®EPA
United States
Environmental Protection
Agency
Great Lakes
National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
EPA 905-R94-009
October 1994
Assessment and
Remediation
Of Contaminated Sediments
(ARCS) Program
BENCH-SCALE EVALUATION OF
SOILTECH'S ANAEROBIC THERMAL
PROCESS TECHNOLOGY ON
CONTAMINATED SEDIMENTS FROM
THE BUFFALO AND GRAND
CALUMEXT RIVERS
United States Areas of Concern
ARCS Priority Areas of Concern
printed on recycled paper
-------
^Bench-Scale Evaluation of SoilTech's Anaerobic
Thermal Process Technology on Contaminated Sediments from
the Buffalo and Grand Calumet Rivers
r\
?c
Prepared by
v>
Michael Giordano and Evelyn Meagher-Hartzell
Science Applications International Corporation
Cincinnati, OH
for the
Assessment and Remediation of Contaminated Sediments (ARCS) Program
U.S. Environmental Protection Agency
Great Lakes National Program Office
Chicago, Illinois
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevarjd, 12th Floor
Chicago, IL 60604-3590
-------
DISCLAIMER
The information in this document has been funded wholly or in part by the U.S. Environmental
Protection Agency (EPA) under Contract No. 68-C8-0062, Work Assignment No. 3-52, to Science
Applications International Corporation (SAIC). It 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.
-------
ACKNOWLEDGEMENTS
This report was prepared by the Engineering/Technology Work Group (ETWG) as part of the Assessment
and Remediation of Contaminated Sediments (ARCS) program. Dr. Stephen Yaksich, U.S. Army Corps
of Engineers (USAGE) Buffalo District, was chairman of the Engineering/Technology Work Group.
The ARCS Program was managed by the U.S. Environmental Protection Agency (USEPA), Great Lakes
National Program Office (GLNPO). Mr. David Cowgill and Dr. Marc Tuchman of GLNPO were the ARCS
program managers. Mr. Dennis Timberlake of the USEPA Risk Reduction Engineering Laboratory was the
technical project manager for this project. Mr. Stephen Garbaciak of USAGE Chicago District and GLNPO
was the project coordinator.
This report was drafted through Contract No. 68-C8-0062, Work Assignment No. 3-52, to Science
Applications International Corporation (SAIC). Michael Giordano and Evelyn Meagher-Hartzell of SAIC
were the principal authors of the report, with final editing and revisions made by Mr. Garbaciak prior to
publication.
This report should be cited as follows:
U.S. Environmental Protection Agency. 1994. "Bench-Scale Evaluation of SoilTech's Anaerobic
Thermal Process Technology on Contaminated Sediments from the Buffalo and Grand Calumet Rivers,"
EPA 905-R94-009, Great Lakes National Program Office, Chicago, IL.
-------
ABSTRACT
The Great Lakes National Program Office (GLNPO) leads efforts to carry out the provisions of
Section 118 of the Clean Water Act (CWA) and to fulfill U.S. obligations under the Great Lakes Water
Quality Agreement (GLWQA) with Canada. Under Section 118(c)(3) of the CWA, GLNPO was responsible
for undertaking a 5-year study and demonstration program for the remediation of contaminated sediments.
GLNPO initiated an Assessment and Remediation of Contaminated Sediments (ARCS) Program to carry
out this responsibility. In order to develop a knowledge base from which informed decisions may be made,
demonstrations of sediment treatment technologies were conducted as part of the ARCS Program. A
bench-scale study using the SoilTech Anaerobic Thermal Process technology is the subject of this report.
This study took place at the development laboratory of UMATAC Industrial Processes in Calgary, AB,
Canada on August 19 to 22, 1991. The specific objectives for this effort were to determine process
extraction efficiencies for polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs);
to conduct a mass balance for solids, water, oil, PCBs, and PAHs; and to examine process effects on
metals, oil and grease, and several other parameters.
The SoilTech ATP technology was tested using sediment samples obtained from the Buffalo and
Grand Calumet Rivers. The concentration of the contaminants of concern in the sediments were .34 and
10.7 mg/kg PCBs respectively and 8.7 and 235 mg/kg PAHs respectively. The PCB removal from the
Grand Calumet River was 72 percent. Because of the very low concentration of PCBs in the Buffalo River
sediment it was not possible to make an effective assessment of the PCB removal. The PAH removal from
both sediments was 99 percent. Metals analysis were performed on the treated solids and untreated
sediments. The data appear to demonstrate that metal removal was significant for the Grand Calumet
River sediment. There is no explanation for these results. It should not be attributable to treatment by the
ATP technology. The feed and treated solids were analyzed for percent moisture, oil and grease, total
organic carbon (TOG), volatile solids, and pH. The reductions in oil and grease, TOC, and total volatile
solids concentrations correspond to sediment PCB and PAH removal. Analytical methods used to measure
these parameters may be used as low-cost methods for estimating performance. A mass balance for
solids, oil, water, PCBs, and PAHs was carried out as part of this study.
HI
-------
CONTENTS
Section page
Disclaimer i
Acknowledgements jj
Abstract jjj
Figures v
Tables vi
1.0 Executive Summary 1
2.0 Introduction 3
2.1 Background 4
2.2 Sediment Descriptions 4
2.3 Sediment Characterization 8
2.4 Technology Description 8
3.0 Treatability Study Approach 11
3.1 Test Objectives and Rationale 11
3.2 Experimental Design and Procedures 13
3.3 Sampling and Analysis 16
4.0 Results and Discussion 19
4.1 Summary of Phase I Results 19
4.2 Phase II Results 20
4.3 Quality Assurance/Quality Control 32
Appendix A - Phase I Bench-Scale Treatability Study Thermal Desorption
Technology for Treatment and Removal of PAHs and PCBs
from Sediments 36
Appendix B - Experimental Design - SoilTech, Inc.'s Thermal Desorption
Treatment Technology for GLNPO: Assessment and Remediation
of Contaminated Sediment Technology Demonstration Support 56
Appendix C - Quality Assurance Project Plan for GLNPO: Assesment and
Remediation of Contaminated Sediment Technology
Demonstration Support 78
Appendix D - SoilTech Phase I Test Results 123
Appendix E - Battelle Data 131
Appendix F - Quality Assurance/Quality Control 160
IV
-------
FIGURES
Number
1 ARCS Priority Areas of Concern 5
2 Grand Calumet River Sample Location 6
3 Buffalo River Sample Location 7
4 Simplified ATP Flow Diagram 10
-------
TABLES
Number
1 Summary of Total PCBs 1
2 Summary of Total PAHs 1
3 Mass Balance Summary 2
4 Battelle Data - Characterization of Feed Sediments 8
5 Parameters for Analysis of ARCS Technologies 12
6 Experimental Conditions Used During Phase I Tests 15
7 Samples Collected by SoilTech During the Phase I Tests 16
8 SoilTech Analyses 17
9 SoilTech Analytical Matrix and Sample Identification 18
10 Summary of Operating Conditions During a Full-Scale Application 19
11 Total PCBs 21
12 Feed and Treated Solids PAH Concentrations 23
13 Metals Concentration in the Feed and Treated Solids 24
14 Removal Efficiencies for Other Parameters 24
15 PAH Concentrations in the Tailings, Water, and Oil 26
16 PCB Concentrations in the Tailings, Water, and Oil 26
17 Solid Mass Balance 28
18 Water Mass Balance 29
19 Battelle Data-Oil Mass Balance 30
20 PCB Mass Balance 31
21 PAH Mass Balance 33
VI
-------
1.0
EXECUTIVE SUMMARY
The SoilTech ATP technology was tested using sediments obtained from the Buffalo River and
Grand Calumet River. The contaminants of concern in the sediments were PCBs and PAHs. Samples of
the feed material and the treated solids produced using the SoilTech ATP technology (i.e., the solids
produced by the Batch Pyrolysis Unit and Batch Combustor) were analyzed by Battelle Marine Sciences
Laboratory for residual PCB contamination. The data from these analyses are presented in Table 1.
As shown in Table 1, a greater than 72 percent removal was associated with the Grand Calumet
River sediment. Since the concentrations of individual Aroclors present within the feed and treated solids
for the Buffalo River sample are very close to or below detection limits, a meaningful removal efficiency
cannot be calculated for this sediment. The potential errors associated with the data prevent the effective
assessment of the PCB removal efficiency associated with the Buffalo River sediment.
Table 1. Summary of Total PCBs
(mg/kg, dry)
Sample
Buffalo River
Grand Calumet River
Feed
0.338
10.7
Retort Solids1'2
<5
<3
Tailings1'3
<5
<3
% Removal
NC
>72
Adjusted to account for sand dilution
2 Solids produced by the Batch Pyrolysis Unit
3 Solids produced by the Batch Combustor
NC= Not Calculated
Feed material and treated solids were also analyzed for residual PAH concentrations. Table 2
outlines the analytical results obtained by Battelle. As shown in Table 2, removals of 98.7 and 99.3 percent
were realized for the Buffalo River and Grand Calumet River sediments, respectively.
Table 2. Summary of Total PAHs
(mg/kg, dry)
Sample
Buffalo River
Grand Calumet
River
Feed
8.72
235
Retort Solids1
<3.6
0.128
Tailings1
0.109
1.61
% Removal1
98.7
99.3
1 Adjusted to account for sand dilution
-------
Metal analyses were performed on the treated solids and untreated sediments (see Table 13). The
elevated percent removals associated with the Grand Calumet River sediment for metals should not be
attributed to treatment by the ATP technology. At this time there is not an explanation for these anomalies.
The feed and treated solids were also analyzed for percent moisture, oil and grease, TOC, volatile solids,
and pH (see Table 14). As the data in Table 14 demonstrate, the reductions in oil and grease, TOC, and
total volatile solids concentrations correspond to sediment PCB and PAH removal. Analytical methods used
to measure these parameters may be used as low-cost methods for estimating performance.
A mass balance was also carried out as part of this study. Table 3 summarizes the results
obtained for the different constituents: solids, oil, water, PCBs, and PAHs. Cross-contamination of the
Batch Pyrolysis Unit between Grand Calumet River and Buffalo River runs may be responsible for the high
oil and PAH recoveries associated with the Buffalo River sediment.
Table 3. Mass Balance Summary (%)
Sample
Buffalo River
Grand Calumet River
Retort Solids
110
92.7
Tailings
78.9
NC
Water
59.4
138.8
Oil
187
28.9
PCBs
29.1
16.2
PAHs
839
69
NC = Not Calculated (broken container caused losses)
"Hopper to hopper" cost estimates for other Great Lake sediments containing similar levels of PAHs
and PCBs were previously estimated by SoilTech at about $180 per ton for a 10 ton-per-hour operation.
Major factors affecting this estimate are the condition and properties of the feed sediment (i.e., moisture,
total contamination, and soil characterization). Pending an engineering evaluation of these parameters,
this estimate is considered preliminary and may vary substantially. Please note, these costs pertain to the
restricted scope of soil/sediment processing, and exclude of other project functions (i.e., general site control
and management, construction of utilities and equipment pads, site health and safety controls, excavation
and materials management, performance testing, permitting, etc.).
Small vials of the residuals from the treatability test were retained and given to the EPA Technical
Project Manager for the GLNPO for "show" purposes. All quantities of the test products (water, solids and
oil residuals) from each treatability test were sent to the analytical laboratory, Battelle, for analysis. Due
to the small quantities generated from the tests, none were retained and shipped to EPA for possible
further treatability studies.
-------
It should be noted that data presented regarding contaminant concentrations within the treated
solids have been corrected for the dilution resulting from the addition of sand to the feed. Furthermore,
since the solids produced after the treatment in the Batch Combustor are representative of the overall
effectiveness of the ATP, removal efficiencies were calculated using the contaminant concentrations found
in the solids. Except for oil and grease, the contaminants introduced with the sand had a minimal impact
on the quality of the treated solids obtained. Thus, adjustments to the concentration of these contaminants
within the treated solids were unnecessary.
2.0 INTRODUCTION
The Great Lakes National Program Office (GLNPO) leads efforts to carry out the provisions of
Section 118 of the Clean Water Act (CWA) and to fulfill U.S. obligations under the Great Lakes Water
Quality Agreement (GLWQA) with Canada. Under Section 118(c)(3) of the CWA, GLNPO was responsible
for undertaking a 5-year study and demonstration program for the remediation of contaminated sediments.
Five areas were specified for priority consideration in locating and conducting demonstration projects:
Saginaw River and Bay, Michigan; Sheboygan River, Wisconsin; Grand Calumet River/Indiana Harbor
Canal, Indiana; Ashtabula River, Ohio; and Buffalo River, New York. In response, GLNPO initiated the
Assessment and Remediation of Contaminated Sediments (ARCS) Program.
In order to develop a knowledge base from which informed decisions may be made, bench- and
pilot-scale demonstrations of sediment treatment technologies were conducted under the ARCS Program.
Information from remedial activities supervised by the U.S. Army Corps of Engineers and the Superfund
program were also utilized. The Engineering/Technology (ET) Work Group was charged with overseeing
the development and application of the bench-scale and pilot-scale tests.
Science Applications International Corporation (SAIC) was contracted to provide technical support
to the ET Work Group. As part of this effort, SAIC was charged with conducting bench-scale treatability
studies on designated sediments to evaluate the removal of specific organic contaminants. The bench-
scale studies using the SoilTech Anaerobic Thermal Process (ATP) technology, which are the subject of
this report, took place at the development laboratory of UMATAC Industrial Processes in Calgary, AB,
Canada on August 19 to 22, 1991. The specific objectives for this effort were: to determine process
extraction efficiencies for polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs);
to conduct a mass balance for solids, water, oil, PCBs, and PAHs; and to examine process effects on
metals, oil and grease, and several other parameters.
-------
2.1 Background
SAIC and its subcontractors have conducted seven bench-scale tests for the ARCS Program on
four different sediments using the following four treatment technologies: ATP (SoilTech), Thermal
Desorption (ReTeC), Wet Air Oxidation (Zimpro Passavant), and B.E.S.T.® Solvent Extraction Process
(RCC). This report summarizes the approach used and results obtained during treatability testing of the
SoilTech ATP. The sediments tested using this technology were obtained from the Buffalo River and Grand
Calumet River areas.
