EPA/540/R-92/079a
July 1993
Technology Evaluation Report
SITE Program Demonstration
Resources Conservation Company
Basic Extractive Sludge Treatment (B.E.S.T.®)
Grand Calumet River, Gary, Indiana
Volume I
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
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ABSTRACT
A Superfund Innovative Technology Evaluation (SITE) demonstration of Resources Conservation
Company's Basic Extractive Sludge Treatment (B.E.S.T.®) Process was conducted between July 1 and
July 22, 1992 in Gary, Indiana. The pilot demonstration was part of an intra-agency cooperative
effort. The other agencies involved in preparing for and conducting the demonstration included the
U.S. EPA Great Lakes National Program Office (GLNPO); the U.S. Army Corps of Engineers (COE),
Chicago District; and the U.S. EPA Region V. The GLNPO through the COE in cooperaton with Region
V arranged for the developer's services and the location where the pilot demonstration occurred. The
B.E.S.T.® Process is a patented solvent extraction system that uses triethylamine at different
temperatures to separate (extract) organic contaminants from soils, sludges, and sediments. The
organics are concentrated in an oil phase, thereby reducing the volume of wastes which require further
treatment.
The demonstration consisted of two separate tests conducted at pilot scale. The material
tested consisted of bottom sediments collected from two distinct transect locations within the Grand
Calumet River in Gary, Indiana. The total volumes of sediment collected from each location were
individually and thoroughly mixed to form two homogenous test sediment types. The test sediments
were designated Sediment A and Sediment B. A total of five test runs for each sediment type were
conducted, three of which were under optimized conditions. Samples of the untreated sediments,
product solids, product water, and product oil were collected and analyzed at a minimum for total
polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and oil and grease (O&G).
The product solids, product water, and product oil were analyzed for residual solvent (triethylamine).
Results of the demonstration tests were reported as averages of the three optimum runs.
Sediment A contained 41 percent moisture; 6,900 mg/kg O&G; 550 mg/kg PAHs; and 12 mg/kg PCBs.
The process removed greater than 98 percent of the O&G, 96 percent of the PAHs and greater than
99 percent of the PCBs. Sediment B contained 64 percent moisture; 127,000 mg/kg O&G; 71,000
mg/kg PAHs; and 430 mg/kg PCBs. The process removed greater than 98 percent of the O&G and
greater than 99 percent of the PAHs and PCBs. The residual solvent in the product solids, product
water, and product oil (Sediment B) was 103 mg/kg, less than 1 mg/L, and 733 mg/kg, respectively.
Product oil was not generated from Sediment A feed due to its low O&G content; however, residual
solvent in Sediment A product solids and product water was 45 mg/kg and less than 2 mg/L,
respectively.
iv
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ACKNOWLEDGMENTS
This report was prepared under the direction and coordination of Mark Meckes, Superfund
Innovative Technology Evaluation (SITE) Program Project Manager, U.S. Environmental Protection
Agency (EPA), Office of Research and Development, Risk Reduction Engineering Laboratory (RREL),
Cincinnati, Ohio. Contributors and reviewers for this report were Michelle Simon and Dennis
Timberlake of EPA RREL; Steve Garbaciak of EPA's Great Lakes National Program Office, Linda Diez
of the U.S. Army Corps of Engineers, Chicago District; and Lanny Weimer, George Jones, and Dale
Owen of Resources Conservation Company (RCC). George Jones served as the RCC Project Manager
and Dale Owen served as the RCC Field Site Manager. Ron Kovach of EPA's Region V Water Division
provided insight into sample collection points along the Grand Calumet River.
This report was prepared for EPA's SITE Program by Science Applications International
Corporation (SAIC), Cincinnati, Ohio for the EPA under Contract No. 68-C0-0048. Thomas Wagner
served as the Work Assignment Manager. Authors include Joseph Tillman, Lauren Drees, and Thomas
Wagner. Laboratory analyses were conducted by Maxwell/S-Cubed Division in San Diego, California;
SAIC in San Diego, California; Triangle Laboratories in Durham, North Carolina; Commercial Testing
in South Holland, Illinois; and IT Air Quality Services in Cincinnati, Ohio.
xi
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NOTICE
This material has been funded wholly or in part by the United States Environmental Protection
Agency {EPA) under contract 68-C0-0048 to SAIC. This document has been subjected to the
Agency's peer and administrative review, and it has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
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FOREWORD
The Superfund Innovative Technology Evaluation (SITE) program was authorized in the 1986
Superfund Amendments and Reauthorization Act. The program is a joint effort between EPA's Office
of Research and Development (ORD) and Office of Solid Waste and Emergency Response, The purpose
of the program is to assist the development of hazardous waste treatment technologies necessary to
implement new cleanup standards that require greater reliance on permanent remedies. This is
accomplished through technology demonstrations that are designed to provide engineering and cost
data on selected technologies.
This project consists of an evaluation of the Resources Conservation Company Basic Extractive
Sludge Treatment (B.E.S.T.®) Process and was part of an intra-agency cooperative effort. The other
agencies involved in preparing for and conducting the demonstration included the U.S. EPA Great Lakes
National Program Office (GLNPO); the U.S. Army Corps of Engineers (COE), Chicago District; and the
U.S. EPA Region V, The GLNPO through the COE in cooperation with Region V arranged for the
developer's services and the location where the pilot demonstration occurred. The SITE Demonstration
took place adjacent to the Grand Calumet River (GCR) in Gary, Indiana. The B.E.S.T.® Process was
performed on river bottom sediments collected from two distinct transect locations within the GCR's
east branch. The sediments contained variable concentration levels of organic compounds including
polynuclear aromatic hydrocarbons, polychlorinated biphenyls, and oil and grease. The demonstration
effort was directed at obtaining information on the performance and cost of the process for use at
other sites. Documentation consists of two reports. This Technology Evaluation Report is contained
in two volumes and describes the field activities and laboratory results. Cost estimates are included
in an Applications Analysis Report.
Additional copies of this report will be available only from the National Technical Information
Service, 5285 Port Royal Road, Springfield, VA 22161, (800) 553-6847 (Order No. xxxx-xxx/xx; Cost:
$xx.xx, subject to change). Reference copies will be available at EPA libraries in the Hazardous Waste
Collection. To inquire about the availability of other SITE reports, call ORD Publications at (513) 569-
7562 in Cincinnati, Ohio. To obtain information regarding the SITE Program and other projects within
SITE, please telephone (513) 569-7696.
E. Timothy Oppelt
Risk Reduction Engineering Laboratory
U.S. Environmental Protection Agency
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CONTENTS
Pace
Notice . ii
Foreword iii
Abstract iv
Figures vii
Tables viii
Abbreviations x
Acknowledgments xi
1.0 Executive Summary 1-1
2.0 Introduction 2-1
2.1 SITE Program Objectives 2-1
2.2 Project Background 2-2
2.3 Experimental Design 2-3
3.0 Process Design 3-1
3.1 Process Introduction 3-1
3.2 Process Description 3-2
3.3 Process Equipment 3-8
4.0 Demonstration Site Description 4-1
4.1 Site Location and History 4-1
4.2 Demonstration Sample Collection Locations 4-2
4.3 Demonstration Test Area 4-3
5.0 Field Activities 5-1
5.1 Prescreening and Homogenization of Feed 5-1
5.2 Bench-Scale Treatability Tests 5-4
5.3 Pilot-Scale Demonstration Tests 5-5
v
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CONTENTS (continued)
Paoe
6.0 Sampling and Analytical Program 6-1
6.1 Introduction 6-1
6.2 Sampling Locations 6-1
6.3 Sampling Procedures 6-3
6.4 Analytical Methods and Physical Tests 6-7
7.0 Performance and Data Evaluation 7-1
7.1 Introduction 7-1
7.2 PAH Removal 7-2
7.3 PCB Removal 7-9
7.4 Oil and Grease Removal 7-9
7.5 Triethylamine Residual Testing - Treated Solids, Product Water
and Oil Phases 7-11
7.6 Triethylamine Air Emissions Testing - Vent Gas 7-13
7.7 Triethylamine Biodegradation Testing - Treated Solids 7-14
7.8 Organic Analyses of Product Water, Recovered Solvent, and Product Oil .... 7-17
7.9 Moisture Contents - Raw Feed and Treated Solids 7-20
7.10 Effects on Metals 7-21
7.11 Supplemental Analyses 7-24
7.12 Mass Balance Determinations 7-31
8.0 Conclusions 8-1
8.1 Removal of Organic Compounds 8-1
8.2 Triethylamine Residual in Products 8-7
8.3 Mass Balance 8-9
8.4 Other Conclusions 8-9
9.0 Quality Assurance/Quality Control 9-1
9.1 Introduction 9-1
9.2 Procedures Used for Assessing Data Quality 9-2
9.3 Analytical Quality Control 9-5
9.4 Audit Findings 9-31
9.5 Modifications to and Deviations from the QAPP 9-35
9.6 Special Studies 9-36
9.7 Field QC Samples 9-38
9.8 Sample Holding Times 9-40
9.9 Conclusions and Limitations of the Data 9-43
10.0 References 10-1
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FIGURES
Number Page
2-1 Experimental Design Flow Diagram 2-3
3-1 Generalized Diagram of the B.E.S.T.® Solvent Extraction Process 3-3
3-2 Solvent Recovery Process 3-4
3-3 Solids Drying Process 3-6
3-4 Solvent Recovery from Water by Stripping 3-7
3-5 Photograph of the RCC B.E.S.T.® Pilot Plant 3-9
3-6 Schematic of the RCC B.E.S.T.® Pilot Plant Identifying Most of Primary Equipment . . 3-10
4-1 Regional Location Map 4-1
4-2 Sediment Collection Locations - East Branch of the Grand Calumet River 4-3
4-3 Demonstration Test Area 4-5
5-1 Flow Diagram Showing Sediment Preparation Sequence 5-3
6-1 Solid and Liquid Sample Locations 6-4
6-2 Vent Gas Sampling Setup 6-5
8-1 PAH Contaminant Removal - Sediment A 8-4
8-2 PAH Contaminant Removal - Sediment B 8-4
8-3 PCB Contaminant Removal - Sediment A 8-6
8-4 PCB Contaminant Removal - Sediment B 8-6
8-5 O&G Contaminant Removal - Sediment A 8-8
8-6 O&G Contaminant Removal - Sediment B 8-8
8-7 Triethylamine Biodegradability 8-10
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TABLES
Number Pace
5-1 Chronology of Field-Related Activities Conducted for the RCC B.E.S.T.®
SITE Demonstration 5-2
5-2 Extraction Sequence Used for Sediment A 5-8
5-3 Extraction Sequence Used for Sediment B 5-8
5-4 Solvent and Feed Volumes Used - Sediment A 5-10
5-5 Solvent and Feed Volumes Used - Sediment B 5-11
5-6 Solids Drying Temperatures - Sediments A and B 5-12
5-7 Water Stripping and Oil Polishing Temperatures 5-13
6-1 Summary of Analyses Conducted for the RCC B.E.S.T.® SITE Demonstration .... 6-2
6-2 Specific PAHs Analyzed for the RCC B.E.S.T.® SITE Demonstration 6-3
7-1 PAH Concentrations in Sediment A Feed 7-3
7-2 PAH Concentrations in Sediment A Treated Solids 7-4
7-3 PAH Concentrations in Sediment B Feed 7-5
7-4 PAH Concentrations in Sediment B Treated Solids 7-6
7-5 PAH Removal Efficiencies 7-7
7-6 PCB Concentrations and Removal Efficiencies —
Sediment A and B Feeds and Treated Solids 7-10
7-7 Oil and Grease Concentrations and Removal Efficiencies -
Sediment A and B Feeds and Treated Solids 7-11
7-8 Triethylamine Concentrations - Sediment A and B Treated Solids,
Product Water, and Oil Phases . 7-12
7-9 Triethylamine Concentrations - Sediment A and B Vent Gas 7-15
7-10 Triethylamine Biodegradability in Treated Solids 7-17
7-11 PAH, PCB, and Oil and Grease Analysis of Product Water 7-18
7-12 PAH and PCB Analysis of Recovered Solvent 7-18
7-13 PAH and PCB Analysis of Sediment B Product Oil 7-19
7-14 Moisture Contents - Sediment A and B Feeds and Treated Solids 7-21
7-15 Total Metals in Test Sediments 7-22
7-16 Leachable Metals in Test Sediments 7-23
7-17 Supplemental Analyses Results - Sediment A and B Feeds and Treated Solids .... 7-25
7-18 PCB Congener Analysis Results (Method 680) - Sediment A and B Feeds
and Treated Solids 7-26
7-19 Particle Size Analysis Results - Sediment A and B Feeds and Treated Solids 7-26
7-20 Supplemental Analyses Results - Sediments A and B Product Water 7-28
7-21 Total Metals in Product Water 7-29
7-22 Supplemental Analyses Results - Oil/Solvent Mixture and Product Oil 7-30
7-23 PAH and PCB Concentrations in Oil/Solvent Mixtures 7-31
7-24 Supplemental Analyses Results - Sediment B Feed Decant Water 7-32
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TABLES {Continued}
Number
Page
7-25
Mass Balances - Sediment A inputs
7-33
7-26
Mass Balances - Sediment A Outputs
.... 7-34
7-27
Mass Balances - Sediment B Inputs
.... 7-35
7-28
Mass Balances - Sediment B Outputs
.... 7-36
7-29
Mass Balance Summaries
7-37
8-1
Summary of Conclusions - B.E.S.T.® SITE Demonstration
8-2
8-2
Comparison of Organic Analyses (SITE and RCC)
8-3
9-1
PAH Surrogate Recoveries for Sediment A
9-6
9-2
PAH Surrogate Recoveries for Sediment B
9-7
9-3
PAH MS/MSD/MST Results for A21 -US-004
9-10
9-4
PAH MS/MSD/MST Results for A21-TS-004
9-11
9-5
PAH MS/MSD/MST Results for A22-WP-005
9-11
9-6
PAH MS/MSD/MST Results for A21-OP-004
9-11
9-7
PAH MS/MSD/MST Results for A21-RS-003
9-12
9-8
PAH MS/MSD/MST Results for B22-US-010
.... 9-12
9-9
PAH MS/MSD/MST Results for B22-TS-010
. . . . 9-12
9-10
PAH MS/MSD/MST Results for B22-WP-010
9-13
9-11
PAH MS/MSD/MST Results for B22-OP-010E
9-13
9-12
PAH MS/MSD/MST Results for B22-RS-010
9-13
9-13
LCS Recoveries - Sediment A
9-14
9-14
LCS Recoveries - Sediment B
9-14
9-15
PCB Surrogate Recoveries
9-16
9-16
PCB MS/MSD/MST Results for Sediment A
9-19
9-17
PCB MS/MSD/MST Results for Sediment B
9-19
9-18
PCB LCS Recoveries
9-20
9-19
EPA Oil and Grease Replicate Results
9-22
9-20
B.E.S.T.® Oil and Grease Replicate Results
9-22
9-21
Oil and Grease LCS Recoveries
9-23
9-22
TCLP Metals MS/MSD/MST Results for A21-US-004
9-24
9-23
TCLP Metals MS/MSD/MST Results for A21-TS-004
9-25
9-24
TCLP Metals MS/MSD/MST Results for B22-US-010
9-25
9-25
TCLP Metals MS/MSD/MST Results for B22-TS-010
9-26
9-26
Metal LCS Recoveries
9-26
9-27
Moisture Matrix Triplicate Results
9-27
9-28
Triethylamine MS/MSD/MST Results
9-28
9-29
TRPH MS/MSD Results for B13-TS-008
. . . . 9-29
9-30
Method 680 Internal Standard Recoveries
. . . . 9-31
9-31
Triethylamine Method Performance Data
9-36
9-32
Triethylamine Holding Time Study
9-37
9-33
Biodegradation Results
. . . . 9-38
9-34
PAH, PCB, O&G, and TSS Results for Analyses of Field QC Samples
9-39
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ABBREVIATIONS
AAR Applications Analysis Report O&G
AOC Area of Concern ORD
ASTM American Society for Testing and
Materials OSWER
B.E.S.T.® Basic Extractive Sludge Treatment
BOD biochemical oxygen demand PAHs
BOP basic oxygen process
Btu British thermal unit PCBs
CFR Code of Federal Regulations PPE
COE U.S. Army Corps of Engineers ppm
CWA Clean Water Act QAPP
DFTPP decafluorotriphenylphosphine QC
DOT Department of Transportation RCC
EZ Exclusion Zone RCRA
EPA U.S. Environmental Protection
Agency RSD
GC/ECD gas chromatograph/electron SAIC
capture detector
GC/FID gas chromatography SARA
flame ionization detector
GC/MS gas chromatography/ SITE
mass spectroscopy
GCR Grand Calumet River SW-846
GLNPO Great Lakes National Program
Office
GPC gel permeation chromatography TCMX
IDEM Indiana Department of TCLP
Environmental Management
IHC Indiana Harbor Canal TDS
LCSs laboratory control samples TER
mg/kg milligrams per kilogram TIC
mg/L milligrams per liter TOC
mg/m3 milligrams per cubic meter TRPH
mL/min milliliters per minute
MS matrix spike TSCA
MSD matrix spike duplicate TSR
MST matrix spike triplicate TSS
NIOSH National Institute for Occupational
Safety and Health
NPDES National Pollutant Discharge
Elimination System
oil and grease
Office of Research and
Development
Office of Solid Waste and
Emergency Response
polynuclear aromatic
hydrocarbons
polychlorinated biphenyls
personal protective equipment
parts per million
Quality Assurance Project Plan
Quality Control
Resources Conservation Company
Resource Conservation and
Recovery Act
relative standard deviation
Science Applications International
Corporation
Superfund Amendments and
Reauthorization Act
Superfund Innovative Technology
Evaluation
solid waste publication 846 -
Test Methods for Evaluating
Solid Wastes
tetrachloro-m-xylene
Toxicity Characteristic Leaching
Procedure
total dissolved solids
Technology Evaluation Report
total inorganic carbon
total organic carbon
total recoverable petroleum
hydrocarbons
Toxic Substances Control Act
Technical Systems Review
total suspended solids
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SECTION 1
EXECUTIVE SUMMARY
This report summarizes the activities and results of the pilot-scale demonstration testing of the
Resources Conservation Company (RCC) Basic Extractive Sludge Treatment (B.E.S.T.®). The
demonstration tests were conducted between July 1 and July 22, 1992 at a central location adjacent
to the Grand Calumet River (GCR) in Gary, Indiana. The material treated during the tests was river
bottom sediment contaminated with organic compounds and heavy metals.
The B.E.S.T.® Process is a solvent extraction system that separates organic contaminants from
sludges, soils, and sediments. The primary distinguishing feature of the process is the extracting
agent, triethylamine, used to separate the contaminated material into its oil, water, and solids fractions.
Organic contaminants in the material concentrate in the oil fraction after separation.
Triethylamine, which is produced by reacting ethyl alcohol with ammonia, has the property of
inverse miscibility. At temperatures below 60°F triethylamine is miscible with water; however, above
60°F the solvent is only slightly miscible with water. Therefore, by utilizing a combination of
extractions conducted at different temperatures, solids can be initially dewatered at a cold temperature
while oil containing organic contaminants is simultaneously solvated. The remaining organic
contaminants can be extracted subsequently using warm and hot extractions.
The material treated during the demonstration was collected from two separate transect
locations from along the GCR. The locations were chosen to acquire one sediment type having
relatively high metal concentrations with relatively low organic content (GCR-Transect 28), and a
second sediment type having relatively high levels of organic contaminants such as polynuclear
aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and oil and grease (O&G) (GCR-
Transect 6). Prior to the demonstration, the total volume of sediments collected from each location
were separately prescreened and thoroughly mixed to form two homogeneous test sediment types.
The mixture originating from Transect 28 was designated Sediment A. The mixture originating from
Transect 6 was designated Sediment B. Both test sediments were subjected to bench-scale treatability
1-1
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testing. Results of the bench-scale tests, which were conducted by RCC, provided initial operating
conditions, such as feed loading volumes, number of extraction cycles, and settling times.
The demonstration consisted of two separate tests, one for each sediment type. Each test
consisted of two phases: Phase I involved determination of optimum process variables from the results
of three runs, and Phase II consisted of two additional runs at the determined optimum conditions (for
a total of three optimum runs), For each of the five test runs for each sediment type, samples of the
untreated sediments, product solids, product water, and product oil were collected and analyzed at a
minimum for total PAHs, PCBs, and O&G. The product solids, product water, and product oil were
also analyzed for residual solvent (triethylamine).
Results of both tests are reported as an average of three optimum runs. Sediment A contained
41 percent moisture; 6,900 mg/kg O&G, 550 mg/kg PAHs; and 12 mg/kg PCBs. The B.E.S.T.®
Process removed greater than 98 percent of the O&G, 96 percent of the PAHs, and greater than 99
percent of the PCBs. Sediment B contained 64 percent moisture; 127,000 mg/kg O&G; 71,000 mg/kg
PAHs; and 430 mg/kg PCBs. The process removed greater than 98 percent of the O&G, and greater
than 99 percent of the PAHs and PCBs. Product oil was not generated from Sediment A feed due to
its low O&G content; however, residual solvent in Sediment A product solids and product water was
45 mg/kg and less than 1 mg/L, respectively. The residual solvent in the product solids, product
water, and product oil in Sediment B was 103 mg/kg, less than 2 mg/L, and 733 mg/kg, respectively.
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SECTION 2
INTRODUCTION
2.1 SITE PROGRAM OBJECTIVES
In response to the Superfund Amendments and Reauthorization Act (SARA) of 1986, the U.S.
Environmental Protection Agency (EPA) established a formal program called the Superfund Innovative
Technology Evaluation (SITE) Program. The SITE Program was established to accelerate the
development, demonstration, and implementation of innovative technologies at hazardous waste sites
across the country. There are four parts to the SITE Program:
• To identify and, where possible, to remove impediments to the development and
commercial use of alternative technologies
• To conduct a demonstration program for the more promising innovative technologies to
establish reliable performance and cost information for site characterization and cleanup
decision-making
• To develop procedures and policies that encourage the selection of available alternative
treatment remedies at Superfund sites
• To structure a development program that nurtures emerging technologies
The objective of the first part of the program is to identify and evaluate these impediments and
remove them or design methods to promote expanded use of alternative technologies. The second
part, the demonstration portion of the SITE Program, is a significant ongoing effort involving the Office
of Research and Development (ORD), the Office of Solid Waste and Emergency Response (OSWER),
EPA Regions, and the private sector. The demonstrations will provide Superfund decision-makers with
the information necessary to evaluate the use of these technologies in future cleanup actions. The
third part of the SITE Program focuses on establishing methods for selecting treatment technologies
for Superfund sites from the expanding range of available remedies, including these innovative
technologies. Finally, the SITE Program provides a means of assisting in the development of emerging
technologies.
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2.2 PROJECT BACKGROUND
SITE demonstrations are initially conceived when EPA solicits and evaluates proposals from
technology developers to demonstrate their innovative technologies. Resources Conservation Company
(RCC) of Bellevue, Washington submitted a proposal for its B.E.S.T.® technology to demonstrate the
potential effectiveness of its process at pilot scale. The RCC B.E.S.T.® Process is claimed by the
developer to separate organic compounds from sludges, soils, and sediments effectively, isolating the
organics in the oil phase, thus, reducing the volume of wastes requiring further treatment.
The RCC B.E.S.T.® pilot-scale demonstration was unique in that the SITE Program was part of
an intra-agency cooperative effort. The other agencies involved in preparing for and conducting the
demonstration included EPA's Great Lakes National Program Office {GLNPO); the U.S. Army Corps of
Engineers (COE), Chicago District; and EPA Region V. GLNPO arranged for the developer's services
and the location where the demonstration occurred through the COE in cooperation with Region V .
The location of the demonstration, the Grand Calumet River (GCR), was of mutual interest to
the cooperative parties. GLNPO leads efforts to carry out the provisions of Section 118 of the Clean
Water Act (CWA). Under Section 118(c)(3) of the CWA, GLNPO is responsible for undertaking a 5-
year study and demonstration program for assessment and remediation of contaminated sediments.
The Chicago District COE has authorization by the way of the Rivers and Harbors Act of 1910 to
maintain harbor channels by periodic dredging. This includes the federal channel at Indiana Harbor,
downstream of the GCR. EPA has designated the bottom sediments as moderately polluted, heavily
polluted, and toxic. As a result, materials to be dredged from the Indiana Harbor and Canal are not
suitable for open-water disposal in Lake Michigan. At the present time, an environmentally acceptable
disposal facility for dredged materials from Indiana Harbor does not exist. Consequently, dredging to
maintain adequate navigation depths has not been conducted at this harbor since 1972.
The demonstration took place between July 1 and July 22, 1992 at a central location
immediately adjacent to the GCR in Gary, Indiana. The material treated during the demonstration was
river bottom sediment collected from two separate transect locations along the GCR. Both sediment
types contained organic contaminants, including oil and grease (O&G), polynuclear aromatic
hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs).
The goals of the demonstration test were to:
• Assess the ability of the B.E.S.T.® solvent extraction technology to remove organic
contaminants present in two types of bottom sediments having contrasting levels of the
same organic contaminants
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• Assess the quality of the treated solids, the residual product water, and the concentrated
oil/contaminant product
• Develop capital and operating costs for the technology that can be readily used in the
Superfund decision-making process
• Provide an overall mass balance for organic contaminants around the B.E.S.T.® pilot plant
for the feedstocks processed
• Evaluate the technology's potential beneficial effect on the metals found in the sediments
by changing chemical compounds to less toxic or leachable forms
• Assess the biodegradation of residual triethylamine in product solids.
2.3 EXPERIMENTAL DESIGN
The purpose of an experimental design is to ensure that a logical sequence of events leading
up to and including the demonstration is followed. This will result in a scientifically sound technical
evaluation of a technology's effectiveness. For this SITE demonstration, a specific sequence of
predemonstration and demonstration activities were conducted to achieve the technical evaluation.
Figure 2-1 shows the sequence of events leading up to the demonstration. Because the
primary goal of the SITE demonstration was to evaluate the B.E.S.T.® technology on two sediments
having different contaminants or contrasting concentration levels of the same contaminants,
preliminary sediment characterization was conducted. The purpose of the sediment characterization
was to;
• Qualitatively determine sediment composition so that both critical and non-critical
parameters could be identified in the project Quality Assurance Project Plan (QAPP)
• Determine certain analytical sample preparation aspects of the sediments (i.e., spiking
levels) to aid data quality
• Determine solids-to-water ratio so that a sufficient volume of each sediment would be
collected to provide enough solids for processing during the demonstration
Collection of
River Test
Material
Prescreening and
Homogenization
of Test Material
Demonstration
Tests
River Sediment
Characterization
Sampling
Bench-Scale
Treatability Tests
Figure 2-1. Experimental design flow diagram.
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Results of the sediment characterization analyses aided in selecting the analytes for the
demonstration. These results also helped in designating certain analyses and measurements as critical
in respect to other parameters deemed non-critical. This was necessary for finalizing the experimental
design as stated in the QAPP. In order to achieve the project objectives, the following measurements
were identified as critical:
• PAHs and PCBs in all solid and liquid process streams
• O&G in the feed material, treated solids, and water phase. (O&G was identified as critical
because oil is a process residual)
• Triethylamine in the treated solids, water phase, oil phase, and vent emissions
• Moisture in the feed material and treated solids
• Toxicity Characteristic Leaching Procedure (TCLP) metals in the feed material and treated
solids
• Masses of feeds (including steam and caustic) and treated residuals (solids, oil, water, and
recovered solvent)
Approximately 10 days before the start of the demonstration, the test sediments were collected
from the same specific river transect locations from which the sediment characterization samples had
been collected. Sediments were collected by driving hollow aluminum tubes approximately 5 feet into
the soft river bottom sediment and emptying the cores into 5-gallon buckets. Sediment collection was
immediately followed by prescreening of oversize material and homogenization (mixing) of each
sediment type separately. This step was conducted prior to bench-scale treatability testing to ensure
that the bench-scale tests and pilot-scale (demonstration) tests utilized the same prescreened and
homogeneous feed material.
Representative samples from the demonstration test feed inventory were sent to the developer
for bench-scale testing. The results of the tests were used to establish the initial operating conditions
for the pilot-scale testing.
After determination of initial operating conditions, the actual demonstration testing was
initiated. Two tests were conducted, one for each sediment type. A two-phase approach was used
for each of the tests.
2-4
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• Phase I of each test involved the determination of optimum process variables for that
particular sediment type. The processes which were varied included number of extraction
cycles, mixing times, and extraction temperature. Three sets of conditions, as determined
by the developer, were tested,
• Phase II of each test consisted of two additional test runs at the determined optimum
conditions. This yielded a total of three optimal runs for each sediment, the purpose being
to demonstrate process reproducibility.
2-5
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SECTION 3
PROCESS DESIGN
3.1 PROCESS INTRODUCTION
The RCC pilot B.E.S.T,® technology is a mobile batch solvent extraction process designed to
remove organic contaminants from soils, sludges, or sediments. The B.E.S.T.® Process is distinguished
from other solvent extraction and related soil washing systems by the use of triethylamine as the
extraction agent. Triethylamine is an aliphatic amine that is produced by reacting ethyl alcohol with
ammonia. The geometry of the triethylamine molecule is tetrahedral. A nitrogen atom is at the center
of a three-sided pyramid; the four points of the structure are occupied by three ethyl functional groups
and one electron cloud. This structure gives triethylamine the dual polarity which is responsible for
its unique properties.
The property that is key to the success of triethylamine extraction is the property of inverse
miscibility. At temperatures below 60°F, triethylamine is miscible with water (i.e., triethylamine and
water are each soluble in the other). Above this temperature, triethylamine and water are only partially
miscible. This physical property can be exploited by using cold triethylamine (i.e., chilled below 60°F)
to solvate oil and water simultaneously.
The B.E.S.T.® Process utilizes the physical property of inverse miscibility by mixing the
feedstock with chilled triethylamine solvent to create a single-phase extraction liquid. This liquid is a
homogenous solution of triethylamine and the water present in the feedstock. This solution solvates
the organic contaminants (such as oils) present in the feedstock and enables the triethylamine to
achieve intimate contact with solutes at nearly ambient temperatures and pressures. This allows the
B.E.S.T.® Process to maintain efficient extraction when handling feed mixtures with high water
content. Therefore, by utilizing solvent chilled below 60°F, solids can be dewatered while organic
contaminants are simultaneously extracted. Afterwards the remaining organic contaminants can be
removed at temperatures above 60°F.
3-1
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In addition to inverse miscibility, characteristics that enhance triethylamine's use in a solvent
extraction system include the following:
• A high vapor pressure (therefore the solvent can be recovered from the extract by way
of simple steam stripping)
• Formation of a low-boiling azeotrope with water (therefore the solvent can be recovered
from the extract to very low residual levels)
• A heat of vaporization one-seventh of water (therefore, solvent can be recovered from the
treated solids by simple heat with a very low energy input)
• Triethylamine is alkaline (pH = 10); therefore, some heavy metals can be converted to the
hydroxide form, which precipitate and exit the process with the treated solids
3.2 PROCESS DESCRIPTION
The B.E.S.T.® pilot plant is a solvent extraction system, the main purpose of which is to
demonstrate the effectiveness of the B.E.S.T.® Process design. It enables onsite testing to be
performed at a pilot scale. There are four basic operations involved in the system: extraction, solvent
recovery and oil polishing, solids drying, and water stripping. The extraction operation for materials
having relatively high water content is additionally broken down into two types of extraction cycles.
