the QC analyses), but not for the greater than 2 mm
fraction. Therefore, a majority of the sieve/hydrometer data are estimated (qualified "J") due to the
uncertainty in the representativeness of the gravel fraction which will also affect the percentages of
the other fractions.
Overall precision of the sieve/hydrometer data were acceptable based upon laboratory
split/duplicate and field co-located pair results. The ATEC sieve/hydrometer data are usable for
general geotechnical classifications and ratios of fractions. Data users are cautioned that the data
are questionable for other purposes due to insufficient quantities of the coarse fraction resulting in
a potential bias in the gravel results, and, therefore, in the smaller size fraction results as well. The
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direction of this potential bias cannot be determined. Data users should note that, due to a minor
transcription error, five results were not qualified as estimated (J) in the project database. As
TAMS/Gradient considers all these data usable as estimated values, this omission does not affect the
use of the data for project decisions.
C.2.1.2 Laser Grain Size Distribution Data
Due to the nature of the high resolution sediment coring study, only small volume samples
(about 5 cc, or 10 gm) were available for grain size analysis from the same core interval analyzed
for PCBs (since multiple analytical parameters were being aliquoted from a slice only 2 to 4
centimeters [cm] thick). The laser method utilized was selected specifically since it can be
performed on small samples (a few grams); it does not require the large sample weights specified
for the sieve/hydrometer method. In addition, the high resolution sediment coring locations were
specifically selected based on anticipated deposition of fine-grained material; locations expected to
contain significant sand or gravel were excluded from the high resolution sediment coring study.
In addition to the small volume samples, a single large volume (200 to 500 cc, or about 500 to 1000
gm) sample was taken from a co-located core at each location (except Core 25). These large volume
samples were taken from a larger interval (the top 8 cm) than the small volume samples, and no other
analytical samples were taken from the same core and interval as the large volume grain size sample.
The large volume samples provide a representative sample for complete grain size distribution
analysis by the combined sieve/laser method. Small volume grain size sample data should only be
used to represent differences among samples in the fine-grained fractions, i.e., silt and clay. The
accompanying large volume sample can provide a means to assess the presence of coarser fractions
in the samples and therefore minimize the uncertainty in the overall distribution. The absence of
gravel and coarse sand in the high resolution sediment samples supports the assumption that these
sample locations are areas of fine-grained material and the use of the small sample volume to
characterize the particle size distribution of these samples does not introduce any measurable bias.
The qualitative descriptions (gravel, sand, etc.) reported by GeoSea were based on the British
Wentworth system, which is not comparable with the ASTM classification used in the United States
and used for all other grain size data in this program. Therefore, TAMS converted the qualitative
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classifications of high resolution sediment coring and confirmatory sediment sampling grain size
data on to the ASTM classification in order to make the GeoSea laser data comparable to other
qualitative descriptions used in the Hudson River program. Laser grain size data reported by GeoSea
in "phi" units were converted to millimeters (mm) using the equation -log10(diameter in mm)/log|02.
The "mm" units were then assigned to the appropriate ASTM bins (sand, silt. clay). The updated
classifications are included in the TAMS/Gradient database (Revision 3.1).
Additionally, the sieves used by GeoSea (their largest was 4.0 mm, corresponding to the No.
5 sieve) do not exactly correspond to the sieves used for ASTM classification, so there may be an
overstatement of the gravel content inferred from GeoSea data, and a corresponding understatement
of the coarse sand fraction, due to the necessity of including data from the 4.0 to 4.75 mm interval
as gravel in the GeoSea data. This bias is not expected to be large; however, it will be further
evaluated quantitatively during review of the low resolution grain size data analysis, in which the
laboratory was explicitly requested to use both the 4.0 and 4.75 mm sieves.
The precision criterion originally specified in Volume 1 of the Phase 2A SAP/QAPP
(TAMS/Gradient, 1992) for grain size distribution was based on the relative percent difference
(RPD) of each individual particle size fraction. This criterion proved to be unworkable for the laser
data, since particle size distributions were reported for 16 or more individual fractions (also referred
to as "bins" for the laser data), some of which represented only a very small percentage of the total
mass of the sample. Therefore, after a review of the initial grain size data was performed by TAMS,
the criteria was modified to "percent similarity", rather than RPD. Percent similarity is a statistical
test that compares the similarity of the two complete distributions and was developed specifically
for the evaluation of laser particle size analyses (Shillabeer et al, 1992). This criterion was used for
the precision evaluation of all laser particle data generated for the Hudson River project and has been
specified as the applicable criterion in the Phase 2A SAP/QAPPs developed for subsequent parts of
the program.
Overall precision of the laser grain size data met acceptance criteria for a majority of the data
(based upon the percent similarity of the distribution curves for laboratory duplicate pair results and
field duplicate pair results). The mean correlation coefficient (r2) of all the sample and duplicate pair
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results is 0.92, indicating acceptable agreement based upon linear regression statistics. The
exceptions include one laboratory duplicate pair and five field duplicate pairs. These few data that
did not meet the percent similarity precision criterion of greater than 80% represents 1% of the total
number of sediment samples collected for laser grain size analysis. The variation in these duplicate
results may be caused by the presence of significant amounts of organic material (e.g.. wood chips)
or gravel relative to the small sample size. The results may not be representative of the sample
because the quantity of organic matter or gravel relative to the small sample size causes a skewing
of the weight distribution. Therefore, the gravel fraction and the finer fractions may be improperly
represented. Note, however, that less than 20% of the laser grain size samples contained gravel;
therefore, the laser data were not significantly impacted. This was expected as a majority of the laser
data were of the high resolution sediment core samples for which specific locations were chosen to
represent the fine-grained material, i.e., gravel was not expected in the samples.
Wood fragments and very low sample volumes, both of which may result in skewing of the
weight distributions, accounted for the remainder of the laser data that were considered estimated.
Based upon results presented in the main table of the project database, 110 confirmatory sample
results (37% of reported results) and two high resolution sediment coring sample results (0.4% of
reported results) for the laser grain size analyses were estimated (qualified J). All laser data are
considered usable for project decisions for a completeness level of 100% for this parameter.
C.2.1.3 Summary Usability of Sieve/Hydrometer and Laser Grain Size Distribution
Results
For the confirmatory sediment sampling study, the sample size limitations of the high
resolution sediment coring study did not exist and confirmatory sediment samples were taken in
areas where coarse grained material might be anticipated. Therefore, all confirmatory sediment
samples analyzed by GeoSea and ATEC were large volume samples. Comparison of the 52 pairs
(analyzed by both sieve and laser methods) indicates acceptable agreement on the gravel fraction
(both methods averaged about 17% gravel); however, the average sand result was about 10% higher
in the sieve data (the samples analyzed by the sieve method averaged about 78% sand, while the
same samples analyzed by the laser method averaged about 68% sand). Conversely, the silt fraction
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was much lower in the sieve results (averaging about 4%) compared to the laser results (which
averaged about 14% silt). Both data sets confirmed that there was little clay in the confirmatory
sediment (grab and core) samples (0.6% to 0.9%).
The lack of comparability between the laser and sieve/hydrometer results was not
unexpected. Due to the fact that the different methods measure different sedimentology properties
(sieve/hydrometer uses weight and the laser method uses volume), these data should not be
considered equivalent and the results of the two methods cannot be used to assess the accuracy of
the results. These data sets are not comparable; the data user is cautioned that only intra-method
comparisons are valid.
In summary, the grain size data for the confirmatory sediment samples are usable for
qualitative analysis, not quantitative analysis, due to the uncertainty in the gravel fraction that may
cause a bias in the other fractions as well. For the high resolution sediment coring samples, the grain
size data are usable for both qualitative and quantitative analyses. The laser analysis of the fine-
grained material is probably a more accurate representation of the particle size distribution of the
fraction under 75 micron (fim) than the hydrometer analysis. Since gravel is not usually present, the
potential bias due to small sample size is not a concern in the high resolution sediment grain size
distribution data set.
C.2.2 Total Organic Nitrogen (TON) Data
Total Organic Nitrogen (TON) is functionally defined as organically bound nitrogen in the
trinegative oxidation state. The project objective for this measurement was to determine the
importance of inorganic forms of nitrogen in the sediment and to help validate the use of the simple
total carbon/total nitrogen (TC/TN) ratio as a replacement for the organic carbon/organic nitrogen
ratio for the assessment of sediment. Thus, the main data use for TON results was to compare them
to the TN results to evaluate the potential contribution of organic nitrogen to the total nitrogen data
for the Hudson river sediments. Though the TON data are valid, with some qualifications as
described below, they did not meet project objectives and are therefore unusable for comparison to
the TN data. Details of the measurements and QA/QC results, including a comparison of TON and
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TN data, are presented in this section.