The primary objective of this portion of the study was to determine the feasibility and cost-
effectiveness of the SoilTech ATP for treating and removing PCBs and PAHs from the two sediments.
Based upon previous tests performed by SoilTech, it is their experience that the data obtained from the
bench-scale tests simulate full-scale operation. Thus, data generated by these tests may be used to
estimate treatment costs for full-scale operations and to evaluate process feasibility.
2.2 Sediment Descriptions
The sediments used during testing exhibit contamination typical of the sediments encountered in
the Great Lakes and its tributaries. These sediments were obtained from locations around the Great Lakes
which are representative of sites where future field demonstration projects may be conducted. The primary
contaminants in the sediment from both Buffalo River and Grand Calumet River for the purposes of this
study are PCBs and PAHs.
2.2.1 Site Names and Locations for Each Sediment
GLNPO collected sediments for study from the following areas around the Great Lakes: Saginaw
River, Michigan; Sheboygan River, Wisconsin; Grand Calumet River/Indiana Harbor Canal, Indiana;
Ashtabula River, Ohio; and Buffalo River, New York. SAIC was contracted to treat four of the sediments
(from the Grand Calumet River, Buffalo River, Ashtabula River, and Saginaw River) using four different
technologies. Samples from the Grand Calumet River and Buffalo River were treated using the SoilTech
bench-scale ATP. A map is provided in Figure 1 which shows the ARCS Priority Areas of Concern.
Specifics of the sample locations for the Grand Calumet River and the Buffalo River are shown in Figures
2 and 3, respectively.
2.2.2 Sediment Acquisition and Homogenization
Prior to conducting the bench-scale treatability study using the SoilTech technology, the GLNPO
samples were homogenized and stored under refrigeration by the U.S. EPA Environmental Research
Laboratory in Duluth, Minnesota.
-------
ARCS* PRIORITY
AREAS OF CONCERN
ARCS AREAS OF CONCERN
1. SHEBOYGAN RIVER
2. GRAND CALUMET RIVER / INDIANA HARBOR
3. SAGINAW RIVER/BAY
4. ASHTABULA RIVER
5. BUFFALO RIVER
' Assessment and Remediation of Contaminated Sediments
N
0 W 100 160 200
I I I I I
KIOMETER3
US ENVIRONMENTAL PROTECTON AOENCV
GREAT LAKES NATIONAL PROGRAM OFFICE
Figure 1. ARCS Priority Areas of Concern
-------
Sediment sample point
GRAND CALUMET RIVER
M IJ 1.9
I 1 1 milts
Figure 2. Grand Calumet River Sample Location
-------
Sediment sample point
Buffalo River Sample Location
-------
Six 5-gallon containers of the homogenized sediments were sent to SAIC by the Duluth laboratory.
Samples were then transferred by SAIC to SoilTech. SoilTech used these samples to perform a series of
standard tests to determine if the waste sample was compatible with their process and to determine
optimum testing conditions and procedures for the treatability study (Phase I). The sediments used during
the treatability studies also originated from this stock and were forwarded to SoilTech by SAIC.
2.3 Sediment Characterization
SAIC was responsible for the physical and chemical characterization of the raw sediment samples
used during the tests. Table 4 provides characterization data pertaining to the sediments. In order to limit
inter-laboratory variation, the different sediments and their residuals were analyzed by Battelle Marine
Sciences Laboratory in Sequim, Washington. The raw sediment data generated by SoilTech may be found
in Appendix A. The raw sediment samples analyzed by SoilTech and Battelle were collected from separate
sediment samples during different phases of the study.
Table 4. Battelle Data - Characterization of Feed Sediments
(mg/kg, dry, unless specified)
Total PCBs
Total PAHs
Moisture, %, as received
Oil & Grease
TOC, % weight
Total Volatile Solid, %
pH, S.U., as received
Buffalo River
0.338
8.72
68.2
9540
1.78
5.11
8.14
Grand Calumet River
10.7
235
41.5
95000
19.0
15.8
7.82
2.4 Technology Description
The SoilTech ATP separates oily and hazardous organic waste from contaminated soils and
sludges. The treatment process may be separated into five distinct steps arid associated equipment, as
listed:
• ATP Processing Unit
• Feed System
• Vapor Recovery Apparatus
• Flue Gas Cleaning Mechanism
• Tailings Handling System
8
-------
A simplified ATP flow diagram can be found in Figure 4.
According to SoilTech, the ATP process technology is particularly applicable to waste remediation.
This claim is attributed to the following technology characteristics:
• The SoilTech ATP technology employs a rotary kiln which combines four distinct process
steps in one piece of equipment.
• The modified kiln, or ATP unit, applies oxygen-free heating (in the first section) to prevent
oxidative degradation of the organic components.
• Compared to competing thermal destruction units (i.e., incineration), significantly less
energy is needed to achieve decontamination.
• Reductions in net energy consumption result in comparatively less flue gas production and
emissions.
• A significant fraction of feed hydrocarbons can be directly recovered.
• Solids decontamination occurs in a single-unit process, as contrasted with other processes
requiring multiple solids processing steps.
• Particle sizes up to 2-1/2 inches can be processed without size reduction.
As shown in Figure 6, the full-scale ATP has four zones, the preheat zone, the retort zone, the
combustion zone, and the cooling zone. During testing, two bench-scale units, the Batch Pyrolysis Unit
and the Batch Combustor, were used to simulate three of the four zones of the full-scale ATP. The Batch
Pyrolysis Unit was employed to simulate the preheat and retort zones, while the Batch Combustor was
used to simulate the effects that occur in the full-scale ATP unit combustion zone.
The Batch Pyrolysis Unit consists of a rotating retort chamber and off-gas condensation and
collection system. During system operation, the raw feed is introduced to the Batch Pyrolysis Unit, heated,
and the volatiles within the feed are evolved by distillation and thermal cracking of the organic matter.
During operation, a slight vacuum is maintained in order to evacuate the distillate vapors into a tubular
condenser. To determine the extent of the decontamination, a portion of the coke solids (otherwise known
as the retort solids) produced by the Batch Pyrolysis Unit may be analyzed.
To oxidize the remaining coke (carbon-black) present on the inorganic soil fraction, cooled retort
solids are placed in the Batch Combustor. The unit is a stainless steel, rotating, cylindrical chamber with
built-in lifters that shower the solids through a heated air stream (1250°F). The offgases from this unit are
continuously monitored for O2, CO2, NO2, and CO using gas analyzers so that the run may be terminated
when the Og/CO2 combustion ratio is representative of ambient air.
-------
UH.INGS Put
SIMPLIFIED ANAEROBIC THERMAL
PROCESS FLOW DIAGRAM
c«ii
. OIU-M
I |to-4ii-
Rgure 4. Simplified ATP Row Diagram
(Source: SoilTech, Inc.)
-------
Vapors from the Batch Pyrolysis Unit are vented through a vapor pipe into the condensing system.
These vapors pass through the primary and secondary condensers and the resulting liquids are collected
in a glass reservoir. Those gases which do not condense may be measured by a Wet-Test Meter and
analyzed using an on-site gas chromatograph.
During operation of a commercial-scale ATP, all condensed liquid hydrocarbons are collected by
the vapor recovery system. These oils may either be recycled, if suitable, or disposed of. The water
phase, on the other hand, must be pumped to a water treatment facility for further treatment.
Gaseous combustion products from the combustion zone of the full-scale ATP (the heat source for
both the retort and preheat zones), however, are treated in a flue gas handling system and vented to the
atmosphere. Flue gas from the ATP cooling section passes through a cyclone and baghouse for removal
of dust; the gas is then passed through a wet scrubber for removal of any trace particulates or acid gases
prior to venting to the atmosphere. If necessary, activated carbon treatment may be employed as a final
cleanup step to remove trace hydrocarbons from the gas stream.
All of the solids residue (tailings) exiting the full-scale ATP cooling zone are cooled by water
addition, then transported to an outside storage pile by way of screw and belt conveyors. The solids are
generally eligible for non-listed landfill disposal as discharged from the SoifTech ATP unit.
3.0 TREATABILITY STUDY APPROACH
3.1 Test Objectives and Rationale
SAIC was contracted by the ARCS Program to test the effectiveness of four technologies in
removing organic contaminants (PCBs and PAHs) from sediments typical of locations around the Great
Lakes. This treatability study was performed to determine the feasibility and cost-effectiveness of the
SoilTech ATP technology for treating and removing PCBs and PAHs from two different sediments. The
following objectives were critical to the success of the study:
• To record observations and data to predict full-scale performance of the SoilTech technology
• To take samples during the desorption tests and conduct analyses sufficient to allow for
calculation of mass balances for oil, water, solids, and other compounds of interest
• To calculate the desorption efficiency of target compounds
• To obtain treated solids (300 g dry basis), water, and oil for independent analysis
11
-------
Based upon previous tests performed by SoilTech, it is their experience that the data obtained from
the Phase II test simulate full-scale operation. Ultimately, this data may be used to estimate both the
feasibility and treatment costs associated with a full-scale application of the technology.
A two-phase approach was used during this study. During Phase I, SAIC sent samples of the
untreated sediments to SoilTech. These samples underwent a series of initial tests in order to determine
the optimum conditions to be used during the actual Phase II tests. During Phase II, untreated sediments
from the different locations (Buffalo River and Grand Calumet River) were sent to SoilTech. Samples of
the raw, untreated sediments and the various end products generated during the treatability tests (Phase
II) were obtained and analyzed by SAIC. The data generated by SAIC were used to determine treatment
extraction efficiencies. Vendor- or subcontractor-generated data are commented on when available.
This study is only one part of a much larger program and is not intended to evaluate the treatment
of the sediments completely. In order to ensure that the data obtained from this study can be objectively
compared with data generated from the other studies performed in support of the ARCS Program, Battelle
was subcontracted to perform all analyses for the different treatability studies performed by SAIC (seven
treatability studies utilizing four technologies on four sediments). The same set of parameters listed in
Table 5 was analyzed during the characterization of the raw sediments and the end products generated
during the different treatability tests. In addition, representatives from SAIC observed all Phase II
treatability tests.
Table 5. Parameters for Analysis of ARCS Technologies
Parameters
TOC/TIC Arsenic
Total Solids Barium
Volatile Solids Cadmium
Oil & Grease Chromium
Total Cyanide Copper
Total Phosphorus Iron (total)
PCBs (total & Aroclors) Lead
PAHs (16) Manganese
pH Mercury
BOD Nickel
Total Suspended Solids Selenium
Conductivity Silver
Zinc
12
-------
3.2 Experimental Design and Procedures
Numerous test runs were conducted on the Buffalo River and Grand Calumet River sediment
samples during Phase I and Phase II testing. As part of this effort, two types of runs, "ramp" runs and
high-temperature pyrolyses, were performed. During the ramp runs wastes were placed in the bench-scale
Batch Pyrolysis Unit and heated from the ambient temperature to approximately 1200°F. By heating the
system in increments of 50 to 200°F, and then holding the temperature constant until vapor generation had
ceased, condensate production versus temperature was determined, enabling researchers to estimate the
probable end-point temperature for full-scale treatment.
High-temperature pyrolyses simulate the conditions encountered during the direct injection of the
waste into the retort zone of the full-scale ATP system. During the study, the bench-scale Batch Pyrolysis
Unit was preheated to the end-point temperatures determined during the ramp runs. By suddenly heating
the sediment, the effects experienced in full-scale units relative to decontamination, thermal cracking, and
product vapor quality were simulated. The resulting solids are representative of the solids exiting the retort
zone of the ATP. These solids were void of all organic hazardous and toxic organic materials and
contained a small amount of residual carbon black.
Since lake and harbor sediments normally have low granular contents and high liquid contents,
when compared to sludges normally processed by this unit, clean quartz sand was mixed with the
sediments before each test run. This was done to enhance the performance of the bench-scale unit and
to approximate the steady-state temperature conditions of the full-scale ATP more fully.
Procedures for conducting the bench scale test are included in Appendix B of this plan. The
following sections merely summarize testing operations. With slight variations, the same procedure was
used during both phases.
3.2.1 Phase I
Phase I was designed to allow SoilTech to explore a range of variables in order to set test
parameters which would optimize the performance of the ATP technology for the bench-scale tests (Phase
II). In order to accomplish this, 5 gallon samples (wet) of the Buffalo River and Grand Calumet River
sediment were sent to SoilTech by SAIC prior to bench-scale testing.
During Phase I, between 1.4 and 2.4 kg of the sediment/sand feed were placed in the Batch
Pyrolysis Unit (retort unit) and steadily heated in a controlled manner to approximately 1200°F (i.e., during
the ramp runs). By observing the characteristics of the feed and the temperatures at which the water and
13
-------
oil were driven off, data were acquired which were used to determine the boiling point range of the
hydrocarbons in the feed. Ramp run start temperatures of approximately 196°F for the Buffalo River
sediment and SOT for the Grand Calumet River sediment were employed.
Three high temperature pyrolyses were conducted on each sediment at varying temperatures, with
all other parameters held constant. Initial shell temperatures of 777, 950, and 1150°F for the Buffalo River
sediment and 741, 969, and 1175°F for the Grand Calumet River sediment were achieved. The high
temperatures, absence of oxygen, and abundant active surface area of the feed solids caused the organics
to undergo partial coking. The coke coated the soil solids and sediment particles. This coked solid
represents the product of the full-scale ATP retort zone and was tested for organic content to determine
the degree of decontamination achieved by thermal separation. During the high-temperature runs, water
and oil were collected in the condensing circuit and non-condensible gases were stored in a gas bag.
Samples of the water, oil, and solids were collected for analysis. Decontamination achieved by thermal
separation was determined by analyzing for organic content in the retort solids.
The retort solids produced by the bench-scale Batch Pyrolysis Unit are representative of the solids
exiting the retort zone of a full-scale ATP and are the most accurate representation of the effectiveness of
thermal desorption technology. The solids produced after the treatment in the Batch Combustor are
representative of the final product of the ATP system.
Table 6 lists the experimental conditions used during the ramp and high-temperature runs. An in-
depth report addressing Phase I testing conditions and analytical results can be found in Appendix A.