The initial primary extraction cycles are termed "cold extractions"; secondary extractions are termed
"warm" and "hot extractions" depending on the temperature range at which they are conducted. Cold,
warm, and hot extractions were implemented during this demonstration because the river sediments
treated had high water contents (in excess of 40 percent by weight).
The four basic operations of the B.E.S.T.® pilot system are discussed in detail in the following
subsections. The extraction, solids drying, solvent recovery, and water stripping operations overlapped
during the demonstration to increase the efficiency of processing the high-moisture-content sediments.
Oil polishing was only conducted at the end of a test when a sufficient volume of oil had been
accumulated.
3.2.1 Extraction
The B.E.S.T.® extraction process is illustrated in Figure 3-1. Primary cold extraction cycles are
conducted on high-water-content materials (i.e., sludges) and take place in a Premix Tank. The
feedstock and a predetermined quantity of caustic (per bench-scale tests) are added first to the Premix
Tank. The tank is purged with nitrogen gas to remove combustible levels of oxygen. Chilled solvent
is then added to the tank. Usually 10 gallons of feed material and 30 gallons of chilled solvent are
3-2
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used. The caustic, a 50 percent sodium hydroxide solution, elevates the pH of the solution so that the
triethylamine remains in its molecular form. The higher pH thus maintains the solvent's extractive
ability. The feedstock/chilled solvent solution is mixed for 5 to 30 minutes in the Premix Tank by a
paddle impeller within the tank. This mixing is followed by a settling period. The minimum settling
time is established during the preliminary bench-scale testing conducted in the developer's laboratory.
After the majority of solids are settled, the triethylamine/water/oil solution is decanted through decant
ports and transferred to a centrifuge that separates any fine solids remaining in the solution.
Primary Extraction/
D« watering
Filter
Cake
ondary Extraction/
Solids Drying
Solvent Separation
Solvent Recovery
Solvent
Evaporator
Extractor/Dryer
Oil Product
Clean
Solvent
Solvent
Decanter
Water
Stripper
Clean SoMs
Product
Cold Wash Solvent
Water
Receiver
Water Product
Figure 3-1. Generalized diagram of the B.E.S.T.• solvent extraction process (Source: RCC).
This cold extraction cycle process of: (1) filling; (2) mixing; (3) settling; and (4) decanting can
be repeated for high water content feeds before subsequent extractions at higher temperatures are
conducted. The process is repeated in order to accumulate enough solids in the Premix Tank before
dewatered solids are transferred to the Extractor/Dryer vessel for subsequent higher temperature
extractions. The desired solids volume for the dryer to achieve efficient drying following the final
extraction is approximately 8 gallons. Additional batches of feed can be added and processed through
cold extraction cycles until a sufficient volume of dewatered solids remains in the Premix Tank after
the decanting. At this point, all of the dewatered solids can be pumped from the Premix Tank to the
Extractor/Dryer vessel for higher temperature extractions. The fine solids that had been separated from
3-3
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the decant solution in the centrifuge are accumulated in a solids chute. These fines are added to the
larger mass of solids in the Extractor/Dryer, thus accounting for nearly all of the solids originally loaded
into the system as feedstock. The centrate portion of the decant is pumped through a filter and into
a Solvent Evaporator tank.
At the start of the warm and hot extraction cycles, the Extractor/Dryer is filled with solvent
and is heated to temperatures of up to 170°F. The mixture is agitated for 5 to 15 minutes and is then
allowed to settle. The triethylamine/water/oil solution is decanted and sent to the Premix Tank which
also serves as a holding tank on the pilot plant. The decanted liquid is centrifuged and the centrate
is routed to the Solvent Evaporator. The centrifuge solids are collected in the solids chute. As in the
cold extraction cycles process; (1) filling; (2) mixing; (3} settling; and (4) decanting can be repeated
at warm, then hot temperatures. The total number of extraction cycles required for each feedstock
processed during the demonstration was predetermined by the treatability test results and the initial
pilot plant runs. During pilot unit testing, RCC normally conducts one more extraction cycle than the
estimated number of extraction cycles predicted from a bench-scale treatability test model. This extra
extraction is performed solely as a contingency.
3.2.2 Solvent Recovery and Oil Polishing
Solvent recovery is illustrated in Figure 3-2. The triethylamine/oil/water solution is routed to
the Solvent Evaporator where it is heated to its boiling point. Further heating evaporates an azeotrope
of solvent and water, leaving the oil behind. This evaporation process continues until the water is
depleted. At that point, the temperature of the boiling liquid rises until it reaches the boiling point of
pure triethylamine.
Optional Path for Water
Azeotrope Vapor
Main Condenser
Centrate
To Water
Stripper
Water
Receiver
Tank
m, Tempered
Water
MS—-Control
Solvent
Decanter
Solvent
Evaporator
Decanter
Water
To Solvent Storage Tank
Mixing/Polishing
Loop
Figure 3-2. Solvent recovery process (Source: RCC).
3-4
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Evaporation continues at the higher temperature until nearly all of the water or solvent is
removed. The triethylamine/water vapor from the Solvent Evaporator is condensed in heat exchangers
that use cooling water at about 100°F. The resulting condensed vapor forms a heterogeneous
condensate consisting of a solvent phase and a heavier water phase at a temperature of about 110°F.
This mixture is directed to the Solvent Decanter, where the water and solvent phases are separated
by decanting. The Solvent Decanter is maintained at about 100°F so that the water and triethylamine
are only partially miscible. The lighter solvent phase contains about 2 percent water; the heavier water
phase contains about 2 percent solvent.
For the demonstration, a rectifier (an added distillation stage) was installed to limit the
carryover of semivolatile compounds from the evaporator into the recycled solvent. Reflux of recycled
solvent to the rectifier could be adjusted to provide the necessary knockdown of semivolatiles.
The recovered solvent is recycled to the Solvent Storage Tank. The recovered water drains
by gravity into the water storage tank where it is stored until water stripping operations are performed.
Ultimately the water is steam stripped in the water stripper column to remove residual triethylamine.
When oil polishing was possible during the demonstration it was also conducted in the Solvent
Evaporator. This process was initiated following completion of all test runs performed on specific test
sediments. The contents of the Solvent Evaporator were further heated until virtually all the
triethylamine was gone. Then most of the residual solvent was liberated by injecting a small amount
of water into the oil. The water forms an azeotrope with residual solvent which might otherwise never
have been dislodged from the oil. By concentrating the oil further by means of the polishing step, the
volume of hazardous material requiring further treatment is further reduced.
In some cases, the amount of oil available in the Solvent Evaporator is not enough to warrant
oil polishing. This was the case when treating Sediment A during the demonstration, which contained
less than 1 percent O&G. In this instance the oil was left in solution with the solvent and water.
3.2.3 Solids Drvino
Solids drying is illustrated in Figure 3-3. Drying of solids is conducted in the Extractor/Dryer;
the same vessel used for conducting warm and hot extraction cycles. The Extractor/Dryer is equipped
with a steam jacket and direct steam injection ports. To dry the solids, steam is first supplied only to
the steam jacket to heat the Extractor/Dryer and its contents indirectly to about 170°F. After the bulk
3-5
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of the solvent is removed by decantation and indirect heating, steam is injected directly into the vessel
to reduce the triethylamine to less than 1000 mg/kg. The entire drying process is aided by rotating
paddle impellers within the Extractor/Dryer, This mixing increases heat transfer and reduces the drying
time required (proper heat transfer and mixing occurs when the vessel is about one-quarter full). The
triethylamine and direct steam form an azeotrope which is directed to a dryer condenser. After all the
triethylamine is removed, the temperature of the vapor rises to the boiling point of water. Drying
continues past this point for a short time to ensure that residual triethylamine is removed. The steam
condensate left in the solids from the injection of live steam leaves about 5 percent water content by
weight in the solids which keeps the solids from being too dusty. After the drying process is complete,
product solids are removed through a discharge port on the bottom of the Extractor/Dryer and are
collected in a lined receptacle.
Steam & Solvent
Extractor/
Dryer
Jacket
Dry
Condensate Soilds
Return
Jacket
Steam
-Direct Steam
Premix
Solvent
Decanter
Dryer
Condenser
Recycled
Solvent
Centrifuge
-n^_Tempered
Water
^0-*-Control
Water
/
Water
N
Receiver
N
Tank
J
To Solvent Storage Tank
Figure 3-3. Solids drying process {Source: RCC).
The vapor which had been directed to the dryer condenser during the drying cycle is
condensed. The condensate drains into the Premix Tank. The triethylamine/water mixture, and any
carryover dust, are directed to the centrifuge to remove solids. The centrate is then pumped through
the centrate filter and into the Solvent Evaporator and combined with the triethylamine/oil/water
solution already present there.
3-6
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3.2.4 Water Stripping
Solvent recovery from the water stream by stripping is illustrated in Figure 3-4. Decanted
water in the water receiver tank contains about 2 percent triethylamine by weight. This triethylamine
is removed from the water by direct-contact-steam stripping. This steam stripping process is aided by
adding a predetermined amount of caustic solution (50 percent NaOH) to the water receiver tank and
thoroughly mixing the solution to raise the pH of the triethylamine/water mixture. This ensures that
the triethylamine is in the more volatile molecular form rather than in the ionized form.
When the desired pH is achieved, steam is injected directly into the bottom of the vertical
steam stripping column. When the column is heated to the desired temperature, feed water is pumped
through a feed preheater and heated to slightly above the solvent/water azeotropic boiling point. This
hot feedwater enters the top of the column at a rate of approximately 500 mL/min. The feedwater
runs at a constant rate to the column's top tray, then down to all lower trays where it is stripped of
residual solvent by upflowing steam. Water stripper bottoms are returned to the water receiver tank
during startup. When steady state is reached, the water stripper bottoms return can be rerouted and
discharged as product water. The solvent azeotrope vapors generated are directed to the water
stripper condenser and the recovered solvent is recycled into the system for reuse in extractions.
Solvent Azeotrope
Water Stripper
Condenser
Water
Stripper
Water
Preheater
Caustic
Recycled
Solvent
Direct
Steam
Water
Receiver
Tank
Solvent
Decanter
Mixing Pump
Water
Stripped
Product
Water
To Solvent Storage Tank
Bottoms Return
Figure 3-4. Solvent recovery from water by stripping {Source: RCC).
3-7
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3.3 PROCESS EQUIPMENT
The main purpose of the B.E.S.T.® mobile pilot plant is to demonstrate the effectiveness of the
B.E.S.T.® Process design. By using scaled-down versions of actual equipment components, the mobile
pilot plant enables onsite testing to be performed at a pilot scale.
The pilot plant consists of two portable skids which are mounted on a lowboy trailer {8 feet
x 45 feet) on which the unit is transported. The process skid (20 feet x 8 feet) has two levels and
contains most of the B.E.S.T® Process equipment including the Premix Tank, the Extractor/Dryer, the
Solvent Evaporator, the Centrifuge, storage tanks, pumps, and heat exchangers. A second smaller
utility skid (10 feet x 8 feet) contains several utility systems to support the operation of the process
skid. The utility skid includes a refrigeration unit and a tempered cooling water system. Power
requirements for the pilot plant are 480 volts, three-phase power at 225 amps, which is accessed from
a main power source (i.e., electrical drop) by an electrical distribution panel supplied by RCC. A
support trailer accompanies the pilot plant, transporting ancillary equipment and providing a storage
and working facility during testing.
A photograph of the pilot plant showing most of the primary components is presented as Figure
3-5. A schematic of the unit clearly identifying these components is presented in Figure 3-6. Brief
descriptions of each primary component are provided in the subsections that follow.
3.3.1 Feed Hoooer
The Feed Hopper is the device used for adding feedstock and caustic to the Premix Tank at the
beginning of a test (batch). The hopper has a capacity of 12 gallons and is attached to the top of the
Premix Tank. The device is equipped with an inlet seal and an outlet valve which leads to the Premix
Tank. Feed is loaded into the top of the Feed Hopper by opening the seal on top and pouring in the
feed. The top seal is then shut and the bottom valve opened, allowing the feed to drop into the Premix
Tank. The hopper method of adding feed minimizes the release of solvent vapor during loading.
3-8
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v-/>
co
CO
MMil
Figure 3-5, Photograph of the RCC B.E.S.T." Pilot Plant.
-------
A. PremixTank E. Solvent Evaporator (jacketed) I. Treated Solids Receptacle M. Primary Carbon Filter Q. Radiator/Radiator Fan
B. Extractor/Dryer (jacketed) F. Water Receiver Tank J. Polished Oil Collection Tap N. Backup Carbon Filter R. Non Contact Water Tanks
C. Solvent Decanter G. Process Monitors (face opposite side of unit) K. Centrifuge O. Vent S. Refrigeration Units
D. Solvent Storage Tank H. Oil Decanter (not used during demonstration) L Water Stripper Column P. Decant Pump (on opposite side of unit)
Figure 3-6. Schematic of the RCC B.E.S.T.® Pilot Plant
identifying most of primary equipment.
-------
3.3.2 Premix Tank
The Premix Tank is where initial cold extractions are conducted to separate water and oil from
solids when treating materials with high oil and/or water content. The Premix Tank is a wide upright
cylinder with a total capacity of approximately 60 gallons. Within the tank, along the cylindrical axis,
there is a rotating shaft with mixing paddles attached and a bottom scraper. There are also cooling
coils on the inside wall where chilled triethylamine is constantly recirculated to maintain the tank
contents below 60°F. On the outside of the tank there are two decant ports on the side wall and a
suction valve at the tank's bottom for transferring the solids/solvent mixture to the Extractor/Dryer.
3-3.3 Extractor/Dryer
The Extractor/Dryer vessel, as the Premix Tank, is also used for conducting extractions. It is
additionally used for drying of solids. This cylindrical vessel is a commercially available batch blender
with a 34-gallon capacity. All extractions take place in this vessel when treating solids with low oil
and/or water content. When treating solids having high oil and/or water content (as was the case in
this demonstration) the Extractor/Dryer is where the secondary warm and hot extractions are
conducted on sludges and sediments that have first been dewatered in the Premix Tank. The
Extractor/Dryer is equipped with horizontally aligned mixing blades and is surrounded on the outside
by a steam jacket. Steam injected into the jacket provides heat during solids drying and removal of
residual triethylamine. Proper heat transfer and mixing are conducive to best drying results, and occur
when the Extractor/Dryer vessel is one-quarter full (8 gallons) of solids at the completion of the drying
step.
3.3.4 Solvent Evaporator
The Solvent Evaporator is used in the solvent recovery and oil polishing processes. Within this
tank the solvent/water azeotrope formed during heating is evaporated from the oil. Inside the Solvent
Evaporator tank there are coils of stainless steel tubing through which steam is circulated to supply
heat to the tank contents. At the bottom of the tank a recirculation loop maintains the contents as
a homogeneous mixture. All vapors that leave the top of the Solvent Evaporator pass through a set
of condensers overhead, which condense the solvent/water mixture before it is transferred to the
Solvent Decanter.
3-11
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3.3.5 Solvent Decanter
The Solvent Decanter is a relatively small cylindrical tank where condensed solvent/water
vapors are received from the Solvent Evaporator. Within this tank, triethylamine solvent and water are
separated from one another since they are no longer miscible at their elevated temperatures. The
triethylamine is routed to the Solvent Storage Tank (directly beneath the Solvent Decanter) for eventual
reuse in the extraction process. The water is directed to the Water Receiver Tank.
3.3.6 Solvent Storage Tank
The Solvent Storage Tank is a large cylindrical vessel {capacity of approximately 75 gallons)
that serves as the surge volume of triethylamine for the entire pilot plant. Triethylamine is initially
loaded into the tank and can be pumped to the Premix Tank and Extractor/Dryer for extractions.
Recycled triethylamine is returned to the Solvent Storage Tank from the Solvent Decanter.
3.3.7 Water Receiver Tank
The Water Receiver Tank is a stainless-steel barrel-shaped vessel having a capacity of
approximately 50 gallons. This tank receives water that has been separated from solvent in the
Solvent Decanter and serves as the storage vessel for all contact water used in the B.E.S.T.® treatment
process. The tank is equipped with a pump to keep the water recirculating within the tank.
3.3.8 Refrigeration System
The Refrigeration System consists of several components located on the utility skid and is used
to cool the triethylamine solvent that is continuously circulated throughout the pilot plant. Components
include a compressor hermetically sealed within a stainless-stee! box, a condenser, a noncontact
cooling water storage tank, and a thermostatically controlled fan-type radiator that serves as a heat
exchanger.
3.3.9 Water Stripping Column
The Water Stripping Column is used to remove residual triethylamine and other volatiles from
product water. As water is being recirculated by the water stripping pump, it is heated in a heat
exchanger with steam and injected at the top of the stripping column. As water flows down through
the system of baffles within the column, steam injected at the bottom of the column rises up through
the column to remove volatiles in the water.
3-12
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The stripped water is collected in a container at the bottom of the column and is transferred
to a 55-gailon drum for disposal. The solvent and other volatile vapors received at the top of the
column are routed to the vent system, condensed, and returned to the extraction system,
3.3.10 Vent System
There is an atmospheric vent discharge from the B.E.S.T.® pilot plant to eliminate
noncondensible gases from the various condenser systems in order to prevent reduction of heat
transfer efficiency. Normally this vent gas consists primarily of nitrogen purge gas, with traces of
oxygen and other atmospheric gases. Solvent gases present are normally condensed by the
refrigerated vent condenser. However, to ensure that all organic vapors, including the solvent
triethylamine, are recovered with an efficiency of 95 percent or greater in accordance with 40 CFR
Section 61.242-11, an activated carbon adsorber is installed on the vent outlet system. This primary
carbon canister is monitored daily by Draeger tubes; however, a secondary smaller carbon canister is
operated in series in case breakthrough of the primary canister occurs.
3-13
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SECTION 4
DEMONSTRATION SITE DESCRIPTION
4.1 SITE LOCATION AND HISTORY
The GCR is part of a large river and waterway system located in the heavily industrialized areas
of northwest Indiana and south Greater Chicago. The GCR drains approximately 77 square miles of
Lake and Porter counties in northwest Indiana and discharges into Lake Michigan by way of the Indiana
Harbor and Indiana Harbor Canal (IHC). Figure 4-1 is a regional map showing the demonstration
location in respect to other features such as the GCR, Indiana Harbor, and Lake Michigan. Major
industries along the GCR waterway system in northwest Indiana include primarily steel and
petrochemical facilities.
3 Miles
Chicago
North
Indiana
Harbor
Lake Michigan
INDIANA
ILLINOIS
Indiana Harbor
Canal
Sediment B
SITE Demo
Grand Calumet River
Sediment A Gary, IN
Figure 4-1. Regional location map.
4-1
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The sediments treated during this demonstration were collected from the East Branch of the
GCR. This East Branch flows westward from the city of Gary in a much-channelized course. The GCR
system is fed primarily by municipal and industrial wastewater {up to 90 percent of its flow) and a
fairly rapid current is produced by these discharges along several outfalls throughout the river's course.
Flow is diverted due north by way of the IHC which discharges into Lake Michigan at East Chicago.
The GCR and IHC have a long history of water quality problems and have been identified by
the International Joint Commission on the Great Lakes together as an Area of Concern (AOC). The
GCR AOC boundary includes most of the GCR, the IHC, and near the shore of Lake Michigan in Lake
County, Indiana. There have been at least ten major sediment sampling studies directed to GCR/IHC
including those conducted by EPA Region V, the Indiana Department of Environmental Management
(IDEM) and the U.S. Army Corps of Engineers (COE), Chicago District. From these studies the COE
has estimated that there are 3.5 to 4 million cubic yards of contaminated sediments within the AOC
as a whole and 1.4 million cubic yards of contaminated sediments in the East Branch of the GCR.
Contaminants in the GCR AOC include metals; organic compounds such as PAHs, PCBs, and phenols;
and inorganics such as cyanide.
4.2 DEMONSTRATION SAMPLE COLLECTION LOCATIONS
The primary objective of this SITE demonstration was to evaluate the effectiveness of the
B.E.S.T.® solvent extraction technology on two sediment feeds having different contaminants or
contrasting concentration levels of the same contaminants. Therefore, the sediments treated were
collected at two different transect locations along the East Branch of the GCR. Since river sediments
can be highly mobile, it was necessary to confirm the presence and approximate concentrations of
contaminants in the GCR at the same transect locations where the demonstration feedstock would be
collected and characterized. Sediments collected from Transect 28 were designated Sediment A and
those sediments collected from Transect 6 were designated Sediment B.
The transect locations, shown in Figure 4-2 are approximately 2 miles apart. The sediment A
(Transect 28) location was chosen to acquire a sample having relatively high concentrations of metals
and low organic concentration relative to sediments upstream. The Sediment A sample location is
slightly downstream of the National Pollutant Discharge Elimination System (NPDES) Outfall 030 which
receives wastewater from an oil-skimmed settling lagoon. Wastewater from primary bar plate mills and
basic oxygen process (BOP) shops are reported to discharge at Outfall 030 (COE, March 1991). The
Sediment B (Transect 6) location is slightly downstream of NPDES Outfall 010. Wastewater from a
4-2
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coke plant is discharged upstream, thus this location was expected to yield sediment samples having
relatively high levels of petroleum-based contaminants (i.e., O&G and PAHs) but low levels of metals.
°!
V
2,
3,
4, MILES
0 11
i
i 4
51
61 KILOMETERS
EXPLANATION
O Industrial effluent outfall
0 Municipal effluent outfall
Direction of flow
Sediment B
(Transect 6)
Collection Location for
Sediment A
(Transect 28)
LAKEiMICHIGAN
GARY
SITE
DEMO
Gft4N[> CALUMET
Gary Wastewater Treatment
Plant (GWTP)
IND EAST-WEST
Figure 4-2. Sediment collection locations - East Branch of the Grand Calumet River.
4.3 DEMONSTRATION TEST AREA
The demonstration took place at an unused portion of a paved parking lot located immediately
adjacent to the GCR, between the two sediment collection locations. Access to the site was from
Buchanan Street, which runs north from downtown Gary towards Lake Michigan. Buchanan Street is
west of Broadway (the main street in Gary).
Collection Location for
4-3
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Figure 4-3 shows the actual demonstration test layout. Because the demonstration site was
relatively small (approximately 290 feet long and 112 feet wide at the widest point) and already had
permanent fencing enclosing all but the west side, good site security and control were easily
established. A temporary fence was erected to clearly delineate areas that were off-limits to
unauthorized personnel.
The demonstration test area was basically subdivided into five zones; the Exclusion Zone {EZ},
Support Zone, Feed Staging area, Visitor area. Support Zone and Decontamination Corridor. Brief
discussions of each of these zones are presented in the following subsections.
4.3.1 Exclusion Zone
The EZ was a restricted area where the contaminated river sediments were stored, handled,
and treated. Therefore the EZ had the highest risk of exposure. The EZ barrier extended a minimum
of 50 feet away from the pilot plant and was delineated by permanent fencing on three sides and a
temporary fence where permanent fencing was absent {Figure 4-3). The EZ was essential for fire
safety and to exclude unauthorized personnel. Included within the zone were the metal roll-off box
used to store the untreated sediments during the demonstration, the pilot plant, and drums of both
product triethylamine and residual material generated from the tests (which were stored on pallets
located within the bermed containment area).
4.3.2 Feed Staging Area
The Feed Staging Area was unique in that it was set up specifically for remixing untreated
sediment prior to loading into the pilot plant. The rationale for this remixing is presented in Subsection
6.3, Sampling Procedures. Because an electrical drill was used for the remixing, the Feed Staging Area
was placed outside the 50-foot perimeter around the pilot plant. This was to prevent the drill from
posing a threat of igniting the flammable triethylamine solvent used in the pilot plant. This Feed
Staging Area was therefore a special portion of the EZ located outside of the 50-foot perimeter
(Figure 4-3).
4.3.3 Visitor Area
The Visitor Area (unshaded area on Figure 4-3) was north of the Support Zone and west of the
EZ. This area was accessible to the general public during Visitor's Day and to other guests throughout
the demonstration. From this area the pilot plant and related operations were easily observed. "Show
samples," displayed inside the Support Zone, provided visitors with close-up viewing.
4-4
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Tank for Steam
Condensate/Containment
Area Rainwater (5000 gal.)
Water Tank
(5,000 gal.>_^ r J
EXCLUSION ZONE
ffSSNNM
SUPPORT ZQNe
BsrnKKf Cematnmom Are#
Bolt-otf-Box
(Fwxf Storage)
Pilot Unit
RCC Support Tracer
Pump House
Electrical Sediment Feed
Distribution Staging Area
480 Volt
Electrical
Power Drop
Legend
Temporary Fence
Chain Link Fence
Grand Ca umet River
with Barbed Wire
Chain Link Fence
Permanent Steel Posts
Bumper from Old
Parking Lot
Scale (ft)
I
Ol
512A
Figure 4-3. Demonstration test area
-------
4.3.4 Support Zone
The Support Zone was a restricted area where samples of the untreated sediment, product
solids, product water, and concentrated oil fraction were prepared for shipment to analytical
laboratories. This zone was accessed to and from the EZ by a decontamination corridor which served
as a transition zone to prevent contaminated clothing and equipment from entering the Support Zone.
4.3.5 Decontamination Corridor
The Decontamination Corridor was a restricted area that provided a transition zone between
the EZ and Support Zones, All personnel authorized to enter the EZ put on personal protective
equipment (PRE) in the Decontamination Corridor before entering the EZ and decontaminated or
discarded PPE in this zone when leaving the EZ.
Included within the Decontamination Corridor were wash basins for decontaminating outer
protective boots, a cabinet to store reusable PPE, and a drum for discarding contaminated PPE.
4-6
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SECTION 5
FIELD ACTIVITIES
Field activities regarding this SITE demonstration began prior to the actual demonstration tests
and consisted primarily of feed preparation, an important precursor for obtaining a scientifically sound
evaluation of the B.E.S.T.® Process. Feed preparation consisted of sample collection and transport to
the demonstration test area, prescreening and homogenization of feed, and bench-scale treatability
testing. Sample collection was conducted by COE's contractors; prescreening and homogenization
were performed by SITE'S contractor; treatability testing was conducted by the developer, RCC. Table
5-1 is a chronology of all field-related activities prior to and during the demonstration.
Figure 5-1 illustrates the sequence used in preparing the feed material for the demonstration
tests. Prescreening/homogenization and bench-scale treatability testing are described in the following
subsections and are followed by discussions of the field activities performed during the demonstration
testing.
5.1 PRESCREENING AND HOMOGENIZATION OF FEED
Prescreening and homogenization were two preliminary activities performed prior to the actual
demonstration tests. These activities occurred on June 16 and 17, 1992 in coordination with receipt
of the river bottom sediment from COE's contractor. The purpose of the prescreening was to separate
any oversize material in the sediment which could interfere with pilot plant operation.
The largest particle size the pilot unit can process is approximately 1/4 inch in diameter;
however, screening of smaller particle sizes is preferred so that wear and tear on certain components
is minimized. Therefore, it was decided to screen out all material ^ 1/8 inch diameter. The developer
(RCC) provided SITE with a Kason Separator, an electrical vibrating instrument equipped with a 118
inch sieving screen. A lined staging area was set up at the Demonstration Test location and each of
the two sediment types were screened individually by pouring the material into the top of the Kason
separator 1 bucket at a time. The mass of feed screened was recorded by weighing the buckets
before and after loading. As step 2 in Figure 5-1 illustrates, the oversized reject was directed to a
5-1
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container at one side of the separator and the screened feed material was directed into a large trough
on the opposite side of the separator.
TABLE 5-1. CHRONOLOGY OF FIELD-RELATED ACTIVITIES CONDUCTED FOR
THE RCC B.E.S.T.® SITE DEMONSTRATION
Date
Event
Parties Involved
April 14
Sediment characterization sampling
SITE
June 15
Transect 28 (Sediment A) collection
COE
June 16
Sediment A Screening/homogenization
Transect 6 (Sediment B) collection
SITE
COE
June 17
Sediment B Screening/homogenization
SITE
June 18
Pilot Unit shipped from Bellevue, Washington
RCC
June 23
Pilot Unit arrived in Gary, Indiana
RCC
June 23
RCC setup crew arrived onsite
RCC
June 24
Mechanical and electrical hookup of unit began
RCC
June 25
System checkout began/bench-scale testing initiated
RCC
June 26
Pilot unit loaded with solvent
RCC
June 29
System checkout completed
RCC
July 1
Sediment A testing started
RCC, SITE
July 7
Visitors' Day
GLNPO, COE,
RCC, SITE
July 9
Completed testing on Sediment A
RCC, SITE
July 10
Pilot unit decontamination completed and Sediment B
testing started
RCC,SITE
July 21
Completed testing on Sediment B
RCC, SITE
July 23
Final pilot unit decontamination started
RCC
July 25
Pilot unit decontamination completed, demobilization
started
RCC
July 27
Pilot unit demobilization completed
RCC
July 28
Pilot unit departed from Gary, Indiana
RCC
August 3
Pilot unit arrived in Bellevue, Washington
RCC
5-2
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1
aSSS
River sediments collected
from GCR stored in
5-gallon containers
220-gallon
lined trough
Feed
Screened
Feed
Oversize
Kason
Separator
Sediments prescreened
mechanically to remove
material >1/8" diameter
3
Homogenization of
sediments via
industrial mixer
4
Four gallons of homogenized sediment
(feed) sent to developer for bench-
scale treatability testing
START DEMONSTRATION
Figure 5-1. Flow diagram showing sediment preparation sequence.
5-3
-------
A total of 1806 pounds of Transect 28 sediment were wet screened. Of this total only 14
pounds (approximately 0.8 percent) of the material were rejected. A total of 1461 pounds of Transect
6 sediment were wet screened. Of this total, only about 8% pounds (approximately 0.6 percent) of
the material were rejected. The rejected oversized material was placed in a DOT-approved drum for
disposal.
After prescreening was completed each sediment type was separately homogenized as
illustrated in Step 3 of Figure 5-1. To accomplish a thorough mixing the entire contents of each of the
screened sediment types were collected in separate 220-gallon troughs. An industrial mixer was
mounted on a wooden support that rested on the trough walls and was moved along the entire length
of the trough. After each sediment type was thoroughly mixed, the material was transferred back into
the original 5-gallon metal containers and put into storage until completion of bench-scale testing.
These containers were then retrieved upon initiation of the demonstration tests.
The purpose of the homogenization was to ensure that the entire volume of screened sediment
collected for each of the two transect locations was consistent in sediment type, water content, and
contaminant concentration. Each sediment type was therefore formed into a discrete sample that
would be consistent during bench-scale treatability testing and during each test run of the
demonstration. Designations of Sediment A (Transect 28) and Sediment B (Transect 6) were assigned
to each feed mixture to simplify sample identification and reporting requirements and to coincide with
the order of treatment. Both of these sediment types were later analyzed by laboratory sieving for
physical characterization. This data is presented in the Performance and Data Evaluation section of
this report (Section 7, Table 7-19).