C.2.2.1 TON QA/QC Results
The TON results were validated for data completeness, holding times, calibration
verification, laboratory and field blank and duplicate results, laboratory control sample results,
detection limit results, and sample result verification based on the method requirements, USEPA
Region II data validation guidelines, wherever applicable, the DQOs specified in the Phase 2A
SAP/QAPP, and professional judgment.
A total of 207 sediment samples, of which 18 were field duplicates, plus 13 field blanks were
collected and analyzed during the high resolution sediment coring study. Analysis was conducted
by Chemtech through the USEPA SAS program. All samples were prepared for TON analysis using
^„.idard Methods for the Examination of Water and Wastewater" (Standard Methods) (18th ed.)
semi-micro Kjeldahl Method 4500-Norg and analyzed by USEPA "Methods for the Chemical
Analysis of Water and Wastes" (USEPA, 1983) Method 351.3. The reported data measure Total
Kjeldahl Nitrogen on a sample from which the ammonia has been removed prior to analysis.
Therefore, the resultant value is considered, functionally, TON. Data are reported on a dry weight
basis using units of mg/kg. The reportable quantitation limit for 'these sediments is 40 mg/kg. No
TON data were rejected during data validation.
Field and laboratory precision of TON measurements were acceptable. Field co-located
samples were collected at a frequency greater than the project DQO of 5% and laboratory duplicates
at a minimum frequency of 5% . Although two of the 18 field duplicate pairs did not meet precision
criteria defined in the Phase 2A SAP/QAPP and the USEPA Region II guidance (< 100% RPD for
soil/sediment) for data validation (USEPA, 1992), the majority (16 of 18 pairs) showed acceptable
precision.
Though the duplicate precision results indicate that the sample aliquots collected were
reasonably representative of the sediments from specific locations of collection, the
representativeness of some samples collected for TON may have been compromised due to low
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percent solids content. Half of the TON results were considered estimated, i.e., qualified "J" or "UJ".
due to low solids content of the samples ranging from 20% to 49.5%. It is difficult to obtain a
representative aliquot for analysis of a sample with low solids content. This may effect the
representativeness and precision of the TON results. However, based on a review of the precision
for the percent solids measurement (the average RPD for % solids duplicate pairs was 9.0%) and that
the majority of the field co-located pairs met project-specific precision criteria, shows that the
potential effect of the low percent solids is not a significant quality issue.
Accuracy, as measured by holding times, calibration QC (initial and continuing calibration
checks and blanks), method blanks, and matrix QC (matrix spike samples) met acceptance criteria
as set forth in the SAS request. Sensitivity of several results were compromised due to observed
field blank contamination. Due to a communication problem among the involved parties (SMO,
RSCC, TAMS, and Chemtech), the laboratory only analyzed two of the 13 field blanks. Both of the
field blanks (but none of the laboratory blanks) exhibited low level contamination (blank
concentrations of 0.6 and 1.0 milligrams/liter (mg/L), which correspond to sediment concentrations
of 239 and 416 milligrams/kilogram [mg/kg], respectively). The source of the contamination could
not be determined during the data review/data validation process, although it may be attributable to
the water used for the field blanks (which was not the same as the water used by the laboratory).
Due to the observed field blank contamination, some results were negated during validation.
Initially, detections were reported for all sediment samples. As a consequence of data validation,
43 results (21%) were changed to not detected, i.e., qualified "U", with an elevated quantitation limit
due to the field blank contamination. These samples are associated with the only two field blanks
analyzed, which had been found to be contaminated. Since the remaining samples have no
associated field blank data, they are considered estimated, i.e., qualified "J", due to the potential for
field contamination.
C.2.2.2 Comparability of TON to TN
Agreement between the TON data as reported by Chemtech and the TN data reported by
LDEO (discussed below in Section C.2.3) is not acceptable. Most TON results reported by
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Chemtech were typically in the 250 to 700 parts per million (ppm) range, although higher values
(1000 to 3000 ppm) were reported from the first two cores (HR-001 and HR-002). With the
exception of most of the Core 1 samples, the TON data are consistently lower than the TN data,
usually by a factor of three to ten. despite the fact that a potential high bias is suspected in the TON
data. These data (TON and TN) have been plotted together, and a regression analysis was
performed. The slope of the fit, which ideally should be 1.0 (based on the assumption that most of
the nitrogen in the sediments is organically bound) was less than 0.1, and the correlation coefficient
(r) was also poor (r2 about 2 x 10° for all data, and r about .05 for TN less than 0.1%). The drop-
off in reported TON values in Cores 3 through 28 (compared to the TON values reported for Core
1, and to some extent, Core 2) was also not consistent with the TN data.
The difference between the TON and the TN was significant and though the TN correlated
well with the TC, the TON did not. The methods for TON do have interference problems from high
organic contents, high inorganic salts, and the type of catalyst used in the preparation. All these
interferences can cause a potential low bias in the TON results. Though TAMS/Gradient considers
all the TON results as valid based on method compliance, some with qualification as stated above,
these results are not comparable to the total nitrogen (TN) results determined by LDEO. The TON
results are not usable for comparison to other data sets (including the TN data generated for this
project by LDEO) or for evaluating the contribution of inorganic nitrogen to the TN value in the
sediments.
C.2.3 Total Carbon/Total Nitrogen (TC/TN) Data
The data uses for the TC/TN results include: using the TC as a measure for either potential
PCB contamination or potential adsorption of PCBs to establish a relationship between total organic
carbon (TOC) and PCB contamination; and to use the TC/TN ratio to indicate the presence of wood
material in a sediment sample which, in turn, could be used as an indication of relative measure of
potential PCB contamination in the sediments based upon the historical association of wood
cellulose in the Upper Hudson with high levels of PCB contamination. TAMS/Gradient considers
94% of the sample data planned for TC/TN in Phase 2A to be usable to meet these project objectives.
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A total of 250 confirmatory sediment sample results and 457 high resolution sediment core
sample results were provided by Lamont-Doherty Earth (formerly Geological) Observatory (LDEO)
for TC/TN analyses. The analytical method used was adapted from a non-routine method developed
for low-volume samples (small sample mass) and is described in Appendix G of the Phase 2A
SAP/QAPP (TAMS/Gradient, 1992). The samples were dried and pulverized prior to analysis. An
additional 40 samples were not analyzed due to the fact that the samples were ungrindable after
drying. Six results for TN and one result for TC were rejected during validation as unusable.
Therefore, confirmatory sediment analytical completeness is 84%. This completeness level does not
meet project DQO of 95%. Nonetheless, 100% completeness was achieved for TC/TN analyses in
support of the high resolution sediment coring study. Overall completeness of 94% was achieved
for TC/TN in Phase 2A sampling and analyses.
The TC and TN results were validated for data completeness, holding times, calibration
verification, laboratory and field duplicate results, laboratory control sample results, detection limit
results, and sample result verification. TAMS/Gradient developed validation criteria for TC and TN
analyses based on USEPA Region II data validation guidelines, wherever applicable, the DQOs
specified in the Phase 2A SAP/QAPP, and professional judgment.
Through review of the data and direct quality assurance oversight during sample analysis,
TAMS/Gradient determined that overall precision and accuracy DQOs were met for the TC/TN.
This was determined from QA/QC results including calibration criteria, initial and continuing
calibration verification results, laboratory blank results, laboratory control samples, and duplicate
precision specified in the Phase 2A SAP/QAPP. Although all TC/TN data are considered usable at
this time, several method problems that required subsequent corrective actions or qualification of
the data were discovered. Discrepancies or deviations from the quantitation and reporting criteria
were found; these were corrected by the data validators, so that the final validated data reflect
reporting and quantitation criteria and protocols as established for this project.