3.2.2 Phase II
The procedures applied during Phase II mirror those employed during Phase I with one exception;
only one high-temperature pyrolysis run was performed. This run was executed at the operating conditions
determined in Phase I. Phase II test temperatures were selected to span the actual range of higher system
temperatures in the full-scale system. Because of the high moisture content of the feed samples, the
temperature in the Batch Pyrolysis Unit was raised from initial values of approximately 443 and 586°F
(similar to temperatures encountered in the hot end of the preheat zone in a full-scale unit) during Phase
II to values corresponding to the maximum discharge temperature from the retort zone (1210 and 1177°F),
where the limit of contaminant distillation is reached. The lower temperatures encountered at the beginning
of the runs allowed the unit to boil off the moisture at rates that would not over-pressure the test system.
According to the results obtained during Phase I, only 1 gallon of each wet sediment was needed to
generate enough solid and liquid residual to satisfy analysis requirements.
14
-------
Table 6. Experimental Conditions Used During Phase I Tests
(Source: SoilTech, Inc.)
Buffalo River Grand Calumet River
Ramp Batch 1 Batch 2 Batch 3 Ramp Batch Batch Batch 3
1 2
Sediment, g 1355.8 1254.2 1313.0 1345.8 1166.3 1154.8 1146.7 1139.2
Silica Sand, g 0.0 1000.0 1000.0 1000.0 0.0 1000.0 1000.0 1000.0
Initial Shell Temp., °F 196 777 950 1150 80 741 969 1175
Final Shell Temp, °F 1252 786 966 1135 1318 778 981 1154
Feed Water, calc. wt % 41.958 45.595 39.139 40.961 61.981 61.153 60.984 55.642
Feed Dry Mass, calc. wt % 58.042 54.405 60.861 59.039 38.019 38.84739.016 44.358
Please note that although the condensed water was initially clear, fines eventually settled within
the aqueous sample, causing the Grand Calumet River water to turn blackish and the Buffalo River
sediment to turn a light green. Since a significant quantity of the condensed oil remained in the tubing, the
aqueous condenser tube and aqueous sample collector were rinsed with methylene chloride (MeCy in
order to extract any oil adhering to the surfaces of these units. The resulting MeC\Jo\\ solution was
subsequently analyzed as the "oil" sample. Solids adhering to the sides of the condenser tube and
aqueous sampler were also removed during rinsing, giving the MeCL/oil solution a black appearance.
3.2.2.7 Procedures
During Phase II testing, up to 3 kg of material was placed into the steel cylindrical rotating retort
chamber (Batch Pyrolysis Unit). The chamber was rotated at 4 (rpm) and heated by electrical heat tracing
to temperatures up to 1300°F. During operation, a vacuum of 1 inch of H2O was maintained in order to
extract distillate vapors from the chamber continuously.
The cooled solids were placed in the aerobic Batch Combustor where they were showered in an
air stream at temperatures of approximately 1250°F. The rotational speed was maintained at 4 rpm and
the offgases were continuously monitored for O2, CO2, NO2, and CO using gas analyzers. The run was
terminated when the O2 concentrations achieved levels representative of ambient air, indicating combustion
was complete.
15
-------
3.3 Sampling and Analysis
The Quality Assurance Project Plan is provided in Appendix C.
3.3.1 Phase I
3.3.7.7 Sampling
During Phase I samples were collected by SoilTech as outlined in Table 7. The majority of the
water and hydrocarbons were thermally separated from the sediments and collected from the Batch
Pyrolysis Unit. The amount of water, liquid hydrocarbons, and solids generated during Phase I is
dependent on the characteristics of the sediment and was used to estimate Phase II production.
Table 7. Samples Collected by SoilTech, During the Phase I Tests
Ramp Run
Run 1
Run 2
Run 3
Water
Yes
Yes
Yes
Yes
Liquid Hydrocarbon
Yes
Yes
Yes
Yes
Retort Solids
Yes
Yes
Yes
Yes
Tailings
No
(optional)
(optional)
(optional)
3.3.1.2 Analysis
During Phase I, SoilTech analyzed the sediment samples for volatile organic carbons (VOCs) ,
PAHs, and PCBs. Although the samples were analyzed for PAHs and PCBs, detailed analyses were not
conducted. Data from these analyses may be found in Appendix A. Table 8 summarizes the analyses
performed by SoilTech.
3.3,2 Phase II
3.3.2.1 Test Sample Preparation
The contaminated samples from the Buffalo River and Grand Calumet River Sites were gray-
colored sediments with very little debris present. Both of the samples contained free-standing water. As
it was very difficult to homogenize the samples with the free-standing water present, this water was
decanted prior to conducting the bench-scale tests and was proportionally recombined with the portion used
for the bench testing. As mentioned previously, sand was added to the sediment prior to introducing the
sediments to the Batch Pyrolysis Unit. This is done to moderate sample handling characteristics and does
not affect organic removal during testing.
16
-------
Table 8. SoilTech Analyses
Analyte/Method
PCB - EPA 8080
VOC - EPA 8240
Priority PAH - EPA 8270
Total Organic Carbon
Oil & Grease
Total Suspended Solids
Metals - ICP Scan1
TCLP
Raw
Feed
yes
yes
yes
no
no
no
no
no
Condensate
Water
yes
no
no
yes
yes
yes
no
no
Distillate
Oil
no
no
no
no
no
no
no
no
Retort
Solids
yes
yes
no
yes
yes
no
yes
no
Tailings
yes
no
no
no
no
no
yes
yes.
1 Selected metals identified in the SAIC feed characterization data were analyzed. Toxicity characteristic leaching procedure
(TCLP) was applied to determine if the final product is resistant to leaching and thus sufficient for backfill in place.
3.3.2.2 Sampling
At the beginning of the Phase II treatability test, SAIC personnel observing Phase II packed and
shipped a sample of the untreated Buffalo River and Grand Calumet River sediments to SAIC's subcontract
laboratory, Battelle, in accordance with written detailed instructions supplied to the SAIC on site
representative. Each sample was representative of material introduced to the Batch Pyrolysis Unit. These
samples were obtained by compositing the separate, previously unopened containers of the sediments sent
for Phase II testing.
Residuals from the ATP consist of a liquid hydrocarbon phase (oil) and a water phase from the
vapor recovery system; gaseous products from the combustion zone; and solid residue (tailings and retort
solids) that exit the Batch Pyrolysis Unit and Batch Combustor. After treatment, samples of the various
residuals produced by the Batch Pyrolysis Unit and Batch Combustor were distributed to SAIC. As
specified in the Quality Assurance Project Plan (QAPP), a minimum of 300g (dry basis) of solid material
was required in order for Battelle to be able to complete the necessary analyses. The actual quantities of
oil and water produced by the technology were not sufficient to perform all the analyses in Table 9,
therefore only PCB and PAH analyses were performed on the water and oil.
17
-------
Table 9. SollTech Analytical Matrix and Sample Indemnification
Buffalo River (B) and Grand Calumet River (Q) Sediment
Parameters
Total Solids
(Moisture)
Volatile Solids
O&G
Metals
PCBs
PAHs
TOC
Total Cyanide
Total Phosphorus
pH
BOD
Total Suspended
Solids
Conductivity
QC Sample O
and
Method Blank
(1)
YES
(1)
YES
(1)
YES
(0)
YES
(1)
YES**
(1)
YES**
(0)
YES
(0)
YES
(0)
YES
(0)
YES
NA
NA
NA
Untreated
Sediment
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
(2)
B,G
-
;,\'- s**
'•• s -. ^
~ ..*• •• •• % S%
MS
i,xf--V
;^>:
K \
(1)
B
(1)
B
(1)
R
NA
NA
NA
^% -i
>*. >
Tripli-
cate
(2)
B
(2)
B
(2)
B
(2)
B
(2)
B
(2)
B
NA
NA
NA
NA
^ s
*N* i%%Y
>* ^i^-.-,'
Treated
Solids
W
Bx,By.Gx,Gy
(4)
Bx,By-Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
(4)
Bx,By.Gx,Gy
"4 , %
*«*^»& £*
.tcC^W^ .. *5
'IP^-Sls I*CVS^
MS
^>> *;
*** t$
* si\ij*
? •." *.? " .
•>
* <
(1)
BY
(i)
By
(1)
By
NA
NA
NA
"* •• ""
"^
mnmj.T."Mi
ViV 5"i
K«*~^i
L*^L
^::V-
^\
^•JV^
f \
•• %
(1)
By
(1)
By
NA
-. "*
\ .
%
\ -"
* -k% > "* ; :
"---^ \
Tripli-
cate
(2)
By
(2)
By
(2)
By
(2)
By
"•^ ^S$s
V?V W'
NA
NA
NA
NA
NA
NA
V j£
;-.
•s-><"*\
"^y, •/
<*?!&
AfSD
^ s^s> ^
% fe* *
»riS^-
'I^S^
•?^^
0^s S-*s
NA
NA
*\ > ^f^
f \
%
\» * -\
1
S V ^
••> - ^
N-lliiihiiini
\
v "X*vi
•• *
4i^;v3
Tripli-
L cate
>^'i
NA
NA
NA
•. V
\^% ^ .
^.
NA
NA
NA
NA
NA
NA
NA
Oil
?"-'*
<&$*
-:^\
" -
(3)
B,G
(3)
B,G
*j
MS
%; '^
•••^f1^"?''
MHIlitll
:^>
^^'
V* '
y\-X.^
(1)
B
(1)
B
-
%
% 5 v"
sSx -!
Tripli-
cate
,4*x° %1
ws> "• s<^
f - ' -;
iiiiiijiHiimiii
-A, i
^V^".'>ij
,,£^;j
* * * \
(2)
B
(2)
B
j "" % '
s :
'"f ''
\ ;
x-V -.";
CO
This technology has two treatment stages. After the first step the sediment is disignated with a V
i.e., Bx is Buffalo River Sediment after the first treatment stage. After the second step a "y" will
be used i.e., By. The treated solids after both steps will be analyzed, but the fully treated
will be used for QC analyses.
* Not Analyzed
** A laboratory pure water spike is required for recovery determination
MS = Matrix Spike
MSD = Matrix Spike Duplicate
-------
3.3.2.3 Analysis
Following the Phase II treatability test, Battelle conducted analyses on the two raw sediments and
their end products. The number of analyses conducted on these sediments and their residuals are listed
in Table 9. Descriptions of the analytical methods employed can be found in the QA Section of this report.
4.0 RESULTS AND DISCUSSION
4.1 Summary of Phase I Results
SoilTech performed a series of initial tests on the raw Buffalo River and Grand Calumet River
sediments to determine specific operating parameters which would optimize the performance of the ATP
technology during Phase II testing. These data were used to estimate the following parameters relative
to their effect on performance for the full-scale ATP: feed rate, rotation rate of the kiln, operating
temperature of the preheat zone, operating temperature of the reaction zone, pressures of preheat and
reaction zones, rate of heat of application, percentage of clean solids internally recycled, and flow rate of
non-condensible gases in the condenser. Table 10 briefly summarizes the operating conditions of a full-
scale ATP as ascertained from Phase I results. A report by SoilTech addressing these parameters may
be found in Appendix D.
Table 10. Summary of Operating Conditions During a Full-Scale Application
Parameters
Operating Conditions Employed During a Full-Scale Application of the ATP
Feed Rate
Rotation Rate of the
Kiln
Temperature of the
Preheat Zone
Temperature of the
Reaction Zone
Pending more complete data, the existing ATP unit is expected to achieve its
design operating rate of 10 tons-per-hour if dewatering is employed. Since
wet sediments limit the feed rate of the commercial ATP unit, the sediments
would require dewatering to reach cost-effective production rates.
During full-scale applications, the rotational speed of the kiln is expected to
range from 3.5 to 5 rpms. This range is typical of the ATP and depends on
the system heat transfer efficiency, feed rate, and vacuum system controls.
The preheat zone is responsible for drying the feed material. The
temperature in the preheat zone ranges from 250 °F at beginning of the zone
to 600 °F at the far end of the zone.
The test temperatures in this project were selected to show optimal
decontamination effectiveness. Rate optimization would entail further
sediment characterization and shakedown testing at the start of full-scale
remediation. To optimize the sediment processing rate, the temperature is
kept as low as possible without jeopardizing quality-control during the
decontamination process. During commercial treatment of the sediment,
temperatures in the retort zone should be allowed to range from 900 to 1200
19
-------
Table 10. (continued)
Parameters
Operating Conditions Employed During a Full-Scale Application of the ATP
Pressure of the
Preheat Zone
Rate of Heat of
Application
Percentage of Clean
Solids Internally
Recycled
Flow Rate of Non-
Condensible
Gases in the
Condenser
The preheat and reaction zones of the full-scale ATP are maintained at a very
slight negative pressure (i.e., just below atmospheric pressure), as determined
in the early phases of full-scale operation.
The rate of heat application determines the operating temperature of the
reaction and preheat zones. Heat generation within the full-scale ATP is
automatically regulated through fuel addition and combustion air injection.
Nominal peak rates of about 10 million BTU per hour are assumed. The rate
of heat generation is adjusted to maximize feed processing rates, while
holding numerous other process variables within system design range.
To improve the thermal efficiency of the full-scale ATP, a portion of the tailings
from the combustion zone (which have been heated to about 1300 to 1400 °F)
are recycled into the retort zone. This operation serves as the primary heat
transfer mechanism. The rate at which these solids are recycled is projected
to be about three times the solid flow rate entering the retort zone.
The flow rate of the combustion air helps to control the temperature of
combustion and to control CO and NOX emissions. During commercial
application of the ATP, combustion air flow will be automatically regulated to
meet the heat demand of the process. The flow is governed according to real-
time measurements of flue gas composition, with principal attention to carbon
monoxide and trace hydrocarbons.
The rate of hydrocarbon condensation depends on the contamination levels of
the feed material and the sustainable net plant feed rate. The analytical data
for the Phase I and Phase II samples showed total organic loadings (including
natural organics) in the feed in the range from 1 to 7 weight percent, with one
value of 12.3 percent.