5.2 BENCH-SCALE TREATABILITY TESTS
Bench-scale treatability testing of both sediment types was conducted by RCC at its laboratory
in Bellevue, Washington just prior to the demonstration. The purpose of the treatability testing was
to provide guidelines for the operation of the pilot unit for each of the two sediment types. To
effectively simulate the B.E.S.T.® pilot-scale process on a smaller bench-scale, RCC utilizes laboratory
equipment resembling the pilot plant components. For instance, a resin kettle is used as an extraction
vessel. This is immersed in a cooling bath for cold extractions and in a heated bath for warm and hot
extractions. Graduations that correspond to decant port levels on the Premix Tank or Extractor/Dryer
vessel are marked on the kettle, depending on the type of extraction being simulated. An air-driven
prop is placed in the kettle to mix feed material and a floor mounted centrifuge is employed to remove
5-4
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fines from the decant following extractions. A forced-draft oven is used to dry product solids.
The data collected included settling data, compositional data, pH data, and soil agglomeration
observations. Settling data were collected to predict the level to which the material would settle in
the pilot unit and the amount of time required to reach that level. Compositional information was
compiled by the RCC lab in Bellevue and was used to determine the amount of material to load per
batch. The pH data were used as a basis for the addition of caustic with the feed during pilot testing.
Observations such as centrifugation performance and soil agglomeration helped the pilot plant operator
recognize discrepancies from normal occurrences during pilot testing.
5.3 PILOT-SCALE DEMONSTRATION TESTS
5.3.1 Unit Setup
During the bench-scale testing, the pilot plant was mobilized to the demonstration test area for
preparation. The SITE contractor provided a secure storage facility (locking metal roll-off box) for the
feed material and constructed a bermed containment area for the pilot plant. RCC personnel
supervised or conducted all phases of the pilot unit setup and operation. The setup phase was
considered complete when all process components had been installed as a complete unit and each
piece of equipment had been operated on an individual basis. This phase took 2 days.
The B.E.S.T.® pilot plant was first positioned over the bermed containment pad and leveled.
All components removed for shipping were assembled and all connections were made. Utilities were
then connected and tested. Unit checkout began after it was determined that all equipment had been
properly installed. After all functions had been individually tested, solvent was loaded into the unit for
complete checkout, which took 1 day. Both setup and checkout were conducted in conjunction with
the support trailer setup.
5.3.2 Feed Preparation and Loading
There were a total of five separate test runs or batches conducted for each sediment type.
The goal in loading the sediment feed material was to load enough so that after completion of the
drying step the Extractor/Dryer vessel would be one-quarter full (8 gallons).
Approximately 5 buckets of one sediment type would be retrieved from the storage area.
Before representative samples of the untreated feed could be collected, separated floating phases had
to be mixed back in with solids that had settled while the buckets were in storage. The separated
5-5
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water and oil were reincorporated with the solids by mixing the bucket contents with a stainless-steel
dry wall mud mixer rotated by a variable speed drill. Mixing was conducted with a lid fixed on top of
each bucket to minimize splattering of the slurry-type material. (The mixer was inserted through a hole
drilled in the center of the metal lid).
After each bucket was mixed, an equal volume of sample was taken from each, except for the
last bucket from which a proportional amount of the smaller volume used was collected. These aliquot
samples were composited in a stainless-steel pail. Each bucket was then individually weighed on a
platform scale (the scale had been checked for accuracy with a 100 pound check weight prior to use).
Once the desired volumes of sediments were loaded incrementally into the pilot unit, the emptied
buckets were reweighed to acquire the mass of sediment treated in the unit. This measurement was
critical for subsequent mass balance determinations.
Loading of feed was conducted entirely by RCC. The buckets were individually carried to the
upper level of the process skid where a stainless steel chute was fitted over a large diameter pipe (Feed
Hopper) connected to the Premix Tank. The Feed Hopper has an inlet seal and an outlet valve which
leads to the Premix Tank. The feed was loaded into the top of the Feed Hopper by opening the seal
on top and pouring in the feed. The top seal was then shut and the bottom valve was opened,
allowing the feed to drop into the Premix Tank. This hopper method of adding feed minimized the
release of solvent vapor during loading.
Level C PPE was worn by RCC personnel as buckets were emptied into the chute. For the
treatment of Sediment A, there was only one incremental feed loading for each of the five runs. A
total of 813% pounds of Sediment A feed were loaded for an average of approximately 162 % pounds
per run. For treatment of Sediment B, there were three to four incremental feed loadings per test run
due to an increased number of extraction cycles. A total of 907% pounds of Sediment B feed were
loaded during the test; between 40 and 69 pounds of sediment were loaded at any one time.
5.3.3 Pilot-Scale Testing
After initial feed was added, the triethylamine solvent was added by opening the Premix Tank
solvent fill valve and pumping clean, cold solvent from the Solvent Storage Tank into the Premix Tank.
The Premix Tank was filled with solvent until full (the 55-gaIlon level) and the contents were mixed
for 5 minutes. After mixing, the contents of the Premix Tank were allowed to settle. The liquid
triethylamine/oil/water mixture was then drained off the top. This made room for another incremental
5-6
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portion of the feed to be added, along with caustic arid solvent. This procedure was repeated until the
entire feed load had been added to the Premix Tank. After decanting all the liquid, the concentrated
solids remaining in the bottom of the Premix Tank were pumped into the Extractor/Dryer vessel for
further extractions. All of the extractions conducted in the Premix Tank were performed cold
(preferably below the temperature where water and triethylamine are miscible). All of the subsequent
extractions conducted in the Extractor/Dryer vessel were performed at elevated temperatures (greater
than 90°F). Because most of the water had already been removed during the cold extractions, it was
no longer necessary to continue operating in the cold temperature range.
Before testing of a batch began, RCC assembled a list of primary control parameters. Many
of the potentially manipulated variables were changed during testing. Most changes in variables
occurred during the first three runs comprising the Phase I testing because Phase I of the pilot scale
testing was specifically designated for process optimization. RCC used these initial runs to adjust
process parameters and obtain the best treatment efficiency for both sediment types. These changes
were most evident in: the number of extraction cycles conducted, extraction temperatures, and
sequence of extraction cycles conducted.
Table 5-2 presents the sequence of extraction cycles conducted on Sediment A for each of the
five runs, including the total number of extractions conducted and the temperature at which each was
conducted. Table 5-3 presents the same information for Sediment B testing. As indicated in the
tables, the optimum conditions chosen for each sediment type were significantly different.
During testing of each batch, RCC recorded other process operation information required for
mass balance determinations. Most of the information was corroborated by SITE and included volumes
of sodium hydroxide (caustic) added to the Premix Tank, Water Stripper Column, and Extractor/Dryer
vessel; volumes of solvent and water used for extractions; and the volume of water used for steam
generation. The volume of caustic added during a test was determined by incrementally pouring the
solution from a graduated cylinder into the desired vessel (usually 50 ml at a time). Solvent and water
volumes were determined by visually monitoring tank levels that are equipped with sight glass gauges.
The water added to the Water Stripper Column was measured by monitoring the pressure drop across
an orifice in the steam line.
Following testing of each batch, the process product streams (treated solids, product water,
and product oil) had their masses determined by weighing the contained products on a platform scale;
just as was done with the feed.
5-7
-------
TABLE 5-2. EXTRACTION SEQUENCE USED FOR SEDIMENT A
EXTRACTION TEMPERATURE (°F)
Extraction
Cycle
Run 1
PHASE I
Run 2
1
2
3
4
5
cold (62)
warm (106)
warm (95)
warm (95)
warm (103) warm (125)
cold (50)
cold (40) ;;
cold (38) warm (100) "
warm (98) |||||j|ii||:ii
hot (170)
hot (160)
hot (160)
Note: Shaded columns indicate the three optimum runs.
PHASE II
;:i. .V.". ¦... i..| .......i;;. y jl; jji;....,.,............
cold 1481
"I hr
hot (163)
TABLE 5-3. EXTRACTION SEQUENCE USED FOR SEDIMENT B
EXTRACTION TEMPERATURE (°F)
Extraction
Cycle
Run 1
PHASE I
¦111111
Run 2
Run 3
1A 1
1A 2
1A 3
1B 1
1B 2
1B 3
2
3
4
5
cold (49)
cold (47)
(NC)
cold (41)
cold (53)
cold (52)
hot (145)
hot (152)
hot (161)
hot (148)
hot (157)
hot (143)
llllillpll cold (32)
III
cold (40)
cold (40)
cold (29)
lliilli c°id <38»
fllBll cold (46)
hot (151)
hot (150)
hot (152)
hot (151)
1111IIIII hot (146)
hot (150)
MM
PHASE II
Run 4
Rurt 5
cold (28)
cold (48)
cold (39)
cold (51)
cold (53)
cold (46)
hot (147)
hot (156)
hot (170)
hot (155)
hot (158)
cold (51)
cold (41)
cold (39)
cold 139)
cold (45)
. cold (44)
hot (146)
hot (160)
hot (153)
hot (154)
hot (152)
Notes:
Shaded columns indicate the three optimum runs.
Because of the high moisture content of Sediment B, both sediment and solvent were fed to the Premix Tank in
portions to limit the temperature rise of the solvent/water phase due to the heat of the solution to an acceptable
level. Table 5-5 details the incremental additions of feed and solvent for Sediment B treatment.
NC = Not Conducted
5-8
-------
An example of how optimum Phase II conditions were chosen from Phase I testing is explained
as follows. The best conditions chosen for treating Sediment A were two initial cold extractions below
60°F followed by one warm, three hot, and a warm extraction (for a total of seven extractions). A
primary factor contributing to large variation in extraction temperatures when treating Sediment A was
the water content of the solids product.
Treated solids generated during Run 1 were wet and soupy. This was likely due to inadequate
dewatering accomplished by only conducting one cold wash at 62°F, a temperature near the
triethylamine-water miscibility threshold. When two cold extractions were conducted during Run 2 at
temperatures well below 60°F, the treated solids contained much less moisture, but were still wet
enough to form balls and clumps. Under the extraction scenario shown in Table 5-2 for Run 3 the
treated solids generated were essentially dry and were slightly cohesive, thus that extraction scenario
was run twice in Phase II Testing for Sediment A.
Tables 5-4 through 5-7 present additional process operation data recorded by the SITE field
crew during both demonstration tests. Tables 5-4 and 5-5 present the solvent and feed volumes added
for each extraction cycle of each run for treatment of Sediments A and B, respectively. Table 5-6
presents approximate drying times and temperatures recorded for both Sediment A and Sediment B
product solids. Table 5-7 presents the approximate temperatures at which product water was
separated during treatment of Sediments A and B and gives approximate temperature readings from
within the Solvent Evaporator tank during Sediment B oil polishing.
5.3.4 Decontamination
The B.E.S.T.® pilot plant is decontaminated by RCC after exposure to PCBs and other wastes,
prior to demobilization. Decontamination of the pilot plant was conducted twice at the test site. The
first decontamination occurred between sediment types. Sediment A (the lesser contaminated
sediment) was treated first; the pilot plant was decontaminated prior to testing Sediment B. The
second decontamination was conducted after treating Sediment B, which concluded the demonstration.
The decontamination procedure for the pilot plant complies with the PCB decontamination
requirements of 40 CFR 761.79. RCC conducted the decontamination of the system components;
however, both RCC and SITE collected samples to determine adequacy of the cleaning. The cleanup
is accomplished by pumping clean triethylamine through those portions of the pilot plant system that
contacted feed material. The tanks on the pilot plant, such as the Premix Tank and Extractor/Dryer
are filled with clean solvent via the same fill lines used in testing. Rinsing is repeated for thoroughness.
5-9
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Eventually the contaminants in the system, including PCBs, are flushed to the Solvent
Evaporator Tank. The contaminated triethylamine rinse is evaporated to a certain level and drained to
a barrel. About 6 gallons of clean triethylamine are added to the evaporator and recirculated through
its associated piping. Following the internal cleanout of the pilot plant, all the plant equipment external
surfaces are cleaned with a steam cleaner.
TABLE 5-4, SOLVENT AND FEED VOLUMES USED - SEDIMENT A
SOLVENT ADDED (gallons)
PHASE I I PHASE II
11111
Extraction
Cycle
Run 2
Total Feed
Volume (gal.)
Note: Shaded columns indicate the three optimum runs.
a The solvent and solid remaining after decantation in the Premix Tank are sufficient to fill the Extractor/Dryer,
5-10
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TABLE 5-5. SOLVENT AND FEED VOLUMES USED - SEDIMENT B
SOLVENT ADDED {gallons)/FEED ADDED (gallons)
Extraction
Cycle
PHASE I
Run 1
!".
lillilllll
¦f-xmt
Run 3
PHASE II
Run 4
Run 5
1A1
1A2
1A3°
1B1
1B2
1B3
2
3
4
5
6
7
Total Feed
Volume (gal.)
11111:1^:'::.
20
lllllitll
15
44/4.5
34/4 5
26/-
47/4.5
32/4.5
26A
0°
18
18
18
18
18
48/4.3
36/4 3
25/-
50/4.3
34 f4 3
27/-
o-
18
18
18
18
17
Note: Shaded columns indicate tha three optimum runs.
a Solvent transferred with solids from Premix Tank is used for first extraction in the Extractor/ Dryer,
b 2.4 gallons of decant water was removed from raw feed prior to loading.
c Following completion of cycle 1 A3, the contents of the Premix Tank was transferred to the Extractor/Dryer.
NC = Not Conducted
5-11
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TABLE 5-6. SOLIDS DRYING TEMPERATURES - SEDIMENTS A AND B
APPROX. TIME EXTRACTOR/DRYER AVG. TEMP. (°F)/
RUN NO. INTERVAL TEMPERATURE PROGRESSION (°F)* NO. OF READINGS
SEDIMENT A
Run 1
NOT AVAILABLE
Run 2
1 % hrs.
168,
170, 170, 186, 205, 213
185/6
Run 3
11/« hrs.
140,
170, 170, 168, 214
172/5
Run 4
40 min.
206,
180b
193/2
Run 5
11/2 hrs.
170,
192, 173, 218
188/4
SEDIMENT B
Run 1
1J4 hrs.
169,
168, 180, 213
183/4
Run 2
1 % hrs.
170,
170, 212
184/3
Run 3
1 hr.
168,
170, 184, 216
185/4
Run 4
% hr.c
176,
215
196/2
Run 5
1 % hrs.
167,
216, 196
193/3
Notes:
a A temperature progression is presented because the temperatures usually increase as drying continues with a big
increase of temperature to over 200°F when steam is added at the end of the drying cycle to remove the triethylamine
remaining in the solids.
b For Run 4, Sediment A, values were probably not recorded las an oversight) until just when steam was added;
therefore, the progression of 206"F to 180°F is likely indicating cooling down of the Extractor/ Dryer after steam
stripping.
c The Run 4 drying interval for Sediment B is believed to be incorrect due to insufficient record keeping.
5-12
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TABLE 5-7. WATER STRIPPING AND OIL POLISHING TEMPERATURES
APPROX. TIME AVG. TEMP. (°F)/
RUN NO. INTERVAL TEMP. RANGE <"F) NO. OF READINGS
SEDIMENT A
Run 1
NOT AVAILABLE
Run 2
3% hrs.
169 - 195
186/11
Run 3
3% hrs.
175 - 196
192/8
Run 4
1 '/* hrs.
187 - 190
189/5
Run 5
2% hrs.
177 - 197
189/6
SEDIMENT B
Run 1
2% hrs.
177 - 188
184/9
Run 2
2% hrs.
188 - 195
192/3
Run 3
% hr.
174 - 186
181/3
Run 4
3% hr.
170 - 191
184/3
Run 5
2Vz hrs.
171 - 189
183/5
SEDIMENT B Oil
Polishina
Run 5
3% hrs.
193 - 215
209/7
5-13
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SECTION 6
SAMPLING AND ANALYTICAL PROGRAM
6.1 INTRODUCTION
As part of the SITE demonstration, a sampling and analysis strategy was designed and
employed to evaluate the performance of the RCC B.E.S.T.® pilot plant. The sampling and analysis
program developed was based on the test objectives stated in Section 7.
Samples were collected and analyzed in accordance with a sampling plan specified in the
Demonstration Plan and Quality Assurance Project Plan (QAPP), Table 6-1 identifies the parameters
analyzed for each process stream and related media sampled during the demonstration. Table 6-2 lists
the specific compounds included in the PAH analysis. PAHs, PCBs, and O&G were critical analyses
for all media except for the vent gas. These organic contaminants were known to be present in both
sediment types and were the primary constituents targeted for removal by the B.E.S.T.® Process.
Triethylamine was a critical analysis for the three product streams and the vent emissions because of
its potential as a process residual. Moisture and TCLP metals analyses were critical measurements
because both Sediment A and B had high moisture contents and contained significant amounts of
heavy metals.
A few minor changes were made to the original sampling plan and are discussed in detail in
Subsection 9.5 of this report. The major deviation from the sampling plan was that no product oil
sample was collected from treatment of Sediment A. Sediment A contained less than 1 percent O&G;
consequently, not enough oil was produced to warrant oil polishing.
6.2 SAMPLING LOCATIONS
A minimum of six process streams were sampled and analyzed for each of the two tests
conducted during the demonstration. These included the following:
• Untreated sediments (raw feed)
• Product solids
• Product water
• Product oil or oil/solvent mix
• Recycled solvent
• Vent emissions
6-1
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TABLE 6-1. SUMMARY OF ANALYSES CONDUCTED FOR THE RCC B.E.S.T.® SITE DEMONSTRATION
Treated
Sediment
(Product Solids)
Untreated
Sediment
(Raw Feed)
Intermediate
Solvent/Oil
Mixture
Water Phase
(Product Water)
Decant Water
(from Raw Feed)
Oil Phase
(Product Oil)
Solvent Feed and
Recycled Solvent
Parameter
Critical
PAHs
Oil and Grease
Moisture
lAltffhM
Triethylamine
TCLP Metals3
Non-Critical
mmm
::::: : • ¦ <: 7 !\"
Proximate/Ultimate
isi ill
Total Metals4
TRPH
Volatile Solids
Total Cyanide
Reactive Cyanide
P
h'ih rrltivriVu
IHI IMMMMJ.'.M.M.'.; ¦*!
Reactive Sulfide
Particle Size
MiSi III
Total Phosphorus
I*
TOC/TIC
W* *K
Conductivity
Special Studies
Biodegradation
Specific PAH compounds analyzed for are presented in Table 6-2,
2 Moisture was critical for all samples except for the oil phase.
3 TCLP metals include As, Ba, Cd, Cr, Pb, Hg, Se, and Ag.
4 Total metals include Sb, As, Ba, Be, Cd, Cr, Cu, Mn, Hg, Ni, Se, Tl, Va, and Zn.
-------
TABLE 6-2. SPECIFIC PAHs ANALYZED FOR THE RCC B.E.S.T.® SITE DEMONSTRATION
PAHs
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo{b)fluoranthene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Chryserie
Dibenz{a,h)anthracene
Fluoranthene
Fluorene
lndeno(1,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
In addition to these standard process streams, decant water collected from buckets holding the
feed material was sampled from one of the Sediment B batches. This oily water phase was analyzed
to determine the quality of sediment water phase that would have to be treated separately if pre-
treatment decanting of sediments were to be considered an option. Each of the two lots of product
triethylamine was also sampled prior to use to determine its purity.
Figure 6-1 graphically shows the solid and liquid sampling locations which, except for the raw
feed, were located on or immediately adjacent to the pilot plant. Figure 6-2 diagrammatically shows
the vent gas sampling setup, which was located on the upper level of the RCC pilot plant process skid.
6.3 SAMPLING PROCEDURES
Generally speaking, samples were collected in accordance with the sampling plan described in
the Demonstration Plan and QAPP. The deviations from those plans are discussed in Subsection 9.5.
Each the process streams and product materials sampled is discussed briefly in the following
subsections.
6-3
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Untreated
Sediment
Primary Extraction/
Dewatering
Feed Buckets
Secondary Extraction/
Solids Drying
Triethylamine
Drum
Solvent Recovery
O)
i
if
Premix
Tank
M
Cold Wash Solvent
Solid
Sample
~quid
Sample
1
1~T
_L
Solvent
Evaporator
Extractor/Dryer
Clean
Solvent
T
Steam
Clean Solids
Product
Product
Solids
Product
IfTriethylamine
Solvent Storage
Solvent Separation
1®1
)=
Oil
Decanter
Centrifuge
Solvent
Makeup
Solvent
Solvent
Decanter
Water
Stripper
water
Receiver
Water
Product
Recycled
Triethylamine
Product
Oil
Figure 6-1. Solid and liquid sample locations.
-------
Flame
Arrestor
Exhaust at
Ambient Temperature
Pump
Rotometer
1 1/2 foot
Teflon Line
Dryer \J
Column |—
Elbow
Midget Bubbler
(Impinger)
Backup
Carbon
Scrubber ft DraegerTube
Test Point
Vapors from Pilot Plant
Water Stripper Column
Primary
Carbon Scrubber
Figure 6-2. Vent gas sampling setup.
6-5
-------
6.3.1 Untreated Sediments (Raw Feed)
The sediments collected at each transect were stored in 5-gallon buckets prior to treatment.
At the start of each test run a predetermined approximate volume of sediments that ranged between
four and five buckets was retrieved. Each bucket was individually and equally mixed to incorporate
separated oil and water phases back in with the solids. (The solids had settled during storage.)
Aliquots from each remixed bucket were proportioned out and composited in a common container
(stainless-steel pail). Sediment was then scooped from the composited mixture and placed in sample
jars.
6.3.2 Product Solids
Product solids were released by way of a port in the bottom of the Extractor/Dryer and fell into
a large trash can lined with plastic. Solids were scooped out with a laboratory-cleaned sample jar and
transferred into prelabeled sample jars. These samples were considered representative of the entire
batch of solids since the Extractor/Dryer contents are thoroughly mixed with impellers during solids
drying. A respirator was worn by the individual collecting the samples during this procedure to protect
against inhalation of dust.
6.3.3 Product Water
Product water was sampled at two locations. Product water that was to be analyzed for
triethylamine (a volatile compound) was collected directly into 40 mL vials from a hose running from
the Water Stripper Column once the developer determined that stripper temperature and water pH had
stabilized. The vials were then immediately sealed and cooled. The majority of the sample product
water was sampled out of 55-gallon drums, where product water was contained after stripping. A
teflon bailer was used to collect the samples.
6.3.4 Product Oil
Product oil is the concentrated organic-rich oily liquid left in the Solvent Evaporator tank after
oil polishing has removed practically all triethylamine. Product oil was produced from Sediment B only;
Sediment A did not originally contain enough O&G to warrant oil polishing. Product oil was collected
directly in sample containers via a tap in the line extending from the Solvent Evaporator tank. Samples
of the unpolished oil/solvent mixture produced from Sediment A treatment were also collected in this
manner.
6-6
-------
6.3.5 Oil/Solvent Mix
Following each test run, an intermediate type sample of the oil/solvent mix accumulating in the
Solvent Evaporator tank was collected. This sample was taken from the tap in the line extending from
the Solvent Evaporator. This sample was taken to provide a rough estimate of the buildup of
contaminants within the Solvent Evaporator as they were being extracted from solids.
6.3.6 Recycled Solvent
The solvent that was separated from the contaminated phases following extraction was
recycled back into the B.E.S.T.® extraction process for reuse. This recycled solvent was sampled prior
to the start of each test run to determine its purity at the time of use. The samples were collected
directly into 40 ml vials from a valve tap located on the cooling loop.
6.3.7 Vent Emissions
Samples were taken of vent gas to determine if the pilot plant scrubber system was efficient
in preventing triethylamine from being released to the atmosphere. The samples were collected at a
constant rate for each test run. Because the individual test runs often extended from one day to
another and interruptions to the runs would occur, collection times and rates varied from one test run
to another. Two to four integrated gas samples were collected over the duration of each test run.
Samples were collected using a sampling port in the 3-inch diameter vent pipe located 6.5
inches downstream from an elbow and 100 inches upstream from a flame arrestor (Figure 6-2). The
tip of the sample probe line was positioned near the center of the vent cross section. The sampling
rate for each run was held constant at a value depending on the expected process operation time
required to achieve a minimum sampling volume of 100L. Sampling rates ranged from 140 to 830
mL/min. Actual sample volumes ranged from 73L to 158L and sampling times varied between 90 and
850 minutes.
6.4 ANALYTICAL METHODS AND PHYSICAL TESTS
Table 6-1 summarizes the analytical test program for the B.E.S.T.® demonstration. The primary
analytical and physical test methods used for the B.E.S.T.® pilot plant demonstration tests are briefly
described in the following subsections. More detailed information is presented in Section 9 of this
report.
6-7
-------
6.4.1 Method 3540 - Extraction for Semivolatile Organics - Solid Samples
The untreated sediment (raw feed) samples and treated solid samples were prepared for
semivolatile organic analysis (PAHs, PCBs) by Soxhlet extraction. Soxhlet extraction basically involves
repetitive extractions that utilize clean solvent for each extraction cycle. The extracting solvent used
was a 50 percent acetone and 50 percent hexane solution (1:1 volume/volume).
6.4.2 Method 3520 - Extraction for Semivolatile Oroanics - Aqueous Samples
The product water samples were prepared for semivolatile organic analysis (PAHs, PCBs) by
continuous extraction with methylene chloride. For PCBs, the methylene chloride extract was
exchanged with hexane for injection into the gas chromatograph/electron capture detector (GC/ECD).
6.4.3 Method 3580 - Extraction for Semivolatile Oroanics - Non-Aaueous Wastes
For the product oil generated from Sediment B, product triethylamine, and recycled
triethylamine, samples were prepared for semivolatile organic analysis (PAHs, PCBs) by dilution with
a solvent appropriate for the analysis to be performed. Method 8270 uses methylene chloride; Method
8080 uses hexane.
6.4.4 Additional Cleanup Procedures
Due to the oily nature of the raw feed and some of the process samples, additional cleanup
was necessary prior to instrumental analyses. Cleanup procedures included Method 3620 (Florisil),
Method 3640 (gel-permeation chromatography), and sulfuric acid. The use of cleanup techniques was
decided by the analytical laboratory following sample extraction and those used are discussed in
Section 9.
6.4.5 Method 8270 - GC/MS Analysis of Semivolatile Oroanics
PAHs were analyzed by gas chromatography/mass spectroscopy (GC/MS). After sample
extraction, internal standards (method-recommended) were added to the extract. The extract was
injected into the GC/MS where compounds of interest are separated, identified, and quantitated.
Surrogate compounds used for Method 8270 included nitrobenzene-dB; 2-fluorobiphenyl; terphenyl-d14;
phenol-d5; 2-fluorphenol; 2,4,6-tribromophenol; and anthracene-d,0. Internal standards included 1,4-
dichlorobenzene-d4, naphthalene-8, acenaphthene-d10, phenanthrene-d10, chrysene-d12, and perylene-
d12.
6-8
-------
6.4.6 Method 8080 - GC Analysis for PCBs
Following extraction, PCBs were analyzed by GC with electron capture detection. Specific PCB
Aroclors were identified and quantitated. Quantitation was based on the total area of 5 peaks within
designated retention windows.
6.4.7 B.E.S.T.* - Triethvlamine Analysis bv GC
Triethylamine analysis was performed using gas chromatography/flame ionization detection
(GC/FID). The final water phase samples were directly injected into the instrument after pH adjustment
and filtration. The treated solid samples had to be extracted with distilled water prior to analysis. The
final oil product samples (Sediment B) were first dissolved in methylene chloride and then analyzed.
6.4.8 Method 9070 - Oil and Grease Analysis - Aqueous Samples
The product water samples were extracted with freon, which was then evaporated. The O&G
concentrations were determined gravimetrically.
6.4.9 Method 9071 - Oil and Grease Analysis - Solid Samples
Untreated sediment and treated solid samples were Soxhlet-extracted with freon. The freon
was evaporated and the O&G determined gravimetrically. Comparative analyses using RCC's
methylene chloride procedure were also conducted, and those results are used for the mass balance
determination presented in Section 7. This is because recovery rates acquired when extracting with
methylene chloride were found to be higher than those required when using freon.
6.4.10 Method 3540 - Moisture - Solid Samples
Representative portions of untreated sediment and treated solids were weighed and dried at
105°C to a constant weight. The weight loss was then used to determine the moisture content of the
original sample.
6.4.11 Method 1311 - TCLP Metals - Solid Samples
Untreated sediments and treated solid samples were leached according to the TCLP procedures
for nonvolatile species. The leachate was then analyzed for arsenic, barium, cadmium, chromium, lead,
mercury, selenium, and silver as instructed in Method 1311.
6-9
-------
6.4.12 Method 680 - GC/MS Congener Analysis for PCBs - Solid Samples
Untreated sediment and treated solids samples were Soxhlet-extracted according to Method
3540, and then analyzed for individual PCB congeners by Method 680.
6.4.13 ASTM Methods D3172 and D3176 - Ultimate and Proximate Analysis - Solid Samples
Ultimate/proximate analysis of the untreated sediment, treated solids, and Sediment B product
oil was conducted according to ASTM Methods D3172 and D3176. These analyses, combined, are
a determination of the moisture, volatile matter, total carbon, fixed carbon, hydrogen, nitrogen, sulfur,
and ash content of a sample (as weight percentages). Also determined is Btu per pound, which
indicates a materials fuel contribution when burned in an incinerator.
6.4.14 NIOSH Method S152 - Triethvlamine Analysis - Air Samples
All air samples were collected in midget bubblers to determine triethylamine concentrations in
vent emissions. The sample in each bubbler was analyzed separately. The pH of the samples was
adjusted by adding 1 mL of concentrated sodium hydroxide; aliquots were analyzed by direct-injection
GC/FID. The sample with the highest triethylamine level was also analyzed by GC/MS to confirm
qualitatively the presence of triethylamine.
6-10
-------
SECTION 7
PERFORMANCE AND DATA EVALUATION
7.1 INTRODUCTION
This section summarizes the performance data obtained during the demonstration testing of
RCC's pilot plant in Gary, Indiana. The feasibility of employing a full-scale system during actual
remediations is evaluated in an accompanying Applications Analysis Report (AAR).
The majority of results presented in this section are in tabular form; evaluations are
incorporated in the narrative presentations. The data are presented in the selected order of technology
evaluation importance, beginning with the data pertaining to the removal of organic compounds. To
facilitate the evaluation, the following critical and noncritical objectives were defined in the
Demonstration Plan and QAPP.
7.1.1 Critical Objectives
To assess the ability of the RCC B.E.S.T,® solvent extraction technology to:
• Remove PAH and PCB organic contaminants from river sediments in the range of 96
to 99 percent
• Achieve a mass balance of feed material mass into the pilot unit versus total products
mass (solids, water and oil) in the range of 85 to 115 percent
• Produce product streams of water, solids, and oil having triethylamine concentrations
of < 80 mg/L, <150 mg/kg, and < 1000 mg/kg, respectively
7.1.2 Noncritical Objectives
To determine the technology's general applicability and to document process performance by
analyzing for:
• O&G in the solids and water (process) streams
• PAHs and PCBs in all streams, except for vent emissions
• Moisture in solids and oil streams
• Proximate/ultimate parameters in solids and oil streams
7-1
-------
• TDS, TOC/TIC, BOD, arid conductivity in water streams
• TCLP metals in solids streams
• Total metals in solids and water streams
• Total and reactive cyanide in solids streams
• Total phosphorus, reactive sulfide, TRPH, volatile solids, and pH in solids and water
streams
• Triethylamine in vent emissions
• Biodegradation of triethylamine in product solids
7.2 PAH REMOVAL
Both Sediment A and Sediment B feed contained a wide distribution of PAH compounds, which
had been anticipated from results of the sediment characterization analyses. Sediment A, collected
from the GCR at the Transect 28 location, was the lesser contaminated of the two feeds used in the
demonstration. However, the analyses of the feed still confirmed the total PAH concentration to be
in excess of 500 mg/kg. Sediment B feed, on the other hand, contained total PAHs in excess of
70,000 mg/kg. This was anticipated since Sediment B feed was collected at the Transect 6 location,
which is approximately 2 miles upstream of Transect 28 and immediately downstream from a coke
plant outfall.