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C.2.3.1 Total Nitrogen (TN) Data Usability
Total nitrogen results for the initial analytical batches for the confirmatory sampling program
are considered estimated (qualified "J"), due to uncertainty in the quantitation caused by an
instrument air leak. This problem persisted throughout the entire program and over 85% of the
confirmatory TN data were qualified as estimated for this reason. In the high resolution TN data set,
100% of the data were similarly estimated (qualified "J"). (Data users should note that the project
database (Version 3.1) contains a transcription error. Two TN results were left unqualified. These
results should have been qualified as estimated ("J"). This omission does not affect data usability
as TAMS/Gradient considers all estimated results to be usable for TN.) Additionally, six results (2%
of the data reported) were rejected due to severe QA/QC problems and are unusable for project
decisions and 40 sediment samples collected could not be analyzed because they could not be
ground. A completeness of 94% for TN data in both the confirmatory sediment sampling study and
esolution sediment coring study was achieved.
Sensitivity met project requirements for TN, but required correction during data review. In
accordance with the SOP for the method (TAMS/Gradient, 1992) the method detection limit was
raised from 0.001% (10 ppm) TN to 0.02% (200 ppm) TN.
As previously discussed, the agreement between the TON results generated by Chemtech and
the TN data from LDEO is poor. The TN values are three to ten times higher than the TON results.
This difference may be due to a method bias in the TON data (see TON discussion). Since the cause
of the discrepancy could not be determined, both the TN and TON data should be used with caution
for any use other than evaluating relative concentrations within the individual data sets. These
results are not comparable.
C.2.3.2 Total Carbon (TC) Data Usability
Some sediment samples exhibited a matrix effect for carbon. During the initial analysis, the
affected samples were not completely combusted; therefore, the laboratory recombusted the sample
and summed the first and second combustion results to obtain the total carbon value.
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TAMS/Gradient considers the affected data as usable, but estimated (qualified J) due to potential
uncertainty caused by matrix effects. This matrix effect was found mainly in samples collected in
the Upper Hudson River during the confirmatory sediment sampling study. This problem was
largely non-existent during the high resolution coring sediment study, as these matrix effects were
observ ed in only about 2% of the high resolution sediment samples. In addition to the incomplete
combustion problems, other TC data were qualified due to poor duplicate precision, reported values
exceeding the calibration range, and lack of associated method blanks. Overall, 57% of the
confirmatory TC data and 12% of the TC data from the high resolution coring samples were
qualified as estimated. Only one TC result was rejected (in the confirmatory sampling program).
C.2.3.3 Summary of TC/TN Data Usability
TAMS/Gradient considers all unqualified and estimated TC/TN data to be usable. Due to
the uncertainty associated with the estimated values, data users should understand that the
uncertainty in the individual results carries through to derived data, such as the TC/TN ratio, which
depend upon both these data sets. Data users should note that the project database did not always
carry through the qualifiers to the calculated ratios. The seven rejected results (qualified "R") are
not usable for project decisions. Additionally, 40 confirmatory samples collected could not be
processed for analyses due to sample matrix. An overall completeness of 94% was achieved for
TC/TN analyses in the confirmatory sediment sampling study and high resolution sediment coring
study.
C.2.4 Total Inorganic Carbon (TIC) Data
The purpose of the TIC measurements was to characterize sediment and to determine total
organic carbon (TOC) content of the sediment by subtraction of TIC from TC. The estimated (J) and
unqualified TIC results are usable for these project objectives. Five TIC results were rejected
(qualified R) and are unusable for the project. As for the TC/TN analyses, 40 confirmatory samples
• collected could not be processed for analysis due to the sample matrix. Therefore, the TIC
completeness achieved for both the confirmatory and high resolution core data sets was 94%.
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TIC analyses were performed on the same samples analyzed for TO'TN. This method, which
was also developed for use on a small sample mass, is described in Appendix H of the Phase 2A
SAP/QAPP (TAMS/Gradient. 1992). The TIC results were validated for data completeness, holding
times, calibration verification, laboratory and field duplicate results, laboratory control sample
results, detection limit results, and sample result verification. TAMS/Gradient developed validation
criteria for TIC analyses based on USEPA Region II data validation guidelines, wherever applicable,
the DQOs specified in the Phase 2A SAP/QAPP. and professional judgment.
TAMS/Gradient found no routine QA problems during the oversight and data validation
review of these data. The required QC, including initial and continuing calibration checks, duplicate
precision, and sensitivity were met in most cases. Approximately 81 % of the confirmatory TIC data
and 96% of the high resolution sediment coring TIC data have been accepted without qualification;
the remaining data considered were estimated for QC issues including low continued calibration
verification (CCV) recovery, poor lab duplicate precision, or lack of a method blank associated with
the samples. Five confirmatory TIC results were rejected due to severe QC exceedances. These
results are unusable for project objectives.
TAMS/Gradient reviewed the TIC results, as compared to the TC results, to assess the overall
contribution of TIC to TC. The TIC results were less than 2% of the TC values (less than 0.05% TIC
absolute) in over 90% of the confirmatory sediment samples and less than 10% of the TC for 90%
of the high resolution sediment samples (less than 0.8% TIC absolute). Based upon these results,
TAMS/Gradient concluded that inorganic carbon vas not a significant contributor of total carbon
in most of the sediments analyzed. Therefore, for practical purposes, the carbon in the sediments
analyzed is predominantly organic and the TC results can be considered equivalent to TOC. with
some exceptions as indicated below.
During the high resolution sediment coring study, eight sample results exhibited significant
TIC levels. These samples had TIC levels that were about 80% of the TC values. In other words,
in these sediments, the inorganic carbon accounted for the majority of the total carbon in the
samples. These eight samples were collected from the seven deepest samples from Core 20 and the
deepest sample from Core 23. These samples were unique in several other ways, including relatively
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high percent solids content for river sediments (65% to 70%) and relatively low total carbon content
(even in these samples the TIC was on the order of 1.5% to 2.0%) and low weight-loss-on-ignition
(less than 2% WLOI). Samples from other phases of the Hudson River program, with the exception
of some samples that were collected during the low resolution sediment coring study, were not
collected at depths from which this anomaly was likely to be present. TIC was not analyzed for the
4
low resolution sediment coring samples. Therefore, TC data from the deeper low resolution
sediment coring data should be reviewed in conjunction with percent solids and WLOI data, along
with TC data from the other core intervals, to evaluate the possibility that this effect of a significant
contribution from inorganic carbon to the total carbon load, may occur.
C.2.5 Calculated Total Organic Carbon (TOC) Data
The TC and TIC data were used to determine the contribution of inorganic carbon to the total
carbon content in the sediments and calculating an organic carbon value by difference.
TAMS/Gradient calculated total organic carbon (TOC) as the difference between the total carbon
(TC) result and the total inorganic carbon (TIC) result for the same split or co-located sample for
both the high resolution and confirmatory sediment sample data. There is no TOC data by an
alternate (direct analytical) method to provide an independent basis for evaluating this derived value
in sediments. Data users should note that though the TOC calculated values were not qualified in
the project database, any uncertainty already described in the TC or TIC data for some samples
(estimated results qualified "J"), is carried over into the calculated TOC result. The single rejected
TC result in the confirmatory sediment data set was not used and therefore a TOC value does not
exist for this sample.
Since the TOC data is derived, these data were not formally validated as such; however, the
analyses on which the calculation is derived - TC and TIC - were formally validated. The calculated
TOC achieved the same percent completeness as the component analyses (94%). TAMS/Gradient
considers all calculated TOC results as usable for the project objectives. As noted above, for the
purposes of this program, TC and TOC (in sediment) are sufficiently similar to be used
interchangeably for all the confirmatory sediment and all but eight high resolution sediment coring
sample results.
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C.2.6 Weight-Loss-on-Ignition Data
The objective of collection of WLOI data was to use the WLOI as an estimate of TOC. The
WLOI data covered by this section of the report consists of 457 analyses performed by LDEO on
sediment samples from the high resolution sediment coring study. WLOI represents the
determination of weight loss via combustion at a specified temperature (375°C) of previously dried
sediment or of non-filterable suspended solids retained by a glass-fiber filter. TAMS/Gradient
defined the WLOI combustion temperature at 375°C so that the data generated would be comparable
to historical data combusted at this temperature. The analytical procedure used for determination
of WLOI is described in Appendix F of the Phase 2A SAP/QAPP.
CDM validated the WLOI results for data completeness, holding times, calibration
verification, laboratory and field duplicate results, laboratory control sample results, detection limit
is^aits, and sample result verification. TAMS/Grauient developed validation criteria for WLOI
analyses based on USEPA Region II data validation guidelines, wherever applicable, the DQOs
specified in the Phase 2A SAP/QAPP, and professional judgment. In general, all data met the
project QA/QC requirements for accuracy, precision, and sensitivity (detection limits).