4.2
Phase II Results
As stated previously, the concentrations of PAHs, PCBs, metals, total solids, volatile solids, and
oil and grease present in the untreated sediments and treated solids are the critical measurements
associated with this study. Oil and water residuals were analyzed to determine the fate of the contaminants
of concern from the process. The following sections briefly address the analytical results pertaining to
contaminant concentrations in the raw sediments and the process residuals (i.e., treated solids, water, and
oil), as well as applicable removal efficiencies. The discussion of Phase II results concludes with an
analysis of the mass balance of the media and contaminants. A complete copy of the data generated by
Battelle for this treatability study can be found in Appendix E.
20
-------
Individual PAH compounds, PCB Aroclors, and metals were quantified during sample analyses.
In order to determine overall removal efficiencies for each class, it was necessary to sum these individual
results. In instances where all reported results were less than the analytical detection limits, total
concentrations are reported as less than the sum of the individual detection limits. When one or more of
the individual components are above detection limits, total concentrations are reported as the sum of the
detected values.
4.2.1 Sediments/Treated Solids
The following sections address sediment quality before and after treatment. Each section expands
upon a different contaminant type and the reductions experienced following treatment. Although solids
were obtained from both the Batch Pyrolysis Unit (i.e., retort solids) and Batch Combustor (i.e., tailings),
percent removal has only been determined relative to the contaminant concentrations present in the
tailings. Since the Batch Combustor provides the final level of treatment, this by-product should most
closely represent the final product from a full-scale system.
Since the wet sediments were mixed with sand before being introduced into the Batch Pyrolysis
Unit, the contaminant concentrations obtained for the treated solids were adjusted for the dilution resulting
from the addition of the sand. This has been accomplished by multiplying the contaminant concentrations
found for the different sediments by the percent increase in solids associated with the different
sediment/sand feeds. Except for oil and grease, contaminants present in the sand had little impact on
retort solid quality and therefore have not been adjusted when reporting treated solids concentrations.
4.2.1.1 PCBs
Samples of the feed material and the treated solids produced using the SoilTech ATP technology
were analyzed for PCB contamination. The data from these analyses are presented in Table 11.
Table 11. Total PCBs (mg/kg, dry)
Sample
Buffalo River1
Grand Calumet River1
Feed
0.338
10.7
Retort Solids2
<5
<3
Tailings2
<5
<3
% Removal2
NC
>72
1 Identified primarily as Aroclor 1248
Adjusted to account for sand dilution
NC = Not calculated
21
-------
As demonstrated by these data, a total PCB concentration of <3 mg/kg was found in the tailings
generated from the Grand Calumet River sediment. This corresponds to a PCB removal efficiency
of >72 percent. Due to the low PCB concentrations initially present in the untreated Buffalo River sediment
and the high analytical detection limits achieved by Battelle, the PCB removal efficiency achieved by the
Buffalo River sediment cannot be determined. Since the errors associated with analytical readings increase
as the contaminant concentration approaches its analytical detection limit, the relevance of the Buffalo River
data is questionable. Thus the effective assessment of the removal experienced by the Buffalo River
sediment was not possible.
4.2.1.2 PAHs
Feed material and treated solids were also analyzed for PAHs. As shown in Table 12, total PAH
concentrations of 0.11 mg/kg and 1.61 mg/kg were found in the tailings produced by treating the Buffalo
River and Grand Calumet River sediments, respectively. These values correspond to removal efficiencies
of 98.7 and 99.3 percent. Clearly, PAHs are effectively removed from the sediments using this technology.
4.2.7.3 Total Metals
The data in Table 13 highlight the recoveries achieved for the metal contaminants present in the
untreated feed and the treated retort solids and tailings. Except for the removal experienced for mercury,
the elevated percent removals experienced on the Grand Calumet River sediment should not in theory be
attributable to treatment by the ATP technology. At this time there is no explanation for these anomalies.
4.2.1.4 Other Analyses
The feed sediments and treated solids were analyzed for percent moisture, oil and grease, TOC,
volatile organic solids, and pH as shown in Table 14. By comparing data in Tables 10 and 11 with data
in Table 14, it becomes apparent that reductions in oil and grease concentrations, TOC, and total volatile
solids correspond to PCB and PAH removal. Thus, analytical methods which assess either oil and grease,
TOC, or total volatile solids could possibly be used as a low-cost indicator of technology effectiveness for
a given sediment. The shift in pH is probably attributable to the conversion of anions in the untreated
sediment to oxides in the treated solids.
22
-------
Table 12. Feed and Treated Solids PAH Concentrations (mg/kg, dry)
Buffalo River
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a) anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Total PAH
Feed
0.099
<0.080
<0.101
0.158
1.04
0.562
1.53
1.44
0.653
0.762
0.626
0.435
0.551
0.429
0.104
0.335
8.72
Retort
Solids1
<0.2
<0.3
<0.3
<0.3
<0.2
<0.3
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<3.6
Tailings1
<0.2
<0.2
<0.2
<0.2
0.109
<0.2
<0.2
<0.2
<0.2
<0.2
<0.08
<0.08
<0.2
<0.08
<0.08
<0.08
0.11
%
Removal1
NC
NC
NC
NC
89.4
>64.6
>86.9
>86.1
>69.7
>73.9
>86.7
>80.7
>63.8
>81.2
>24.0
>75.0
98.7
Feed
4.11
2.06
4.01
4.42
15.8
4.86
33.1
30.8
19.0
26.1
20.0
13.8
20.6
15.2
6.64
14.5
235
Grand Calumet River
Retort
Solids1
0.128
<0.1
<0.2
<0.2
<0.1
<0.2
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.05
<0.1
<0.1
<0.05
0.128
Tailings1
0.525
<0.1
<0.2
0.118
0.591
0.118
0.147
0.113
<0.1
<0.1
<0.1
<0.05
<0.1
<0.1
<0.1
<0.05
1.61
%
Removal1
87.2
>95.1
>95.0
97.3
96.3
97.6
99.6
99.6
>99.5
>99.6
>99.5
>99.6
>99.5
>99.3
>98.5
>99.7
99.3
Adjusted to account for sand dilution.
NC = Not Calculated
23
-------
Table 13. Metals Concentration in the Feed and Treated Solids (mg/kg, dry)
Buffalo River
Silver
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Zinc
Feed
0.28
13.3
396
1.98
127
72.8
45600
0.473
700
44.7
108
0.70
190
Retort
Solids1
0.47
24
596
2.17
182
123
68300
<0,003
1080
61.8
148
<2
278
Tailings1
0.654
14.5
443
1.54
232
142
53000
<0.003
668
69.7
133
<2
264
Removal1
NC
NC
NC
22.2
NC
NC
NC
>99.4
4.6
NC
NC
NC
NC
Feed
5.15
<13.0
288
7.33
1086
256
184000
1.59
2040
95.0
789
5.65
3100
Grand Calumet River
Retort
Solids1
2.46
<1
199
4.76
548
163
9.60
<0.002
1020
80.4
414
<1
1600
Tailings1
1.24
12
252
2.38
400
40.4
75600
<0.002
761
102
365
<1
1150
Removal1
75.9
NC
12.5
67.5
63.2
84.2
58.9
>99.9
62.7
NC
53.7
>82.3
62.9
Adjusted to account for sand dilution
Table 14. Removal Efficiencies for Other Parameters
(mg/kg, dry, unless specified)
Contaminant
Buffalo River
Retort
Feed Solids1 Tailings1
Removal1
Grand Calumet River
Retort %
Feed Solids1 Tailings1 Removal1
Total RGBs
Total PAHs
Moisture, %, as received
Oil & Grease2
TOG, % weight
Total Volatile Solids, %
pH, S.U., as received
0.338
8.72
68.2
9540
1.78
5.11
8.14
<5
<3.
0.05
51 02
1.02
1.02
9.95
<5
0.109
0.01
3672
<0.08
0.22
10.72
NC
98.7
96.2
>99.5
95.7
10.7
235
41.5
95000
19.0
15.8
7.82
<3
0.128
0.01
6782
9.83
6.85
9.78
<3
1.61
0.02
7392
1.61
1.32
9.96
>72
99.3
99.2
91.5
91.6
1 Adjusted to account for sand dilution
2 Corrected for concentration of oil in sand
NC = Not Calculated
24
-------
4.2.2 OH
During the treatability study, because of the small quantity produced, extracted oil could not be
collected directly from the condenser. In order to obtain as much of the extracted oil as possible, the
condenser tube and aqueous sample collector were rinsed with MeCI2. This rinse was assumed to contain
the bulk of the oil collected from the soil and was analyzed as the official oil sample. The trapped solids
in the condenser tube were transferred with the oil. The impact of this material on the "oil" analysis is
unknown.
The concentrations of PAHs and PCBs in the oil extracted from the two sediments can be found
in Tables 15 and 16. Final concentrations in the process solids and water have been included as a
comparative measure of performance. PAH and PCB concentrations are adjusted for the MeCI2 content
by dividing the PAH and PCB concentrations for the oil/MeCI2 mixture by the percent oil found in the
solution. When the PAH and PCB concentrations are adjusted, any error in this oil analysis may be
conveyed to the new concentrations. Thus, the possibility for introducing error to these corrected oil
concentrations exists.
4.2.3 Water
The concentrations of PAHs and PCBs in the water extracted from the two sediments can also be
found in Tables 15 and 16. As expected, both PCBs and PAHs concentrated within the oil residual.
4.2.4 Mass Balance
Mass balances were performed for solids, water, oil, PCBs, and PAHs. The following sections
address the different mass balances and expand on the factors that influenced their closure. Tables 17
through 21 contain the data used to calculate the mass balances.
During the subsequent discussions, terms are introduced which require definition. These definitions
are as follows:
• Input solids include the solids initially present in the sample plus those solids introduced by
sand addition.
• Retort solids are the solids produced by the Batch Pyrolysis Unit.
• Tailings are the solids produced by treating a portion of the Retort solids with the Batch
Combustor.
• Input water includes the water initially present in the sample plus the water contributed by the
addition of sand.
• Output water consists of the volume of product water condensed by the Batch Pyrolysis Unit.
25
-------
Table 15. PAH Concentrations in the Treated Solids, Water, and Oil
Contaminant
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3-cd)pyrene
Dibenzo(a.h) anthracene
Benzo(g,h,i)perylene
Total PAH
Table 16.
Contaminant
Total PCBs
Solids
(ug/kg)
<200
<200
<200
<200
109
<200
<200
<200
<2CX)
<200
<200
<80
<200
<80
<80
<80
110
Buffalo River
Residual
Water
(ug/L)
1130
66.8
87.5
165
281
130
133
120
42.6
54.1
36.2
18.5
30.0
1.80
2.17
12.7
2310
PCB Concentrations in
Solids
(ug/kg)
<5000
Buffalo River
Residual
Water
(ug/L)
66
Grand Calumet
Residual
Oil
(ug/kg oil)
2230000
91200
80000
652000
1820000
549000
735000
628000
279000
407000
331000
45600
121000
57100
21800
47700
8100000
the Treated
Solids
(ug/kg)
525
<100
<200
118
591
118
147
113
<100
<100
<100
<50
<100
<100
<100
<50
1600
Solids, Water,
Residual
Water
(ug/L)
402
107
106
111
203
120
252
230
103
135
88.1
51.8
74.0
38.1
12.4
27.1
2,060
and Oil
Grand Calumet
Residual
Oil
(ug/kg)
<800000
Solids
(ug/kg)
<300
Residual
Water
(ug/L)
64
River
Residual
Oil
(ug/kg)
1610000
119000
139000
773000
1700000
595000
1030000
1050000
787000
926000
773000
342000
578000
313000
173000
346000
11300000
River
Residual
Oil
(ug/kg)
77800
26
-------
4.2.4.1 Solids
To simulate the performance of a full-scale ATP system, a portion of the solids produced by the
Batch Pyrolysis Unit (retort solids) was fed into the Batch Combustor. The closures obtained by
determining the amount of the solids entering and exiting the Batch Pyrolysis Unit (Table 17) were good
(i.e., 110 percent for the Buffalo River sediment and 92.7 percent for the Grand Calumet River sediment).
Although 78.9 percent closure was obtained for the Buffalo River solids entering and exiting the Batch
Combustor, closure could not be calculated for the Grand Calumet River sediment.
A series of accidents during testing of the Grand Calumet River sediment prevented the calculation
of solids closure from the Batch Combustor. When the tailings from the Grand Calumet River test were
collected from the Batch Combustor, the glass jar used to capture the tailings shattered and a portion of
the tailings fell to the floor and was lost. SoilTech personnel then attempted to collect the sample
remaining in the combustor with an aluminum "spout" can. Unfortunately, the seam at the bottom of the
can separated (due to the heat) and portions of the remaining sample were lost. The SAIC representative
attempted to salvage as much of the sample as possible, however a mass balance for solids entering and
exiting the Batch Combustion Unit was precluded.
Since the values used to determine closure were simple weights rather than analytical results, the
mass balances were not compromised by errors associated with analytical methods. However, solids
deposited in the vessels and containers used during the treatability study, specifically the sides of the retort
chamber, vapor tube, and the combustor chamber, as well as solids found in the MeCL/oil rinse and air
emissions from the Batch Pyrolysis Unit and Batch Combustor, were not accounted for in the mass
balance. Since material adheres to the interiors of the Batch Pyrolysis Unit and the Combustion Unit, a
less than 100 percent recovery is expected for both units. Furthermore, the potential impact of any residual
water or oil present in the retort solids or tailings is considered negligible and has not been accounted for
in the mass balances.
4.2.4.2 Water
As shown in Table 18, closures of 59.4 percent and 138.8 percent were obtained for the water
initially present in the Buffalo River and Grand Calumet River feeds. Water adhering to the condensing
system and present in the non-condensible emissions did not contribute to the output water recovered.
Because the majority of the water was removed from the raw sediments during by the Batch Pyrolysis Unit,
closure calculations are based on data obtained during the first half of the treatment process. Furthermore,
the potential impact of any residual water present in the retort solids or tailings is considered negligible and
has not been accounted for in the mass balance.
27
-------
Table 17. Solid Mass Balance
Buffalo River
Grand Calumet River
Input - Batch Pyrolysis Unit
Sediment, g
H2O, %
Dry Sediment, g (dry)
Oil, % dry wt.