Tables 7-1 and 7-2 present the analytical results of 17 individual and total PAH compounds
detected in each of the five runs for Sediment A feed and Sediment A treated solids, respectively.
Average concentrations for all five runs as well as the three optimum runs are included in these tables.
Tables 7-3 and 7-4 present the analytical results of these same parameters for Sediment B feed and
Sediment B treated solids, respectively. Table 7-5 provides the percent removals for individual PAH
compounds and for the summed total PAH concentrations for both Sediment A and Sediment B. These
removal efficiencies are based on feed and treated solids PAH concentrations that are the average of
the three optimum runs for each sediment type. For Sediment A, the optimum runs were Runs 3, 4,
and 5. For Sediment B, the optimum runs were Runs 2, 4, and 5.
7-2
-------
TABLE 7-1. PAH CONCENTRATIONS IN SEDIMENT A FEED
weight)
PAH Analyte
R1
R2
R3
R4a
R5
Avgb
Standard
Deviation15
Acenaphthene
56
65
63
70
72
65/68
6.3/4.7
Acenaphthylene
3,1
3.4
3.4
<16
5.5
< 1 6/<16
—
Anthracene
16
19
18
24
25
20/22
3.9/3.8
Benzofalanthracene
19
22
19
24
32
23/25
5.4/6.6
Benzo(a)pyrene
17
19
18
24
30
22/24
5.4/6.0
Benzo(b)fluoranthene
18
21
17
25
27
22/23
4.3/5.3
Benzo(k)fluoranthene
13
13
12
17
21
15/17
3.8/4.5
Benzo(ghi)perylene
9.6
11
11
15
19
13/15
3.4/4.0
Chrysene
21
24
19
25
32
24/25
5.0/6.5
Dibenz(a,h)anthracene
<18
2.9
<17
<18
<17
< 18/<18
...
Fluoranthene
59
66
62
81
84
70/76
10.2/11.9
Fluorene
39
47
48
52
54
48/51
5,8/3.1
IndenoU ,2,3-cd)pyrene
10
11
11
16
19
13/15
3.5/4.0
2-Methylnaphthalene
20
24
23
25
26
24/25
2.3/1.5
Naphthalene
10
<17
<17
<18
<17
< 18/< 18
—
Phenanthrene
80
92
78
105
92
89/92
10.9/13.5
Pyrene
56
66
55
65
82
65/67
10.8/13.7
Total PAHs
447
506
457
568
620
520/548
78/83
a Concentrations for Run 4 are the average of three replicate measurements rounded to the appropriate number of significant
digits.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Runs 3, 4,
and 5),
7-3
-------
TABLE 7-2. PAH CONCENTRATIONS IN SEDIMENT A TREATED SOLIDS
PAH Analyte
R1
Concentration Per Run (mo/kg dry weight)
R2 R3 R4a R5 Avgb
Standard
Deviation1"
Acenaphthene 1,6 1.5
Acenaphthylene <2.1 0.17
Anthracene 1.8 1.7
Benzo(a)anthracene 0.83 0.81
Benzo(a)pyrene 0.61 0.58
Benzo(b)fluoranthene 0.52 0.61
Benzo(k)fluoranthene 0.41 0.34
Benzo!ghi)perylene 0.29 0.23
Chrysene 0.87 0.82
Dibenz(a,h)anthracene <2.1 <0.80
Fluoranthene 3.0 2.6
Fluorene 3.1 2.1
lndeno(1,2,3-cd)pyrene 0.32 0.31
2-Methylnaphthalene 1.4 5.2
Naphthalene 6.4 5.4
Phenanthrene 5.6 4.4
Pyrene 1.4 1.6
Si*!*:
MMIl
1.2
0.18
1.1
0.56
0.37
0.40
0.17
0.20
0.56
<0.69
1.4
1.8
0.20
3.5
4.4
3.3 .
1.3
1.7
<0.8
1.7
0.61
0.44
0.44
0.34
0.25
0.62
<0.76
2.0
2.4
0.25
4.5
6.9
4.7
0.96
1.0
0.15
1.0
0.39
0.22
0.24
0.15
0.14
0.40
<0.67
0.82
1.6
0.10
3.1
4.1
2.9
0.76
1
1.4/1.3
<2.1/<0.8
1.5/1.3
0.64/.52
0.44/0.34
0.44/0.36
0.28/0.22
0.22/0.20
0.65/0.52
<2.1/<0.76
2.0/1.4
2.2/1.9
0.24/0.18
3.5/3.7
5.4/5.1
4.2/3.6
1.2/1.0
¦1
0.3/0.4
0.4/0.4
0.2/0.1
0.1/0.1
0.1/0.1
0.1/0.9
0.06/0.06
0.2/0.1
0.9/0.6
0.6/0.4
0.1/0.1
1.5/0.7
1.2/1.5
1.1/0.9
0.3/0.3
rnxmrng
a Concentrations for Run 4 are the average of three replicate measurements rounded to two significant digits.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Runs 3, 4,
and 5).
7-4
-------
TABLE 7-3. PAH CONCENTRATIONS IN SEDIMENT B FEED
Concentration Per Run (mo/kg dry weight)
Standard
PAH Analyte
R1
R2
R3
R4a
R5
Avgb
Deviation1*
Acenaphthene
8400
12000
17000
10400
16000
12800/12800
3660/2880
Acenaphthylene
1000
230
280
160
240
380/210
350/44
Anthracene
3000
2000
3700
2700
2400
2760/2370
640/350
Benzo(a)anthracene
960
1100
1000
860
1200
1020/1050
130/170
Benzo(a)pyrene
800
780
850
700
950
816/810
92/128
Benzo{b)fluoranthene
980
730
670
740
1100
844/857
186/211
Benzo(k)fluoranthene
680
500
640
480
620
584/533
89/76
Benzo(ghi)perylene
1200
400
470
390
580
608/457
340/107
Chrysene
970
950
1000
860
1000
956/937
58/71
Dibenz(a,h)anthracene
100
150
<230
90
180
<230/140
~/46
Fluoranthene
3800
4400
4100
3330
5100
4150/4280
664/891
Fluorene
5300
7000
9200
6470
8400
7270/7290
1550/997
IndenoU ,2,3-cd)pyrene
510
520
470
450
670
524/547
86/112
2-MethyInaphthalene
4500
6400
9700
3830
9000
6690/6410
2620/2585
Naphthalene
13000
14000
25000
19000
23000
18800/18700
5310/4510
Phenanthrene
7400
9800
14000
10470
12000
10700/10800
2470/1130
Pyrene
3600
3100
3000
2530
2800
3010/2810
397/285
Total PAHs
56200
64100
91100
63500
85200
72000/70900
15200/12400
a Concentrations for Run 4 are the average of three replicate measurements rounded to the nearest multiple of ten,
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Runs 2, 4,
and 5),
7-5
-------
TABLE 7-4. PAH CONCENTRATIONS IN SEDIMENT B TREATED SOLIDS
Concentration Per Run (mg/kg dry weight)
PAH Analyte
R1
R2
R3
R4a
R5
Avgh
Standard
Deviation15
Acenaphthene
41
40
20
34
53
38/42
12/9.7
Acenaphthylene
5.8
6.4
3.2
5.1
8.2
5.7/6.6
1.8/1.6
Anthracene
15
16
7.3
13
20
14/16
4.7/3.7
Benzo(a)anthracene
5.2
4.6
1.9
3.7
5.8
4.2/4.7
1.5/1.1
Benzo(a)pyrene
5.2
4.4
1.8
3.6
5.8
4.2/4.6
1.6/1.1
Benzo(b)f!uoranthene
3.9
3.9
1.8
3.2
5.2
3.6/4.1
1.2/1.0
Benzo(k)fluoranthene
3.6
3.6
1.3
2.6
4.7
3.2/3.6
1.3/1.1
Benzo{ghi)perylene
2.6
2.6
0.92
1.5
2.7
2.1/2.3
0.8/0.7
Chrysene
5.0
4.6
2.0
3.7
5.9
4.2/4.7
1.5/1.1
Dibenz(a,h)anthracene
0.92
<2.9
<2.6
<2.8
<2.7
<2.9/<2.9
—
Fluoranthene
15
15
6.7
13
20
14/16
4.8/3.6
Fluorene
35
34
17
28
42
31/35
9.3/6.9
lndeno(1,2,3-
cdlpyrene
2.5
2.4
0.88
1.6
2.6
2.0/2.2
0.7/0.5
2-Methylnaphthalene
56
77
42
53
120
70/83
31/34
Naphthalene
170
180
170
190
320
206/230
64/77
Phenanthrene
40
40
18
33
51
36/41
12.1/9.1
Pyrene
Total. PAHs
13
420
12
447
5.1
300
9.7
402
15
HI
11/12
450/510
3.8/2.7
llMlPo
a Concentrations for Run 4 are the average of three replicate measurements rounded to two significant digits.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs {Runs 2, 4,
and 5).
7-6
-------
TABLE 7-5. PAH REMOVAL EFFICIENCIES
SEDIMENT A
SEDIMENT B
PAH Analyte
Feed8
Treated
Solids"
%
Removal1"
Feed®
Treated
Solids"
%
Removal6
Acenaphthene
68
1.3
98.1
12800
42
99.7
Acenaphthylene
<16
<0.8
...
210
6.6
96.9
Anthracene
22
1.3
94.1
2370
16
99.3
Benzo{a)anthracene
25
0.52
97.9
1050
4.7
99.6
Benzoialpyrene
24
0.34
98.6
810
4.6
99.4
Benzo(b)fluoranthene
23
0.36
98.4
857
4.1
99.5
Benzo(k)f!uoranthene
17
0.22
98.7
533
3.6
99.3
Benzo(ghi)perylene
15
0.20
98.6
457
2.3
99.5
Chrysene
25
0.52
97.9
937
4.7
99.5
Dibenz(a,h)anthracene
<18
<0.76
—
140
<2.9
>97.9
Fluoranthene
76
1.4
98.2
4280
16
99.6
Fluorene
51
1.9
96.3
7290
35
99.5
lndeno(1,2,3-
cd)pyrene
15
0.18
98.8
547
2.2
99.6
2-Methylnaphthalene
25
3.7
85.2
6410
83
98.7
Naphthalene
<18
5.1
...
18700
230
98.8
Phenanthrene
92
3.6
96.1
10800
41
99.6
Pyrene
Total PAHs
67
548
1.0
22 -:|f
98.5
96.0
2810
70920
12
iimmi
99.6
39.3
a Concentrations reported in mg/kg (dry weight basis) and are the average of the three optimum runs for each sediment.
(Sediment A = Runs 3, 4, and 5; Sediment B = Runs 2, 4, and 5).
b Percent Removals = Feed Concentration - Treated Solids Concentration v 10A
Feed Concentration
7-7
-------
In scanning the PAH compositional data for both sediment feeds, an immediate observation is
apparent. There is little variation in the data on a per run basis. This consistency of data is an
indication that both sediment types collected from the GCR were very homogeneous after mixing and
provided the feed consistency that was desired from project outset. For example, the relative standard
deviation (RSD) for total PAH concentrations, as an average of all five runs, is 15 percent for Sediment
A and 21 percent for Sediment B. This consistency of data is as good as that acquired for field
replicate and laboratory triplicate analyses (see Section 9) and is most likely attributed to the
thoroughness of the predemonstration screening and mixing operations (see Subsection 5.1).
Sediment A feed contained on average about 550 mg/kg of total PAHs, approximately 65
percent of which consisted of five specific compounds (acenaphthene, fluoranthene, fluorene,
phenanthrene, and pyrene). Sediment B feed contained on average about 71,000 mg/kg of total PAHs,
approximately 85 percent of which consisted of the same PAHs previously mentioned, but which
included naphthalene at concentrations close to 19,000 mg/kg. Naphthalene was detected in only one
Sediment A feed sample at a very low concentration (10 mg/kg). Because naphthalene is more water
soluble than the other PAH compounds, it would diminish in concentration more quickly away from its
source in an aqueous environment (like the GCR) relative to the other less soluble PAH compounds.
The data in Tables 7-2, 7-4, and 7-5 provide the information to determine how well the
B.E.S.T.® Process performed in removing PAH compounds from the GCR test sediments. The
efficiency for removing total PAHs from Sediment A feed solids was 96 percent, which met the vendor
claim of 96 to 99 percent removal of total PAHs. The efficiency of removing total PAHs from
Sediment B feed solids was even better, as measured at 99.3 percent. This increased removal
percentage is attributed to the much higher PAH content in Sediment B feed, which contained over
100 times the amount of total PAHs as Sediment A feed.
Of the specific PAH compounds measured above detection limits in Sediment A feed, eight
were removed at efficiencies greater than 98 percent. Only two PAH compounds were removed by
less than 96 percent (anthracene at 94 percent and 2-methylnaphthalene at 85 percent). Of the 17
specific PAH compounds detected in Sediment B Feed solids, the lowest calculated removal efficiency
was 97 percent (for acenaphthylene). Thirteen of the specific PAH compounds were removed by
greater than 99 percent.
7-8
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7.3 PCB REMOVAL
Both Sediment A and Sediment B feeds contained PCBs, although at substantially different
levels. Total PCBs detected in Sediment A feed averaged 12 mg/kg, which is well below the TSCA
regulatory threshold of 50 mg/kg. Conversely, Sediment B feed averaged approximately 430 mg/kg
total PCBs, well above the TSCA threshold. Aside from the regulatory implications, the disparity
between the two feeds was encouraging from a research point of view since the removal efficiency
of the B.E.S.T® system was evaluated using a relatively low initial constituent level as well as a
relatively high level.
Table 7-6 presents the individual and average PCB analytical results for the feed and treated
solids for both of the sediment feeds and the respective percent removal efficiencies. As Table 7-6
shows, the B.E.S.T.® Process was very effective in removing PCBs from both test sediments. The
efficiencies for removing PCBs from Sediments A and B were 99,7 percent and 99.6 percent,
respectively, for the optimum run averages. These results exceeded the vendor claim of 96 to 99
percent removal of PCBs under optimized conditions. In addition, the treated solids produced from all
optimum runs from both sediments contained less than 2.0 mg/kg PCBs, except for the 2.1 mg/kg
value reported for Sediment B, Run 2. Although not a vendor claim, RCC desires to remove PCBs to
below the 2 mg/kg level because that concentration is commonly a regulatory cleanup goal.
7.4 OIL AND GREASE REMOVAL
O&G were the most prevalent contaminants within both sediment feeds and best defined the
physical observable characteristics of the feed material. This was especially true for the Sediment B
feed which had an O&G content of almost 13 percent. Sediment B was nearly pitch black in color and
had a strong hydrocarbon odor. Sediment A on the other hand was a very dark brown color with a
green tint which may have been due to metals present. The high percentage of water and oil in both
feeds could justify them being defined as a slurry, especially during mixing.
Table 7-7 presents the O&G individual and average analytical results for the feed and treated
solids for both of the sediment feeds and the respective removal efficiencies. As Table 7-7 shows,
the B.E.S.T.® Process was quite effective in separating and removing O&G from both sediment feeds.
There was no specific claim made for O&G removal, however, removal efficiencies in excess of 98
percent were achieved on average for both Sediments A and B.
7-9
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TABLE 7-6. PCB CONCENTRATIONS AND REMOVAL EFFICIENCIES - SEDIMENT A AND B
FEEDS AND TREATED SOLIDS
Parameter Test Runs
Standard
R1 R2 R3 R4a R5 Avgb Deviation6
Sediment A
Total PCBs - Feed
(mg/kg - dry weight)
Total PCBs - Treated
Solids (mg/kg - dry weight)
Percent Removal (%)
Sediment B
Total PCBs - Feed
Smg/kg - dry weight)
Total PCBs - Treated
Solids (mg/kg - dry weight)
Percent Removal (%)
7.33 6.41 8.01 11.8 16.4 10.0/12.1 4.1/4.2
<0.07 0.20 0.05 0.04 0.04 0.08/0.04 0.07/0.006
>99 96.9 99.4 99.7 99.8 99.2/99.7
364 316 495 462 497 427/425 82/96
1.5 2.1 1.2 1.8 1.4 1.6/1.8 0.35/0.35
99.6 99.3 99.8 99.6 99.7 99.2/99.6
a Concentrations reported for Run 4 are the average of three replicate measurements rounded to the appropriate number of
significant digits.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Sediment A =
Runs 3, 4, and 5 and Sediment B = Runs 2, 4, arid 5).
7-10
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TABLE 7-7. OIL AND GREASE CONCENTRATIONS AND REMOVAL EFFICIENCIES -
SEDIMENT A AND B FEEDS AND TREATED SOLIDS
Test Runs
Standard
Parameter R1 R2 R3 R4" R5C Avgb Deviation13
Sediment A
Total Oil & Grease - Feed
(mg/kg - dry weight) 9400
Total Oil & Grease -
Treated Solids {mg/kg -
dry weight) 195
Percent Removal (%) 97.9
7800 7400 6600
169 203 66
97.8 97.3 99.0
7580/
6700 6900 1130/436
65 140/111 69/79
99.0 98.2/98.4
Sediment B
Total Oil & Grease - Feed 103,000/ 41,600/
(mg/kg - dry weight) 66,400 116,000 67,300 167,000 99,100 127,000 35,300
Total Oil & Grease -
Treated Solids - (mg/kg - 1530/
dry weight) 1800 1330 1490 1230 1810 1460 266/310
Percent Removal {%) 97.3 98.9 97.8 99.3 98.2 98.5/98.9
a Concentrations reported for Run 4 are the average of three field replicate measurements rounded to the appropriate number
of significant digits.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Sediment A =
Runs 3, 4, and 5 and Sediment B = Runs 2, 4, and 5).
c Concentrations reported for Run 5 are the average of samples analyzed in triplicate.
7.5 TRIETHYLAMINE RESIDUAL TESTING - TREATED SOLIDS, PRODUCT WATER,
AND OIL PHASES
Triethylamine was the extracting agent used during the RCC B.E.S.T.® SITE demonstration.
As part of the claimed efficiency of the process, the triethylamine is recycled and reused in extraction
cycles conducted after the initial extraction takes place (refer to Subsection 3.2 for process
description). Because the solvent contacts the solids, water, and oil phases of the sediments treated,
claims were made for concentration levels of solvent residual in the three process streams. The claims
for residual triethylamine were less than 150 mg/kg for treated solids, less than 80 mg/L for product
water, and less than 1000 mg/kg for product oil.
7-11
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Table 7-8 presents the triethylamine analytical results for the treated solids and product water
for Sediments A and B, and the triethylamine residual in the Sediment B product oil. There was not
enough O&G content in the Sediment A feed (less than 1 percent) to produce product oil after
treatment of Sediment A, As a result, the percentage of triethylamine present in the oil/solvent mixture
(left in the Solvent Evaporator tank after Sediment A treatment) is included in Table 7-8.
TABLE 7-8. TRIETHYLAMINE CONCENTRATIONS - SEDIMENT A AND B TREATED SOLIDS,
PRODUCT WATER, AND OIL PHASES
Test Runs*
Standard
Parameter Claim R1 R2 R3 R4b R5 Avgc Deviation0
Sediment A
Triethylamine in
Treated Solids <150 61.7 93.1 27.8 28.0 79.6 58/45 29.6/29.8
(mg/kg)
Triethylamine in
Product Water (mg/L) <80 <1 <1 <1 <1 2.2 <2/<2
Triethylamine in Oil
Phase (%) 65.8* 3.8
Sediment B
Triethylamine in
Treated Solids <150 106 88.7 55 130 89.3 94/103 27.4/23.7
(mg/kg)
Triethylamine in
Product Water (mg/L) <80 <1 1.0 <1 <1 <1 < 1/< 1
Triethylamine in
Product Oil (mg/kg) <1000 - 733e 135
a Concentrations reported for each of the five test runs for each sediment are the average of laboratory triplicate analysis
conducted on the sample.
b Concentrations reported for Run 4 are the average of three field replicate measurements, each of which are the average
of laboratory triplicate analysis.
c Two values are given for treated solids and product water; the first pertains to all five runs arid the second pertains to the
three optimum runs (Sediment A = Runs 3, 4, and 5; Sediment B = Runs 2, 4, and 5).
d The % values reported for the Sediment A oil/solvent mixture is the average of triplicate analysis of a single sample.
e The value for the Sediment B product oil is the average of five aliquot (field replicate) measurements which were each
analyzed in triplicate.
7-12
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The analytical methods used for measurement of triethylamine in solid, aqueous, and
nonaqueous (i.e., oil) media are nonstandard methods. However, RCC had refined test methods for
these determinations based on their familiarity with triethylamine. The SITE Program performed a
validation study of the B.E.S.T.® method for determination of triethylamine prior to the demonstration
and conducted laboratory triplicate analysis on all samples measured for triethylamine (see Volume II
for Validation Study and detailed RCC methods).
As indicated in Table 7-8, all of the developer claims made for solvent residuals were easily
met. All triethylamine concentrations in solids and water were below their respective target
concentration threshold on every run, and the test averages for both total and optimum runs were well
below the claims. For instance, water produced from the treatment for Sediments A and B averaged
less than 2 mg/L and less than 1 mg/L triethylamine respectively, well below the claim of 80 mg/L.
The only measurement that was somewhat close to a claim threshold was the oil produced from
Sediment B (the average triethylamine concentration was 733 mg/kg and the claim was less than 1000
mg/kg). However, this is the least critical of the residual measurements since the oil phase contains
the concentrated organics separated by the solids and thus must be disposed of as hazardous,
regardless of triethylamine content.
The additional observation evident from Table 7-8 is that there was little to no variation in
solvent residual measurements between averages of all five runs and averages of designated optimal
runs.
7.6 TRIETHYLAMINE AIR EMISSIONS TESTING - VENT GAS
One of the noncritical objectives of this SITE demonstration was the evaluation of the emission
control effectiveness of the B.E.S.T.® pilot plant. To do this, samples of the air vented to the
atmosphere from the pilot plant were collected and analyzed for triethylamine, the volatile solvent used
in the B.E.S.T.® solvent extraction process.
Emissions from the B.E.S.T.® pilot plant are controlled by a primary carbon adsorber and backup
carbon adsorber connected in series. Between two and four integrated gas samples were collected
over the duration of each of the five test runs conducted on both Sediments A and B. In all, a total
of 23 samples were collected at the outlet of the final carbon canister, upstream from the flame
arrestor at the tip of the vent pipe.
7-13
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Table 7-9 summarizes the vent gas triethylamine concentrations and sample identifications.
As shown, only two samples contained detectable amounts of triethylamine. When no triethylamine
was detected, the concentrations were calculated by use of the detection limit value. The variations
in detection limit concentrations reflect differences in sample volumes (both gas volumes and final
solution volume). The sample collected on July 20, 1992 was also analyzed by GC/MS; this analysis
confirmed the presence of triethylamine in the sample.
The Vent Gas Triethylamine Test Report detailing sampling and analytical procedures and
calculations is included in Volume II of this TER.
7.7 TRIETHYLAMINE BIODEGRADATION TESTING • TREATED SOLIDS
The triethylamine biodegradation testing was not critical to the B.E.S.T.® SITE demonstration
evaluation; it was added to the demonstration plan because it was indirectly related to the B.E.S.T.®
Process. RCC has referenced an EPA report (EPA-600/2-82-001 a) that shows triethylamine at a level
of 200 ppm in water was degraded completely in 11 hours by Aerobacter, a common soil bacteria.
The use of this reference implies that triethylamine may biodegrade in the treated solids. The testing
was thus intended to see if triethylamine would biodegrade in the treated solids produced during the
SITE demonstration by simply mixing the treated solids with soil.
The biodegradation test was conducted by mixing an equal portion (1:1 mass) of viable potting
soil with treated product solid samples collected from three of the demonstration test runs (two
Sediment A samples and one Sediment B sample). For each of the three sediment samples, two sets
of 12 test vials were prepared; the first set contained unaltered mixtures and the second "control" set
contained the same homogeneous mixture spiked with mercuric chloride to prevent native bacteria
from degrading the solvent. The samples were then stored away from light at room temperature as
test sample/control sample pairs. Each pair was analyzed at four separate time intervals; initially at
Day 0 and then at the end of 2 weeks, 4 weeks, and 8 weeks. No pH adjustments or nutrient
additions were performed.
7-14
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TABLE 7-9. TRIETHYLAMINE CONCENTRATIONS - SEDIMENT A AND B VENT GAS
Concentration*
Date (July 1992)
Clock Time {24-h)
Sample No.
mg/m3
ppm
SEDIMENT A
1
1325-1800
A11-VG-1A
<0.3
<0.08
2
0815-1220
A11-VG-1B
<0.4
<0.1
3
0910-1940
A12-VG-2A
<0.3
<0.07
4
0730-1135
A12-VG-2B
<0.3
<0.07
4
1210-1950
A13-VG-3A
<0.2
<0.06
6
0800-1330
A13-VG-3B
<0.2
<0.05
6
1340-1820
A21-VG-4A
<0.3
<0.06
7
0815-1615
A21-VG-4B
<0.2
<0.05
7
1630-1800
A22-VG-5A
<0.4
<0.1
8
0730-1620
A22-VG-5B
<0.4
<0.1
9
0630-0940
A22-VG-5C
<0.3
<0.07
SEDIMENT B
10
1345-1815
B11-VG-6A
<0.3
<0.06
11
0745-1650
B11-VG-6B
<0.3
<0.08
13
1200-1725
B11-VG-6C
<0.3
<0.08
15
0630-1120
B11-VG-6D
<0.2
<0.06
15
1130-2110
B12-VG-7A
<0.2
<0.06
16
0630-2040
B12-VG-7B
0.40
0.096
17
0700-2000
B13-VG-8A
<0.3
<0.07
18
0630-1240
B13-VG-8B
<0.2
<0.06
18
1300-2050
B21-VG-9A
<0.2
<0.05
19
0830-1820
B21-VG-9B
<0.2
<0.06
20
0830-2120
B22-VG-1 OA
0.59fa
0.14
21
0750-2015
B22-VG-1 OB
<0.2
<0.05
a Milligrams per cubic meter at 25°C arid 760 mm Hg; ppm is parts per million by volume,
b Presence of triethylamine qualitatively confirmed by GC/MS analysis.
7-15
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Table 7-10 summarizes the biodegradation test data. The results of the biodegradation study
are quite variable. However, there is rio evidence that triethylamine present at 25 to 100 ppm in the
treated solids is biodegraded within 2 months of application. This data is supported by a previous
study which used acclimatized, activated sewage sludge (Chudoba, J,, et al; Chem Prum 19; 76-80,
1969). In contrast, it has been reported that triethylamine is degraded in Aerobacter (bacterial) culture
(USEPA, Treatability Manual Vol 1, EPA 600/8-80-042). The difference between the soil/sludge
studies and the bacterial culture study appears to be the result of the amine binding to humic fraction
of the soil, a well-recognized phenomenon in soil chemistry. Binding to the humic fraction would
decrease the amount of triethylamine available to the soil microflora and may inhibit its movement
through leaching (Bollag, J-M; "Decontaminating with Enzymes" ES&T 26: 1876-1881, 1992). This
study indicates that low levels of triethylamine are bound to soil and remain for at least 8 weeks when
not exposed to sunlight. Complete soil metabolism experiments generally utilize 14C-labeled analytes
in microcosms in order to, elucidate unambiguously the fates of applied chemicals, be they weakly
bound, covalently bound, or degraded to 14C02. However, this simple study does not preclude the
possibility that triethylamine could be biodegraded after pH adjustment and further nutrient or organism
augmentation.
A positive aspect one can consider from the likelihood that low levels of triethylamine are
bound to the soil is the immobilization of the compound. Triethylamine bound to the humic fraction
in soil cannot be volatilized under natural conditions, which would preclude the compound from being
an inhalation hazard. A more detailed description of the biodegradation study (i.e., sample preparation
and test procedures) and data on individual sample replicates are reported in "Analytical Results -
Triethylamine" by Tsang, Marsden, and Chau (SAIC/10-21-92), which is included in Volume II of this
TER.
7-16
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TABLE 7-10. TRIETHYLAMINE BIODEGRADABILITY IN TREATED SOLIDS
Test Sample
(Run No.)a
Day 0
Time Interval Concentrations (mg/kg)b
Day 14 Day 28
Day 56
Sediment A (R1)
85.8
85.5
55.0
66.9
Control Sample
73.6
92.3
68.9
57.0
Sediment A (R4)
42.4°
53.1
65.0
64.7
Control Sample
30.4°
50.4
70.9
71.4
Sediment B (R4)
147
140
148
152
Control Sample
146
155
146
158
a Sediment test samples are an equal mix (1:1 mass) of treated product solids and viable potting soil. Corresponding control
samples are identical but are spiked with mercuric chloride,
b All concentrations are the average of three replicate runs, one of which was analyzed in duplicate.
c Duplicate analysis was not performed on any of the three replicate run samples.
7.8 ORGANIC ANALYSES OF PRODUCT WATER, RECOVERED SOLVENT, AND PRODUCT OIL
This subsection presents the PAH, PCB, and 0&G analysis results of three process streams that
were in direct contact with feed contaminants as a mixture during extraction processes. Two of these
process streams, product water and recovered triethylamine, were analyzed to determine how free of
contamination they were and the product oil was analyzed to determine how contaminated it had
become.
Tables 7-11 and 7-12 present the individual and average organic analytical results for product
water and recovered solvent, respectively, for samples collected during testing of Sediments A and B.
Table 7-13 presents the analysis of the oil produced from the treatment of Sediment B. A total of five
aliquots (field replicates) of product oil were collected following final removal of triethylamine in the
Solvent Evaporator at the end of the fifth and final run. This "oil polishing" distillation procedure was
not conducted for the oil-deficient Sediment A, therefore there was no Sediment A oil product.
7-17
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TABLE 7-11. PAH, PCB, AND OIL AND GREASE ANALYSIS
OF PRODUCT WATER
Parameter
R1
R2
R3
Test Runs
R4a
R5
Avgb
Sediment A
Total PAHs fug/L)
<10
<10
<10
<10
<10
< 10/< 10
Total PCBs (ug/L)
<3
<3
<3
<3
<3
<3/<3
Oil and Grease (mg/L)
5.6
3.0
3.6
3.2
3.8
3.8/3.5
Sediment B
Total PAHs (ug/L)
<10
<10
<10
<10
<10
<10/<10
Total PCBs (ug/L)
<10
<1
<1
<1
<1
<3/< 1
Oil and Grease (mg/L)
2.7
1.8
3.8
2.7
3.1
2.8/2.5
a Concentrations reported for Run 4 are the average of three replicate measurements.
b Two average values are given; the first pertains to all five runs and the second pertains to the three optimum runs
(Sediment A = Runs 3, 4, and 5 and Sediment B = Runs 2, 4, and 5).