The WLOI data generated by LDEO for the high resolution sediment core samples represent
a consistent and accurate data set and can be used for any appropriate analysis by data users. Over
90% of the WLOI data have been accepted without qualification. Although a few samples were
reported to have TC values greater than the WLOI value, these samples without exception had high
TIC concentrations. The calculated organic carbon concentrations for these samples do not exceed
the WLOI values, and therefore the results are considered reasonable. Overall, 100% completeness
was achieved with 10% of the usable results considered as estimated values due to minor QC issues.
C.2.7 Radionuclide Data
The objective of collecting radionuclide data was to provide a means of establishing the
sediment core chronology. Results for beryllium-7 (7Be). cobalt-60 (60Co), and cesium-137 (,37Cs)
were generated to establish at least four radionuclide events expected to be seen in the sediments of
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the Lower Hudson and three in the sediments of the Upper Hudson. Based upon QA oversight
during analysis and review of radionuclide calibrations, data packages, and data validation reports.
TAMS/Gradient considers all the 7Be, l37Cs, and 60Co data generated for the high resolution coring
program as usable for these project objectives. The achieved completeness was 100%.
Radionuclide analyses were performed by LDEO and Rensselaer Polytechnic Institute (RPI)
using the gamma spectrometry method in Appendix L of the Phase 2A SAP/QAPP and the QA/QC
protocols defined in the Phase 2A SAP/QAPP (TAMS/Gradient, 1992). Dried and homogenized
sediment aliquots were analyzed for the three principal radionuclides. For the high resolution
sediment coring study, a total of 468 sediment sample results for 60Co, 137Cs, and 98 ^e results from
core tops are presented in the project database. For a total of 1,034 radionuclide results in the project
database, 130 (12% of the total) detected values were considered estimated (qualified "J") and 559
(54%) of the nondetected results were considered estimated (qualified "UJ") at the detection level.
During data validation, a majority of the results were estimated for statistical counting error which
contributes to the uncertainty in the accuracy of the concentration reported. As these radionuclide
data are to be used to discern trends in a core, TAMS/Gradient considers all estimated data usable
for project objectives. No radionuclide result was rejected (qualified "R") during validation or data
usability assessment.
C.2.7.1 Radionuclide Data Validation
The radionuclide results were validated for data completeness, holding times, calibration
verification, laboratory and field duplicate results, laboratory control sample results, statistical error,
and sample result verification. TAMS/Gradient developed validation criteria for radionuclide
analyses based on USEPA Region II data validation guidelines, wherever applicable, the DQOs
specified in the Phase 2A SAP/QAPP, and professional judgment. In general, acceptable criteria
were met for these QA/QC parameters with the exception of potential uncertainty in the accuracy
of the data near the background concentrations or in cases of low activity counts.
The radionuclide method requires that activities (results) be corrected for background, blanks,
the radionuclide branching ratio, the efficiency geometry of the detector, and for the radionuclide
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specific decay. TAMS/Gradient established data validation criteria for radionuclides to verify that
sample results were accurate, included appropriate corrections, and accounted for background
activities to verify that detected activities reported were statistically different from background.
TAMS/Gradient established the statistical error evaluation to set criteria for the estimation and
negation of activities based upon statistical error. Interpretation of radionuclide results as affected
by the statistical error and background correction protocols are discussed in the following section.
C.2.7.2 Interpretation of Negative, Zero, and Background Activities for Radionuclides
TAMS/Gradient defined validation criteria for the statistical counting error for the
radionuclide results. Specifically, all sample results with a statistical error (i.e., counting standard
deviation) of greater than 10% and less than 50% of the sample concentration (i.e., the percent
difference between the sample result and the statistical error in the sample result between 10% and
50%) were considered estimated (qualified "J") due to the uncertainty in the result based upon the
statistical error. TAMS/Gradient considers these estimated results as statistically different from zero,
with some uncertainty due to counting errors. In general, radionuclide results qualified "J" for
counting statistics were reported at relatively low activities. Sample results that had statistical errors
of greater than 50% of the sample result were considered to be nondetected with an estimated
detection limit (qualified "UJ"). At the one sigma statistical error level, as calculated by LDEO,
these values are not significantly different from zero.
In some cases, the procedure of subtraction of measured background counts from sample
counts during the calculation of radionuclide concentrations resulted in negative concentration
values, which should be considered zero for purposes of data interpretation. Zero and negative
activities are not statistically different from background activity and therefore, have been qualified
"UJ" regardless of the percent difference between the reported activity and the activity's statistical
error (TAMS/Gradient, 1995). Low-level activities, for which the counting statistics show a high
relative error (counting error of greater than 50% of the reported result) as described in the above
criteria, are also considered not significantly different from background. These evaluations have
been applied to the data during validation; therefore, some low-level positive values have been
considered as not detected, i.e., no activity, following data validation. Note that the statistical
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counting errors, representing one standard deviation, have been maintained in the database to give
the data user additional information on the uncertainty of the reported radionuclide activities.
C.2.8 Percent Solids
Percent solids analysis was performed by LDEO by drying the samples at 110°C for two
hours. The high resolution sediment core samples analyzed by Chemtech for TON were also subject
to solids analysis (by drying overnight at 103°C to 105°C) in order to report the TON data on a dry
weight basis. Visual (non-rigorous) inspection of the two solids data sets indicates good agreement,
with a few exceptions. TAMS/Gradient recommends the use of the percent solids data from LDEO
as the definitive results because they were performed solids on a large volume aliquot and therefore
are likely to be more representative than the Chemtech solids determinations (which were performed
on 2 to 3 gram aliquots of sediment samples submitted for TON analysis).
The slightly different temperatures used by Chemtech and LDEO for the solids determination
are not expected to have any significance with respect to the comparability of the data. However,
some samples analyzed for PCBs or for archiving were dried at significantly lower temperatures
(35°C) and for significantly longer times; these solids determinations are not necessarily comparable
to those determined at 105°Cto 110°C.
Of 291 confirmatory sediment samples analyzed by LDEO for percent solids, 7 results (2%
of the total) were qualified as estimated based upon poor field duplicate (co-located and/or split
samples) precision. LDEO reported 457 results for percent solids of the high resolution coring
samples. These results were not validated and were accepted as reported by the laboratory.
TAMS/Gradient considers all LDEO percent solids data as usable. Therefore, a completeness level
of 100% was achieved.
C.2.9 Field Measurements
Field measurements recorded during the high resolution sediment coring study and
confirmatory sediment sampling study consisted of reduction/oxidation potential (redox or Eh
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potential) measurements of sediment pore water and the associated temperature at which the
measurement was taken. The objective of this measurement was to serve as a rough indication of
where sediment zones of reducing potential exist in the cores collected in order to correlate these
zones with areas of extensive PCB dechlorination. The field procedure is described in Appendix N
of the Phase 2A SAP/QAPP (TAMS/Gradient. 1992). Redox measurements (in millivolts, or mv)
of the pore water were taken by LDEO personnel (under TAMS supervision). Approximately 12
to 15 readings were recorded for each core.
TAMS reviewed the field notes and tabulated results to assess data usability. The data were
properly recorded and appropriate calibration and measurement procedures were followed. Cores
were typically stored on ice overnight prior to processing; therefore, the recorded temperature should
not be interpreted as the ambient or in-situ sample temperature at time of collection. Notebook pages
are neat and legible and the data can be reconstructed from the field notes. The temperature at which
neasurement was taken is recorded in the fie'd notes and also recorded on the tabulated
(spreadsheet) data. One transcription error (between the raw field notes and the Excel spreadsheet;
value for HR-022-1216P should be changed from "94 mv" to "-94 mv") was observed during the
usability review. With the caveat that these are field data, the redox (Eh) data are of a quality
consistent with the measurement system employed and as such are considered fully usable for the
project objectives.
C.3 Water-Column Monitoring Program and Flow-Averaged
Sampling Programs
The water-column monitoring program (January 29,1993 through August 24,1993) included
samples analyzed for dissolved organic carbon (terminology used interchangeably with total organic
carbon; see discussion below), total suspended solids, weight-loss-on-ignition, and chlorophyll-#.
The flow-averaged sampling program included total organic carbon, total suspended solids, and
weight-loss-on-ignition.