Total Sediment Solids, g (dry)
Sand, g
H2O, %
Dry Sand, g (dry)
Oil, % dry wt.
Total Sand Solids, g (dry)
Total Input Solids, g (dry)
962.7
68.2
306.1
0.954
303.2
1925.3
1.31
1900.1
0.027
1899.6
2202.8
888.7
41.5
519.9
9.50
470.5
1777.4
1.31
1754.1
0.027
1753.6
2224.1
Output - Batch Pyrolysis Unit
Solids from Retort Chamber, g
Fines deposited in Vapor Tube, g
Total Solids from Batch Pyrolysis Unit, g
2416
15.9
2431.9
2049.2
12.8
2062
Recovery from Batch Pyrolysis Unit, %
110
92.7
Input - Batch Combustor
Retort Solids, g
Output - Batch Combustor
Combustor Solids, g
1000
789
1000
399.41
Recovery from Batch Combustor. %
78.9
NC
1 Losses from broken collection container explains most of this low recovery
NC = Not calculated
28
-------
Table 18. Water Mass Balance
Input
Sediment, g
H20, %
H20,9
Sand, g
H20, %
H20,g
Total Input Water, g
Buffalo River
962.7
68.2
656.6
1925.3
1.31
25.2
681.8
Grand Calumet River
888.7
41.5
368.8
1777.4
1.31
23.3
392.1
Output
Water Recovered, g 405.0 544.3
Recovery, % 59.4 138.8
A number of possible explanations exist for the poor water recoveries realized during the pilot-scale
tests. Water losses attributed to insufficient condensation within the condenser apparatus may be
responsible for the low recovery realized by the Buffalo River sediment. The condenser may simply be
inadequate for condensing the vapors released from the pyrolysis unit. On the other hand, water may be
exiting or entering the system through a crack in the condenser, which depending on the pressure in the
condenser, can lead to an influx or outpouring of water-laden vapors. In this situation, the disparate water
recoveries realized during the runs may be credited to different condenser pressures occurring between
the runs. Since these runs occurred on different days, variations within the internal pressure are more
likely. However, since there is no way to check whether the vapors exiting the condenser were stripped
of moisture or if the condenser flow rate was equivalent for both runs, verifying these occurrences is
impossible.
4.2.4.3 Oil
Closures of 187 percent and 28.9 percent were obtained for the oil present in the Buffalo River and
Grand Calument River feeds (see Table 19). Any oil present in either the process water or air emissions
was not accounted for in the mass balance. In order to retrieve the residual oil adhering to the sides of
the condensing system, MeCI2 was used to rinse the condenser tube and aqueous sample collector.
Unfortunately, although the amounts of MeCI2 used to rinse the tube and collector were recorded, the
weights of the resulting MeClj/oil mixtures were not recorded. Subsequent mass balance calculations
assume a net loss of 2 percent MeCI2. Evaporation of the MeCI2 caused by contact with the hot vapor tube
is believed to compensate for particulate and oil additions to the resulting MeGl/oil solutions.
29
-------
Table 19. Battelle Data - Oil Mass Balance
Input
Sediment, g
H20, %
Dry Sediment, g
Oil & Grease, % dry wt.
Oil.g
Sand, g
H20, %
Dry Sand, g
Oil & Grease, % dry wt.
Oil, g
Total Input Oil, g
Output
MeCI2 & Oil, g
Oil, %
Oil, g
Retort Solids, g
H20, %
Dry Retort Solids, g
Oil, %
Oil.g
Tailings, g
H2O, %
Dry Tailings, g
Oil, %
Oil, g
Total Oil Recovered, g
Recovery, %
Buffalo River
962.7
68.2
681.8
0.954
2.92
1925.3
1.31
1900.1
0.027
0.51
3.43
400.0
1.38
5.49
1431.9
0.05
1415.2
0.0434
0.6
789
0.01
788.9
0.0312
0.2
6.4
187
Grand Calumet River
888.7
41.5
519.9
9.50
49.4
1777.4
1.31
1754.1
0.027
0.47
49.9
431.9
3.06
13.4
1062
<0.01
1061.9
0.0672
0.7
399.4
0.02
399.3
0.0732
0.3
14.4
28.9
Battelle determined the percentage of oil present in the resulting solutions (1.38 percent for the
Buffalo River solution and 3.06 percent for the Grand Calumet River solution) and compensated for these
percentages when reporting final data. Error may have been introduced to the mass balance calculations
when compensating for the percent oil. Furthermore, although the resulting MeClj/oil solutions were
assumed to contain the bulk of the oil collected from the soil, a significant amount of solids were transferred
with the oil. The impact of this material on subsequent analyses is unknown.
30
-------
4.2.4.4 PCBS
The closures of the PCBs were poor; 29.1 percent for Buffalo River and 16.2 percent for Grand
Calumet River (see Table 20). The PCB mass balance was calculated using the amount of PCBs found
in the feed, product oil (with MeCy, and water. No PCBs were found in the retort solids or tailings. The
need to compensate for the excess MeCI2 present in the MeCL/oil solutions may have introduced errors
to the PCB concentrations found in the product oils. These errors could have been conveyed to the PCB
mass balance closures. The low recovery experienced by the Grand Calumet River sediment may also
be attributed in part to the high detection limits associated with the analysis of PCB in the MeClj/oil mixture.
The low recovery achieved on the Buffalo River sediment can be attributed to the low concentration of
PCBs initially present in the untreated Buffalo River sediment, and the relatively high detection limits
achieved by Battelle during these analyses. Sediments with either low initial concentrations or with
contaminant concentrations close to analytical detection limits are often substantially impacted by analytical
error.
Table 20.
Input
Sediment, g
Solids, %
Dry Solids, %
PCBs Cone., ug/kg dry wt.
Total Input PCBs, mg
Output
Oil:
MeCI2 & Oil, g
PCBs Cone., ug/L
Density of MeCI2 & Oil, a/ml
PCBs, mg
H2O:
H2O, ml
PCBS Cone., ug/L
PCBs, mg
Total PCBs Recovered
Recovery, %
PCB Mass Balance
Buffalo River
962.7
31.8
306.1
0.338
0.103
397.5
<6000
1170
<2.01
405.0
66
0.03
0.03
29.1
Grand Calumet River
888.7
58.5
519.9
10.7
5.56
436.6
2170
1130
0.84
544.3
64
0.03
1.06
16.2
This number does not impact the value for total PCBs recovered because it is derived from a concentration which is the sum of
the detection limits for the individual PCBs tested.
31
-------
4.2.4.5 PAHs
The closures of the PAHs were calculated using the amount of PAHs found in the feed, product
water, and product oils (with MeCy. The contribution of the PAHs found in the retort solids and tailings
was negligible and therefore not included in the mass balance calculations.
PAH balance closure for the Grand Calumet River sediment was good; with a return of
approximately 69 percent (see Table 21). The closure experienced by the Buffalo River sediment,
however, was excessively high at 839 percent. This recovery may possibly be attributed to cross-
contamination between the runs. The Buffalo River sediment was treated after the Grand Calumet River
sediment, from which approximately 38.4 mg of PAHs were unrecovered. If the ATP system was not
completely decontaminated between these runs, particularly the condenser, PAHs from the first run could
have contaminated the products (the MeCl/oil rinse) generated during the Buffalo River run. Since the raw
Buffalo River sediment contained significantly less PAHs than the raw Grand Calumet River sediment (2.67
mg as compared to 122.2 mg), the impacts of cross-contamination could be substantial. Furthermore, since
the bulk of the PAHs recovered during the Buffalo River run (21.5 out of 22.4 total recovered) were found
in the MeCL/oil rinse, it seems likely that contamination is responsible for the 839 percent recovery
experienced by the Buffalo River sediment. This excessively high recovery may have been avoided by
either running the Buffalo River sediment first or by thoroughly decontaminating the condenser. The
condenser was not taken apart but was simply flushed with MeCI2. Data for sediments with either low initial
concentrations or contamination concentrations close to analytical detection limits may be substantially
impacted by analytical error.
4.3 Quality Assurance/Quality Control
The conclusions and the limitations of data obtained during the evaluation of Soil Tech's ATP
Technology are summarized in following paragraphs.
Upon review of all sample data and associated QC results, the data generated for the Soil Tech
treatability study have been determined to be of acceptable quality. In general, QC results for accuracy
and precision were good and can be used to support technology removal efficiency results.
In some cases, the demonstration of removal efficiency for PAHs and PCBs may be limited if
relatively small amounts of these compounds are present in the untreated sediments. If minimal amounts
are present, then detection limits become a factor. Removal efficiency demonstration may be limited by
the sensitivity of the analytical methods.
32
-------
Table 21. PAH Mass Balance
Buffalo River
Grand Calumet River
Input
Sediment, g
Solids, %
Dry Solids, %
PAHs Cone., mg/kg dry wt.
Total Input PAHs, mg
962.7
31.8
306.1
8.72
2.67
888.7
58.5
519.9
235
122.2
Output
Oil:
MeCI2 & Oil, g
PAHs Cone.,
Density of MeCI2 & Oil, g/L
PAHs, mg
H2O:
H2O, ml
PAHs Cone., ug/L
PAHs, mg
Total PAHs Recovered, mg
Recovery, %
397.5
63300
1170
21.5
405.0
2310
0.94
22.4
839%
436.3
214000
1130
82.7
544.3
2060
1.12
83.8
69%
Due to the minimal quantity of oil generated by the process, it was necessary to rinse the oil
collection vessel with MeCI2 in order to create a sample for analysis. The oil/MeCI2 mixture was analyzed
as received for PAHs, PCBs, and percent oil. Results for PAHs and PCBs were then corrected for the
concentration of oil determined. As these oil concentrations were approximately 1 and 3 percent for the
two sediments tested, error could have been introduced in making these corrections. Oil results for PAHs
and PCBs should be used with caution.
Refer to Appendix F for the complete analysis related to Quality Assurance/Quality Control.
33
-------
This page intentionally left blank.
34
-------
This page intentionally left blank.
35
-------
APPENDIX A
PHASE I BENCH-SCALE TREATABIUTY STUDY
THERMAL DESORPTION TECHNOLOGY FOR TREATMENT
AND REMOVAL OF PAHs AND PCBs FROM SEDIMENT
1.0 INTRODUCTION
Soiltech, Inc. (SoilTech) conducted bench-scale tests on two samples under a
technology evaluation program for the Great Lakes National Program Office
administered by Science Applications International Corporation (SAIC). These tests
were conducted to determine the applicability of the SoilTech Anaerobic Thermal
Process (ATP) system for treating these sediments that contain polycyclic aromatic
hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs).
The general objectives of the test program are to demonstrate removal of organics from
the sediments and to indicate whether metals in the sediments or in the contaminants
become susceptible to leaching at rates that would give the treated solids hazardous
qualities.
The sediment samples were from a Buffalo River site and from an Indiana Harbor site.
The PAH concentrations of each sample were as follows:
PAH concentration,
Sample ID Sample Location in parts per million (pom)
910705-1 Buffaio River 123
910705-2 Indiana Harbor 441
In the SoilTech bench-scale simulation of the ATP unit, thermal desorption reduced the
residual PAH concentrations on the sample solids to below the 0.3 ppm detection limit.
For the range of feed concentrations stated above, this level is equivalent to PAH
removal efficiencies of 99.8 to 99.9 percent.
PCB concentrations in both of the feed sediment samples were not detectable at a 0.01
ppm detection limit.
36
-------
The leaching tests of the treated sediments showed that the Toxicity Characteristic
Leaching Procedure (TCLP) metals all were at least one order of magnitude below their
respective limits in the leachate. The condensate from the pyrolysis tests included very
little free oil.
The ATP system can reduce PAHs to non-detectable concentration levels well below
typical cleanup guidelines. Metals were not made leachable by the process. The water
product recovered from the sediments in the process contained very little oil, which is
consistent with the low-feed hydrocarbon levels. The water product should be readily
treatable to appropriate discharge standards.
37
-------
2.0 REMEDIAL TECHNOLOGY DESCRIPTION
The SoilTech ATP unit is a thermal extraction process for separating hydrocarbons from
host materials. The process is centered around a rotary processing vessel in which
waste heat recovery and thermal desorption occur. Products from the ATP unit are the
hydrocarbon and water vapor streams, the clean, dry solids stream, and the combustion
flue gas stream. Figures 1 and 2 depict the process flows.
In an ATP treatment plant, soils, sediments and/or sludges are progressively heated to
a peak treatment temperature approaching 1100 degrees Fahrenheit (°F) while being
vigorously agitated by rotary tumbling. Virtually 100 percent of the moisture and nearly
all of the organic content of the feedstock will be vaporized. Some fraction of the
organics will be thermally cracked, which will yield a nearly pure coke (carbon) and light
hydrocarbon gases.
The hydrocarbon and water vapors exit the rotary ATP unit and pass through cyclones,
a vapor scrubber, direct-contact and shell-and-tube condensers and oil/water separators
that separate the streams into manageable components. These components are
bottoms oil, heavy oil, light oil, preheat water and sour water. Each of these substreams
goes to separate storage or treatment. The noncondensable gases are internally
recycled to the ATP unit as auxiliary fuel.
The solids product stream exits the ATP unit as "tailings" after transferring most of its
heat to the incoming material. The tailings stream is wetted on the discharge conveyor
to control dust and, depending on metals content, is suitable for direct landfilling.
38
-------
The flue gases pass through a cyclone, baghouse, a wet scrubber and an activated
carbon bed before being discharged to the atmosphere. Control of acid-gas emissions
is achieved by adding basic reagents to the wet scrubber. Vapor-phase carbon
adsorption equipment provides additional assurance of quality of gas emissions.
39
-------
3.0 BENCH-SCALE TEST DESIGN AND PROCEDURES
3.1 Thermal Desorption Batch Tests
'SoilTech has carried out nearly 2,000 batch tests on various feedstocks to provide
treatability data and scale-up correlations between the batch units and the 10 tons per
hour (tph) full-scale ATP unit. Batch tests are used to study the effects of process
variables on yields and qualities of products. Detailed material balances and product
closures are calculated, but it should be noted that this type of apparatus is not suitable
for detailed thermal balances. Thermal efficiency is approximated based oh analyses
of the moisture and organic content of the feed sample, its physical characteristics and
references to the demonstrated operational capabilities of the full-scale ATP system.