TABLE 7-12. PAH AND PCB ANALYSIS OF RECOVERED SOLVENT
Parameter
R1
R2
Test Runs
R3 R4
R5
Avgb
Sediment A
Total PAHs (mg/kg)
Total PCBs (mg/kg)
<40
<2
<40
<2
<40
<2
<40
<2
<40
<2
<40/<40
<21 <2
Sediment B
Total PAHs (mg/kg)"
Total PCBs (mg/kg)
<40
<20
8.9
<20
<20
32
<20
66
<20
40.4/35.6
<20/<20
a Tha values indicated for Runs 2 through 5 are detections of naphthalene.
b Two average values are given; the first pertains to all five runs and the second pertains to the three optimum runs
(Sediment A = Runs 3, 4, and 5 and Sediment B = Runs 2, 4, and 5).
7-18
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TABLE 7-13. PAH AND PCB ANALYSIS OF SEDIMENT B PRODUCT OIL
Aliauots*
Standard
Parameter 1 2 3 4 5 Avg. Deviation
Total PAHs 498,000 438,000 299,000 297,000 436,000 394,000 90,600
(mg/kg)
Total PCBs 2030 1750 2520 2150 2180 2130 278
(mg/kg)
a The aliquots 1 through 5 ware collected incrementally as the product oil in the Solvent Evaporator tank was drained by a
hose into a drum.
As indicated in Table 7-11, water produced during the demonstration testing was essentially
free of the semivolatile organic compounds detected initially in the water-laden feed materials. PAHs
and PCBs were not detected in any of the water produced from either test and only small amounts of
O&G were detected in product water from each run. For Sediment A product water, O&G
concentrations averaged below 4.0 mg/L; and for Sediment B product water, O&G concentrations
averaged below 3.0 mg/L.
Recovered solvent, which was triethylamine recycled back into the B.E.S.T.® system for reuse
after each extraction, was also found to be essentially free of organics. The only exceptions were
relatively small concentrations of naphthalene detected in the recovered solvent used for the last four
runs of Sediment B testing. As shown in Table 7-12, naphthalene was detected between 32 and 66
mg/kg in solvent used for Runs 3, 4, and 5 extractions. Because naphthalene is the lightest and most
volatile of the PAH compounds, its presence in the solvent may be due to its partial distillation within
the solvent/water azeotrope. It should be noted, however, that since the naphthalene content in the
Sediment B feed exceeded 18,000 mg/kg, the small amount of naphthalene detected in the solvent
could not contaminate the feed.
Product oil from Sediment B contained roughly 400,000 mg/kg PAHs (40 percent by
weight) and roughly 2,100 mg/kg PCBs (0.2 percent by weight) per Table 7-13. The remainder of the
oil is assumed to be other O&G constituents along with the negligible amount (0.07 percent) of
triethylamine detected. Aside from indicating that the organic compounds do indeed concentrate in
the oil phase following extractions, the significance of the PAH and PCB concentrations in the oil phase
7-19
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is in the determination of mass balance for those analytes. Mass balances data are presented and
discussed in Subsection 7,12.
7.9 MOISTURE CONTENTS - RAW FEED AND TREATED SOLIDS
Moisture content was a critical parameter for all feed material processed and for all product
solids. Although the developer did not make a specific claim regarding the moisture content of treated
materials, their literature states that the B.E.S.T.® Process' use of triethylamine can overcome solvent
extraction difficulties typically encountered with handling samples with high water content and that
dry treated solids are produced from the process. It should be noted that the water content of the final
product solids may not be critical in determining the technology's effectiveness as long as organics
have been removed. In fact, there are certain instances where a wetter treated solids product may
be desired. For example, in certain circumstances it would be an advantage to have the treated
material in pumpable form for transfer via pipeline.
Table 7-14 presents a comparison of the measured moisture percentages for the raw feeds to
the moisture percentages of the respective treated solids products, for each of the test runs for both
Sediments A and B. Sediment A averaged 41 percent moisture and Sediment B averaged about 64
percent moisture; although the latter visually appeared less wet. This was probably due to most of
the water having been immobilized by the large amount of O&G coating the solids.
As shown in Table 7-14, the initial test run (Sediment A - Run 1) produced the wettest solids
(37.1 percent), which was a soupy semiliquid. One single cold extraction was conducted during this
run, at a temperature slightly above 60°F. Conducting just one cold extraction, at a temperature at
which triethylamine and water are not totally miscible with one another, resulted in inadequate
dewatering in the Premix Tank. As a result, wet solids were produced. When two cold extractions
were conducted at temperatures well below 60°F for Run 2, the moisture content in the solids
produced was more than halved (17,1 percent!. These product solids were lumpy in appearance and
would ball up when handled. All subsequent runs produced solids having even further reduced
moisture contents, ranging anywhere between 13.6 and 2 percent. These product solids were
essentially dry and ranged from slightly cohesive to somewhat dusty. The moisture contents for
Sediment B product solids were much more consistent than those for Sediment A product solids, due
most likely to the insight RCC acquired during Sediment A testing. The moisture contents of Sediment
B product solids varied 6.7 percent between all five runs and just 3.7 percent between the three
optimum runs.
7-20
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TABLE 7-14. MOISTURE CONTENTS - SEDIMENT A AND B FEEDS
AND TREATED SOLIDS
Parameter
Test Runs
Standard
R1 R2 R3 R4a R5 Avgb Deviation6
Sediment A
Moisture in Feed (%)
44.5 41.5 40.2 41.6 41.3 41.8/41.0 1.6/0.7
Moisture in Treated Solids (%) 37.1 17.1 4.1 12.6 2.0 14.6/6.2
Sediment B
Moisture in Feed (%)
65.2 62.3 57.1 61.9 67.2 62.7/63.8 3.8/3.0
Moisture in Treated Solids (%) 12.2 13.6 6.9 12.2 9.9 11.0/11.9
a Percentages reported for Run 4, Sediment A are the average of three field replicate measurements.
b Two values are given; the first pertains to all five runs and the second pertains to the three optimum runs (Sediment A =
Runs 3, 4, and 5; Sediment B = Runs 2, 4, and 5).
7.10 EFFECTS ON METALS
To determine the potential beneficial effect of the B.E.S.T.® Process on transforming metals
into less leachable forms, total metals and Toxicity Characteristic Leaching Procedure (TCLP) testing
was conducted on the feed material and product solids of both sediment types. The results of these
analyses are not critical to the demonstration; however, investigating changes in TCLP leachability of
metals was a secondary objective of the demonstration. For this reason, and to ensure that the
product solids were not hazardous due to TCLP leachability, the TCLP analysis of regulated metals was
designated as critical and was conducted for samples collected for all test runs conducted. Total
metals analysis, however, was a noncritical analysis and thus was only conducted on feed and product
solids collected from one test run for each sediment type.
Table 7-15 presents the results of the total metals analyses for both sediment types. There
is a significant difference in feed versus treated solids concentrations for some individual metals, as
reported in Table 7-15. For example, there is an apparent reduction of the mercury concentrations
between Sediment B feed and treated solids. However, the data presented are single value
determinations from which no conclusions should be drawn. RCC analyzed all 5 runs of feed and
treated solids, and the average mercury concentration in feed and treated solids are almost the same
and are between the values of 14.1 and 0.58 mg/kg reported in Table 7-15.
7-21
-------
TABLE 7-15. TOTAL METALS IN TEST SEDIMENTS
SEDIMENT A
Analyte (mg/kg-dry wt.) Feed8 Treated Solids"
SEDIMENT B
Feed8 Treated Solids"
Antimony
82.2
35.5
<25.2
<10.9
Arsenic
8
10.5
32.1
12
Barium
60.5
52.9
126
133
Beryllium
2.2
<0.62
1.1
1.4
Cadmium
13.7
8.1
3.2
2.7
Chromium
402
302
568
526
Copper
172
161
131
131
Iron
363,000
353,000
192,000
162,000
Lead
1030
877
484
433
Manganese
6260
5640
1800
1700
Mercury
1.4
2.1
14,1b
0.58b
Nickel
130
70.9
119
106
Selenium
<1.1
<0.93
8.3
1.9
Silver
NA
NA
9
<1.1
Thallium
<110
<95.2
107
<34.9
Vanadium
47.6
42.9
33.7
28.5
Zinc
9510
8210
1,690
1,690
a Total metals analysis was conducted on only one run for each sediment type. All results are reported in mg/kg - dry weight
basis.
b No conclusions should be drawn from this single analysis; vendor data indicates no significant reduction in concentration.
NA Not analyzed
Table 7-16 presents the results of the TCLP analyses for both sediment types. Because the
results for both feeds indicated that the eight RCRA-reguIated metals were not originally leachable from
the feed by way of the TCLP test, it was not possible to evaluate the B.E.S.T.® Process' effect on
transforming those metals into less leachable forms. Of those eight metals (arsenic, barium, cadmium,
chromium, lead, mercury, selenium, and silver) only barium was leached out of both feeds and treated
solids at concentrations above the detection limit. These concentrations were also very small
7-22
-------
(approximately 0.7 to 0.8 mg/L in the feeds and approximately 0.5 to 1.0 mg/L in the treated solids)
and therefore considered insignificant.
TABLE 7-16. LEACHABLE METALS IN TEST SEDIMENTS
SEDIMENT A
SEDIMENT B
Reg. Levelb
(mg/L)
Feed"
(mg/L)
Treated Solids*
(mg/L)
Feed8
(mg/L)
Treated Solids"
(mg/L)
Regulated Metals
Arsenic
5
<0.03
<0.03
<0.03
<0.03
Barium
100
0.66
0.48
0.76
1.03
Cadmium
1
<0.03
<0.03
0.03
<0.03
Chromium
5
<0.04
<0.04
<0.04
<0.04
Lead
5
<0.21
<0.21
<0.21
<0.21
Mercury
0.2
<0.002
<0.002
<0.002
0.005
Selenium
1
<0.03
<0.03
<0.03
<0.03
Silver
5
<0.05
<0.05
<0.05
<0.05
Non-Regulated Metals
Antimony
<0.48
<0.48
NA
NA
Beryllium
<0.01
<0.01
NA
NA
Copper
<0.03
0.03
NA
NA
Iron
4.43
0.034
NA
NA
Manganese
9.67
2.48
NA
NA
Nickel
<0,11
<0.11
NA
NA
Thallium
<1.53
<1.53
NA
NA
Vanadium
<0.07
<0.07
NA
NA
Zinc
0.52
0.46
NA
NA
a Results are the average of all five runs for each sediment, with the fourth run value being the average of laboratory triplicate
analysis.
b Levels presented are RCRA regulatory thresholds for hazardous materials.
NA Not analyzed
7-23
-------
It should be noted that there is some evidence that iron and manganese were less leachable
in treated solids than in the original feed, TCLP analyses for unregulated metals were conducted on
Sediment A feed and treated solids only. An order of magnitude reduction in leachable iron was
indicated by the data {4.43 mg/L in feed versus 0.34 mg/L in treated solids) and a significant reduction
in leachable manganese was indicated by the data (9.67 mg/L in feed versus 2.48 mg/L in treated
solids). These trends may be noticeable only because of the very high iron and manganese
concentrations in the Sediment A feed, relative to other metals. Sediment A consisted of
approximately 36 percent iron and 0.6 percent manganese (Table 7-15), which are very high levels.
However, although there may be an effect on these two metals, a similar effect cannot be assumed
for the other metals present at much lower levels.
7.11 SUPPLEMENTAL ANALYSES
There were five types of supplemental analyses performed on samples collected during the RCC
B.E.S.T.® SITE demonstration. The first type was a set of noncritical analyses performed on the
sediment feeds and their respective treated solids for the primary purpose of fully characterizing those
process streams. The second type was a set of noncritical parameters performed on product water
for determining concentrations of parameters commonly used as criteria for discharging wastewater.
The third type was a set of noncritical parameters performed on the oil/triethylamine mixture left after
treatment of Sediment A and the oil produced from treatment of Sediment B. These analyses were
performed solely to characterize the primary wastestream of the B.E.S.T.® Process. The fourth type
was organic analysis conducted on the oil/triethylamine mixture accumulating in the Solvent Evaporator
tank. This intermediate phase was analyzed for PAHs and PCBs to provide supplemental (though
crude) mass balance information. The fifth type was a set of critical and noncritical parameters
conducted on an oily water phase that was decanted from Sediment B, Run 3 feed material prior to
B.E.S.T.® treatment. These analyses were conducted to determine the quality of a sediment water
phase that would have to be treated separately if pretreatment decanting of sediments was to be
considered an option for full-scale operation.
7,11.1 Supplemental Analyses - Sediment Feed and Treated Solids
Supplemental analyses were performed on both sediment feeds and their respective treated
product solids. The primary purpose of these analyses was to more fully characterize the material
treated and the solids produced from the treatment. Because of their noncritical nature, most of these
analyses were only conducted on samples collected from one run from each test. Tables 7-17 through
7-19 summarize the results of the supplemental analyses for the feeds and treated solids for Sediments
A and B. Table 7-17 presents organic analyses utilizing alternative analytical test methods, inorganic
7-24
-------
analyses, and Proximate and Ultimate tests. Table 7-18 presents individual PCB congener data as
determined by Method 680. Table 7-19 presents particle size analysis for the sediment feed (by way
of wet sieve testing) and for treated solids (by way of dry sieve testing).
TABLE 7-17. SUPPLEMENTAL ANALYSES RESULTS - SEDIMENT A AND B
FEEDS AND TREATED SOLIDS
Parameter (units)3
SEDIMENT A
Treated
Feed Solids
SEDIMENT B
Treated
Feed Solids
TRPH (mg/kg)b
4730
<20
15,900
<20
Volatile Solids (%)b
8.5
7.1
31.8
17.1
Total PCBs (mg/kg)c d
6.0
0.07
397
1.1
Oil and Grease (mg/kg)b e
7400
570
197,000
12,000
Total Cyanide (mg/kg)c
17.7
12.2
43.2
96.1
Reactive Cyanide (mg/kg)b
<0.5
<0.4
<0.8
<0.3
Reactive Sulfide (mg/kg)b
152
<39
<77
53
Total Phosphorus (mg/kg)°
68
7.4
44.6
165
pHf
8.6-8.9
10.8-12.4
8.3-8.5
10.5-10.8
Proximate/Ultimate Testsb
- Moisture (%)
52.14
7.30
56.09
9.24
- Carbon (%)
11.85
11.40
39.45
23.53
- Ash (%)
87.31
79.49
50.13
65.40
- Sulfur (%)
0.16
0.17
0.88
0.79
- Oxygen (%)
0.33
8.26
6.18
8.09
- Hydrogen (%)
0.25
0.58
2.26
0.93
- Nitrogen (%)
0.10
0.09
1.11
1.26
- Btu/lb.
1892
1318
6675
3274
a All concentrations and percentages are reported on a dry weight basis,
b Results are the average of all five runs,
c Analysis was conducted for one run only.
d Supplemental PCB analysis results are from test method 680. Individual congener data are reported in Table 7-18.
e Supplemental 0&G analysis utilized the RCC B.E.S.T.® test method as opposed to the EPA SW-846 Method 9071 used for
data reported in Table 7-7.
f Results are the range of all five runs.
7-25
-------
TABLE 7-18. PCB CONGENER ANALYSIS RESULTS (METHOD 680) - SEDIMENT A AND B
FEEDS AND TREATED SOLIDS
Congener8
SEDIMENT A
Feed Treated Solids
(mg/kg) (mg/kg)
SEDIMENT B
Feed Treated Solids
(mg/kg) (mg/kg)
Mono -
<0.01
0.001
<0.04
<0.001
Di -
<0.01
0.01
14
<0.001
Tri -
2.3
0.03
104
0.30
Tetra -
2.3
0.02
201
0.53
Penta -
0.92
0.003
68.1
0.18
Hexa -
0.39
0.001
7.9
0.04
Hepta -
0.11
<0.001
2.2
0.01
Octa -
0.01
<0.001
0.58
0.002
Nono -
<0.01
<0.001
0.05
<0.001
Deca -
<0.01
<0.001
<0.04
<0.001
a Only those peaks meeting both retention time and ratio criteria were reported.
TABLE 7-19. PARTICLE SIZE ANALYSIS RESULTS - SEDIMENT A AND B
FEEDS AND TREATED SOLIDS
Test Sample
(Run No.)
Percent of Total
> 4.75mm"
4.75-2.00mmb
2.00mm-425/ymc
425-75//md
< 75/ymB
Sediment A
Feed'
0.00
4.60
27.55
40.16
27.69
Treated Solids0
0.31
3.86
14.60
49.87
31.36
Sediment B
Feed'
0.00
0.10
4.25
57.20
38.45
Treated Solids0
2.38
12.01
60.01
23.83
1.78
a Retained by No. 4 sieve,
b Retained by No, 10 sieve,
o Retained by No. 40 sieve,
d Retained by No. 200 sieve.
e Passes No. 200 sieve,
f Wet sieve
g Dry sieve
7-26
-------
7.11.2 Supplemental Analyses - Product Water
Supplemental analyses conducted on water produced during each run from treatment of both
sediment feeds included total recoverable petroleum hydrocarbons (TRPH), pH, total suspended and
total dissolved solids (TSS/TDS), and total organic carbon and total inorganic carbon (TOC/TIC).
Additionally, water produced from one of the optimum runs performed on each sediment type was
analyzed for total metals, total volatile solids, total cyanide, total phosphorus, biochemical oxygen
demand (BOD), and conductivity. The purpose of these analyses was to characterize the water for
determining disposal options and/or whether further treatment is necessary.
Table 7-20 presents the supplemental analyses performed on product water generated during
the demonstration tests except for total metals, which is presented in Table 7-21. From a regulatory
standpoint, the most notable value listed is the average pH of 12.2 measured for Sediment A product
water. RCRA regulates liquids having a pH of 12.5 or greater as corrosive. RCC has stated that the
pH of the water product was caused by excessive caustic added during water stripping operations.
7.11.3 Supplemental Analyses - Oil/Solvent Mixture and Sediment B Product Oil
Supplemental analyses conducted on the oil/solvent mixture from treatment of Sediment A and
the Sediment B product oil included moisture determination and proximate and ultimate analyses. The
purpose of these data is to characterize these concentrated wastestreams and make general
determinations as to their fuel value upon their disposal. It had been a foregone conclusion from the
start of the demonstration that the concentrated oily process streams collected from the Solvent
Evaporator would have to be incinerated due to the high levels of PCBs.
Table 7-22 presents the results of the supplemental analyses conducted on the Sediment A oil/
triethylamine mixture and Sediment B product oil.
7-11.4 Supplemental Analyses - Intermediate Oil/Solvent Mixture
Supplemental analyses for PAHs and PCBs were performed on the intermediate oil and
triethylamine mixture that accumulated in the Solvent Evaporator during treatment of each sediment.
The purpose of the analyses was to obtain a crude estimation of the removal of PAH and PCB
contaminants from the raw feed material and their buildup in the oil phase. The information served as
a backup for crude mass balance determinations in the event that product oil analyses could not be
validated. The data also gave insight into the incremental progress of each of the two tests.
7-27
-------
TABLE 7-20. SUPPLEMENTAL ANALYSES RESULTS - SEDIMENTS A AND B PRODUCT WATER
Parameter img/L)a
Sediment A
Sediment B
TRPHb
<0.44
17.5d
Total Volatile Solids0
116
7350®
Total Cyanide {ug/L)°
<5
<5
Total Phosphorus0
0.33
0.39
pHb
12.2
11.9
Total Suspended Solids'3
11
6
Total Dissolved Solids'5
1380
1670
Total Organic Carbonb
16.9
49.7
Total Inorganic Carbonb
17.1
13.2
Biochemical Oxygen Demand0
8.3
9.6
Conductivity (umhos/cm)c
2990
1520
a AH measurements ara reportad ir> mg/L except where indicated otherwise,
b Results are the average of all five runs,
c Analysis was conducted only for one run.
d The value given is misleading; all runs had values of <0.44 mg/L except for Run 5 where a value of 87.5 mg/L was reported
for TRPH.
e The value given is suspected to be incorrect because total volatile solids cannot exceed the sum of total suspended solids
and total dissolved solids (TDC), which it does. The TDCs average value is believed correct because all individual run values
of this measurement were comparable with one another.
7-28
-------
TABLE 7-21. TOTAL METALS IN PRODUCT WATER
Reg. Levelb
(mg/L)
SEDIMENT A" (mg/L)
Product Water
SEDIMENT Ba (mg/L)
Product Water
Regulated Metals
Arsenic
5
<0.03
<0.03
Barium
100
<0.06
<0.012
Cadmium
1
<0.03
<0.006
Chromium
5
<0.04
0.02
Lead
5
<0.21
<0.042
Mercury
0.2
<0.002
0.001
Selenium
1
<0.03
<0.03
Silver
5
NA
<0.01
Non Regulated Metals
Antimony
<0.48
<0.096
Beryllium
<0.01
<0.002
Copper
<0.04
0.042
Iron
0.63
0.56
Manganese
<0.010
0.01
Nickel
<0.11
<0.022
Thallium
<1.5
<0.31
Vanadium
<0.07
0.014
Zinc
0.13
0.07
a Results are reported for one optimal run.
b Levels presented are RCRA regulatory thresholds for hazardous materials,
NA Not analyzed
7-29
-------
TABLE 7-22. SUPPLEMENTAL ANALYSES RESULTS - OIL/SOLVENT MIXTURE AND PRODUCT OIL
Oil/Triethylamine Product Oil (from
Parameter (all values except) Mixture (from treatment treatment of
moisture, reported on dry wt. basis) of Sediment A) Sediment B)
Proximate/Ultimate Tests
- Moisture (%)
- Carbon {%)
- Ash (%)
- Sulfur (%)
- Oxygen (%)
- Hydrogen (%)
- Nitrogen (%)
- Btu/lb.
a Includes loss of triethylamine by air drying.
Table 7-23 presents the total PAH and PCB concentration in the oil/triethylamine mixture as
a progression of each run during treatment of both sediments. For sediment B, the concentration of
organics in the oil product (after removal of the solvent) is also presented. It is of note that the
cumulative buildup of organic contaminants (PAHs and PCBs) in the Solvent Evaporator is exponential
based on the limited data.
7.11,5 Supplemental Analyses - Sediment B Decant Water
Analyses of raw feed decant water was not included in the QAPP. However, during the
demonstration, the developer chose a process variation of treating raw feed that had first been
decanted of its oily water phase. This variability in treatment was consistent with the Demonstration
Plan, although this specific variation was not known by SITE beforehand.
The decanting of the oily water phase from the settled solids was conducted just prior to the
third run of Sediment B treatment. For all other runs conducted during the demonstration, the oily
water phase had been remixed with the settled solids prior to loading into the B.E.S.T.® pilot plant.
SITE collected approximately 6 L of decanted oil water from buckets of Sediment B feed for the
laboratory analyses. Parameters tested included PAHs, PCBs, O&G, TRPH, total metals, andTSS/TDS.
34.2"
0.81
87.1
88.6
1.34
0.59
0.34
0.70
0.22
2.4
10,9
7.2
0.03
0.5
19820
17250
7-30
-------
TABLE 7-23. PAH AND PCB CONCENTRATIONS IN OIL/SOLVENT MIXTURES
Parameter
R1
R2
Test Runs
R3
R4
R5
Sediment A
Total PAHs (mg/kg)
301
727
960
2510
11,800
Total PCBs (mg/kg)
6.7
11.5
14.6
28.2
190
Percent Accumulation® (%)
2.6
6
8
21
100
Sediment B
Total PAHs (mg/kg)
63,500
104,000
141,000
66,800b
394,000
Total PCBs (mg/kg)
248
730
627
358b
2,130
Percent Accumulation® (%) 1.6 26.4 35.8 17b 100
a The percent accumulation is the sum of the PAH and PCB concentrations for each of the first four runs as a percentage
of the PAH arid PCB concentration sums for Run 5, which is assumed to ba 100 percent of the PAHs and PCBs
concentrated in the Solvent Evaporator at the completion of all five runs.
b The Run 4 values are depressed because the Solvent Evaporator was emptied prior to acquiring the sample, thus the
organic accumulation was interrupted at this point.
Table 7-24 presents the results of analyses conducted on the Sediment B, Run 3 decant water.
The purpose of these analyses was to characterize the water phase that would have to be treated
separately if pretreatment decanting of sediments was to be considered an option for full-scale
operation.
7.12 MASS BALANCE DETERMINATIONS
Mass balances were performed for individual physical matrices, such as water, oil, and solids,
as well as for PCBs, PAHs, and O&G entering and exiting the system during system operation. These
balances were obtained by comparing the weights and volumes of raw feed and process additives (i.e.,
solvent, sodium hydroxide, etc.) entering the system with the various product fractions and samples
recovered during testing. Analytical data regarding contaminant concentrations within the various
fractions, as well as percent solids, water, etc., were used in conjunction with measurements recorded
during the demonstration. Since material holdup within the system could distort the individual material
balances obtained for each run (batch), the mass balances calculated within this report evaluate overall
performance during the five runs cumulatively. Cumulative balances comparing net mass entering and
exiting the B.E.S.T.® system were also performed.
7-31
-------
TABLE 7-24. SUPPLEMENTAL ANALYSES RESULTS - SEDIMENT B FEED DECANT WATER
Concentration" Concentration
(mg/L) (mg/L)
PAH Analytes
Total Metals
Acenaphthene
56
Antimony
4.8
Acenaphthylene
2, 7
Arsenic
<0.03
Anthracene
15
Barium
3.9
Benzo(a)anthracene
4.1
Beryllium
<0.1
Benzo(a)pyrene
3.3
Cadmium
<0.3
Benzo(b)fluoranthene
2.9
Chromium
<0.5
Benzo(k)fluoranthene
2.8
Copper
<0.4
Benzo(ghi)perylene
1.2
Iron
375
Chrysene
3.9
Lead
<2.1
Dibenz(a,h)anthracene
3.9
Manganese
4.2
Fluroanthene
18
Mercury
<0.001
Fluorene
30
Nickel
<1.1
Indenod ,2,3-cd)pyrene
1.8
Selenium
<0.03
2-Methylnaphthalene
73
Silver
NA
Naphthalene
73
Thallium
<15.3
Phenanthrene
42
Vanadium
<0.7
Pyrene
13
Zinc
3.1
Other Parameters
Total PCBs iug/L)a
880
Oil and Grease (mg/L)a
630
TRPH (mg/L) <0.44
Total Suspended Solids (mg/L) 238
Total Dissolved Solids (mg/L) 576
a Concentrations are the average of duplicate analyses.
Tables 7-25 and 7-26 present the mass balance summations for Sediment A inputs and outputs
respectively. Tables 7-27 and 7-28 present the mass balance summations for Sediment B inputs and
outputs respectively. Table 7-29 presents the input and output totals for each process material for
each of the two test sediments and provides the corresponding percent recoveries. The total materials
7-32
-------
balance results and results of the individual material balances are discussed separately in the following
subsections.
TABLE 7-25. MASS BALANCES - SEDIMENT A INPUTS
Input Material Masses (lbs.)
Total
Input Sources
Water
Solids
Oil & Triethyl-
Grease" amine
Total
PAHsc
Total PCBs0
Mass
(lbs.)
Feed
Run 1
68.64
85.04
0.57
0.0383
0.000628
154.25
Run 2
73.56
103.05
0.64
0.0525
0.000665
177.25
Run 3
65.02
95.82
0.91
0.0442
0.000775
161.75
Run 4
67.79
90.90
0.81
0.0521
0.001082
159.50
Run 5
65.98
93.22
0.55
0.0581
0.001538
159.75
Steam
Drying Stages1"
37.80
...
—
...
—
37.80
Stripping Stagesb
82.90
...
...
...
...
82.90
Water
Test Startupb
61.10
—
-
...
...
61.10
Decanting
26.40
~
...
...
—
26.40
Caustic
Extractions
2.70
2.70
...
...
...
5.40
Drying Stages
3.00
3.00
...
—
...
6.00
Stripping Stages
0.60
0.60
...
...
...
1.20
TriethYlamine
—
—
751.00
...
...
751.00
Totals
555.49 474.33
3.48 751.00 0.2452 0.004688 1784.30
a Values are derived from the B.E.S.T.® test method for determination of O&G.
b Values were acquired from RCC.
o These masses are presumed to be included in the mass of O&G.
7-33
-------
TABLE 7-26. MASS BALANCES
- SEDIMENT A OUTPUTS
OutDut Material Masses (lbs.)
Total
Output Sources
Water
Solids
Oil &
Grease"
Triethyl-
amine
Total
PAHsc
Total PCBs0
Mass
(lbs.)
Treated Solids
Run 1
29.21
49.51
0.022
0.005
0.0014
<4 x 10-6
78.75
Run 2
19.57
94.89
0.026
0.011
0.0027
1.9 x 10"6
114.50
Run 3
2.85
66.59
0.058
0.002
0.0014
<3.3 x 10-8
69.50
Run 4
12.82
88.87
0.055
0.003
0.0025
3.6 x 10"8
101.75
Run 5
1.44
71.01
0.045
0.009
0.0012
2.8 x 10"6
72.50
Product Water
Run 1
113.99
0.29
0.0006
...
<2 x 10"B
<3 x 10"7
114.28
Run 2
93.17
0.11
0.0003
...
<2 x 10"5
<3 x 10"7
93.28
Run 3
137.14
0.14
0.0005
...
<2 x 10B
<4 x 10"7
137.28
Run 4
117.65
0.11
0.0004
...
<2 x 10'6
<4 x 10"7
117.76
Run 5
126.90
0.16
0.0005
...
<2 x 10s
<4 x 10*7
127.06
Product Oil
(65.8% Solvent)
0.09
0.43
7.44
15.32
0.2737
0.00441
23.28
Solvent Drained
19.50
...
...
565.00
...
...
584.50
Solvent left in unitb
—
...
...
44.00
...
...
44.00
Decon. Residualb
...
45.60
...
...
—
...
45.60
Vent Filter
...
—
...
8.50
...
...
8.50
RCC Samples*
0.03
0.42
0.06
3.01
...
...
3.52
Solvent Decanterb
17.60
...
...
14.50
...
...
32.10
Filterb,d
...
1.60
...
1.60
—
...
3.20
Totals
691.96
419.73
7.71
651.96
0.2829
0.00444
1771.36
a Values are derived from the B.E.S.T.® test method for determination of O&G.
b Values were acquired from RCC,
c These masses are presumed to be included in the mass of O&G.
d The triethylamine and solids masses presented for the filter are estimated to each represent half of the total measured mass of
filtered material (a 50/50% split).
7-34
-------
TABLE 7-27. MASS BALANCES - SEDIMENT B INPUTS
Input Sources
Input Material Masses (lbs.)
Oil & Triethyl- Total
Water
Solids
Grease"
amine
PAHsc Total PCBsc
Total
Mass
(lbs.)
Feed
Run 1
134.48 55.76
16.01
4.03
0.02613
206.25
Run 2
Run 3
Run 4
Run 5
Steam
Drying Stagesb
Stripping Stagesb
Water
Test Startupb
Decanting
Oil Polishing
Caustic
Extractions
Drying Stages
Stripping Stages
Triethylamine
Solvent added
Solvent left in
unitb
Totals
112.14
92.50
112.97
113.28
46.30
75.20
26.40
44.00
4.65
4.46
0.52
57.14
56.30
56.67
49.19
4.65
4.46
0.52
10.72
13.20
12.86
14.53
4.35
6.33
4.41
5.43
766.90 284.69
847.00
44.00
67.32 891.00 24.55
0.02144
0.03440
0.03212
0.03167
0.14576
180.00
162.00
182.50
177.00
46.30
75.20
26.40
44.00
9.30
8.92
1.04
847.00
44.00
2009.91
a Values are derived from the B.E.S.T.® test method for determination of O&G.
b Values were acquired from RCC.
c These masses are presumed to be included in the mass of O&G.