Two sets of "equilibration study" samples were taken during the water-column transect
sampling program. The first - EQ1 - were taken concurrently with water-column Transect 2, and
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the second set were taken along with Transect 6. Although these samples were taken during the
programs under consideration in this report, the "equilibration study" samples were taken solely to
calculate the PCB distribution coefficient KD. Therefore no specific discussion of these samples is
in this appendix. The water-column monitoring program sampling procedures, analytical protocols,
and QC/QA requirements are presented in the Phase 2A SAP/QAPP and summarized in Appendix
B.
C.3.1 Dissolved Organic Carbon (DOC) Data
The objective for this analysis was to provide a continuation of an existing database of DOC
measurements that has been correlated with many historic water-column PCB analyses. The Phase
2A SAP/QAPP defined split samples for analysis by two different methods. The LDEO persulfate
oxidation method adopted by RPI under contract to TAMS was performed to generate comparable
data to the historic data set. The USEPA water quality method, performed by a USEPA SAS
laboratory, Chemtech, was defined for generating a reference data set using a standard USEPA
method (EPA Method 415.1; USEPA, 1983).
Dissolved organic carbon (DOC) is defined for this program as the total organic carbon
analysis of a sample which was filtered in the field through a glass fiber filter. For the flow-averaged
sampling program and the water-column monitoring programs, the terms "DOC" and "TOC" have
both been used to describe this parameter, though functionally, it is dissolved organic carbon. The
data evaluated in this section include a total of 136 water-column monitoring and flow-averaged
samples analyzed by RPI using the persulfate method as defined in Appendix C of the Phase 2A
SAP/QAPP (TAMS/Gradient, 1992) and 115 water-column monitoring samples analyzed by
Chemtech using EPA Method 415.1. The samples analyzed by RPI and Chemtech are splits of the
same field sample.
Note that though field blanks were collected and analyzed for the DOC sampling and analysis
program, they are not considered as a reliable indicator of field contamination and are not reviewed
in this data usability assessment. Justification for this approach is found in a memorandum from
USEPA Region II, dated April 12, 1993, concerning the Phase 2A SAP/QAPP for the Hudson River
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PCB RJ/FS (USEPA, 1993). In this memorandum, it states "Field (equipment rinse) blanks are not
required for TOC field samples and should not be collected. Analyte-free water does not need to be
analyzed for TOC. TOC should not be considered an analyte. but rather a water quality parameter."
C.3.1.1 DOC Results - RPI
The DOC data generated by RPI are usable with some cautions. All of the DOC data were
qualified as estimated ("J") by the validator (TAMS/Gradient for SDG 001, and CCJM under
subcontract to CDM for SDGs 002 through 008) for method blank and control sample deviations.
Review of the validation reports and other information suggests that these deviations did not
significantly compromise data quality. Laboratory and field duplicate results for DOC indicated
generally good precision, with only one duplicate pair substantially exceeding the defined precision
objective (38.9% RPD for Transect 4 Station 6 duplicate, exceeding the 20% maximum RPD
objective).
Validators estimated some of the early water-column data due to exceedances of holding
times, in some cases substantial exceedances of several months. Based upon method requirements
for preparing the samples by persulfate oxidation, TAMS/Gradient consider these data usable
because they were "fixed" in sealed tubes prior to being held for analysis. Persulfate was added to
the sample aliquot and purged of all CO: w ith a stream of helium. The ampule was then sealed and
heated to 90°C for 4 hours. It was this sealed ampule that was held, past holding times, prior to
analysis.
TAMS/Gradient instituted several corrective actions during a laboratory audit of RPI. These
included: 1) performance of method detection limit and blank water studies; 2) routine analysis of
a verified DOC standard following daily calibration; 3) routine analysis of matrix spiked samples
at a frequency of 1 in 20; and 4) requirement of adherence to holding time of 28 days from sample
collection to fixing the sample in an ampule for DOC analysis. These corrective actions resulted in
usable data generated, with the quantitation limit for DOC increased from 0.025 mg/L, as listed in
the Phase 2A SAP/QAPP (1992), to 0.25 mg/L, based upon results of the MDL/blank studies. The
increase in MDL did not affect data quality as DOC values were consistently in the 4 to 5 mg/L
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range, and even the suspect Saratoga Springs sample values were two to three times the revised
MDL.
DOC values from Station 9 (Saratoga Springs, selected as a background sample location)
were relatively low compared to those from other stations (typically 0.9 - 0.9 mg/L, as opposed to
4 to 5 mg/L for other stations). Although Saratoga Springs is expected to have low organic carbon
content, it cannot be determined whether the low values for this station are representative of the
actual values or are biased low due to matrix interference (floe formation suspected to be iron
hydroxide) as observed in the TSS/WLOI aliquots. Therefore, TAMS/Gradient considers the Station
9 DOC data as estimated values that may be biased low.
In Transect 4. the sample collected from Station 7 (SW) also exhibited an anomalous low
DOC value (0.94 mg/L). This value is in poor agreement with other DOC values from this transect,
and also does not agree well with the three other DOC . alues obtained at this station (which ranged
from 4.26 to 5.22 mg/L). It is therefore likely that this value is not representative of conditions at
this station, but rather is an outlier. Station 7 was deleted from the water-column monitoring
program after the fourth transect was completed.
The Station 12 (Hoosic) data from Transect 3 are not legally defensible due to contradictions
in documentation and therefore in establishing the identity of samples labeled TW-003-0012 and -
0012D. Review of the field logs, as well as the analytical results, suggests that 0012D is not a
duplicate of 0012, but rather was taken three days later than 0012, during the spring thaw. However,
the formal chain-of-custody documentation indicates that both 0012 and 0012D were taken at the
same time and day (March 27, 1993).
Several results for the flow-averaged sampling are unusable due to suspected sample bottle
contamination. Whereas DOC values determined for the flow-averaged samples range from 4.0 to
6.0 mg/L, four flow-averaged composites for the second sampling event showed DOC values
significantly higher, i.e., from 10 to 16 mg/L. The eight individual DOC samples that made up the
composite value were then analyzed separately for each of these stations. These individual analyses
show that, for each station, at least one anomalous high DOC result is present. For example, for
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Station 4, sample FW-208-0004 showed 118 mg/'L DOC. This value is more than an order of
magnitude higher than all other DOC results for the flow-averaged samples. The field crew noticed
that some of the samples foamed when placed in the sample bottles. It is suspected that
contaminated sample bottles were the cause of the extremely high DOC values. TAMS/Gradient
re-calculated the composite DOC for the affected flow-averaged sampling stations by deleting results
for the contaminated samples. Sample bottle storage and use protocols were improved after this
event and no such anomalous results were observed in subsequent data.
Overall, the RPI DOC data reported as estimated (J) or reported unqualified are usable for
project objectives as the DOC values obtained compare well with historical data. Several results
were rejected as unusable due to bottle contamination. An overall completeness of 96% was
achieved for the DOC results obtained in the water-column monitoring and flow-averaged sampling
programs. This meets the project DQO of 95% completeness.
C.3.1.2 TOC Results - Chemtech
The DOC analyses performed by Chemtech using the USEPA method were validated by
CDM. Though CDM found no problems which would render these data unusable, anomalous results
were reported for several stations. For example, samples from Station 9 (Saratoga Springs)
consistently had anomalous high results (in the 300 to 500 ppm range) for DOC. As spring water
samples, the Saratoga Spring samples would have high inorganic carbon (as carbonate)
concentrations; the inorganic carbon is supposed to be removed by acidification of the sample prior
to analysis. The detection of high organic carbon concentrations in the Saratoga Springs samples
suggests that the laboratory either did not perform the acidification step, or performed it
inadequately. TAMS/Gradient considers all Chemtech DOC data as potentially biased high (due to
inorganic carbon being reported as organic carbon). Chemtech data therefore represent a worst-case
(maximum) value for organic carbon in the water-column. Since there are RPI data available for the
same samples, and the persulfate oxidation method used to determine DOC did not have a high bias,
TAMS/Gradient recommends that data users rely on the RPI DOC data set for project uses.