Additional analytical work is usually performed to characterize the batch test products.
These products are chemically analyzed to determine their environmental acceptability
or requirements for further treatment.
3.1.1 Bench-Scale Test Unit
The bench-scale ATP test unit, or batch retort, simulates the conditions present in the
preheat and reaction zones of the commercial ATP unit. It is used for testing candidate
feedstocks at a small scale. The test equipment consists of the following apparatus:
1. Test Reactor - The test reactor, or retort, is a drum, 12 inches in diameter and
4 inches long. The drum is rotated at speeds of 3 to 16 rpm by a variable-
speed, electric drive, and heated by electrical elements installed on the
outside of the steel shell. A 3-inch thick layer of insulation covers all hot drum
surfaces. Thermocouples provide three steel shell temperatures, three
internal bed temperatures and a central hot vapor temperature. A series of
40
-------
slip rings are used to provide electric power to the heaters and to obtain the
thermocouple outputs. The drum has a 4-inch, quick-lock cap for loading the
feed charge and extracting the treated solids.
2. Hot Vapor Condensing System - Hot vapors produced in the reactor flow
through a rotary seal to an inclined condenser tube. The condenser tube is
externally cooled by cold water circulation. Condensed liquids drain by
gravity to a liquid collector vessel, which accumulates the water and oil liquids
and allows gases to disengage.
3. Gas Metering and Sampling System - Non-condensed vapors pass up a tube
to a gas filter trap. Any liquids that condense along this tube drain back to
the liquid collector vessel or are trapped in the gas filter. Gases passing the
filter are discharged to a plastic gas collector bag through a wet gas meter.
This meter measures the quantity of gas evolved during the test. A gas
vacuum pump is used to evacuate the gas bag and pressurize a gas sample
bomb, which is then analyzed by an off-line gas chromatograph.
4. Purge Gas System - A centrally located pipe passing through the drive
assembly of the reactor introduces purge gas into the reactor during a test
run. The purge gas, normally nitrogen, displaces air and provides an inert
atmosphere for the batch process. The inlet purge gas passes through a wet
gas meter then through a rotating seal and into the reactor feed pipe. The
combination of purge gas plus water vapor and organic vapors generated
from the test sample exits the retort vessel through the other previously
mentioned rotary seal and gas tube to the condenser.
5. Feed Addition and Coked Sand Discharge - As stated previously, a 4-inch
quick-lock cap is used to access the reactor. The feed sample is loaded as
-------
a prepared charge for rapid delivery into the reactor. During the test runs, the
sample temperature is raised to the range of 1000 - 1300 °F. The exact end-
point temperatures depend on observations of the completion of condensate
formation. The high temperatures, absence of oxygen and abundant active
surface area of the feed solids cause the organics to undergo partial coking.
The coke coats the solid soil or sediment particles.
At the end of a test run, the feed cap is removed and the coked sand charge
is dumped as the unit rotates. The spent material is cooled, weighed,
sampled and subsequently analyzed.
This coked solid product represents the product of the full-scale ATP unit's
retort zone. It is tested for organic content, in particular, to determine the
degree of decontamination achieved by thermal separation.
3.1.2 Pvrolvsis Batch Test Conditions and Procedures
In this project, two sets of tests were run on ostensibly identical sediment samples. The
Phase I tests were run so that SoilTech could empirically target the optimal treatment
conditions for the particular sediment samples. Table 1 shows the run results.
For Phase II, additional feed samples were provided by SAIC, and the entire test
program was monitored by SAIC and Environmental Protection Agency (EPA)
personnel. The Phase II tests were limited to the optimal conditions selected from
Phase I, and are still pending.
42
-------
3.1.2.1 Phase I
Eight test runs were conducted on the samples received from SAIC during Phase I
testing. Two "ramp" runs were completed, where the materials were taken from a
relatively low initial temperature to a final temperature of approximately 1200 °F to
observe the rate of water and oil production with respect to elapsed time and
temperature intervals. Ramp run start temperatures were about 196 °F for the Buffalo
River sample and about 80 °F for the Indiana River sample.
Other runs were conducted at higher and nearly constant temperatures to simulate
direct injection of the waste into the retort zone of the full-scale ATP unit. The Buffalo
River samples were run at shell temperatures of about 775, 950 and 1150 °F. The
Indiana Harbor samples were run at shell temperatures of about 740, 970 and 1175 °F.
The retort solids from these runs were used for analyses.
Water and oil were collected in the condensing circuit, and noncondensable gases were
stored in a gas bag. Samples were taken from the solid and liquid streams, weighed
for material balances and kept for detailed laboratory analyses. The gas samples were
analyzed by gas chromatography. Table 1 shows a more detailed account of the
pyroiysis run conditions.
3.1.2.2 Phase II
After analyses of the Phase I batch tests, an optimum run was conducted on each of
the new samples. All effluent streams, except noncondensable gases, were collected
and sent to SAIC for independent analyses. The gases were analyzed on-site using gas
chromatography. A portion of retort solids from these runs were used in the Phase II
combustion tests.
43
-------
3.2 Combustion Batch Tests
As described above, in the commercial ATP unit, the treated solids move progressively
through the system, encountering the combustion zone after being coked and fully
decontaminated in the retort zone. Bench-scale combustion testing simulates this step.
The product of the combustion test best simulates the final product of the ATP process
with respect to leachability.
The batch combustion unit is similar to the batch thermal separator reactor. It is a drum
24 inches in diameter and 4 inches long, with piping for nitrogen purge and combustion
air injection. It is also rotated by an electric motor and heated electrically. The drum
contains lifters to lift and drop the coked material through the air stream. The unit is
preheated to the process temperature of approximately 1350 °F and purged of air before
the test charge is loaded. The test charge is introduced into the unit through a port on
the drum's circumference. Combustion air is then injected through an axial pipe.
Combustion gases are removed through a similar axial pipe at the other end of the
vessel. The combustion product gases pass through the same gas metering and
sample collection system described in Section 4.1.1.
3.2.1 Combustion Batch Test Conditions and Procedures
The coked solids from Phase I and Phase II testing were burned in the batch
combustion unit. The solid products from Phase I testing were analyzed for leachability
at SoilTech's contract laboratory. The solid products from Phase II testing were sent
to SAIC for independent analyses.
44
-------
4.0 SAMPLING AND ANALYSES
4.1 Thermal Desorption Batch Tests
Tables 2 through 5 contain all analytical data for samples tested for Phase I. Samples
of the feed, retort solids, condensate liquids and noncondensable gases were collected
from each of the test runs. The feed and retort solids were analyzed for volatile organic
compounds (VOCs), PAHs and PCBs.
Using the SoilTech methodology, the retort, or coked, solids have experienced only
high-temperature distillation (i.e., evaporation of organics in a nearly oxygen-free
environment). Analyses of the organics in the coked solids gives the best indication of
the ATP system's decontamination effectiveness. As summarized in Section 6 and
shown in detail in Tables 2 and 3, the ATP unit achieves very aggressive organic
removal. After consulting with SoilTech's contract laboratory, the positive sample results
in Table 2 with an "r" suffix are due to laboratory contamination. These values should
not be detectable at a 10 parts per billion detection limit.
The condensate liquids were analyzed for VOCs, PAHs, oil and grease, total suspended
solids and total organic carbon. The noncondensable gases were analyzed for various
organic and inorganic compounds.
4.2 Combustion Batch Tests
The solid product from the combustion batch tests in Phase I was analyzed for TCLP
metals. That product most closely resembles the tailings stream leaving the full-scale
45
-------
ATP system. If metals are present in the source material, then following exposure to
high-temperature oxidation, the metals would be expected to be most susceptible to
leaching. The TCLP test of the tailings gives the worst-case indication of the tailings
suitability for landfilling. Table 6 shows the results from these ainalyses.
46
-------
5.0 SUMMARY OF RESULTS
PAHs in both sediment samples were reduced from their initial concentrations of greater
than 100 ppm to below a 0.3 ppm detection limit. PCBs were not found in the feed
samples at a 0.01 ppm detection limit. An almost negligible amount of condensable oil
was formed from the bench-scale testing. The tailings easily met all the criteria for
leachability of solids under the TCLP test method.
47
-------
co
TABLE 1
INDIVIDUAL RUN CONDITIONS
Run Number
Waste source
Recycle type
Feed charge, g
Recycle charge, g
Initial shell temp.. oF
Final shell temp., oF
Feed water, calc. wt%
Feed dry mass, calc. wt%
CO + CO2, wl*, on he product
C3&- gas (c/w H2 + H2S).wt%olhc
Total C4& t , wt% of he
Total ccSo make, wt% of he
Overall mass balance closure, %
Mass bal. closure, % no N2* O2
Ethylene/ethane vol. ratio
CO/CO2vol ratio
C4&4 oil at 6O oF, g/cc
C4& t oil gravity, API
1473
Buffalo River
0
13558
000
196
1252
41 958
58042
5926
533
5973
9437
99 11
9881
0628
0077
08505
3472
1474
Buffalo River
Silica Sand
125420
100000
777
786
45595
54405
1582
165
3516
79014
993
99 18
1 182
005
08476
3b29
1475
Buffalo River
Silica Sand
131300
100000
050
066
39139
60861
35499
10338
10767
43396
9969
9951
0982
0089
07299
62.19
1476
Buffalo River
Silica Sand
13458
100000
1150
1135
40961
59039
11825
538
3758
79036
9991
9957
1 466
0 138
0708
68 18
1477
Indiana Harbor
n/a
1166.3
0.00
BO
1318
61981
38019
49374
12558
4818
3325
9897
9802
0438
0231
08123
4253
1479
Indiana Harbor
Silica Sand
11546
100000
741
778
61.153
38847
7.763
1 566
1 866
88805
9968
99 77
0662
0.157
0819
41 1
1480
Indiana Harbor
Silica Sand
11467
100000
969
981
60984
39016
10421
0892
2144
86543
9979
9928
1 201
0065
08089
4327
1481
Indiana Harbor
Silica Sand
1139.2
100000
1175
1154
55642
44358
8088
5 179
2962
83772
9968
9935
1521
0 157
07083
6808
U'illlL
-------
TABLE 2
VOLATILE ORGANIC COMPOUND CONCENTRATIONS - METHOD 8240
(Concentrations in ppb)
Sample ID
Sample
Descriotion
Compound
acetone
benzine
bromodichloromettiane
bromoform
bromomethane
carbon disulfide
carton tetrachloride
chloro benzene
chlorodibromomethane
chloroethane
2-butanone
chloroform
chloromathane
dibromomethane
1,1-dichloroethane
1 .2-dichloroethane
1,1-dichloroetfiene
M.2-dichloroethane
1 ,2-dichloropropane
c-1 ,3-dichloropropene
t-1 ,3-dichloropropene
ethylbenzene
2-hexanone
lOdomethane
methylene chloride
4-methyl-2-pentanone
styrene
1 , 1 ,2,2-tetrachtoroetriarie
tetrachloroethene
toluene
1,1,1-trichloroethane
1 , 1 ,2-tnchloroethane
trlchloroethene
trichlorofluorometfiane
1 ,2.3-trichloropropane
vinyl acetate
vinyl chloride
xylenes (total)
Notes:
910705-02
Indiana
Harbor Feed
1003f
trace (20)
NO (10)
NO (10)
trace (50)
trace (85)
ND (10)
ND (10)
NO (10)
ND (10)
trace (220) r
ND (10)
trace. (50)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
1130r
ND (10)
NO (10)
ND (10)
ND (10)
trace (20) r
ND (10)
ND (10)
NO (10)
ND (10)
ND (10)
ND (10)
ND (10)
20
91-0705-02
Indiana
Harbor Tailings
18080 r
20r
ND (10)
ND (10)
trace (60) r
trace (100) r
ND (10)
ND (10)
ND (10)
ND (10)
305r
trace (220) r
trace (60) r
trace (60) r
ND (10)
ND (10)
ND (10)
ND(10)
ND (10)
ND (10)
ND (10)
40r
ND (10)
trace (20) r
875 r
ND (10)
ND (10)
ND (10)
trace (20) r
3270r
245 r
ND(10)
ND (10)
trace (40) r
ND (10)
ND (10)
ND (10)
155r
91-0705-01
Buffalo River
Sediment
trace (1015) r
trace (15)
ND (10)
ND (10)
ND (10)
trace (325)
ND (10)
100
ND (10)
ND (10)
trace (175) r
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
NO (10)
ND(10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND(10)
ND (10)
ND (10)
NO (10)
ND (10)
ND (10)
ND (10)
ND(10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
trace (15)
910705-01
Buffalo River
Tailmas
990r
trace (20) r
ND (10)
ND (10)
ND (10)
105 r
ND (10)
ND (10)
ND (10)
ND (10)
trace (280) r
ND(10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
ND (10)
30r
ND (10)
ND (10)
6025 r
trace (155) r
NO (10)
ND (10)
trace (20) r
595 r
trace (20) r
ND (10)
ND (10)
ND (10)
ND (10)
ND(10)
ND (10)
170r
1. ND (x) - Jelected above detection limit, x.
2. trace (y) -dicatea component Is present above blank levels, but lower than the quantitation limit, y.
3. r • result should be rejected due to laboratory contamination.
49
-------
TABLES
HPLC SCREEN FOR PRIORITY PAHs
(Concentrations in ppm)
Sample ID
Sample
Description
Compound
acenapthene
acenapthylene
anthracene
benzo (a)anthracene
oenzo(a)pyrene
benzo (b)fluoranthene
benzo (k)fluoranthene
benzo (g,h,i)pery1ene
cnrysene
dibenzo(a,h)anthracene
fluorene
fluoranthene
maeno(1,2.3,c,d)pyrene
naphthalene
phenanthrene
pyrene
2-methylnaphthalene
Motes:
91-0705-2
Indiana
Harbor Feed
11
ND (0.3)
trace (1.0)
14
135
99
ND (0.3)
ND (0.3)
3
ND (0.3)
11
73
ND (0.3)
27
17
91
trace (1.0)
91-0705-02
Indiana
HarDor Tailinos
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
91-0705-01
Buffalo River
Sediment
5
NO (0.3)
trace (1.0)
13
4
2
ND (0.3)
ND (0.3)
ND (0.3)
• :.3)
;,^ ,0.3)
37
ND (0.3)
6
25
31
ND (0.3)
910705-01
Buffalo River
Tailmas
ND (0 3)
ND (0 3)
ND (0.3)
ND (0.3)
NO (0.3)
NO (0.3)
NO (0.3)
ND (0 3)
ND (0 3)
ND (0 3)
ND (0 3)
ND (0.3)
ND (0 3)
ND (0 3)
ND (0 3)
ND (0 3)
ND (0 3)
1 ND (x) « not detected above detection limit, x.
2 trace (y) = indicates component is present above blank levels, but lower than the guantitation limit, y.