7-35
-------
TABLE 7-28 MASS BALANCES - SEDIMENT B OUTPUTS
Output Sources
Water Solids
Output Material Masses (lbs.)
Oil & Triethyl-
Grease8 amine
Total
PAHsc
Total PCBs0
Total
Mass
(lbs.)
Treated Solids
Run 1
5.79
41.25
0.455
0.005
0.0175
6.3 x 10-®
47.50
Run 2
7.34
46.07
0.589
0.005
0.0209
9.8 x 10 B
54.00
Run 3
4.26
56.76
0.730
0.003
0.0172
6.9 x 10B
61.75
Run 4
8.23
58.50
0.759
0.009
0.0238
1.07 x 10 4
67.50
Run 5
6.59
60.22
0.681
0.006
0.0415
<8.5 x 10"6
67.50
Product Water
Run 1
146.31
0.074
0.004
...
<2 x 10s
<2 x 10"6
146.38
Run 2
149.74
0.145
0.0003
...
<2 x 10-6
<1 x 10-7
149.88
Run 3
101.60
0.280
0.0004
—
<1 x10*
<1 x 10"7
101.88
Run 4
159.86
0.576
0.0004
...
<2 x 10"8
<2 x 107
160.44
Run 5
154.45
0.082
0.0004
...
<2 x 10-6
<2 x 10"7
154.53
Product Oil
0.61
1.16
72.93
0.055
29.43
0.1589
74.75
Triethylamine
Solvent Drained
128.00
...
—
591.00
...
—
719.00
Solvent in Evaporator
...
...
3.61
51.39
1.46
0.0039
55.00
Solvent left in unitb
—
...
...
44.00
—
—
44.00
Decon, Residualb
—
33.70
...
...
...
—
33.70
Vent Filter
—
...
...
14.00
...
...
14.00
RCC Samples'3
0.10
0.29
0.21
5.40
—
...
6.00
Solvent Decanter6
15.40
...
...
14.50
...
...
29.90
Filterb
...
7.00
...
7.00
...
...
14.00
Totals
888.28
306.11
79.97
727.37
31.01
0.1632
2001.71
a Values are derived from the B.E.S.T.® test method for determination of O&G.
b Values were acquired from RCC.
c These masses are presumed to be included in the mass of O&G,
7-36
-------
TABLE 7-29. MASS BALANCE SUMMARIES
Test Sediment
Materials
Oil & Triethyl-
Water Solids Grease®
amine
Total
PAHs
Total PCBs
Total
Mass
Sediment A
Input Total (lbs.)
Output Total (lbs.)
Recovery15 (%)
555.49 474.33 3.48 751.00 0.2452 0.004688 1784.30
691.96 419.73 7.71 651.96 0.2829 0.00444 1771.36
124.6 88.5 222 86.8 115.4 94.7 99.3
Sediment B
Input Total (lbs.)
Output Total (lbs.)
Recoveryb (%)
766.90 284.69
888.28 306.11
115.8 107.5
67.32 891.00 24.55
79.97 727.37 31.01
118.8 81.6 126.3
0.14576 2009.91
0.1632 2001.71
112.0 99.6
a Values are derived from B.E.S.T.® test method for determination of O&G.
b Percent recoveries = output total x 100
input total
7.13.1 Total Materials Balance
Mass balances for all materials entering and exiting the process were also calculated. Closures
of 99.3 percent and 99.6 percent were obtained for Sediments A and B, respectively (Table 7-29).
These closures are very good and show that even though individual balances may vary because of the
considerable number of analyses involved, no significant amount of material was lost during treatment
of either Sediment A or Sediment B.
7.13.2 Solids Balance
Solids balances were performed during the demonstration by comparing the amount of solids
entering the system as part of feed sediment to the process solids recovered. Solids balance closures
of 88.5 and 107.5 percent were obtained for Sediments A and B respectively (Table 7-29). These
results are consistent with demonstration test objectives of closures between 80 and 130 percent.
7-37
-------
7.13.3 PCB Balance
Closures of approximately 95 and 112 percent were obtained for PCBs during the treatment
of Sediments A and B, respectively {Table 7-29). The amount of PCBs entering the system was
calculated by multiplying the analytically determined value for PCB concentrations present within the
feed by the weight of the feed entering the system. This value was then compared with the
cumulative amount of PCBs deposited in the various system products, particularly the oil product. The
PCB balance results are consistent with the demonstration test objectives of closures between 80 and
130 percent.
7.13.4 PAH Balance
Like PCBs, all of the PAHs entered in the feed sediment, while the majority exited in the
product oil. Closures of approximately 115 and 126 percent were obtained for PAHs during the
treatment of Sediments A and B, respectively (Table 7-29). These closures meet the demonstration
test objectives of closures between 80 and 130 percent.
7.13.5 Oil and Grease Balance
Closures of approximately 222 and 119 percent were obtained for O&G during the treatment
of Sediments A and B, respectively (Table 7-29). The amount of O&G entering the system was
calculated by multiplying the analytically determined value for the concentration of O&G present within
the feed by the weight of the feed entering the system. Values for O&G exiting the system were
determined using analytical data regarding O&G concentrations within the oil product. The closure for
Sediment B met the demonstration test objective of closure between 80 and 130 percent. The
elevated recovery obtained for Sediment A can in part be attributed to inaccuracies in the analytical
values achieved for O&G concentrations associated with the low oil content of the sediment entering
the system. The determination of the mass of O&G in the product oil/solvent mixture is difficult
because of the high percentage of solvent that remained in this mixture. It is possible that some
triethylamine was extracted out of the treated solids by the methylene chloride, and was thus
inadvertently included in the mass value for O&G. Also, O&G in feed sediments were analytically
determined by extraction with methylene chloride, while the pilot unit used triethylamine as its
extraction solvent.
7-38
-------
7.13.6 Water Balance
Water balances were performed during the demonstration by comparing the amount of process
water entering the B.E.S.T,® system to the mass of product water exiting the system. Although the
majority of the process water enters the system as part of the feed, a portion enters the B.E.S.T.®
system in the Extractor/Dryer vessel and during steam stripping of the product water. Closures of
approximately 125 percent and 116 percent were obtained for testing performed on Sediments A and
B, respectively (Table 7-29). Demonstration objectives of closures between 80 and 130 percent were
met during the processing of Sediment A and Sediment B.
7.13.7 Solvent (Triethylamine) Balance
Triethylamine is used as the extraction solvent in the B.E.S.T.® system. The used triethylamine
is recovered and reused without exiting the system, although small amounts of triethylamine remain
in the treated solids, water product, and oil product. Solvent mass balance closures of approximately
87 percent and 82 percent were obtained for Sediments A and B, respectively (Table 7-29). The
demonstration test objectives were closures between 80 and 130 percent. Therefore, these results
are within the targeted objectives. The lower recovery value obtained for Sediment B represents the
difficulty of allocating mass between water and solvent at the end of a series of runs for a given
sediment. Different portions of the process yield liquid containing both solvent and water in separate
phases.
7-39
-------
SECTION 8
CONCLUSIONS
This section summarizes conclusions reached regarding the performance of the RCC B.E.S.T.®
pilot plant during the SITE demonstration testing performed between July 1 and July 22, 1992 in Gary,
Indiana. The conclusions that follow are based on interpretations made about the data results
presented in Section 7 of this report. The validity of the data is discussed in Section 9 of this report.
Evaluation of the demonstration test data indicates that the RCC B.E.S.T.® Process was very
effective in removing organic contaminants from test sediments collected from the GCR, at a pilot-
scale. All vendor claims made prior to the demonstration regarding percent removal of organics,
solvent residual in process products, and system mass balance were met. The more important
conclusions made regarding the technology's effectiveness in treating the GCR sediment are
summarized in Table 8-1. All conclusions reached are discussed in the following subsections.
8.1 REMOVAL OF ORGANIC COMPOUNDS
Removal of organic compounds from GCR sediments ranged from 96 percent (for PAHs in
Sediment A feed) to greater than 99 percent (for PCBs in both sediment feeds). These organic removal
efficiencies, which are discussed in the following subsections, are based on analytical results generated
by the primary SITE project laboratory, Maxwell/S-Cubed Division. Although the validity of this data
is thoroughly discussed in Section 9 of this report, it can be further substantiated by comparison to
analytical results reported by the developer. Complying with their agreement with the COE, Chicago
District, RCC conducted independent analyses of split samples collected during the demonstration.
Table 8-2 provides a comparison of SITE'S organic analysis results to those of the developer. The
similarity in data results, generated independently by two different and totally independent laboratories,
serves to further substantiate the demonstration results.
8-1
-------
TABLE 8-1. SUMMARY OF CONCLUSIONS - B.E.S.T.® SITE DEMONSTRATION
Contaminant Removal
Contaminant Results Conclusion
PAHs 96% removal in Sediment A, Claims met; B.E.S.T.® effective in removing
>99% removal in Sediment B ^96% of PAHs in GCR test sediments
PCBs >99% removal in both Claims exceeded; B.E.S.T.® effective in
sediments removing >99% of PCBs in GCR test
sediments
O&G >98% removal in both {no claim); B.E.S.T.® effective in removing
sediments >98% of O&G in GCR test sediments
Mass Balance
Results (% recovery)
Category
Sediment A
Sediment B
Conclusion
Total Mass Balance
99.3
99.6
Demonstration claim met for total mass
- Solids Balance
88.5
107.5
balance. B.E.S.T.® system materials
- Water Balance
125
116
accounted for to >99% {which is
considered a very good mass balance
- Solvent Balance
86.8
81.6
closure). Variations in individual material
- PAH Balance
115
126
mass balance recoveries are considered
- PCB Balance
94.7
112
minor, except for O&G recovery.
- O&G Balance
222
119
Process Operation
Operation Results Conclusion
Extraction Efficiency Sediment A optimum The optimum extraction sequence for
extraction sequence = 2 cold, attaining best results in treating GCR
1 warm, 3 hot, and 1 warm. sediments in the most efficient manner is to
Sediment B optimum extraction conduct a minimum of one cold extraction
sequence = 2 cold and 5 hot. initially to dewater the feed, followed by
warm and/or hot extractions to remove any
remaining organic contaminants.
83% avg. decrease in moisture B.E.S.T.® dewatering via cold solvent
of product solids vs feed solids extractions coupled with steam aided drying
and ¦£, 103 mg/kg of solvent in following hot extractions result in a
product solids relatively dry and solvent residual-free solids
product.
<2 mg/mL residual solvent in B.E.S.T.® distillation and stripping processes
all product water effectively remove most solvent from
water.
733 mg/kg of residual B.E.S.T.® oil polishing effectively recovers
triethylamine in Sediment B solvent from oil, thus minimizing the volume
product oil of hazardous oil phase
Solids Drying
Water Separation
Oil Polishing
8-2
-------
TABLE 8-2. COMPARISON OF ORGANIC ANALYSES (SITE AND RCC)
Analyte (Laboratory)
Feed*
Sediment A
Treated
Solids*
%
Removal1"
Feed*
Sediment B
Treated
Solids*
%
Removal1"
Total PAHs
SITE
548
22
96
70,920
510
99.3
RCC
782
34
95.7
87,500
716
99.2
Total PCBs
SITE
12.1
0.04
99.7
425
1.8
99.6
RCC
5.5
0.07
98.7
580
1.1
99.8
Oil & Grease
SITE*
7,400
570
92.3
197,000
12,000
93.9
RCCC
18,500
710
96.2
219,000
15,400
93
a Concentrations reported in mg/kg (dry weight basis) and are the average of the three optimum runs for each sediment.
{Sediment A = Runs 3, 4, and 5; Sediment B = Runs 2, 4, and S).
b Percent removals = Feed concentration - Treated Solids Concentration ^ 100
Feed concentration
o Value acquired from B.E.S.T® Test Method.
8.1.1 Removal of PAHs
When using the raw sediment feed and treated solids average PAH concentrations for the three
optimum runs, the efficiency for removing PAHs from Sediment A feed was 96 percent. This met the
vendor claim of 96 to 99 percent removal of total PAHs. When using the same optimum run averages
scenario, the efficiency of removing total PAHs from Sediment B feed solids was even better, as
calculated at 99.3 percent. This increased removal percentage is attributed to the much higher PAH
content in Sediment B feed, which contained approximately 71,000 mg/kg of total PAHs as compared
to 548 mg/kg for Sediment A feed. Figures 8-1 and 8-2 graphically illustrate the PAH contaminant
removal on a per run basis, for Sediments A and B, respectively. Both figures clearly illustrate that
fairly high removal efficiencies were attained for all runs conducted and that field optimization either
increased those efficiencies by about 2 percent {as in the case of Sediment A) or did not have much
effect on an apparently already optimized system (as in the case of Sediment B). This observation
confirms the importance of the preliminary bench-scale treatability testing conducted on the sediments,
which apparently had the greatest impact on optimization.
8-3
-------
mg/kg
800
Sediment A
600
400
200-
Run 1 Run 2 Run 3 Run 4 Run 5
Figure 8-1. PAH contaminant removal - Sediment A.
mg/kg
100000-f:
75000-!!!
50000
25000
Sediment B
Untreated
Treated
91,000
85.2000
64,100
63,500
56,200
Run 1
Run 2
Run 3
Run 4
Run 5
Figure 8-2. PAH contaminant removal - Sediment B.
8-4
-------
Of the 14 specific PAH compounds measured above detection limits in Sediment A feed, 8
were removed at efficiencies greater than 98 percent. Only two PAH compounds were removed by
less than 96 percent {anthracene at 94 percent and 2-Methylnaphthalene at 85 percent). Of the 17
specific PAH compounds detected in Sediment B Feed solids, the lowest calculated removal efficiency
was 97 percent (for acenaphthylene). Thirteen of the PAH compounds were removed by efficiencies
of greater than 99 percent.
8.1.2 Removal of PCBs
The efficiency for removing total PCBs from both sediment feed solids exceeded 99 percent
when averaging either the three optimum runs or all five runs, although the average removals for the
optimized runs were higher. Treatment of Sediments A and B under optimized conditions resulted in
average PCB removals of 99.7 and greater than 99.6 percent, respectively. This easily exceeded the
vendor claim of achieving organic removals in the range of 96 to 99 percent.
On a per run basis, treatment of Sediment A resulted in total PCB removals exceeding 99
percent for all test runs except for Run 2, where the removal was calculated at 96.7 percent. Under
optimized conditions, total PCB removals ranged from 99.4 to 99.8 percent. On a per run basis,
treatment of Sediment B resulted in total PCB removals exceeding 99 percent for all test runs and
under optimized conditions the total PCB removals ranged from 99.3 to 99.8 percent. Figures 8-3 and
8-4 graphically illustrate the PCB contaminant removal on a per run basis for Sediments A and B,
respectively.
The PCB data results from the two demonstration tests may have been the most important
information acquired from the demonstration as a whole. This is because the total PCBs were at such
contrasting levels in the two sediment types. Sediment A feed contained, on the average, a very small
concentration of PCBs {12 mg/kg) while Sediment B feed contained an average PCB concentration an
order of magnitude higher (425 mg/kg). By achieving high removal efficiencies for both sediment
types, the B.E.S.T.® Process was found effective in removing PCBs to very low levels (i.e., less than
the commonly required regulatory cleanup level of 2 mg/kg) regardless of the initial concentrations in
untreated material.
8-5
-------
Sediment A
mg/kg
20
15
10
5
0
Run 1 Run 2 Run 3 Run 4 Run 5
Figure 8-3. PCB contaminant removal - Sediment A.
~ Untreated
| Treated
Sediment B
mg/kg
200-
100
2.1
1.2
1.8
Run 1 Run 2 Run 3 Run 4 Run 5
Figure 8-4. PCB contaminant removal - Sediment B.
8-6
16.5
11.8
/ 31
7.33
8.01
6.41
/
<0.07
7-
0.20
zd
0.05
0.04
0.04
I/ //
-------
8,1,3 Removal of Oil and Grease
The efficiency for removing O&G from both sediment feed solids exceeded 98 percent when
averaging either the three optimum runs or all five runs, although the average removals for the
optimized runs were slightly higher. Optimized B.E.S.T.® Process treatment of Sediments A and B
resulted in average removals of 98.4 and 98.9 percent, respectively. This met the vendor claim of
achieving specific organic contaminant removals in the range of 96 to 99 percent, even though no
specific claim for O&G removal was made.
On a per run basis, treatment of Sediment A resulted in O&G removals easily exceeding 97
percent for ail test runs. Under optimized conditions, O&G removals ranged from 97.3 to 99.0
percent. On a per run basis, treatment of Sediment B resulted in O&G removals also exceeding 97
percent for all test runs. Under optimized conditions, removals ranged from 98.2 to 99.3 percent.
Figures 8-5 and 8-6 graphically illustrate the O&G contaminant removal on a per run basis for
Sediments A and B, respectively.
8.2 TRIETHYLAMINE RESIDUAL IN PRODUCTS
All claims for residual triethylamine solvent in the product solids, product water, and product
oil generated during the SITE demonstration were met. The optimum run average for residual solvent
in Sediment A and B treated solids was 45 mg/kg and 103 mg/kg, respectively. Since residual solvent
concentrations in both product solids were below the claim of less than 150 mg/kg, it can be
concluded that pilot plant operations effectively remove triethylamine from the separated solids once
the extractions are completed.
The reported analysis results for residual solvent in product water was less than 2 mg/L for the
Sediment A water phase and less than 1 mg/L for the Sediment B water phase, well below the claim
of less than 80 mg/L. It can thus be concluded that practically all (if not all) the triethylamine can be
stripped from product water with the aid of caustic to adjust pH. It should be noted, however, that
addition of caustic to enhance removal of triethylamine is a somewhat precise undertaking that can
result in production of RCRA corrosive water (pH a 12.5) if close attention is not given.
The residual solvent in the Sediment B product oil was detected at 733 mg/kg, below the claim
of less than 1000 mg/kg. Thus it can be concluded that the B.E.S.T.® oil polishing stage conducted
within the Solvent Evaporator is an effective distillation-type procedure for recovering most of the
triethylamine from the organic concentrated product oil. The effectiveness of the oil polishing is
important for minimizing the volume of the organic-rich hazardous oil phase since further treatment
(i.e., incineration) is commonly required for that process wastestream.
8-7
-------
Sediment A
mg/kg
innnn-/[~9,40Q
7,800
7,400
6,700
7500
6,600
5000-
2500
195
203
169
Run 4
Run 5
Run 1
Run 3
Run 2
Figure 8-5. O & G contaminant removal - Sediment A.
M Untreated
I Treated
Sediment B
mg/kg
200000
167,000
150000
116,000
99,100
zrz
100000
67,300
66,400
50000
1,490
1,230
1,810
1,330
1,800
Z7
Run 5
Run 1
Run 4
Run 2
Run 3
Figure 8-6. O & G contaminant removal - Sediment B.
8-8
-------
With respect to the pilot-scale demonstration tests, the volume reduction achieved from the
production of concentrated oil product from the initial raw feed material was significant. For treatment
of approximately 813 pounds of Sediment A raw feed, approximately 23 pounds of oil/solvent mixture
was produced. This mixture consisted of 65.8 percent solvent; therefore, assuming oil polishing would
remove all of the solvent, approximately 8 pounds of oil was produced from the 813 pounds of feed
(a reduction factor of approximately 100). For treatment of approximately 907 pounds of Sediment
B raw feed, approximately 75 pounds of oil was produced (a reduction factor of approximately 12).
Although it should be noted that RCC did dispose of four drums of triethylamine solvent recovered from
the demonstration tests, the volume of solvent disposed of during full-scale operation is expected to
be negligable compared to disposal of product oil (since the solvent can be recycled numerous times).
8.3 MASS BALANCE
The vendor claim of attaining mass balance closure of between 85 and 115 percent of feed
material mass into the B.E.S.T.® pilot unit versus total products mass {solids, water, and oil) was met.
The closures obtained, 99.3 percent for Sediment A testing and 99.6 percent for Sediment B testing,
are considered very good and show that practically all materials were accounted for as a total during
the demonstration tests.
All individual materials balances fell within SITE'S 80 to 130 percent range objective for both
Sediment A and B tests, except for the Sediment B O&G recovery (222 percent). This variation is
thought to be most attributed to error associated with the analysis test method used for determining
O&G concentrations.
8.4 OTHER CONCLUSIONS
8.4.1 TCLP Leachabilitv of Treated Solids
The leachability of regulated heavy metals from the treated solids products of both Sediments
A and B could not be evaluated, because neither of the sediment feeds could be leached of any
regulated metals by way of the TCLP. However, based on iron and manganese TCLP results from
Sediment A (which had the much higher metals content), those metals were less teachable in treated
solids than in the raw feed.
8-9
-------
8.4.2 Biodeoradabilitv of Triethvlamine
Based on the simple biodegradation testing conducted for the demonstration (see subsection
7.7), no evidence was generated indicating that triethylamine present at 25 to 100 ppm is biodegraded
in soil within 2 months of application. The most likely reasons for lack of biodegrading activity is
believed to be amine binding to the humic fraction and not optimizing pH and nutrients for this test.
Figure 8-7 shows plots of triethylamine concentrations versus the biodegradation time for both
the test soil (unaltered) and corresponding inhibited control samples for Sediment A, Run 1 test soil
and Sediment B, Run 4 test soil. In both cases, the triethylamine concentration in the unaltered test
soils mimics the triethylamine concentration in the control samples and it can be concluded that the
triethylamine residual is not biodegrading. Also, because triethylamine concentrations remain relatively
constant over the testing period, it is further concluded that the residual solvent is not volatilizing.
Since the triethylamine residual in the treated solids did not volatilize, it should not pose an inhalation
hazard.
175
150
I
I
a
125
>»
£
#
i-
100
2
E
50
DAY0
DAY 14
DAY 28
DAY 56
Sediment A (R1) —-O-— Control A
Sediment B (R4) -—A— Control B
Figure 8-7. Triethylamine biodegradability.
8-10
-------
SECTION 9
QUALITY ASSURANCE/QUALITY CONTROL
9.1 INTRODUCTION
In order to obtain data of known quality to be used in evaluating the B.E.S.T.® Process for the
two sediments, a Quality Assurance Project Plan (QAPP) was prepared. The QAPP specified the
guidelines to be used to ensure that each measurement system was in control. In order to show the
effectiveness of the technology, the following measurements were identified in the QAPP as critical;
PAHs, PCBs, TCLP metals, moisture, O&G, and triethylamine in the untreated and treated sediments.
Other parameters analyzed in the sediments included pH, total cyanide, total phosphorus, volatile
solids, total metals, reactive cyanide, reactive sulfide, particle size, and ultimate/proximate analyses,
The water product was analyzed for PAHs, PCBs, O&G, triethylamine, TSS, TDS, TOC/TIC, pH, TRPH,
volatile solids, total cyanide, total phosphorus, BOD, conductivity, and total metals. The oil product
was analyzed for PAHs, PCBs, triethylamine, moisture, and ultimate/proximate analyses. The solvent
feed and recovered solvent were analyzed for PAHs, PCBs, and TSS as a check for contamination.
The intermediate oil/solvent mixture (prior to polishing) was analyzed for PAHs and PCBs as a check
on their fate from the sediment treatment. Vent gas was continuously monitored for triethylamine.
The associated quality control (QC) data will be discussed in this section.
Also included in this section are discussions of the QC results, modifications and deviations
from the QAPP, and the results of audits performed. Any possible effects of deviations or audit
findings on data quality are presented.
Samples in this section are identified by the number assigned at the time of sampling. A
coded sample identification system was employed that related each sample to the sediment type, test
phase, run number, sample medium, chronologic order of collection, and quality assurance status. This
self-explanatory code enabled SITE field and laboratory personnel to know the most important aspects
of each sample without having to access a cross reference.
The following numbering system was used and should be used as a reference.
9-1
-------
Run No. (Run 1)
pSampIe Number
Phase No.(Phase 1}
A11 - US - 001 D
Duplicate Sample
Sediment Type
(A = Sediment from Transect 28)
(B = Sediment from Transect 6)
Process Stream
(US = Untreated Sediment)
(TS = Treated Solid)
(WP = Water Phase)
(OP = Oil Phase)
(IO = Internal Drummed Oil)
(SF = Solvent Feed)
(RS = Recovered Solvent)
(EB = Equipment Blank)
(DW = Decant Water)
(VG = Vent Gas)
(EB/PP = Equipment Blank/Pilot Plant)
9.2 PROCEDURES USED FOR ASSESSING DATA QUALITY
The indicators used to assess the quality of the data generated for this project are accuracy,
precision, completeness, representativeness, and comparability. All indicators will be discussed
generally in this subsection; specific results for accuracy and precision are summarized in later
subsections.
9.2.1 Accuracy
Accuracy is the degree of agreement of a measured value with the true or expected value.
Accuracy for this project will be expressed as a percent recovery (percent).
Accuracy was determined during this project using matrix spikes (MS) and/or laboratory
control samples (LCSs). Matrix spikes are aliquots of sample spiked with a known concentration of
target analyte(s) used to document the accuracy of a method in a given sample matrix. For matrix
spikes, recovery is calculated as follows:
%R = Cl " C° x 100
Ct
9-2
-------
where: C, = measured concentration in spiked sample aliquot
C„ = measured concentration in unspiked sample aliquot
Ct = actual concentration of spike added
An LCS is a blank matrix spiked with representative target analytes used to document laboratory
performance. For LCSs, recovery is calculated as follows:
%R = Si X 100
Ct
where: Cm = measured concentration of LCS
C, = true concentration of LCS
In addition, for the organic analyses, surrogates were added to all samples and blanks to
monitor extraction efficiencies. Surrogates are compounds which are similar to target analytes in
chemical composition and behavior. Surrogate recoveries will be calculated as shown above for LCSs.
9.2.2 Precision
Precision is the agreement among a set of replicate measurements without assumption of
knowledge of the true value. When the number of replicates is two, precision is determined using the
relative percent difference IRPD):
ppp _ " ^2) x 100
________
where: C, = the larger of two observed values
C2 = the smaller of two observed values
When the number of replicates is three or greater, precision is determined using the relative standard
deviation {RSD):
RSD = S/X x 100
where: S = standard deviation of replicates
X = mean of replicates
9-3
-------
Precision was determined during this project using matrix duplicate (MD) and matrix triplicate
(MT) analyses or matrix spike/matrix spike duplicate/matrix spike triplicate (MS/MSD/MST) analyses.
An MSD is a second spiked sample aliquot with a known concentration of target analyte used to
document accuracy and precision in a given sample matrix; an MST is a third aliquot. If the spike
concentration did not double that present in the sample, then the RSD was calculated using
MS/MSD/MST results uncorrected for native concentrations. If the spike concentration did at least
double that present in the sample, then RSD was calculated using MS/MSD/MST results corrected for
native concentrations. Precision was also determined for replicate field samples collected for each
sample matrix.
9.2.3 Completeness
Completeness is a measure of the amount of valid data produced compared to the total
amount of data planned for the project. For the B.E.S.T.® demonstration, no samples were lost due
to field or analytical problems. Though all guidelines for QA objectives were not met, all data
generated were deemed usable.
9.2.4 Representativeness
Representativeness refers to a degree with which analytical results accurately and precisely
represent actual conditions present at locations chosen for sample collection. Sediment samples were
collected prior to this demonstration and were typical of the area to be remediated. These sediment
samples were thoroughly homogenized prior to testing. Samples of untreated and treated sediment
and residuals were taken by SAIC personnel and shipped under chain-of-custody to Maxwell/S-Cubed
Laboratory in San Diego, California. Therefore, the data are representative of material actually treated.
9.2.5 Comparability
Comparability expresses the extent with which one data set can be compared to another. As
standard EPA, ASTM, or NIOSH procedures were used in nearly all cases, results should be comparable
to data generated for other similar projects. Two exceptions include the non-standard procedures used
for triethylamine in soil and water matrices and the B.E.S.T.® method for O&G. These analyses were
performed to verify the developer's results.
9-4
-------
9.3 ANALYTICAL QUALITY CONTROL
The following subsections summarize and discuss analytical procedures and the results of the
QC indicators of accuracy and precision for each measurement parameter for the B.E.S.T,® technology
demonstration.
9.3.1 PAHs
9.3.1.1 PAH Procedures
Untreated sediments and treated solids were extracted by SW-846 Method 3540 (Soxhiet)
with 1:1 hexane/acetone (V/V). Water product samples were extracted using SW-846 Method 3520.
Oil product and solvent samples were diluted according to the procedures in SW-846 Method 3580.
The extracts of the sediments, treated solids, oils, and solvents were cleaned by gel-permeation
chromatography (GPC! prior to analysis. All extracts were analyzed by GC/MS using SW-846 Method
8270.
Seven surrogates were added to all samples and blanks to monitor extraction efficiency. Acid
surrogates were added only to provide additional information; no corrective action was performed
based on these recoveries. Daily mass tuning was performed using decafluorotriphenylphosphine
(DFTPP) to meet the criteria specified in Method 8270. The instrument was calibrated at 5 levels for
17 PAHs. Initial and continuing calibration procedures followed those specified in Method 8270.
Internal standards were added to all extracts prior to analysis.
9.3.1.2 PAH Surrogates
Surrogate recoveries for all PAH samples for the B.E.S.T.® demonstration are summarized in
Tables 9-1 and 9-2. If any of the four base-neutral surrogates fell outside the control limits used,
corrective action (re-analysis) was necessary. Three acid surrogates were added only to provide
additional information about the analysis; no corrective action was required if advisory control limits
were exceeded.
All base-neutral surrogate recoveries for Sediment A samples were within the control limits
specified in the QAPP. As can be seen in Table 9-1, some acid surrogates were outside advisory
control limits, possibly due to the basic nature of the process residuals. Critical PAH concentrations
should not be affected.
9-5
-------
TABLE 9-1. PAH SURROGATE RECOVERIES FOR SEDIMENT A (Percent)
Sample
Nitrobenzene-
2-
Fluorobiphenyl
Tarphenyl-
du
Phenol-
d6
2-
Fluorophenol
2,4,6-
Tribromopheno!