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C.3.2 Total Suspended Solids and Weight-Loss-on-Ignition (TSS/WLOI) Data
The objective of collection of TSS and WLOI data was to associate these values with the
suspended matter/dissolved phase distributions of PCB congeners and use these results to help model
PCB transport and water-column concentrations under seasonal flow variations. The TSS and WLOI
data evaluated include a total of 856 results reported by RPI for TSS collected for the water-column
transect, flow-averaged sampling, and high-flow suspended matter studies; 111 water-column
transect samples analyzed for TSS by Chemtech under the USEPA SAS program, and 418 samples
analyzed for WLOI by RPI for all three studies. Both RPI and Chemtech performed TSS using
USEPA Method 160.2 (USEPA, 1983). The material analyzed for WLOI is the dried matter retained
on the filters from the TSS analysis; WLOI represents the determination of weight loss by
combustion at a specified temperature (375°C) of the dried sediment or non-filterable suspended
solids retained by a glass fiber filter.
C.3.2.1 Weight-Loss-on-Ignition Data
The historical WLOI data are reported for combustion at 375°C. For this reason, the Phase
2A SAP/QAPP specified that WLOI data for the Hudson River project be combusted at the same
temperature. However, due to laboratory error, samples from the water-column Transect 1 were
combusted at 450°C. In an effort to determine the effect of this method change, RPI performed the
WLOI at two furnace temperatures (375°C and 450 C) for the remainder of the water-column
monitoring program samples. TAMS reviewed 76 analytical pairs of results at both temperatures
and found that the WLOI result at the higher temperature is consistently about 20% higher than that
at the lower temperature. Using the two data sets. TAMS developed a correlation between the results
at the two combustion temperatures to convert results at 450°C to the 375°C equivalent WLOI (refer
to Figure C.l). TAMS calculated a factor of 0.8636 by forcing the regression of the two sets of
results through zero. Therefore, data users can obtain a conversion of WLOI from 450°C to a 375°C
equivalent by multiplying the result for WLOI obtained at 450°C by 0.864. This calculated WLOI
value has an uncertainty of approximately 20%.
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In addition, TOC was not analyzed for the water-column samples in Phase 2A, thus TAMS
further developed a correlation between WLOI at 375° C and TOC from the sediment sample data
(refer to Figure C.2). Organic carbon content can be estimated (calculated) from WLOI data by the
equation: TOC = WLOI (375°) - 0.611.
Due to the uncertainty associated with the Transect 1 WLOI values after the application of
the conversion factor, data users may consider eliminating these results from their interpretation if
there are sufficient data from Transects 2 through 6 for their intended use.
Precision of the WLOI results a function of the sample size. For this analysis, sample size
is the mass of dried suspended solids recovered in the TSS analysis. For the 1-liter samples, the
WLOI values have greater uncertainty when the TSS results were less than about 2 mg/L. These
results should be used with the understanding that they are estimated values. WLOI data are more
reliable from larger volume samples (3 to 4 liters) and samples with higher TSS values, since the
relative impact of the weighing error decreases with increased weight.
Due to the formation of a floe believed to be iron hydroxide, TAMS/'Gradient considers
unusable all TSS/WLOI data from Station 9 (Saratoga Springs). These results were rejected
(qualified R).
C.3.2.2 Total Suspended Solids (TSS) Data
TSS analyses were also performed by Chemtech on samples from the six water-column
monitoring sampling events. Reported field blank contamination is a significant data quality issue
for this data set. TAMS validated and rejected (qualified "R") all TSS data from the first two
transects because of field blank contamination. TSS contamination was detected at 5 mg/L in all
three field blanks from Transect 3, which should have been cause for rejection of all, but three
sample results (all data <25 mg/L TSS), although no action was taken by the validator. The single
TSS field blank submitted with Transect 4 was not contaminated and data were acceptable (except
field duplicate pair qualified estimated for poor precision). No field blank was submitted with the
fifth transect, so TSS data from Transect 5 were qualified as estimated. Variable contaminant levels
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(not detected at 1 mg/L to [detected at] 4 mg/L TSS) were reported in the field blanks associated
with Transect 6.
The rejected data are completely unusable; it is further recommended that the remainder of
the TSS results reported by Chemtech not be used due to the overall uncertainty and probable high
bias of the results. Analyses for TSS performed by RPI are more reliable and TAMS/Gradient
recommends that the RPI data be used as the definitive TSS results for the water-column transect.
The Chemtech data have been eliminated from the main table of results in the project database.
C.3.2.3 Flow-Averaged Sample Results
TSS/WLOI data were generated from six flow-averaged sampling events from April 23 to
September 23, 1993. Each event was a separate SDG; the data from the second event (SDG 010)
were validated by TAMS/Gradient, and the remaining fiow-averaged TSS/WLOI data were validated
by CDM (Federal Programs Corp.). Analytical methodologies were the same as for the water-
column monitoring analyses discussed above. For the flow-averaged WLOI analyses, RPI
combusted all samples at 375° (as well as at 4501); therefore none of the WLOI data needs to be
adjusted due to combustion temperature.
The TSS method used for these analyses (EPA method 160.2) has a detection limit of 4
mg/L, based on drying the material to a constant weight (defined as ±0.5 mg) and using a 250 mL
sample (the 4 mg/L is derived from two weightings each of 0.5 mg maximum error, or total error of
1.0 mg for 250 mL). The detection limit can be improved by increasing the aqueous sample volume,
since the limiting factor is the mass of suspended matter retained on the filter. In order to obtain
reportable results (i.e., positive values greater than the detection limit), the sample volume was
increased (approximately 1000 mL was filtered for the daily RPI TSS analyses; the composite (X09-
000X) samples were typically 3500 to 4000 mL); the weight of suspended matter was greater than
1.0 mg for all samples except one. It should be noted that in some cases the data validator (CCJM)
negated low reported values (less than 1.6 mg/L) for which the raw data showed that more than 1.0
mg of solids were retained; these values have been reinstated by TAMS/Gradient. Only reported
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results for which the mass of suspended matter was less than 1.0 mg have been considered to be non-
detected (qualified "U" or "UJ").
The data set for the flow-averaged data includes individual (daily) analysis of samples, as
well as a composite sample result, for each station (location). RPI performed a mechanical
composite (i.e., poured aliquots of the eight individual samples to create a composite sample "9")
and analyzed this composite as a sample. The data for the mechanical composite has been replaced,
in the project database, by a mathematical composite. The mathematical compositing was performed
during the data usability review by taking the eight individual TSS values for a flow-average transect
and mathematically combining them using transect-specific volumes normalized to the flow rate for
that particular sampling event. This mathematical composite is a more technically valid result than
the mechanical composite for the following reasons:
1. For the mechanical composite, seven 1 of the individual TSS samples were out of
holding times. This may introduce a low bias in the result.
2. Error may be introduced into the mechanical deposit because it is difficult to obtain
a representative aliquot of the individual samples. Particles may start settling as the
aliquot is being poured thereby introducing uncertainty in the representativeness of
the sample aliquots that make up the mechanical composite. This may cause a low
bias in the result.
3. A review of the flow-averaged data showed that some of the mechanically composite
results were biased low, relative to the mathematically-derived composite result. For
the several of the 15-day composites evaluated, the mathematically-derived TSS
value was up to 29% larger than the composite, and averaged 15% higher. This is
consistent with the direction of the bias expected if the mechanically derived
composites were not representative in TSS for individual aliquots due to settling of
suspended solids particles during the process of compositing. For Transect 3, data
shows a significant low bias of the composites as opposed to the calculated flow-
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averaged value; the calculated values exceed the composites by over 28% for all four
stations.
The values for flow-averaged Transect 3, day seven at Station 4 (FW-307-0004 at 19.24
mg/L TSS) and flow-averaged Transect 2. day seven at Station 4 for the field co-located sample
(FW-207-0004 field co-locate at 18.09 mg/L) appear to be outliers. It is likely that sediment was
disturbed during the collection of these samples. These values have been rejected (R), along with
the WLOI values for these samples, and the data are unusable. Therefore, the mathematical
composites calculated for these stations include seven, rather than eight, individual TSS and WLOI
values. The composite results were re-calculated during the data usability assessment and have been
updated in the project database.
RPI performed three weighings as part of the TSS determination. In cases where there was
a significant discrepancy between the driest weight and the other two weights, RPI performed a forth
drying cycle and weighing. This procedure was performed for some of the samples associated with
the flow-averaged Transect 2. For affected samples, the TSS was re-calculated using the average
of the four weights, rather than the driest weight. These re-calculations were performed during the
data usability assessment and the corrected values are reported in the project database. The technical
justification for these re-calculations include:
1. the laboratory noticed a problem with the consistency of the weights; therefore, they
performed an additional weighing;
2. the average of the four weights will give a more representative TSS result than using
the driest weight if there was a potential for inconsistency in weightings.