3. AJI feed and retort solids samples had non-detectable levels of PCSa at a detection limit of 0.01 ppm
•1 AJI condensate samples had non-detectable levels of PCBs at a detection limit of 0.1 ppm.
50
-------
TABLE 4
GAS CHROMATOGRAPHY ANALYSIS
(Volume Percent)
Run Number
Sample
Description
— ^— — —
Compound
hydrogen
propane
propytene
isobutane
hydrogtn sulfide
n-butane
1 -butane
trans-2-buten»
cis-2-but«n»
isopentana
n-pemana
neo-pentane
1-pantan*
trans-2-pantene
cis-2-pem»ne
cvclopemane
oxygen
nitrogen
methane
caroon monoxide
carbon dioxide
ethytene
ethane
Iil3
Buffalo
River
^^_>MBI_BI
0.104
0.308
0.190
0.004
0.000
0.019
0.050
0.013
0.023
0.003
0.007
0.003
0.007
0.003
0.003
0.000
1.570
78.324
1.908
1.193
15.587
0.162
0.258
0.262
1474
Buffalo
River
0.000
0.109
0.062
0.004
0.000
0.018
0.018
0.009
0.018
0.002
0.007
0.003
0.008
0.004
0.002
0.000
2-246
86.509
0.087
0.445
3.905
0.624
0.528
0.392
^475
Buffalo
River
0.000
0.417
0.705
0.016
0.000
0.149
0.314
0.089
0.143
0.009
0.059
0.000
0.100
0.034
0.026
0.000
2.884
78.239
2.442
0.962
10.7S5
1.003
1.021
0.604
1476
Buffalo
River
•^•••^•^M^^^^
0.635
0.424
1.396
0.011
0.001
0.114
0.479
0.104
0.313
0.007
0.055
0.006
0.158
0.031
0.021
0.000
1.576
70.814
4.391
1.737
12.571
Z567
1.751
0.837
1477
Indiana
Harbor
11.825
0.385
0.287
0.014
0.000
0.056
0.042
0.030
0.040
0.008
0.026
0.015
0.021
0.014
0.005
0.000
3.703
58.297
6.643
3-292
14.277
0-248
0.562
0.212
1479
Indiana
Harbor
0.388
0-262
0.279
0.008
0.000
0.062
0.070
0.035
0.055
0.005
0.028
0.015
0.039
0.007
0.010
0.000
4.100
76.377
3.640
1.783
11.346
0.385
0.582
0.521
1480
Indiana
jHarbor
0.115
0.190
0.132
0.012
0.000
0.048
0.041
0.019
0.035
0.007
0.023
0.008
0022
0.010
0.005
0.000
2.037
83.961
0.853
0.706
10.815
0.275
0.229
0.457
1481
Indiana
Harbor
0 401
0541
1 875
0.016
0.000
0 125
0392
0.131
0414
0.008
0050
0035
0.195
0037
0024
0000
1 769
65547
8390
1 927
12.241
2956
1 943
0982
total
100.001
100.000
100.001
99.999
100.000
99.997
100.000
100.000
51
-------
TABLE 5
OIL AND GREASE, SUSPENDED SOLIDS,
AND TOTAL ORGANIC CARBON ANALYSES
Sample ID Test Description
Sample Description Oil and Grease Total Suspended Solids Total Organic Carbon
910705-02
Indiana Harbor Sediments 0.2 ppm 0.4 ppm 0 2 wt %
91-0705-02
Indiana Harbor Tailings 176 ppm - 8.07 wt %
91-0705-02
Indiana Harbor Condensate 321 ppm 11,200 ppm I3.86wt%
91-0705-01
Buffalo River Sediment 0.2 ppm 0.4 ppm 0.2 wt %
91-0705-01
Buffalo River Tailings 49 ppm • 4.24 wt%
91-0705-01
Buffalo River Condensate 91 ppm 16,200 ppm 9 66 wt %
52
-------
TABLE 6
ICP SCAN FOR METALS
(Concentrations in ppm)
Sample 10
Sample
Description
Compound
aluminum
barium
beryllium
boron
cadmium
calcium
cnromium
cobalt
copper
iron
lead
lithium
magnesium
manganese
molybdenum
nickel
potassium
silicon
sodium
strontium
titanium
vanadium
zinc
910705-02
Indiana
Harbor Tailingt
2590
59.2
0.3
<1.0
3.9
7100
246
1.9
60.5
36400
153
1.8
1990
384
0.3
30.2
436
155
275
13.1
33.3
40.2
654
910705-02
Indiana Harbor
Comburton Solids
1060
23.5
0.1
1.8
40.1
2750
121
0.4
18.2
4460
189
0.3
547
64.7
0.3
16
275
63
235
6.6
31.5
7.6
54.2
910705-02
Ind. Harbor Comb.
Solid! Le«ch«te
11.8
0.19
0.4
0.06
< 0.001
185
0.081
0.006
0.13
2.12
0.14
<0.01
34.2
1.3
0.005
0.049
3.1
21.1
203
0.31
0.005
0.034
0.63
910705-01
Buffalo River
Tailing*
6530
66.7
0.4
4.1
1 5
8350
2.2
2.8
32.8
15100
38.7
4.4
2850
217
0.1
17.7
2020
247
368
23.5
101
11.7
80.5
910705-01
Buffalo River
CpmbustionJTailings
6420
99
0.4
45
0.8
7410
175
3.9
26.7
13000
31.1
2.7
2500
189
<0 1
22.7
2160
309
435
22.7
78.2
11 7
799
910705-01
Buffalo P Corns
Jaihnas Leacnate
126
02
0005
0 1
0003
323
0 18
0008
034
39
0077
002
485
2 12
0003
0 0^7
79
25 5
201
0 57
0006
0005
073
CJff^~ r
. •*"„ ,'i Vz..-—; "-
~
53
-------
Ul
1
to
tN
1
O
Cn
• .
0)\
C1EAN DRY C .
TAILINGS SAND o • ' •*•
loilTech ATP UNIT
GAS
COOLING ZONE
^REHEAT ZONE
^. EVOLVED STEAM
v_l JL
SPENT SAND X
^L / issufo foo meAi«»uTY SIUDV t/* L»J. /
DA1E ISSUE / DIVISION MN BY Lin)
BY AT'D Wi
COMBUSTION ZONE
) AUXILIARY
' ' * O BURNER
REACTION ZONE
^** HYDROCARBON VAPORS ^
-^ COKED
/ 1
-' X
V_ D COMBUSTION
INTERNAL PROCESS FLOW DIAGRAM
PREPARED FOR
SCIENCE APPLICATIONS
INTERNATIONAL CORPORATION
CINCINNATI. OHIO
' r ' i
1DAIE 9-24 91 1 DRAWING NtlMBFR
bCALE- NFS NUUKL 1 J90-426-A3
-------
ID
* 25
23
O Z
| - '
cn
tn
A
Ho
SoilTech ATP UNIT
STACK
WATER
OIL
FLUE GAS
TREATMENT
FEED
VAPOR
TREATMENT
PREHEAT
VAPOR
VENT
GAS
OFF GAS
SOILTECH
ATP UNIT
AIR
OIL
FUEL
VAPOR
OIL
RECOVERY
PRODUCT
OIL
DECONTAMINATED
TAILINGS
FEED AND
DISCHARGE FLOW DIAGRAM
PREPARED FOR
SCIENCE APPLICATIONS
INTERNATIONAL CORPORATION
CINCINNATI, OHIO
UA1E
ISSUE / Ht VISION
ff
DATE 9-24--91
'oCWE- NTS
FIGURE
DRAWING NIIMBIR
90-426 A4
-------
APPENDIX B
EXPERIMENTAL DESIGN - SOILTECH, INC.'S
THERMAL DESORPTION TREATMENT TECHNOLOGY
FOR
GLNPO - ASSESSMENT AND REMEDIATION OF CONTAMINATED
SEDIMENT TECHNOLOGY DEMONSTRATION SUPPORT
July 1991
Submitted to:
U. S. Environmental Protection Agency
Great Lakes National Program Office
230 S. Dearborn
Chicago, Illinois 60604
Submitted by:
Science Applications International Corporation
635 West Seventh Street
Cincinnati, Ohio 45202
EPA Contract No. 68-C8-0061, Work Assignment No. 2-18
SAIC Project No. 1-832-03-207-40
56
-------
TABLE OF CONTENTS
SECTION
LIST OF TABLES AND FIGURES Hi
1.0 TECHNOLOGY DESCRIPTION 1
2.0 TEST PLAN 7
2.1 Purpose 7
2.2 Approach 7
2.3 Phase I 8
2.4 Phase II 10
3.0 RESIDUAL MANAGEMENT 14
4.0 FINAL REPORT 15
APPENDIX A - SoilTech's Summary of Operation Variables
APPENDIX B - Phase I Letter Report on Process Variables
57
-------
TABLES
NUMBER PAGE
2-1 Samples to be Collected by SoilTech, Inc.,
during the Phase I Test 8
2-2 Hypothetical Schedule of Experimental Conditions
during Phase I Tests 9
2-3 SoilTech's Analyses Schedule for the Phase II Thermal Desorption
of Buffalo River and Indiana Harbor Sediments 12
2-4 SAIC's Analysis Schedule for the Phase II Thermal
Desorption of Buffalo River and Indiana Harbor Sediments 13
FIGURES
NUMBER PAGE
1-1 Simplified Anaerobic Thermal Process Flow Diagram 3
1 -2 Overhead View of the Full-Scale AOSTRA Taciuk Processor 4
1-3 Anaerobic Thermal Processor - Internal Flow Diagram 5
58
-------
SECTION 1
1.0 TECHNOLOGY DESCRIPTION
The SoilTech Anaerobic Thermal Processor (ATP) separates oily and hazardous organic waste
material from contaminated soils and sludges. It is a continuous, fast-acting process made possible by a
proprietary rotary kiln design. The process is comprised of five main systems: the ATP processing unit,
the feed system, the vapor recovery system, the flue gas cleaning system, and the tailings handling system,
each of which is discussed below. A simplified anaerobic thermal process flow diagram is exhibited as
Figure 1-1. An overhead view of the full-scale ATP is shown in Figure 1-2.
The ATP process technology is reported to provide unique capabilities that are particularly desirable
in waste remediation applications. Included are the following:
1. The SoilTech ATP system employs a unique rotary kiln which combines four distinct
process steps into one piece of equipment.
2. The kiln, or ATP unit, applies oxygen-free heating to prevent oxidative degradation of the
organic components.
3. Decontamination by thermal separation is achieved at a fraction of the energy duty of
competing thermal destruction, i.e. incineration.
4. Because of lower net energy consumption, lower flue gas production and emissions result
per unit of waste treated as compared to thermal destruction.
5. A significant fraction of feed hydrocarbons is directly recovered.
6. Solids decontamination occurs in a single unit process, as contrasted with other processes
requiring multiple solids processing steps.
7. Particle sizes to 2-1/2 inches can be processed without size reduction.
The full-scale ATP, as previously discussed, has four zones: the preheat zone, the retort zone, the
combustion zone, and the cooling zone. Figure 1-3 is an internal flow diagram of the ATP Processing Unit
that shows these four separate internal sections. The DMA Industrial Processes Division (DMA) is a parent
company of SoilTech and conducts the bench-scale tests for SoilTech. LIMA uses two bench-scale units
to accurately simulate the four zones of the full-scale ATP. The Batch Pyrolysis unit simulates the preheat
and retort zones illustrated in Figure 1-3. Raw feed is introduced, heated, and allowed to evolve all volatile
matter by both distillation and thermal cracking of organic matter. The coked solid product from this step
59
-------
will be split for chemical analysis to show the extent of decontamination. A portion of the coked solids will
also be processed in the bench-scale Batch Combustor. It oxidizes coke (carbon-black) on the inorganic
soil fraction, simulating the effects that occur in the full-scale ATP unit combustion zone.
The Batch Pyrolysis Unit consists of a rotating retort chamber and off-gas condensation and
collection system. During the bench-scale test, a sample of material is placed into a milled steel cylindrical
rotating retort chamber (chamber). The chamber is capable of holding up to three kilograms of material;
Typically, a charge of contaminated sample feed will be blended with at least a portion of ciean quartz sand
when added to the bench unit. The chamber, which can be rotated at various speeds, is usually rotated
at 4.5 revolutions per minute (rpm) during the tests. The retort chamber is heated by electrical heat tracing
and can achieve temperatures to about 1,300°F. The chamber is also held at a slight vacuum and
continuously purged with a stream of nitrogen to maintain the anaerobic conditions.
Two kinds of tests are typically run: "ramp" runs and high-temperature pyrolyses. A new sample
will first be put through a ramp run, in which a portion of the sample is placed in the test unit while the
equipment is at or near ambient temperature. The system is heated in steps of 50 to 200°F, being held at
each increment until vapor generation for that step ceases. This gauges condensate production versus
temperature and targets the probable end-point temperature for full-scale treatment.
Then, further portions of the feed sample will be tested at elevated temperatures that bracket the
target endpoint by ± 50 to 100°F. The retort chamber is partially loaded with clean quartz sand and
preheated to a selected temperature. Then the feed sample is added. This sudden heating best simulates
the full-scale effects on the feed in terms of decontamination, thermal cracking, and the mix of product
vapors that result.
The solids at this point are representative of the solids exiting the retort zone of the ATP. These
solids are void of all organic hazardous and toxic organic materials and contain a small amount of residual
carbon-black.