Anthracene-
dio
A11-US-001
55
62
66
62
59
50
51
A12-US-002
64
72
75
69
68
61
57
A13-US-003
61
62
66
68
70
62
53
A21-US-004
69
76
90
101
78
110
94
-004D
59
63
66
64
70
60
54
-004T
64
65
73
72
77
58
56
A22-US-005
61
63
69
68
71
61
52
A11-TS-001
99
53
55
532**
535**
53
70
A12-TS-002
46
67
62
68
78
38
64
A13-TS-003
65
73
79
71
63
51
60
A21-TS-004
62
73
80
93
77
135**
94
-004D
67
77
84
105
88
152**
98
-004T
75
74
63
76
84
51
69
A22-TS-005
57
67
68
67
57
50
65
A11-WP-001
79
79
88
42
87
79
80
A12-WP-002
74
80
87
87
89
85
84
A13-WP-003
72
71
74
78
76
83
73
A21 -WP-004
67
70
73
72
79
82
69
-004D
41
65
68
46
28
39
70
-004T
67
70
76
72
58
77
72
A22-WP-005
63
76
89
81
81
72
77
A11-0P-011
46
51
50
66
42
20
41
A12-0P-002
64
74
76
89
25
22
67
A13-0P-003
61
72
78
90
32
26
66
A21-OP-004
86
89
104
Q« #
o»»
70
85
A22-OP-005A
61
64
75
0**
39
98
54
-005B
56
69
67
96
42
41
74
-005C
41
43
51
0**
0*#
68
40
-005D
61
74
70
104
26
40
76
-005E
66
78
72
107
31
39
81
9-6
-------
TABLE 9-1. PAH SURROGATE RECOVERIES FOR SEDIMENT A (Percent)
Sample
Nitrobenzene-
-------
d10
70
71
62
75
92
70
73
64
67
68
75
74
45
72
74
78
67
87
72
87
70
77
76
74
77
73
86
76
67
TABLE 9-2. (CONTINUED}
Nitro
benzene- 2- Terphenyl- Phenol- 2- 2,4,6-
dB
Fluorobiphanyl
<*14
Fluorophenol
Tribromophenol
57
62
83
73
56
62
53
61
84
70
50
59
56
56
76
66
52
66
66
66
87
83
67
61
69
71
71
89
68
34
64
62
79
83
49
63
69
66
80
82
42
76
59
60
72
85
62
65
65
63
75
84
54
40
65
64
77
81
59
25
70
72
87
77
76
65
57
94
82
108
0**
0**
112
81
77
106
89
36
66
72
74
90
46
31
61
71
82
81
91
0*#
78
82
95
84
59
0*»
82
87
92
83
53
0**
87
99
111
77
61
36
73
85
98
60
48
58
101
112
117
84
56
78
64
74
77
107
39
38
66
59
66
122
93
48
70
80
69
118**
96
42
57
94
82
108
0**
o**
59
84
88
63
62
7##
59
83
83
67
88
•j # #
70
84
72
110
46
14**
61
74
95
58
58
Q# *
50
60
78
62
44
0**
9-8
-------
TABLE 9-2. (CONTINUED!
Sample
Nitro
benzene-
d6
2-
Fluorobiphenyl
Terphenyl-
«*14
Pheriol-
<*6
2-
Fluorophenol
2,4,6-
Tribromophenol
Anthracena-
dto
B22-RS-010
61
70
89
74
67
o*»
69
B11-EB/PP-002
67
79
67
87
64
38
78
B13-DW-001
75
172*
103
79
76
96
26*
B13-DW-001D
54
89
57
32
28
36
38
B13-IO-001
68
74
84
93
61
o*#
78
B11-EB-003
65
67
74
61
64
72
75
B11-EB-004
69
68
72
53
67
78
75
B22-EB-005
66
72
88
75
77
80
79
B22-EB-006
71
76
96
76
74
79
84
* Outside control limits
** Outside advisory control limits
For Sediment B samples, several acid surrogates were again outside advisory limits. Two of
the base-neutral surrogates for one sample, B13-DW-001, were outside control limits. No sample
remained for re-extraction. This sample was originally extracted and analyzed in duplicate; the
duplicate results serve to confirm the results of the original analysis. In addition, this sample was
collected outside the scope of the QAPP to provide additional information. Project conclusions are not
affected.
9.3.1.3 PAH Matrix Soikes/Matrix Spike Duplicates/Matrix Soike Triplicates (MS/MSD/MST)
As required by the QAPP, MS/MSD/MST analyses were performed for each matrix for each
sediment. These results are presented in Tables 9-3 through 9-12. The QA objective for accuracy
designated in the QAPP was 50-150 percent recovery of matrix spikes. For precision, an objective of
less than 50 percent RSD among MS/MSD/MST analyses was used.
Precision objectives for MS/MSD/MST analyses were met for all spiking compounds in all
matrices. For A21 -TS-004, recoveries outside the recovery objective of 50-150 percent were obtained
for phenanthrene (30 to 38 percent). Laboratory control samples analyzed with the spiked samples
9-9
-------
were acceptable, indicating a matrix problem rather than an analytical problem. Since all other spiking
compounds demonstrated acceptable recoveries, and since phenanthrene represents only a small
percentage of the total PAHs, the impact to the total PAH concentration should be minimal.
For B22-US-010, the MSD recovery for pyrene was 42 percent (the MST recovery was 58
percent). Any possible low biases in the untreated sediment concentration would not impact project
conclusion; removal efficiencies could potentially be higher.
For A21-OP-004, high recoveries were obtained for pyrene (150-180 percent). A matrix
interference is suspected. As this sample was analyzed only to provide additional information about
the process, project conclusions are not affected.
For B22-RS-010, low recoveries were obtained for benzo(b)fluoranthene (38-46 percent). As
this compound was not detected in any of the solvent samples analyzed, the data are not affected.
TABLE 9-3. PAH MS/MSD/MST RESULTS FOR A21-US-004
Compound
Spike
(mg/kg)
Sample
Cone,
(mg/kg)
MS
(mg/kg)
MS
% R
MSD
(mg/kg)
MSD
% R
MST
(mg/kg)
MST
% R
%
RSD
Acenaphthylene
160
<20
120
75
120
75
120
75
0
Pyrene
160
66
180
71
170
65
170
65
5.4
Phenanthrene
160
140
280
88
270
81
270
81
4.3
Benzo(b)fluoranthene
160
29
180
94
160
82
170
88
7.1
Benzo(g,h,i)-perylene
160
18
160
89
150
82
150
82
4.3
9-10
-------
TABLE 9-4. PAH MS/MSD/MST RESULTS FOR A21-TS-004
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg)
% R
RSD
Acenaphthylene
7.6
<0.8
5.9
78
6.1
80
5.6
74
4.3
Pyrene
7.6
1.0
6.3
70
6.3
70
6.0
66
3.3
Phenanthrene
7.6
5.4
8.3
38*
8.1
36*
7.7
30*
12
Benzo(b)fiuoranthene
7.6
0.48
6.5
79
6.7
82
6.2
75
4.2
Benzo(g,h,i)perylene
7.6
0.27
6.8
86
6.9
87
6.2
78
5.9
* Outside project objectives
TABLE 9-5. PAH MS/MSD/MST RESULTS FOR A22-WP-005
Compound
Spike
(ug/L)
Sample
(ug/L)
MS
(ug/L)
MS
% R
MSD
(ug/L)
MSD
% R
MST
(ug/L)
MST
% R
%
RSD
Acenaphthylene
200
<10
160
80
150
75
160
80
3.7
Pyrene
200
<10
180
90
170
85
180
90
3.3
Phenanthrene
200
<10
150
75
150
75
150
75
0
Benzo(b)fluoranthene
200
<10
170
85
160
80
160
80
3.5
Benzo(g,h,i)peryIene
200
<10
160
80
150
75
150
75
3.8
TABLE 9-6. PAH MS/MSD/MST RESULTS FOR A21-OP-004
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg)
% R
RSD
Acenaphthylene
200
<40
200
100
210
105
200
100
2.8
Pyrene
200
270
590
160
~
630
180
*
570
150
5.1
Phenanthrene
200
400
600
100
630
115
600
100
2.8
Benzo(b)fIuoranthene
200
85
310
112
340
128
310
112
7.4
Benzo(g,h,i)perylene
200
73
300
113
350
138
300
113
12
* Outside project objectives
9-11
-------
TABLE 9-7. PAH MS/MSD/MST RESULTS FOR A21-RS-003
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg!
% R
RSD
Acenaphthylene
400
<40
260
65
260
65
290
72
6.4
Pyrerie
400
<40
260
65
280
70
300
75
7.1
Phenanthrene
400
<40
250
62
250
62
280
70
6.7
Benzo(b)fIuoranthene
400
<40
260
65
270
68
290
72
5.6
Benzo(g,h,i)perylene
400
<40
260
65
260
65
270
68
2.2
TABLE 9-8. PAH MS/MSD/MST RESULTS FOR B22-US-010
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg)
% R
RSD1
Acenaphthylene
1200
240
NS
NA
1300
88
1300
88
0
Pyrene
1200
2800
NS
NA
3300
42*
3500
58
5.9
Phenanthrene
1200
12000
NS
NA
13000
83
13000
83
0
Benzo(b)fIuoranthene
1200
1100
NS
NA
2300
100
2500
117
15
Benzo(g,h,i)perylene
1200
580
NS
NA
1200
52
1400
68
28
1 For this sample, this is actually relative percent difference (RPD).
NS - Not spiked. The MS sample was inadvertently not spiked in the laboratory.
NA = Not applicable
* Outside project objectives
TABLE 9-9. PAH MS/MSD/MST RESULTS FOR B22-TS-010
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg)
% R
RSD
Acenaphthylene
24
8.2
26
74
24
66
28
82
11
Pyrene
24
15
33
75
30
62
34
79
12
Phenanthrene
24
51
72
88
68
71
77
108
6.2
Benzo(b)fluoranthene
24
5.2
28
95
26
87
29
99
6.8
Benzo(g,h,i)perylene
24
2.7
17
60
18
64
22
80
16
9-12
-------
TABLE 9-10. PAH MS/MSD/MST RESULTS FOR B22-WP-010
Compound
Spike
(ug/L)
Sample
Cone.
(ug/L)
MS
(ug/L)
MS
% R
MSD
(ug/L)
MSD
% R
MST MST %
(ug/L) % R RSD
Acenaphthylene
200
<10
150
75
170
85
170
85 7.1
Pyrerte
200
<10
170
85
180
90
190
95 5.6
Phenanthrene
200
<10
150
75
160
80
170
85 6.2
Benzo(b)fluoranthene
200
<10
160
80
160
80
180
90 6.9
Benzo(g,h,i)perylene
200
<10
130
65
140
70
150
75 7.1
TABLE 9-11.
PAH MS/MSD/MST RESULTS FOR B22-OP-010E
Compound
Spike
(mg/kg)
Sample
Cone,
(mg/kg)
MS
(mg/kg)
MS
% R
MSD
(mg/kg)
MSD
% R
MST
(mg/kg)
MST
i % R
%
RSD
Acenaphthylene
2000
1200
3400
110
3400
110
3000
90
11
Pyrene
2000
14000
15000
NC
15000
NC
13000
NC
8.1
Phenanthrene
2000
63000
58000
NC
49000
NC
47000
NC
11
Benzo(b)fluoranthene
2000
5500
6900
70
7100
80
6200
35*
7.0
Benzo(g,h,i)perylene
2000
3100
4400
65
4500
70
4300
60
2.3
NC Not calculated due to insignificant spike concentration.
* Outside project objective
TABLE 9-12. PAH MS/MSD/MST RESULTS FOR B22-RS-010
Sample
Spike
Cone.
MS
MS
MSD
MSD
MST
MST
%
Compound
(mg/kg)
(mg/kg)
(mg/kg)
% R
(mg/kg)
% R
(mg/kg)
% R
RSD
Acenaphthylene
200
<40
180
90
170
85
150
75
9.2
Pyrene
200
<40
180
90
160
80
150
75
9.4
Phenanthrene
200
<40
180
90
170
85
150
75
9.2
Benzo(b)fluoranthene
200
<40
91
46*
88
44*
77
38*
8.6
Benzo(g,h,i)perylene
200
<40
140
70
120
60
110
55
12
* Outside project objective
9-13
-------
9.3.1.4 PAH Laboratory Control Samples (LCSI
An LCS was extracted arid analyzed with each batch of samples as a measure of laboratory
performance. The LCS consisted of the same five compounds used for spiking. The acceptance
criteria for recovery were the same as those used for the matrix spikes. Five LCSs were analyzed with
Sediment A samples; results are presented in Table 9-13. All recoveries were within control limits for
Sediment A. For Sediment B, eleven LCSs were analyzed; results are presented in Table 9-14. Two
of the 55 LCS compound recoveries fell outside control limits. These deviations were random and
slight; no consistent problems were observed. No corrective actions were performed.
TABLE 9-13. LCS RECOVERIES - SEDIMENT A (PERCENT)
SEDIMENT A
LCS 1
LCS 2
LCS 3
LCS 4
LCS 5
Compound
(Solid)
(Solid)
(Aqueous!
(Aqueous)
(Aqueous)
Acenaphthylene
691
61
901
75
80
Pyrene
72
69
90
80
80
Phenanthrene
76
64
75
70
75
Benzo(b)fluoranthene
63
75
85
80
65
Benzo(g,h,i)perylene
52
79
90
100
80
Acenaphthene was actually spiked for this sample.
TABLE 9-14. LCS RECOVERIES - SEDIMENT B (PERCENT)
SEDIMENT B
Compound
LCS 11
LCS 21
LCS 31
LCS 41
LCS 51 LCS 62
LCS 73
LCS 82
LCS 93
LCS 103
LCS 113
Acenaphthylene
75
80
74
85
85
54
65
26*
85
75
70
Pyrene
85
70
72
85
90
64
65
96
75
85
80
Phenanthrene
75
110
79
85
85
61
67
81
110
75
80
Benzo(b)fluoranthene
75
70
70
95
85
67
75
85
75
85
75
Benzo(ghi)pery!ene
70
60
45*
70
90
52
95
69
100
75
80
Aqueous
2 Solid
3 Oil
* Outside project objectives.
9-14
-------
9.3.1.5 Method Blanks
Method blanks were extracted and analyzed with each set of samples extracted. No PAH
compounds were detected in any of the method blanks.
9.3.1.6 Internal Standards
Low internal standard recoveries were obtained for A11-TS-001. The sample was re-
extracted and similar results were obtained, indicating a matrix problem. The results of the first
analysis were reported. The total PAH concentration for this sample was consistent with that for the
other runs. In any case, this run was not performed at optimal conditions, and the results were not
used in evaluating project objectives.
For samples A11-WP-001 and A12-WP-002, perylene-d12 did not meet acceptance criteria
(low but measurable recovery). No target compounds were detected in either sample; re-analysis was
not performed.
Low internal standard recoveries for A21-OP-004 and its MS/MSD/MST were obtained. The
consistency of these recoveries demonstrates a sample matrix interference. Actual PAH concentrations
may be higher than reported. The results of this sample were not used in the evaluation of any project
objectives.
9.3.2 PCBs
9.3.2.1 PCB Procedures
Untreated sediments and treated solids were extracted by SW-846 Method 3540 (Soxhlet)
using 1:1 hexane/acetone (V/V). Aqueous samples were extracted using SW-846 Method 3520.
Solvent/oil samples were diluted according to the procedures in SW-846 3580. Extracts of
nonaqueous samples were subjected to GPC cleanup, sulfuric acid cleanup, and Florisil cartridge
cleanup. Florisil cartridge cleanup was performed for all extracts of aqueous samples as well. All
extracts were analyzed using SW-846 Method 8080. Second column confirmations were performed
for all samples in which PCBs were identified.
Calibrations were performed at five levels for the Aroclors detected. Continuing calibration
checks were performed after every 10 samples. All initial calibrations were within the acceptance
criteria of 30 percent RSD. One continuing calibration check for Aroclor 1260 was outside the
9-15
-------
acceptable range of 85-115 percent. This check bracketed only samples in which no Aroclor 1260
was detected.
9.3.2.2 PCB Surrogates
One surrogate, tetrachloro-m-xylene (TCMX), was added to all samples and blanks prior to
extraction to monitor extraction efficiency. Surrogate recoveries are presented in Table 9-15. A
control limit of 60-150 percent recovery was used.
Recoveries for several water product samples were outside the prescribed limits. Since the
recoveries were measurable and no PCBs were found in any of these samples, no corrective action was
taken; data quality should not be affected.
A very low surrogate recovery was obtained for A13-RS-002. No PCBs were found in any
of the recovered solvent samples.
Surrogate recoveries slightly outside control limits (high) were obtained for B21-TS-009.
Minimal PCBs were found in this sample and these high biases would only indicate that the results may
possibly be lower than obtained. Since removal objectives were met anyway, corrective action was
not performed.
TABLE 9-15. PCB SURROGATE RECOVERIES (PERCENT)
SEDIMENT A
SEDIMENT B
Sample
TCMX
Sample
TCMX
A11-US-001
100
B11-US-006
76
A12-US-002
92
B12-US-007
75
A13-US-003
88
B13-US-008
116
A21-US-004
63
-009D
107
-004D
91
-009T
122
-004T
91
B22-US-010
120
A22-US-005
93
B11-TS-006
D
A11-TS-001
85
B12-TS-007
141
A1 2-TS-002
98
B13-TS-008
142
A13-TS-003
84
B21-TS-009
156*
9-16
-------
TABLE 9-15. {CONTINUED}
SEDIMENT A
SEDIMENT B
Sample
TCMX
Sample
TCMX
A21-TS-004
114
-009 D
149
-004D
109
-009T
151*
-004T
109
B22-TS-010
61
A22-TS-005
110
B11-WP-006
121
A11-WP-001
28*
B12-WP-007
73
A12-WP-002
74
B13-WP-008
80
A13-WP-003
43*
B21-WP-009
46*
A21-WP-004
61
-009D
50*
-004D
74
-009T
52*
-004T
12*
B22-WP-010
62
A22-WP-005
55*
B11-OP-006
116
A11-OP-001
83
B12-OP-007
106
A11-OP-002
106
A13-OP-008
112
A13-OP-003
98
B21-OP-009
109
A21-OP-004
111
B22-OP-010A
75
A22-OP-005A
D
-01 OB
94
-005B
D
-01OC
108
-005C
D
-01OD
118
-005D
D
-01OE
112
-005E
D
B11 -SF-002
129
A11-SF-001
108
-002D
125
-001D
103
-002T
126
-001T
110
B12-RS-006
121
A12-RS-001
95
B13-RS-007
113
A13-RS-002
2*
B21-RS-008
120
A21-RS-003
105
-008D
113
A22-RS-004
80
-008T
111
A22-RS-005
83
B22-RS-009
120
9-17
-------
TABLE 9-15. (CONTINUED)
SEDIMENT A
SEDIMENT B
Sample
TCMX
Sample
TCMX
A11-EB/PP-
92
B22-RS-010
119
001
A11-EB-001
81
A21-EB-002
67
B13-DW-001
D
B13-DW-
D
001D
B13-10-001
108
B11 -EB-003
87
B11-EB-004
92
B22-EB-005
68
B22-EB-006
100
D Surrogates diluted out
* Outside control limits
9.3.2.3 PCB Matrix Spikes/Matrix Spike Duplicates/Matrix Spike Triplicates (MS/MSD/MSTI
As required by the QAPP, MS/MSD/MST analyses were performed for each matrix for each
sediment. These results are presented in Tables 9-16 and 9-17. The QA objective for accuracy
designated in the QAPP was 50 to 150 percent recovery of matrix spikes. For precision, an objective
of less than 50 percent RSD among MS/MSD/MST analyses was used. Aroclor 1242 was used for
spiking in all cases.
Recoveries for matrix spikes were all within control limits except for the MS recovery for A21 -
OP-004 (48 percent). This slight deviation for this noncritical matrix has minimal effect on the data.
The MSD and MST recoveries for the same sample were acceptable.
All RSDs were within specified control limits.
9-18
-------
TABLE 9-16. PCB MS/MSD/MST RESULTS FOR SEDIMENT A
Sample
MS,
MSD,
MST,
Sample
Spike
Cone.1
MS
% R
MSD
% R
MST
% R
% RSD
A21-US-004
16 mg/kg
1.52 mg/kg
16.8
96
14.8
83
15.0
84
7.8
A21-TS-004
380 ug/kg
44 ug/kg
325
74
327
74
312
71
2.5
A22-WP-005
2.0 ug/L
<1 ug/L
1.86
93
2.01
101
1.92
96
3.9
A21-OP-004
400 mg/kg
<4 mg/kg
191
48*
224
56
200
50
8.3
A21-RS-003
20 mg/kg
<0.4 mg/kg
9.9
50
18.1
91
17.2
86
30
Outside project objectives
Concentration of Aroclor 1242 only
This sample was re-extracted.
TABLE 9-17. PCB MS/MSD/MST RESULTS FOR SEDIMENT B
Sample
MS,
MSD,
MST,
Sample
Spike
Cone.1
MS
% R
MSD
% R
MST
% R
% RSD
B22-US-010
1220 mg/kg
<59 mg/kg
1740
143
1730
142
1690
139
1.5
B22-TS-010
44.2 mg/kg
<3 mg/kg
49.2
111
46.0
104
53.0
120
7.1
B22-WP-010
5.0 ug/L
< 1.0 ug/L
5.62
112
4.67
93
6.58
132
17
B22-OP-010E 4000 mg/kg
<200 mg/kg
2760
69
2600
65
2590
65
3.6
B22-RS-010
400 mg/kg
<20 mg/kg
381
95
203
51
431
108
35
Concentration of Aroclor 1242 only
9.3.2.4 PCB Laboratory Control Samples (LCS)
An LCS was extracted arid analyzed with each batch of samples as a measure of laboratory
performance. The LCS was spiked with Aroclor 1242 as for the matrix spikes. The acceptance criteria
were the same as those used for the matrix spikes. Results are presented in Table 9-18. Recoveries
slightly outside control limits (low) were obtained for one water and three oil LCSs. Since these
matrices were not critical to project objectives and the deviations were only minimal, no corrective
action was performed.
9-19
-------
TABLE 9-18. PCB LCS RECOVERIES (PERCENT)
ICS (Aroclor 1242) % Recovery
SEDIMENT A
SEDIMENT B
Aqueous
1 56
2 51
3 57
Solid
1 66
on
1 95
Aqueous
1 46*
2 53
3 50
4 57
Solid
1 118
2 115
3 104
on
1 45*
2 43*
3 48*
* Outside control limits
9.3.2.5 PCB Method Blanks
Method blanks were extracted and analyzed with each batch of samples extracted. No PCBs
were detected in any of the method blanks.
9-20
-------
9.3.3 Oil and Grease
9.3.3.1 Oi! and Grease Procedures
O&G analyses were performed by two different methods. The first followed SW-846
methods. The second procedure was provided by RCC and will be referred to as the B.E.S.T.® method.
EPA
Untreated sediments and treated solids were extracted with freon for 4 hours using SW-846
Method 9071. The extract was then analyzed gravimetrically. Water product samples were
extracted and analyzed gravimetrically using SW-846 Method 9070.
B.E.S.T.®
Untreated sediments and treated solids were analyzed using this procedure in addition to the
EPA method. Samples were extracted with methylene chloride for 16 hours; extracts were
again analyzed gravimetrically. This method was performed for comparison with results from
the EPA method and for comparison with the results generated by the developer.
9.3.3.2 Oil and Grease Matrix Replicates
One untreated sediment, treated solid, and water product sample for each sediment was
analyzed in triplicate to assess precision for this analysis. Results are presented in Tables 9-19 and
9-20. A control limit of less than 25 percent RSD was used for the EPA method; no control limits were
established for the B.E.S.T.® method.
EPA
The RSD for sample B22-US-010 was slightly outside control limits. Since the average of the
replicates fell between the results obtained for the other runs for Sediment B, no corrective
action was performed. Due to the gross amount present, minimal deviation from the control
limits should have little effect on the project conclusions.
9.3.3.3 OH and Grease Laboratory Control Sample fLCSJ
An LCS was extracted and analyzed with each batch of samples extracted to assess accuracy.
A control limit of 75 to 125 percent recovery was used for the EPA method. Results are presented
in Table 9-21. All O&G LCS recoveries were acceptable.
9.3.3.4 Oil and Grease Method Blanks
Method blanks were extracted and analyzed with each batch of samples extracted. No O&G
was detected in any of these blanks.
9-21
-------
TABLE 9-19. EPA OIL AND GREASE REPLICATE RESULTS
Sample
Result 1
Result 2
Result 3
RSD, %
A21-US-004
6700 mg/kg
6700 mg/kg
7300 mg/kg
5.0
A21 -TS-004
63 mg/kg
74 mg/kg
57 mg/kg
13
A21 -WP-004
3.0 mg/L
3.1 mg/L
NA
3.31
B22-US-010
129,000 mg/kg
79,700 mg/kg
88,700 mg/kg
26#
B22-TS-010
2140 mg/kg
1590 mg/kg
1700 mg/kg
16
B22-WP-010
3.5 mg/L
3.1 mg/L
2.7 mg/L
12
1 For this sample, RPD was calculated.
NA Not analyzed
* Outside control limits
TABLE 9-20. B.E.S.T.*
OIL AND GREASE REPLICATE RESULTS
Sample
Result 1
Result 2
Result 3
RSD, %
A21-US-004
5850 mg/kg
10,900 mg/kg
10,800 mg/kg
31
A21-TS-004
618 mg/kg
670 mg/kg
492 mg/kg
15
B22-US-010
225,000 mg/kg
203,000 mg/kg
256,000 mg/kg
12
B22-TS-010
9120 mg/kg
12,100 mg/kg
12,300 mg/kg
16
9-22
-------
TABLE 9-21. OIL AND GREASE LCS RECOVERIES (PERCENT)
Matrix
LCS
Method
Recovery, %
Solid
1
EPA
97
Solid
2
EPA
100
Solid
3
EPA
107
Water
1
EPA
88
Water
2
EPA
88
Water
3
EPA
98
Water
4
EPA
94
Solid
1
B.E.S.T.®
97
Solid
2
B.E.S.T.®
86
Solid
3
B.E.S.T.®
89
Solid
4
B.E.S.T.®
109
9-3.4 TCLP Metals
9.3.4.1 TCLP Metals Procedures
Untreated sediments and treated solids were leached according to the procedures in SW-846
Method 1311 and analyzed for arsenic and selenium by SW-8546 Methods 7060 and 7740,
respectively. Mercury was analyzed using SW-846 Method 7470; and barium, cadmium, chromium,
lead, and silver by SW-846 6010. Method 3010 was used to prepare leachates for ICP analyses.
All initial and continuing calibration criteria were met for the TCLP metals analyses.
9.3.4.2 TCLP Metals Matrix Spikes/Matrix Spike Duplicates/Matrix Spike Triplicates (MS/MSD/MS77
One TCLP leachate from untreated sediment and treated solids sample for each sediment were
spiked in triplicate with the eight TCLP metals to assess accuracy and precision. Control limits of 75
to 125 percent for recovery were specified in the QAPP. Precision control limits of less than 25
percent RSD were also specified. Results are presented in Tables 9-22 through 9-25.
9-23
-------
There were some recoveries and/or RSD which did not meet acceptance limits. As can be
seen in the tables, most of the time this occurred with samples which did not contain any of the
spiking element. Since significant spike recoveries were obtained, data quality is not affected.
For mercury in B22-TS-010, a recovery of 66.8 percent for the MSD was obtained; the
recoveries for the MS and MST were acceptable (the average recovery for the MS/MSD/MST analysis
is 75 percent). A slightly low bias would not affect the project conclusions, as the mercury
concentration in this sample is significantly lower than the RCRA limit.
TABLE 9-22. TCLP METALS MS/MSD/MST RESULTS FOR A21-US-004
(All results in //g/L)
Spike
Sample
MS,
MSD,
MST,
%
Metal
Added
Result
MS
% R
MSD
% R
MST
% R
RSD
As
400
<30
422
105
423
106
427
107
0.6
Ba
100,000
750
106,000
105
106,000
105
107,000
106
0.5
Cd
2500
<30
2550
102
2540
102
2550
102
0.2
Cr
5000
<40
5160
103
5180
104
5240
105
0.8
Pb
2500
<210
2550
102
2270
90.8
2490
99.6
6.1
Hg
10
<2
12.2
122
12.7
127*
13.2
132*
3.9
Se
100
<30
107
107
101
101
87.5
87.5
10
Ag
5000
<50
9170
183*
9010
180*
9360
187*
1.9
Outside control limits
9-24
-------
TABLE 9-23. TCLP METALS MS/MSD/MST RESULTS FOR A21-TS-004
(AH results in ug/L)
Spike
Sample
MS,
MSD,
MST,
%
Metal
Added
Result
MS
% R
MSD
% R
MST
% R
RSD
As
400
<30
440
110
424
106
420
105
2.5
Ba
100,000
850
107,000
106
104,000
103
107,000
106
1.6
Cd
2500
100
2690
104
2640
102
2700
104
1.2
Cr
5000
<40
5250
105
5610
112
5300
106
3.6
Pb
2500
<210
2490
99.6
4020
161*
2390
95.6
31*
Hg
10
<2
13.7
137*
11.2
112
11.7
117
11
Se
100
<30
100
100
113
113
107
107
6.1
Ag
5000
<50
9270
185*
8930
179*
8830
177 #
2.6
Outside control limits
TABLE 9-24. TCLP METALS MS/MSD/MST RESULTS FOR B22-US-010
(All results in ug/L)
Spike
Sample
MS,
MSD,
MST,
%
Metal
Added
Result
MS
% R
MSD
% R
MST
% R
RSD
As
400
<30
470
118
470
118
464
116
0.7
Ba
100,000
660
107,000
106
109,000
108
111,000
110
1.8
Cd
2500
<30
2690
108
2720
109
2760
110
1.3
Cr
5000
<40
5510
110
5550
111
5640
113
1.2
Pb
2500
<210
2860
114
2640
106
2760
110
4.0
Hg
10
<2
18.8
03
00
~
18.8
188*
18.8
188*
0
Se
100
<30
98.5
98.5
127
127*
123
123
13
Ag
5000
<50
8480
170*
8530
171*
9420
188*
6.0
Outside control limits
9-25
-------
TABLE 9-25. TCLP METALS MS/MSD/MST RESULTS FOR B22-TS-010
(All results in //g/L)
Spike
Sample
MS,
MSD,
MST,
%
Metal
Added
Result
MS
% R
MSD
% R
MST
% R
RSD
As
400
<30
448
112
465
116
458
114
1.9
Ba
100,000
1120
110,000
109
110,000
109
109,000
108
0.5
Cd
2500
<30
2650
106
2620
105
2620
105
0.7
Cr
5000
<40
5470
109
5410
108
5410
108
0.6
Pb
2500
<210
2630
105
2550
102
2580
103
1.6
Hg
10
7.12
15.0
788
13.8
66.8*
15.0
78.8
9.3
Se
100
<30
102
102
93.6
93.6
127
127
16
Ag
5000
<50
8920
178*
8840
177*
8730
175*
1.1
Outside control limits
9.3.4.3 TCLP Metals Laboratory Control Samples (LCS!
An LCS was digested and analyzed with each batch of samples prepared for metals analysis.
These results are presented in Table 9-26.
TABLE 9-26. METAL LCS RECOVERIES
SEDIMENT A
SEDIMENT B
Metal
LCS 1
LCS 2
LCS 1
LCS 2
LCS 3
LCS 4
As
111
104
106
104
112
NA
Ba
107
106
104
112
107
109
Cd
104
106
111
107
108
112
Cr
105
106
109
110
109
113
Pb
103
92.8
104
99.6
104
115
Hg
116
93.6
106
95.8
99.1
NA
Se
106
101
98.3
101
108
NA
Ag
NR
NR
171*
169*
172*
175*
NA Not analyzed
NR Not reported
9-26
-------
LCS recoveries for silver show a high bias (this was also observed in the matrix spike analyses
(see Tables 9-22 through 9-25). No silver, however, was detected in any sample leachates and results
are not affected,
9.3.4.4 TCLP Metals Method Blanks
A method blank was digested and analyzed with each batch of samples prepared for metals
analysis. No metals were found in these blanks.