Affected data include flow-averaged Transect 2 for Stations 4, 5, and 8 for days 5 through
8, as listed below:
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Station 2
Station 4
Station 5
Station 8
FW-205-0002 FW-2Q5-0004
FW-206-0002 FW-206
FW-207-0002 FW-207
FW-208-0002 FW-208
FW-208-0005 FW-208-0008
FW-205-0005
FW-205-0004 FCC
FW-206-0004 FCC
FW-207-0004 FCC
Notes: FCC -Field Co-located
These data are considered estimated (J) and are usable as estimated results. Several results
were negated (U or UJ) for TSS due to blank contamination. Associated WLOI results were rejected
(R) because if TSS is not detected, then the measured value for WLOI must be an analytical artifact
or error.
C.3.3 Chlorophyll-a
The objective for this measurement was to collect reliable chlorophyll-a data as an important
factor in defining the partitioning ratios of PCBs between dissolved and suspended matter phases.
Chlorophyll-a data were obtained for water-column samples for the first three transects through the
USEPA SAS contract laboratory. Chemtech. Although these data were "valid", these data are not
useful due to the high quantitation limit reported by the laboratory. The reported detection limit for
these samples (25 mg/L) exceeds the maximum expected concentration (on the order of 10 mg/L to
15 mg/L); therefore, to prevent possible inappropriate use or inferences being drawn from these data,
they have not been included in the database.
Subsequently, Inchcape Analytical Testing - Aquatec Laboratories (Aquatec), under contract
to TAMS, analyzed samples from water-column Transects 5 and 6 for chlorophyll-a using the more
sensitive (spectrophotometric) method (10200-H.3), with a detection limit of 0.5 mg/L. Aquatec
data were consistent with expected values with chlorophyll-a detected in all 27 samples at
concentrations ranging from not detected at 0.5 mg/L to 20.0 mg/L (uncorrected). The method also
provides for a correction to the chlorophyll-a calculation for pheophytin. Aquatec performed this
correction and also reported this result (in the data as "corrected"). The corrected value is typically
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about 0.5 mg/L to 0.8 mg/L chlorophyll-a lower than the uncorrected value, although there are a few
exceptions. TAMS/Gradient recommends that data users employ the corrected with the caution that
any comparisons to data from other sources also be "corrected". TAMS/Gradient considers all the
Aquatec chlorophyll-a data usable for project objectives. Only one result was estimated due to
minor QC issue and 100% completeness was achieved for the Aquatec data.
C.3.4 Field Measurements
The objective of the field measurements, including pH, temperature, conductivity, and
dissolved oxygen was to obtain measurements for standard indicators of water quality conditions.
Field measurements, including pH. temperature, dissolved oxygen, and conductivity, were obtained
during water column monitoring (including both the water column transects and flow-averaged
sampling). A complete set of data was obtained. Due to concerns about the accuracy of some of the
measurements, laboratory determinations of pH and conductivity were made subsequently to the
field determinations. These field measurements are included in the database and data are generally
considered usable, as discussed below.
C.3.4.1 Temperature
Temperature measurements were made concurrently with the determination of other
parameters (pH, conductivity, and dissolved oxygen). The temperature measurements are used to
correct the raw field and readings to a constant temperature (i.e., 25° for conductivity). In the case
of dissolved oxygen, the temperature measurements are used to determine the theoretical oxygen
saturation concentration so that the data can be expressed as percent saturation. The temperature
measurements were made using the same instrument used to measure the parameter of interest {e.g.,
the YSI SCT meter was used to measure the temperature associated with the field conductivity
measurements). While the accuracy of the measurements is assumed to be acceptable, there is some
question as to their representativeness, especially for the first few transects where ambient and water
temperatures were low (5°C and less). The field data indicate temperature variations of as much as
10°C between measurements of the same sample for different parameters, so there may be some
question as to the accuracy of temperature-based corrections for such measurements. However,
C-33 TAMS/Cadmus/Gradient
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review of the field notes also suggests that this discrepancy may be due to differing time lags
between sample collection and measurement of the three field parameters (e.g.. pH readings may-
have been taken 45 minutes after the conductivity measurement).
C.3.4.2 Dissolved Oxygen
Review of the dissolved oxygen readings indicate that they are reasonable and in the
expected range (near 100% saturation for most samples; low values for Station 9 [Saratoga Springs]).
Some measurements correspond to somewhat greater than 100% saturation (101% to 110%) in
perhaps about 10% of the samples; this is not considered significant based on the intended use of the
data (providing a crude estimate of gas exchange capability of various reaches of the river). The
temperature associated with the dissolved oxygen meter is that measured by the instrument (YSI
51B) and is used to determine the saturated oxygen content of water at the measurement temperature.
drometric pressure or altitude correction has bee., made; the maximum elevation of any of the
sampling locations (about 200 ft) introduces less than a 1 % change in the saturated dissolved oxygen
concentration. It is also of note that temperature-specific oxygen saturation concentrations vary by
1% to 2% depending on the reference, or the edition of the reference. The dissolved oxygen data
in the database consist of the raw field reading and the temperature at which it was taken; it is not
converted to percent saturation.
C.3.4.3 Conductivity
Conductivity measurements were made both in the field at the time of collection (using the
YSI Model 33 S-C-T meter with YSI 3310 probe) and later in the RPI laboratory (using a Leeds and
Northrup model 4959 meter and YSI 3417 probe). The RPI narrative indicates that the laboratory,
as opposed to field, measurements are considered more reliable. It should also be noted that a
Hudson-specific temperature correction was applied to the data; this correction factor is non-linear
and results in a slightly higher correction being added to measurements below 25°C than the 1.9%
per degree cited in Standard Methods (17th edition). (The Hudson-specific correction factor, based
on Dr. Bopp's conductivity measurements taken at six different Hudson River tributaries, is Cond25
= Cond^00223'2-"1', where t is the measurement temperature in °C.)
C-34
TAMS/Cadmus'Gradient
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Water-column transect conductivity measurements. For the first two transects (in January and
February'. 1993), measurements at the northern stations (1 through 4) were conducted at low ambient
temperatures (less than 5°C) and it has been reported that the instruments were not stable in the field.
However, laboratory conductivity measurements were taken about 70 to 90 days after the samples
were collected (April 30 through May 10, 1993); a maximum holding time of 28 days is cited both
in Standard Methods (APHA, et al, 1989) (17th edition) and Methods for the Chemical Analysis of
Water and Wastes ("MCAWW: USEPA 1983). Therefore, the laboratory conductivity data for these
two transects cannot be considered reliable. A limited review cf the data indicates generally good
agreement (RPD < 20%), even between data pairs analyzed months apart (Transects 1 and 2):
agreement is better between data sets analyzed closer together (Transects 3 through 6). Review of
the field data in conjunction with the laboratory data suggests that the field data from Transect 1.
Stations 2, 3, and 4, are outliers (the scale of the readings may have been misread by a factor of 10);
otherwise, the field data appear adequate. However, the data entered into the database are the
laboratory data. The laboratory data were selected since measurements were taken at closer to the
normal reporting temperature (25°C) and therefore a smaller correction factor had to be applied.
Flow-Averaged sampling conductivity. Agreement between the field and laboratory conductivity
data was generally good, although an even-dependent bias was noted. All flow averaged
conductivity measurements were made within the 28 day holding time (averaging about 5 days after
collection), although inspection of the data suggests that agreement between field and laboratory data
is related to how soon after sampling the laboratory measurements were made.
Conductivity for three of the flow averaged events (1,3, and 6) were reviewed in detail. In
event 1, the average RPD was about 8.5%, although for 25 of the 27 measurements, the laboratory
results were higher than the field results (after correcting both sets to 25° C); the two exceptions
where field data were higher were two of the three station 8 results. In event 1, laboratory analyses
were conducted an average of about 6 days after sample collection; field sample analysis
temperatures ranged from 5°Cto 13°C. In Transect 3 (excluding Station 8), the average RPD was
about 2.8%, with the field data being slightly higher than the laboratory results. In event 3, the
average interval between field sample collection and laboratory anaylsis was less than one day, and
field sample temperature averaged about 20°C. Station 8 results were much more variable; the
C-35
TAMS/Cadmus/'Gradient
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average RPD for Station 8 was slightly more than 10%. with no consistent bias (laboratory results
for Station 8 ranged from 9% less than the field results to 27.5% greater than the field results).