9.3.4.5 TCLP Metals Other QC
ICP interference check samples, post-digestion spikes, and serial dilutions were analyzed to
identify any possible analytical matrix interferences. No problems were observed with these analyses.
9.3.5 Moisture
Moisture analysis was performed for all solid samples using the procedure outlined in SW-S46
Method 3540. Matrix triplicates (MTs) were analyzed to assess precision for one untreated sediment
and one treated solid sample for both Sediment A and Sediment B. These results are presented in
Table 9-27 (the QAPP specified a control limit of less than 25 percent RSD). No measure of accuracy
was performed.
TABLE 9-27. MOISTURE MATRIX TRIPLICATE RESULTS (PERCENT)
Sample
Result 1
Result 2
Result 3
RSD, %
A21-US-004
38.4
41.7
42.6
5.4
A21-TS-004
12.7
13.0
13.0
1.3
B22-US-010
67.2
62.6
62.2
4.3
B22-TS-010
9.9
9.8
9.6
1.6
9-27
-------
9.3.6 Triethylamine
9.3.6.1 Triethvlamine Procedures
Treated solids, water product samples, and oil product samples were analyzed for
triethylamine using a procedure developed by the SAIC Methods Lab based on procedures routinely
used by RCC. Water samples were pH adjusted to 9.5 ± 0.5 and directly injected into a gas
chromatograph (GC) utilizing a packed column and flame ionization detection (FID). Measured amounts
of solid samples and oils were extracted with acidified water and then adjusted to pH 9.5 ± 0.5 prior
to GC analysis.
Calibration was performed using seven concentration levels of triethylamine. The RSD could
not exceed 20 percent for this initial calibration. Continuing calibration checks were analyzed after
every 10 samples; acceptance criteria were less than ± 20 percent difference. All calibration criteria
were met.
9.3.6.2 Triethylamine Matrix Spike/Matrix Spike Duplicate/Matrix Spike Trioiicates (MS/MSD/MSTl
An MS/MSD/MST analysis was performed for one treated solid and water product sample for
each sediment and an oil product sample for Sediment B. Results are presented in Table 9-28. No
finished oil product was available for Sediment A.
TABLE 9-28. TRIETHYLAMINE MS/MSD/MST RESULTS
Spike
Sample
MS,
MSD,
MST,
%
Sample
Added
Result
MS
% R
MSD
% R
MST
% R
RSD
A21-TS-004
100 ug/g
36 ug/g
119
83.0
130
94.0
135
99.0
8.9
A21-WP-004
100 mg/L
<1 mg/L
83.9
83.9
89.1
89.1
88.9
88.9
3.4
B22-TS-010
100 ug/g
89.3 ug/g
183
93.7
206
117
182
92.7
14
B21-WP-009
100 mg/L
<1 mg/L
95.8
95.8
100
100
99.6
99.6
2.4
B22-OP-010E
5000 ug/g
624 ug/g
6692
121
6514
118
6660
121
1.6
9-28
-------
9.3.6.3 Triethvlamine Method Blanks
The pH-adjusted deionized water blanks were analyzed to verify the absence of contamination
during the extraction and/or analysis for each matrix. No triethylamine was found in any method
blanks above the quantitation limit.
9.3.6.4 Triethvlamine Second Source Check Standard
A triethylamine standard was obtained from a second vendor to verify the purity of the
triethylamine used for calibration. The difference between the two standards was determined to be
only 2 percent.
9.3.7 TRPH
All untreated sediments, treated solids, and water product samples were analyzed for TRPH.
Solid samples were extracted by SW-846 Method 3550; the extract was analyzed by IR using EPA
Method 418.1. Water was extracted and analyzed according to EPA Method 418.1. Laboratory batch
quality control procedures were used.
An MS/MSD analysis was performed for B13-TS-008. These results are presented in Table
9-29. TRPH LCS recoveries ranged from 83 to 95 percent. No blank contamination was detected.
TABLE 9-29. TRPH MS/MSD RESULTS FOR B13-TS-008
(Results in mg/kg)
Sample
MS,
MSD,
% RSD
Spike Added
Cone.
MS
% R
MSD
% R
270
<20
244
90.4
226
83.7
7.7
9-3.8 Other Analyses
Laboratory batch QC analyses were performed for the remaining noncritical measurements.
All QC results were within laboratory control limits with the following exceptions.
9-29
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9.3.8.1 Total Cyanide
MS and sample duplicate analyses were performed for sample A21-TS-004. A recovery of
34 percent and an RPD of 50 percent were obtained. Re-analysis yielded similar results, indicating a
matrix problem. Results may be biased low.
9.3.8.2 Total Phosphorus
A matrix spike performed for sample A21-TS-004 yielded no recovery. Sample results should
be used with caution.
9.3.8.3 Total Metals
Because thallium lines are not sensitive to the ICP technique and oxygen absorbance causes
interferences, several calibration checks and LCSs did not meet acceptance criteria. Thallium was not
detected in any of the samples; qualitative data should not be affected.
The LCS associated with B21-TS-009 did not meet acceptance criteria for iron. Re-analysis
was not performed for this noncritical measurement.
All silver quality control analyses indicated a high bias. No silver was detected; results can
be used to qualify the data.
9.3.8.4 PCBs bv Method 680
Internal standards were added to samples prior to extraction. These internal standards were
quantitated against recovery standards which were added to the extracts prior to analysis. Sample
results obtained were corrected for these internal standard recoveries. (Due to the high concentration
of PCBs in B22-US-010, a post-extraction internal standard spiking scheme was used. No correction
was performed for this sample.) Internal standard recoveries are summarized in Table 9-30.
The method blank associated with A22-TS-004 showed significant PCB contamination. The
effect appears to be minimal since the concentration in the blank was 10 times higher than in that
sample. Isolated contamination from a high level sample is suspected.
9-30
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TABLE 9-30. METHOD 680 INTERNAL STANDARD RECOVERIES (Percent)
Sample
13C-3,4,3',4'-
Tetrachlorobiphenyl
13C-2,2',3,3',5,5',6,6'-
octachlorobiphenyl
A22-US-005
47.0
99.8
A22-TS-005
64.7
73.3
B22-US-010
a
a
B22-TS-010
69.3
27.6
* Internal standard not added prior to extraction.
9.4 AUDIT FINDINGS
One field audit and one laboratory audit, for each of the two laboratories who performed
critical analyses, were performed by EPA in support of the B.E.S.T,® demonstration.
9.4.1 Field Audit
A technical systems review (TSR) of field operations was performed by EPA at the
demonstration site on July 7, 1992. One concern and some minor issues were noted by the auditor;
these are presented below, along with the corrective actions taken.
Onsite Sample Custody and Storage
Minor Issues:
(1) The field team did not record the temperature of the refrigerator used to store samples in the
field. In some cases this refrigerator stored samples for more than 24 hours. To verify that
samples were stored under proper conditions, the reviewer recommended that SAIC verify that
the refrigerator temperature was maintained at less than 4"C. Further, this temperature check
should be conducted at least daily and documented. It should be noted that SAIC indicated
that they had been checking sample storage refrigerator temperatures regularly and found
them to be consistently less than 4°C.
Daily refrigerator temperature monitoring/recording was initiated immediately.
(2) Each individual sample container was not custody sealed. Since the sample storage
refrigerator was located in an unsecured location and left unlocked, it was recommended that
SAIC place custody seals on each sample container to verify that no tampering occurred.
Further, Section 4.4.6.5 of the QAPP requires sealing each sample container with custody tape.
Custody sealing each sample container (in addition to the sample transport cooler) prior to
shipment is also a good practice so that enroute integrity can be verified for each sample
container. If only the cooler is sealed, Integrity Is unknown for all of the containers Inside if
the cooler seal is broken.
9-31
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Beginning immediately, custody seals were placed on each sample container prior to sample
storage in the field refrigerator.
(3) C-O-C forms were not completed at the conclusion of each day of sampling. Field C-O-C
forms are intended to provide a custody record from the time samples are collected until the
time they are received by the laboratory. Accordingly, it was recommended that these forms
should be completed at the conclusion of the sampling day, thereby documenting the
beginning of the chain of custody.
C-O-C forms were completed at the end of each day, when possible, or early the next day.
Process Measurements
Concern
SAIC had not collected the caustic (NaOH) volume addition data by the time of the TSR. This
volume measurement is technically considered a critical process measurement since it is included in
the mass balance calculation; however, the caustic addition represents an extremely small percentage
of the total system mass and failure to record caustic volume at all will have very little effect on total
mass accuracy. The reviewer did recommend that SAIC ensure the collection of caustic volume data
according to QAPP requirements.
It was further recommended that SAIC direct some attention to making sure all process
measurements were collected by RCC and to promptly transcribe all pertinent data. Some process data
were not yet transcribed from RCC at the time of the TSR. Also, it was recommended that SAIC staff
personally observe the collection of process data to ensure the accurate recording of those data.
SAIC immediately took appropriate steps to ensure all process data were properly recorded.
In most cases, this meant that specific SAIC personnel were assigned to collecting process data
directly from field instruments rather than transcribing RCC data. In cases where data could not be
recorded directly by SAIC personnel {e.g., addition of caustic), these data were transcribed to SAIC
records at the end of each day.
Minor Issues:
(1) For the mass calibrations using standard weights, the responsible technician marked "OK"
in the logbook thus indicating the scale met accuracy objectives. It was recommended
that SAIC record the actual result of the standard mass weighing rather than "OK" to
allow for verification of the calibration data.
9-32
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Beginning immediately, the actual numerical result of the standard mass weighing was
recorded.
(2) Field notebooks contained several instances of data which were corrected by overwriting
or scribbling through entries. It was recommended that SAIC follow standard logbook
correction procedure where an incorrect entry is lined out with a single line and the new
entry is accompanied with the corrector's initials and the date.
Standard logbook correction procedures were immediately initiated.
9.4.2 SAIC Methods Laboratory Audit
A TSR of laboratory operations was performed by EPA at the SAIC Methods Laboratory in San
Diego, California, on August 5, 1992. The critical triethylamine analyses were performed by the SAIC
Laboratory. One concern was identified by the auditor.
Sample Receipt/Sample Log-In
Concern
Several samples (A22-WP-005, B11-WP-006, A22-TS-005, B11-TS-006, and A22-OP-005)
were received at the SAIC Laboratory at temperatures approaching room temperature (between 10 and
2(FC).
The problem was traced to the type of cooler (thermos-like) used to transport the samples.
These shipping containers were immediately removed from use.
The effects on data quality appear to be minimal. The results for these samples are all
supported by the results obtained for the other process runs/analyses performed. For all the water
samples, no or minimal triethylamine was detected at a level which was 30 times less the project
objective level. For the oil product sample, sample A22-OP-005 was not oil polished and the results
are to be used only to provide additional information about the process. For A22-TS-005, two other
identical (optimal) runs were performed; all of the treated solids results were similar and were found
to meet project objectives. For B11-TS-006, this run was not optimum and was not used in making
project conclusions.
In summary, data quality and project conclusions do not appear to be affected by this
temperature excursion.
9-33
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9,4.3 S-Cubed Laboratory Audit
A TSR of the laboratory operations was performed by EPA at the S-Cubed Laboratory in San
Diego, California, on August 6, 1992. Several critical and noncritical measurements were performed
by S-Cubed. The concerns identified and corrective actions taken are summarized below.
Sample Log-In and Storage Area
Concerns
(1} The temperature of the temperature blank was not always recorded on the sample receipt
form as the first samples were received.
A policy for appropriately recording the temperature of the temperature blank was instituted
(2) The temperature of the main storage cooler was not recorded from July 7 through July
14, 1992.
Temperature recording for this cooler was resumed on July 15, 1992. No problems were
reported during the period in which temperature recording was not performed.
Oil and Grease Analysis
Concern
(1)A tared flask was used during gravimetric analysis. This flask weighed approximately
110-120 grams. Balance calibration, however, was performed only at 1 gram and 20
grams. The laboratory should verify the sensitivity and precision in the 110-120 range.
It is not known if corrective action was performed.
PCB Analyses
Concern
(1) Chlorinated dibenzofurans may form during the heating of the treated solids to thermally
desorb residual solvent. The PCB molecule has been shown in certain instances to give
rise to chlorinated dibenzofurans when heated in the presence of a base (the triethylamine
extraction solvent is basic).
9-34
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The treated solids were steam-heated to remove residual solvent, meaning temperatures of
only 212°F (at a maximum) were reached. This, as well as the fact the treated solids were expected
to be relatively low in PCBs (maximum concentrations were found to be less than 2 ppm), deemed
chlorinated dibenzofurans analyses unnecessary.
9.5 MODIFICATIONS TO AND DEVIATIONS FROM THE QAPP
Modifications to and deviations from the QAPP occurred during the course of the project
involving both field and laboratory activities. Specific modifications or deviations and their effect on
data quality are discussed in this section.
9.5.1 Field Modifications/Deviations
Due to unanticipated changes in onsite conditions, the following field changes were made:
(1) Sediment A contained insufficient O&G for the oil product to be oil-polished following each
run or even after all five runs of Sediment A were completed. No claim can be made on
the triethylamine concentration of this oil product from Sediment A. This oil/triethylamine
mixture was sampled and analyzed as designated in the QAPP.
(2) Aqueous samples, both unpreserved and preserved with HCI, were collected for
triethylamine, pending results of a holding time study performed by the SAIC Methods
Laboratory (see also Subsection 9.6.2). Both sets of samples were analyzed for
triethylamine. Based on the results of the holding time study, the unpreserved samples
were reported.
(3) Due to the aqueous nature of the untreated sediment, a stainless steel ladle was used for
sample collection rather than a Teflon scoop. Treated solids ranged from a consistency
of sludge to a dry powder; sampling devices changed accordingly. The devices used
were always either metal, a high density plastic, or glass. These changes have no effect
on data quality.
These modifications were documented and submitted to EPA project and QA management the
day after the field TSR was performed.
9.5.2 Laboratory Modifications/Deviations
For the reasons specified, the following laboratory changes were made:
(1) All TRPH extractions were performed using SW-846 Method 3550 instead of Method
9071. This noncritical measurement was used only as an indicator of method
performance. The use of a different extraction procedure will not prevent this
assessment. No comparisons to other data will be made.
9-35
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(2) Due to the high concentrations of PAH contaminants present in the untreated
sediments for Sediment B, only one gram of sample was extracted rather than the ten
grams specified in Method 3540. Because all target PAHs were present in all untreated
sediments (with possibly one PAH compound in a few cases), increased detection limits
are not a problem.
(3) For the oil product samples from Sediment B, 0.1 gram samples were diluted rather
than the 1.0 gram sample specified in Method 3580. Due to the high concentrations
present of nearly all target PAHs in these oil samples, increased detection limits did not
impact data quality.
(4) All triethylamine samples were analyzed in triplicate; the average of these triplicate
results was reported. RSDs among the triplicate values were all less than 25 percent.
9.6 SPECIAL STUDIES
Several special studies were performed in support of the B.E.S.T.® demonstration. Each of
these studies is discussed below.
9.6.1 Triethvlamine Analysis
The procedure used to produce results for the critical triethylamine measurement was based
on an RCC method. The SAIC Methods Laboratory evaluated the RCC method and made modifications
to improve performance. The SAIC Standard Operating Procedure was then verified in terms of
accuracy, precision, and detection limits for each project matrix with respect to project objectives.
Seven replicate analyses were performed for each matrix at two different concentration levels.
Method performance data are summarized in Table 9-31. The results of this method verification
indicated that the triethylamine standard operating procedure could produce results which would meet
project objectives.
TABLE 9-31. TRIETHYLAMINE METHOD PERFORMANCE DATA
Matrix
Aqueous
Soil
Oil
Concentration
50 mg/L
100 mg/L
10 ug/g
100 ug/g
50 mg/L
500 mg/L
Mean Recovery (%)
71.2
101
62.2
68.9
83.0
83.4
Standard Deviation
5.2
5.2
8.7
2.9
9.3
6.6
% RSD
7.3
5.2
13.9
4.2
11.2
7.9
9-36
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9.6.2 Triethvlamirie Holding Time Study
A concern was raised during the EPA QA review of the B.E.S.T.® QAPP regarding the stability
of triethylamine in aqueous samples over the 14-day holding time. In an effort to address this concern,
a holding time study was initiated by the SAIC Methods Laboratory.
An aqueous triethylamine solution was prepared at 100 mg/L and analyzed in triplicate. Three
aliquots of this solution were stored unpreserved at 4°C for 14 days. Three aliquots of this solution
were preserved with HCI and stored at 4°C for 14 days. The preserved and unpreserved aliquots were
analyzed for triethylamine after the 14-day holding period. These results are summarized in Table 9-
32.
TABLE 9-32. TRIETHYLAMINE HOLDING TIME STUDY
(All results in mg/L triethylamine)
Day 0 Day 14 (unpreserved) Day 14 (Preserved with HCI)
1 104 83.1 84.5
2 95.4 89.3 93.2
3 97.1 97.4 91.9
Average 98.8 89.9 89.9
As can be seen in Table 9-32, no difference was observed between results from preserved and
unpreserved samples. All aqueous data were reported using unpreserved sample results.
9.6.3 Biodearadation Study
A biodegradation study was performed to determine if triethylamine would readily degrade in
the treated solids. An aliquot of treated solids sample (one for each sediment) was homogenized with
an equal aliquot of soil. No other adjustments or ammendments were made to the samples. Twelve
vials of this mixture were prepared. Another 12 vials of "sterilized" mixture were prepared by adding
mercuric chloride to each for use as controls. All vials were maintained at 20°C. Three samples from
each group were analyzed for triethylamine at intervals of 0, 2, 4, and 8 weeks. Results are
summarized in Table 9-33.
9-37
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TABLE 9-33. BIODEGRADATION RESULTS
(AH results in ug/g triethylamine)
Sample Week 0 Week 2 Week 4 Week 8
Sample Control Sample Control Sample Control Sample Control
A21-TS-004 42.4 30.4 53.1 50.4 65.0 70.9 64.7 71.4
B21-TS-009 147 146 140 155 148 146 152 158
As can be seen in Table 9-33, no significant reduction in triethylamine concentration was
observed after 8 weeks under the conditions used for testing.
9.7 FIELD QC SAMPLES
Field quality control samples for the B.E.S.T.® demonstration included sampling equipment
blanks, pilot plant equipment blanks, samples of product triethylamine, and field replicates conducted
on the process products. Field replicate data are included in Volume II of this report, and the averaged
replicate values are presented in Section 7. Table 9-34 presents the results of analyses conducted on
the equipment blanks and product solvent. A brief description of these QC samples is presented in the
following subsections.
9.7.1 Sampling Equipment Blanks
Sampling equipment blanks consisted of rinsate samples conducted on the stainless steel pail
used to composite raw feed samples and the teflon bailer used to collect most of the product water.
The purpose of the samples was to determine if the sample collection equipment used was properly
decontaminated thus reducing the potential of cross contamination between samples. This was
especially necessary for the bailer since it was used to collect product water containing low to non-
detectable levels of analytes.
Results of the analyses indicated that no detectable levels of target PAH compounds or total
PCBs were detected in any of the sample equipment blanks (Table 9-34). There were detections of
O&G in two of the pail rinsates (1.2 mg/L and 1.0 mg/L) and in one of the bailer rinsates (1.6 mg/L);
however, these values are not considered significant since they are so close to the detection limit.
9-38
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TABLE 9-34. PAH, PCB, O&G, AND TSS RESULTS FOR ANALYSES OF FIELD QC SAMPLES
Sample
Target PAHs
PCBs
O&G
TSS
A11 -EB-0011
<10 ug/L
<3 ug/L
1.2 mg/L
NA
A11-EB/PP-0012
<40 mg/kg
<2 mg/kg
NA
NA
A11-SF-0013
<40 mg/kg5
<2 mg/kg5
NA
< 20 mg/L
A21-EB-0021
< 10 ug/L
<3 ug/L
1.0 mg/L
NA
B11-EB-0031
<10 ug/L
<0.2 ug/L
<1.0 mg/L
NA
B11-EB/PP-0022
<40 mg/kg
< 2 mg/kg
NA
NA
B11-SF-0023
<40 mg/kg5
<2 mg/kg5
NA
<20 mg/L
B22-EB-0044
<10 ug/L
<2 ug/L
< 1.0 mg/L
NA
B22-EB-0054
<10 ug/L
<1 ug/L
1.6 mg/L
NA
B22-EB-0061
<10 ug/L
<1 ug/L
< 1.0 mg/L
NA
1 Aqueous rinsate of stainless steel pail used for compositing feed samples.
2 Sample of triethylamine solvent following internal decontamination of pilot plant.
3 Sample of product triethylamine collected from manufacturer's product drum.
4 Aqueous rinsate of teflon bailer used to collect samples of product water.
5 Results are the average of three field replicate measurements.
NA Not analyzed
9.7.2 Pilot Plant Equipment Blanks
Pilot plant equipment blanks consisted of two samples of clean triethylamine solvent that had
been pumped through the components that contacted contaminated feed material. The first sample
was taken prior to loading the first batch of Sediment A feed into the pilot unit to determine if any
residual PAHs or PCBs remained in the pilot plant from any previous testing activities. The second
sample was taken prior to processing the first batch of Sediment B to determine if the pilot plant was
adequately decontaminated between test sediments, thus preventing cross contamination.
Results of the analyses indicated that no detectable levels of target PAH compounds or total
PCBs were present in either of the pilot plant equipment blank samples (Table 9-34).
9-39
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9.7.3 Product Triethvlamine Samples
There were a total of four drums of product triethylamine used during the demonstration,
which represented two lots per the manufacturer's drum labels. One sample of each product lot of
triethylamine was collected and analyzed for target PAHs, PCBs, and total suspended solids (TSS).
The purpose of this sampling was to ensure that the product solvent used was free of the critical target
PAH analytes and PCBs and was relatively free of suspended solids that could represent impurities.
Results of the analyses indicated that no detectable levels of target PAHs, total PCBs, and
TSS were present in either product lot of triethylamine used during the demonstration (Table 9-34).
9.8 SAMPLE HOLDING TIMES
Holding time requirements for all sample matrices and analyses were specified in the QAPP.
Any samples analyzed outside these requirements will be discussed in this section for the critical
parameters.
9.8.1 PAHs
9.8.1.1 Sediment A
One untreated sediment (A21-US-004) and two treated solids samples (A21 -TS-004 and A21 -
TS-004D) were extracted outside the 14-day extraction holding time due to an error in spiking. These
samples were all submitted as field replicates in addition to being one of three identical optimal runs.
Comparison of the data for these samples analyzed outside holding times to the data for the field
replicates or identical runs analyzed within holding times show that data quality was not affected. No
significant differences were observed.
Two equipment blanks (A11-EB-001 and A21-EB-002) were extracted 2 days past the 7-day
extraction holding time. No PAHs were present and this deviation should not impact project results.
One water sample (A13-WP-003) was extracted 2 days past the 7-day extraction holding
time. No PAHs were found; this result is comparable to the water samples from the other two optimal
runs. Data quality should not be affected.
9-40
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9.8.1.2 Sediment B
Due to the large concentrations of PAHs in Sediment B and the difficult matrices analyzed,
some samples were analyzed outside holding times. These samples are discussed below.
One treated solids sample {B22-TS-010} was analyzed outside the 40-day extract holding time
due to QC problems. Though the holding time deviation is not expected to affect data quality, the
removal efficiency was high enough {>99 percent) such that objectives would have still been met if
the total PAH concentration in the treated solid sample was actually five times the level found. Project
conclusions should not be affected.
One untreated sediment sample (B13-US-008) was analyzed outside the 40-day extract
holding time. This run was not optimal; the results for this run were not used to determine project
conclusions.
Several intermediate oil extracts were analyzed outside the 40-day extract holding time.
These analyses were performed only to provide additional information about the process and are not
used to support any conclusions.
Several extracts required dilutions due to the high concentrations of PAHs present. These
dilutions were analyzed outside the 40-day extract holding time. Data quality should not be affected.
The following samples were affected:
Several intermediate oil extracts were analyzed outside the 40-day extract holding time.
These analyses were performed only to provide additional information about the process and are not
used to support any conclusions.
Two of the five final oil sample extracts (B22-OP-010A and B22-OP-010B) were analyzed
outside the 40-day extract holding time. These five samples were the same; the RSD among the five
total PAH results was 23 percent, indicating that the exceeded holding times did not affect data
quality.
B11-US-006
B12-US-007
B21-US-009
B22-US-010
B11-TS-006
B12-TS-007
B13-TS-008
B21-TS-009
B11-OP-006
B12-OP-007
B22-OP-010C
B22-OP-010D
B22-OP-010E
B13-DW-001
9-41
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Several recovered solvent extracts were analyzed outside the 40-day extract holding time.
These samples were analyzed to check for contamination; no PAHs were found. The exceeded holding
time does not affect project results.
9.8.2 PCBs
9.8.2.1 Sediment A
One treated solids sample (A11-TS-001) was re-extracted outside the 14-day extraction
holding time due to surrogate problems. This run was not at optimal conditions and was not used to
support project conclusions.
A high detection limit was obtained for A13-TS-003, making demonstration of meeting project
objectives impossible for that run. The sample was re-extracted and appropriately cleaned up to yield
more usable data. The result obtained was very similar to the treated solid results for the other two
optimal runs.
An equipment blank {A 11-EB-001) and two water samples {A13-WP-003 and A21-WP-004)
were extracted outside the 7-day extraction holding time due to surrogate problems. No PCBs were
found and data quality is not affected.
Two recovered solvent samples exceeded holding times but this data was used only as a
check on contaminations. No PCBs were found.
9.8.2.2 Sediment B
Two water samples (B13-WP-008 and B21-WP-009) were re-extracted outside the 7-day
extraction holding time due to surrogate problems. No PCBs were found; data quality should not be
affected.
9.8.2.3 Oil and Grease
One treated solids sample (A13-TS-003) was re-analyzed outside the 28-day holding time.
The initial analyses appeared to be questionable (high) in relation to the results for the treated solids
for the other two runs at optimal conditions. The re-analysis yielded a result which was approximately
one-third of the initial analysis. This re-analysis value also more closely agreed with the other runs and
was used for reporting.
9-42
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9.9 CONCLUSIONS AND LIMITATIONS OF THE DATA
Upon review of all sample data and associated QC results, the data generated for the
B.E.S.T.® demonstration has been determined to be of acceptable quality. In general, excellent QC
results were obtained for accuracy and precision which can be used to support removal efficiency
results.
Field replicate results and replicate process run results also serve to document the quality of
the data. Overall precision was quite good, indicating thorough homogenization of the untreated
sediments and good sampling techniques.
It should also be noted that RCC, the developer, independently collected and analyzed its own
set of samples. Good correlation was observed between these results and the EPA demonstration
results. Project conclusions were consistent, further supporting demonstration results.
9-43
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SECTION 10
REFERENCES
1. American Society for Testing and Materials. Annual Book of ASTM Standards.
2. Department of the Army. (Waterways Experimental Station, Corps of Engineers), Information
Summary, Area of Concern: Grand Calumet River, Indiana, Final Report. March 1991.
3. Indiana Department of Environmental Management. Northwest Indiana Environmental Action
Plan, Draft. Indianapolis, Indiana. 1988.
4. International Technology (IT) Air Quality Services, Vent Gas Triethylamine Test Report,
September, 1992.
5. Maxwell/S-Cubed Division. Analytical Data Report for the B.E.S.T.® Solvent Extraction
Technology. October 30, 1992.
6. Resources Conservation Company. Final Test Report for Pilot Scale Demonstration of the
B.E.S.T.® Solvent Extraction Technology at the Grand Calumet River/Indiana Harbor and Canal
Area of Concern. January 1993.
7. Resources Conservation Company. Test Plan for B.E.S.T.® Solvent Extraction Process to
Conduct Pilot Scale Testing at the Grand Calumet River - Gary, Indiana, Revised June 23,
1992.
8. Science Applications International Corporation. Demonstration and Quality Assurance Project
Plan -Superfund Innovative Technology Evaluation. Resources Conservation Company, Inc.
B.E.S.T.® Solvent Extraction Technology. QAPP Approved July 2, 1992.
9. Tsang, F., P. Marsden, and N. Chau. Science Applications International Corporation.
Analytical Results - Triethylamine. October 21, 1992.
10. U.S. Environmental Protection Agency. Standard Methods for the Examination of Water and
Wastewater, 17th Edition.
11. U.S. Environmental Protection Agency. Methods for Chemical Analysis of Water and Waste
(U.S. EPA-600/4-79-020). Revised March 1986.
12. U.S. Environmental Protection Agency. Test Methods for Evaluating Solid Waste (SW-846)
3rd Edition. November 1986.
13. NIOSH Manual of Analytical Methods. 2nd Edition. Volume III, Department of Health and
Human Resources. Cincinnati, Ohio.
10-1
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TflfcHNIcAL REPORT DATA
(Please read Instructions on the reverse before completingj
1. REPORT NO. 2.
EPA/540/R-92/079a
3. RECIPIENT'S ACCESSION NO.
(PREASSIGNED) PB 93-2271122:
4. title ANDsuBTiTLEjechnology Evaluation Report SITE Program
Demonstration Resources Conservation Company Basic
Extractive Sludge Treatment (B.E.S.T.) Grand Calumet
River, Gary, Indiana Volume 1
5. REPORT DATE
July 1993
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Thomas Wagner
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Science Applications International Corporation
635 West Seventh Street, Suite 403
Cincinnati, OH 45203
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-C0-0048, WA-21
12. SPONSORING AGENCY NAME AND AODRESS
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
13. type OF REPORT AND PERIOD COVERED
Report .
14. SPONSORING AGENCY CODE
EPA/540/
15. SUPPLEMENTARY NOTES
Project Manager
Mark C. Meckes (513)569-7348
16. ABSTRACT
This report summarizes the findings of an evaluation of the Basic
Extractive Sludge Treatment (B.E.S.T.) solvent extraction technology developed
by Resources Conservation Company (RCC). As a part of this evaluation, a
demonstration test was conducted as a cooperative effort between the U.S.
Environmental Protection Agency Region V (U.S. EPA - Region V), the Great
Lakes National Program Office (GLNPO), the U.S. Army Corps of Engineers (COE),
and the U.S. EPA Superfund Innovative Technology Evaluation (SITE) Program.
During this demonstration test, the B.E.S.T. system was used to treat
composited sediments from two areas of the Grand Calumet River.
Contaminant concentration reductions of 96 percent for total polynuclear
aromatic hydrocarbons (PAHs) and greater than 99 percent for total
polychlorinated biphenyls (PCBs) were achieved for Sediment A. Contaminant
concentration reductions of greater than 99 percent for total PAHs and greater
than 99 percent for total PCBs were achieved for Sediment B.
Removal efficiencies in excess of 98 percent were realized for both
sediments for oil and grease (0&G).
This report includes all data obtained during the evaluation.
17 KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. 1DENTIF1E RS/OPEN ENOED TERMS
c. COSATl Field/Group
Solvent Extraction
PCB Treatment
Waste Treatment
Organics Removal
PAH Treatment
Site Remediation
PCBs, Polychlorinated Bi(
PAHs, Polynuclear Aromat"
hydrocarbons
Soils Sludges Sediments
henyls
c
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
151
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 {R«v. 4-7?) previous edition is obsolete
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