During the flow-averaged sampling, the average RPD for all stations (2. 4, 5, and 8) was about 13%;
however, during event 6, the field measurements were consistently higher than the laboratory
measurements (28 of 31 field measurements were higher than the corresponding laboratory
measurement).
The available information on data quality does not indicate a strong reason to believe either
the field or the laboratory flow-averaged data set is better than the other. However, for internal
project consistency, the laboratory flow averaged conductivity data has been included in the
database. The laboratory-measured data set for the flow averaged sampling events is slightly more
complete for the laboratory conductivity data, although the field data includes conductivity
measurements at the west wall of the Waterford bridge (Station 8) which were not included in the
laboratory analyses. Data (in the database) from flow-averaged event 1 may be biased high (based
on comparison to the field data); conversely, a low bias may be present in the event 6 data. No
significant bias is suspected in the event 3 data. The direction of bias, if any, was not evaluated for
flow-averaged events 2, 4. and 5.
The original objective of the conductivity measurements was to obtain general water quality
parameter data. However, when the water-column transect sampling event began, it was discovered
that the US Geological Survey had discontinued flow monitoring at the Waterford gaging station,
leaving the project without flow data for this part of the Hudson River. Therefore, an attempt was
made to assess tributary contributions to main stem flow by means of a dissolved solids balance,
inferred from the conductivity data. These attempts were not successful; partially due to the
imprecision/inaccuracy of the conductivity measurements, and also due to the fact that complete
mixing of the tributary with the Hudson River had not yet occurred at the downstream sampling
station where conductivity was being measured. (For example, the field conductivity measurements
at Waterford illustrate that the Hudson was not fully mixed across its width at that location.)
C-36
TAMS/Cadmus.'Gradient
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C.3.4.4 pH
During the water-column transect sampling, measurements of pH were taken in the field;
subsequent measurements of pH were also taken in the laboratory. During the flow averaged
sampling events, only laboratory-' measurements of pH were made. Field and laboratory
measurements were both made with a Hannah Model 9025 meter and PCI El000 epoxy/gel
combination electrode. There is general consensus in the literature that pH values of water can
change within minutes, and that pH analysis should be conducted as soon as possible (within 2
hours, or less, depending on the source). During the water column transect sampling, the laboratory
pH measurements were made at least three days after sample collection (and in some cases as much
as 90 days later); therefore, the laboratory pH data for w ater column transect sampling are not usable.
Only the field pH data, along with the temperature of measurement, have been entered into the
database. The gel electrode utilized for the pH readings was selected due to its ruggedness; it does
take longer to equilibrate (stabilize) than conventional KCl-filled electrodes. Field pH data
measured when water temperatures were low (less than 10°C or so) may be less accurate and may
be biased low if readings were taken before complete stabilization occurred. Due to the difference
in temperature at which pH readings w;ere taken (instrument temperature compensation circuitry does
not account for all possible temperature-dependent pH effects), as well as the lack of confidence
expressed in the field data in the case narrative, the pFI data are considered approximate.
As indicated in the discussion above, pH data are meaningful only when measurements are
made shortly after sample collection. There are no field (real-time) pH data for the flow averaged
sampling events; laboratory measurements were made an average of five days after sample
collection. Laboratory pH data meausured 24 hours or more after sample collection are unusable
except as qualitative indications of water quality (e.g., approximately neutral; strongly acidic). Only
measurements made on the day of sample collection are considered to have any quantitative validity;
and even these data are considered estimated due to the time lag between collection and
measurement. The only pH measurements made on the day of sample collection during the flow-
averaged sampling were from days 1, 4, 5, 7, and 8 of event 3. The remaining flow averaged pH
data are not considered quantitatively usable. It should be noted that the laboratory pH data are not
quantitatively usable within a single event, since holding times varied widely within events (e.g., the
C-37
TAMS/Cadmus/Gradient
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pH measurement of day 1 during event 6 was made 13 days after collection: the measurement for
day 4 was made 7 days after collection; and the measurement for day 7 was made one day after
collection).
C-38
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References
APHA (American Public Health Association. American Water Works Association, and the Water
Pollution Control Federation. 1989. Standard Methods for the Examination of Water and
Wastewater. 17 Edition. APHA, Washington, D.C.
Shillabeer, N., B. Hart, and A. M. Riddle. 1992. The Use of a Mathematical Model to Compare
Particle Size Data Derived by Dry-Sieving and Laser Analysis. Estucirine, Coastal and Shelf
Science, Vol. 35, pp. 105-111.
TAMS/Gradient. 1992. Phase 2A Sampling and Analysis Plan/Quality Assurance Project Plan
Hudson River PCB Reassessment RI/FS, Revision 2, May.
TAMS/Gradient. 1995. Memorandum from Allen Burton (TAMS) and Lisa Kulju Krovvitz
(Gradient) to Jennifer Oxford (CDM). Hudson River PCB RI/FS, Radionuclide Data Validation,
SDGs 19B and 2IB. March 29.
USEPA. 1983. Method for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, Revised
March 1983.
USEPA 1992. Region II SOP No. HW-2, Evaluation of Metals Data for the Contract Laboratory
Program (CLP) based on SOW 3/90, SOP Revision XI, January 30, 1992.
USEPA. 1993. Memorandum from Laura Scalise, Project Quality Assurance Officer, Monitoring
Management Branch to Douglas Tomchuk, Project Manager. Subject: Hudson River PCB Site -
Reassessment RI/FS, Phase 2B Sediment Sampling & Invertebrate Study Sampling &
Analysis/Quality Assurance Project Plan, Volume 2. April 12, 1993.
C-39
TAMSCadmus/Gradient
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Table C-l
Non-PCB Chemical and Physical Data Collected for the Phase 2A
Sampling and Analysis Programs
Parameter
High Resolution
Confirmatory-
Water-Column/
Sediment Coring
Sediment
Flow-Averaged
Study
Sampling Study
Sampling
Program
grain size distribution
J
y
-
percent solids
v/
y/
-
weight-loss-on-ignition
y
-
v/
total carbon
y
J
-
total inorganic carbon
>/
y
-
total nitrogen
s/
v/
-
total organic nitrogen
y/
-
-
radionuclides (7Be, 60Co, 137Cs)
y/
-
-
dissolved organic carbon
-
-
y/
total suspended solids
-
-
V
chlorophyll-a
-
-
y/
dissolved organic carbon
-
-
y/
field testing - redox
-
y/
-
field testing - temperature. pH,
-
-
y/
conductivity, dissolved oxygen
T A M S ,'C adm u s/G rad ient
-------
Table C-2
Qualifiers for Non-PCB Data
U - The chemical or parameter was analyzed for, but was not detected above the level of the associated
value. The associated value is the sample quantitation limit. The associated value is usable as a
nondetect at the reported detection level.
J - The associated value is an estimated quantity due to QA/QC exceedance(s). The estimated value may
be inaccurate or imprecise. The associated value is usable as an estimated result.
UJ - The chemical or parameter was analyzed for, but was not detected above the level of the associated
value. The associated value is an estimated sample quantitation limit and may be inaccurate or
imprecise. The value is usable as a nondetect value with an estimated detection level.
R - The value (result) is rejected due to significant errors or QA/QC exceedance(s). The result is not usable
for project objectives.
T A M S/Cadm us/G rad ien t
-------
KM!
5?
ITi
f-
(g)
e
o
B
00
c
©
I
v>
V)
©
I
x;
0£
*5
80
60
40
20
For the regression line: slopc=0.8636 and r =~0.97S
Legend:
* Upper Hudson Flow Averaged Composites
v Upper Hudson Transects
+ Lower Hudson
• Tributaries
Regression Line
95% Confidence Interval About the Data
20
40 60 80
Wei ght-Loss-on-Ignition (a) 450"C (%)
100
120
Source; TAMS/Gradient Database TAMS/Cadmus/Cradieni
Figure C-l
Weigh t-Loss-On-Ignition Comparison for Water Column Samples 375°C vs. 450°C
-------
Note:
For the repression line: slope=0.611
and r=~0,936.
Upper Hudson Sediments
Regression l.inc
Weight Loss on Ignition at 375°C (%)
Source: TAMS/Gradient Database TAMS/Cadmus/Gradient
Figure C-2
Comparison Between Weight Loss on Ignition at 375°C
and Total Organic Carbon for Upper Hudson High Resolution Core Sediments
------- |