The vapor given off in the retort chamber passes through a vapor pipe and into the condensing
system. The vapors pass through a primary and water-cooled secondary condensers, which drain into a
glass collection reservoir. The small amount of noncondensible gases which make it through the secondary
condenser are measured by a Wet-Test Meter and collected and analyzed using an on-site gas
chromatograph.
60
-------
O)
m
I
I
o
SCRUBBER
CONDENSER
/t\
AMHIItlC LOCATION
D*TE Siut
SIMPLIFIED ANAEROBIC THERMAL
PROCESS FLOW DIAGRAM
lo.it •-•,-
lsc«it NOUC
I nuimc NUUK»
[io-42i-ii
Figure 1*1. Simplified Anaerobic Thermal Process Flow Diagram
(Source: SoilTech, Inc.)
-------
05
ro
Figure 1-2. Overhead View of the Full-Scale AOSTRA Taciuk Processor
(Source: SoilTech, Inc.)
-------
5!
i
ID
CN
^1-
I
O
O)
8
FLUE GAS
STEAM AND LIGHT
HYDROCARBON VAPOR
FEED SOIL
CLEAN TAILINGS
A
HAIL
I OK ('«<>»•<)'.*!
AUXILIARY BURNER
COOLING ZONE
H
PREHEAT ZONE |
COMBUSTION ZONE
RETORT ZONE
HYDROCARBON VAPOR
COMBUSTION AIR
h U b.l*l U U
ANAEROBIC THERMAL PROCESSOR
INTERNAL ELOW DIAGRAM
'.fA|f MOtll
FIGURE 2
DRAWIMC NUMBER
90-426 A2
Figure 1-3. Anaerobic Thermal Processor - Internal Flow Diagram
(Source: SoilTech, Inc.)
-------
The coded solids are then placed in the bench-scale combustor unit which is used to simulate the
ATP's combustion zone, which effectively removes the remaining carbon-black. The unit is a stainless steel,
rotating, cylindrical chamber with built-in lifters that shower the solids through an air stream at temperatures
of approximately 1250°F. The rotational speed will also be maintained at 4.5 rpms. The gases given off are
continuously monitored for 02, CO2, NO2, and CO by a gas analyzer. A gas sample is collected for off-line
gas chromatography. The run is terminated when the 02/CO2 ratio is representative of ambient air.
The only pretreatment of the sediment materials proposed for the study will be the addition of clean
quartz sand to the retort chamber at the beginning of the test run. Lake and harbor sediments normally
have low granular material content. Clean quartz sand is normally added to materials such as sludges and
sediments with high liquid contents because in the full-scale ATP it enhances performance and maintains
the oxygen-free environment of the reaction zone.
64
-------
SECTION 2
2.0 TEST PLAN
2.1 Purpose
The primary objective of these tests is to determine the feasibility and cost effectiveness of
SoilTech's Thermal Desorption Technology utilizing their ATP for treating and removing PCBs and PAHs from
two sediments. The Great Lakes National Program Office (GLNPO) has obtained and homogenized each
of these sediments from the Buffalo River and Indiana Harbor.
These bench-scale treatability tests are designed to provide data that closely simulates full-scale
performance. The data generated by the tests allows SoilTech and EPA to evaluate feasibility of the process
and to estimate treatment costs for full scale performance.
The Bench-Scale Treatability Test objectives are:
• To record observations and data to predict full-scale performance of SoilTech's ATP
process.
• Take samples during the extraction tests and conduct analysis sufficient to allow for
calculation of mass balances for water, solids and other compounds of interest.
• To calculate the desorption efficiency of target compounds.
• To supply GLNPO with treated solids (300 grams dry basis), water, and solids for
independent analysis.
2.2 Approach
In order to accomplish the test objectives a two-phased approach will be used. Phase I is a
preliminary phase conducted by SoilTech, Inc. to determine the optimum conditions to be used during
Phase II. Phase II is the treatability test at optimum conditions and GLNPO, through its contractor Science
Applications International Corporation (SAIC), will obtain samples of the untreated sediments and treated
residuals for analysis by an independent laboratory. All analyses for this treatability study program
(consisting of seven treatability studies utilizing four technologies on four sediments) will be conducted by
the same laboratory. This arrangement will eliminate interlaboratory variation from the comparison of the
performance of these technologies. In addition, representatives of both GLNPO and SAIC are scheduled
to observe the conduct of Phase II of each treatability study.
65
-------
SoilTech will collect samples during the Phase I tests and have indicated that they will conduct
analyses at least for priority PAHs and PCBs. These samples are summarized below in Table 2-1. During
the ramp run the water and hydrocarbons will be thermally separated from the sediments and collected.
The oil produced will be tested to determine some physical characteristics.
Table 2-1. Samples to be Collected by SoilTech, Inc. during the Phase I Test
Ramp Run
Run 1
Run 2
Run 3
Water
Yes
Yes
Yes
Yes
Liquid
Hydrocarbon
Yes
Yes
Yes
Yes
Retort
Solids
Yes
Yes
Yes
Yes
Combustion
Solids
No
(optional)
(optional)
(optional)
The Phase I bench-scale tests will begin by placing a sample of material in the retort unit and
conducting a ramp run. During the ramp run, the sample is steadily heated from ambient to approximately
1200°F to observe the characteristics of the feed and observe the temperatures at which the water and
organic materials are driven off. This procedure provides data on the boiling point range of the
hydrocarbons in the feed material.
The bench-scale tests will continue with three hot runs conducted at varying temperatures. All three
runs will begin with roughly one kilogram of sediments and one to two kilograms of granular sand being
placed in the retort chamber. All other parameters will be held constant during Phase I. A schedule of
experimental test conditions during the Phase I test is shown in Table 2-2.
66
-------
Table 2-2. Hypothetical Schedule of Experimental Conditions
During Phase I Tests
(Source: SoilTech, Inc.)
Run
Ramp
Batch 1
Batch 2
Batch 3
Weight of
Sample
1 kg
1 kg
1 kg
1 kg
Sand
Added (a)
1-2 kg
1-2 kg
1-2 kg
1-2 kg
Chamber
Temperatures
70°F to
1,200 °F+
950°F
1,050°F
1,150°F
Retention
Time
45 to 90
min.
15 to 30
min.
15 to 30
min.
15 to 30
min.
Quantity of sand added may vary depending on sediment's soil characteristics.
Chamber rotation speed: approximately 4.5 rpm.
Sample is pyrolyzed per the above schedules. Portions of the resultant coked product will be
oxidized in the batch-combustor at approximately 1,250°F for 15 to 30 minutes.
The solids produced by the bench-scale retort unit are representative of the solids exiting the retort
zone of the full-scale ATP. As previously discussed, these solids contain some residual carbon-black that
is combusted in the combustion zone of the ATP. The solids produced in the retort chamber are the most
accurate representation of the effectiveness of thermal desorption technology, where as the solids produced
after the combustion chamber are more representative of the overall effectiveness of the ATP.The latter
solids are tested for leachabilrty to determine whether stabilization is needed; usually it is not needed.
During the high-temperature batch runs 1, 2 and 3 using the retort unit, water, liquid hydrocarbons
and solids samples will be collected for analysis. If desired, some or all of the solids from the retort unit can
be further processed in the combustion unit to accurately simulate the ATP.
The quantities of each phase (water, liquid hydrocarbons and solids) produced will depend on the
characteristics of the sediments samples. The actual quantities produced will be accurately measured during
Phase I and will lead to accurate quantity estimates for Phase II. Detailed analyses will not be conducted
by SoilTech for the Phase I tests.
67
-------
2.3.2 Test Conditions. Process Variables and Schedule
SoilTech will require 5 gallons of wet sediment for each of the two samples (Buffalo River and
Indiana Harbor). The Phase I work, including sample analysis, can be completed in approximately four
weeks after receipt of the sediments. The Phase I work can be initiated approximately one week after
notification to proceed. The actual treatability test may only take one day to conduct.
The process variables for SoilTech's full-scale thermal desorption technology (utilizing the ATP
technology) include the feed rate, rotation rate of the kiln, operating temperature of the preheat zone,
operating temperature of the reaction zone, pressures of preheat and reaction zones, rate of heat
application, percentage of clean solids internally recycled, and flow rate of noncondensable gases in the
condenser. Each of these process variables is discussed in Appendix A.
Based on the data obtained from the analysis listed in subsection 2.3.1, SoilTech will be able to
report the conditions which will be set for the Phase II testing.
2.3.3 Report
At the completion of Phase I, a letter report specifying the process variables (listed in subsection
2.3.2 and discussed in Appendix A) required for Phase II testing will be prepared and sent to SAIC. This
letter report will be attached to this experimental design to complete the specifications for Phase II. Included
with this letter report will be a summary of all analytical results and relevant observations made during Phase
I of this study.
2.4 Phase II
For the Phase II part of the treatability program, SAIC will sample and conduct analyses on both
types of solids produced from SoilTech's thermal process, which include the retort solids from thermal
desorption and combusted solids produced from combusting retorted solids to remove residual carbon-
black.
2.4.1 Procedures
Procedures for Phase II will essentially be the same as those previously discussed for Phase I
(Section 2-3), however, only one run will be performed at the determined optimum conditions for each
sample.
68
-------
2.4.2 Test Conditions, Process Variables and Schedule
SoilTech will require at least one gallon of wet sediments for each of the two samples (Buffalo River
and Indiana Harbor). The Phase II work, including packaging of required residuals for shipment, can be
initiated one week following notification.
It has been estimated that only one run will be necessary to generate the required amount of solid
and water residuals during the Phase II program. The quantity of residuals to be produced is a function of
the solids, water and hydrocarbon content of the sediments, and an accurate estimate will be made by
SoilTech during the Phase I tests.
The process variables for the Phase II will be those determined and reported for Phase I (see
Appendix A).
2.4.3 Sediment Sample Characterization and Analyses
There will be two separate analytical matrices conducted on the two sediments during Phase II, one
by SoilTech and one by SAIC's subcontract laboratory, Battelle. SoilTech will conduct their own analyses
for Phase II. A schedule of analyses to be performed by SoilTech during Phase II tests is presented in Table
2-3.
At the beginning of the Phase II treatability test, SAIC personnel observing Phase II will pack and
ship a sample each of untreated Buffalo River and Indiana Harbor sediments to SAIC's subcontract
laboratory per written detailed instructions supplied to the SAIC on-site representative. This sample will be
obtained from a separate unopened container of the sediments sent for Phase II. The analyses to be
conducted on these sediments are listed in Table 2-4.
Following the Phase II treatability test, SAIC's subcontract laboratory will conduct analyses on the
end products. The number of analyses conducted on the anticipated residuals are outlined in Table 2-4.
2.4.4 Quality Assurance (QA)
SAIC has developed and GLNPO has approved a QA project plan for this project. The QA project
plan is available as a separate document.
69
-------
Table 2-3. SoilTech's Analyses Schedule for the Phase II
Thermal Desorption of Buffalo River and Indiana Harbor Sediments
Raw Distillate Distillate Retort Combusted
Analyte/Method Samples: Feed Water Oil Solids Solids
PCB - EPA 8080 XX X
VOC - EPA 8240 X X
Priority PAH - EPA X X
Total Organic Carbon X
Oil and Grease X
Metals (a)
TCLP
(a) Selected metals may be analyzed if identified in the SAIC feed characterization data. TCLP test will
be applied to determine that the final product is resistant to leaching sufficient for backfill in place.
70
-------
Table 2-4. SAIC's Analysis Schedule for the Phase II
Thermal Desorption of Buffalo River and Indiana Harbor Sediments
'aramelers
olal Solids
Vloislure)
Volatile Solids
0& G
Melals
PC Us
PAIIs
IOC
Total Cyanide
Total Phosphorous
pll
BOD
Total Suspended
Solids
Conductivity
QC Sample ( )
ami
Method Blank
(1)
YES
(1)
YES
(I)
YES
(0)
YLS
(1)***
YES
(1)***
YES
(0)
Y i-:s
(0)
YES
(0)
YES
(0)
YES
NA
NA
NA
( Intreatcil
Sediment
(2)
n,i
(2)
11,1
(2)
H. I
(2)
11,1
(2)
11,1
(2)
11,1
(2)
11,1
(2)
IU
(2)
11,1
(2)
B.l
MS
(1)
H
(1)
H
(1)
I)
NA
NA
NA
Tnpli
cate
(2)
B
(2)
B
(2)
B
(2)
B
(2)
B
(2)
B
NA
NA
NA
NA
Treated*
Solids
(4)
Bx.By.lx.ly
(4)
Bx.By.lx.ly
(4)
Bx,By,lx,ly
(4)
Bx.By.lx.ly
(4)
Bx.By.lx.ly
(4)
Bx.By.lx.ly
(4)
Bx.By.lx.ly
(4)
Bx,By,lx,ly
(4)
Bx.By.lx.ly
(4)
Bx.By.lx.ly
MS
(1)
By
(1)
By
(D
By
NA
NA
NA
MSD
(D
By
(D
By
NA
Tripli-
cate
(2)
By
(2)
By
(2)
By
(2)
By
NA
NA
NA
Water
NA**
NA
NA
(2)
H,l
(2)
B.l
NA
NA
NA
NA
NA
NA
NA
MS
NA
NA
NA
NA
NA
NA
-
MSD
NA
NA
Vip/i-
cate
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Oil
(2)
B.l
(2)
B,l
MS
(I)
B
(D
B
Trip/i
cate
(2)
B
(2)
B
• This technology has 2 treatment stages. After the first step the sediment is designated with a "x" i.e. Bx is Buffalo River Sediment
after the first treatment stage. After the second step a "y" will be used i.e., By. The treated solids after both steps will be analyzed,
but the fully treated solid By will be used for QC analyses.
'" Not Analyzed MS = Matrix Spike
'"A laboratory pure water spike is required for recovery determination MSD = Matrix Spike Duplicate
(1)= Number of Analyses
B = Buffalo River Sediment
I = Indiana Haibot Sediment
-------
SECTION 3
3.0 RESIDUAL MANAGEMENT
Residuals from the ATP may consist of a liquid hydrocarbon phase (oil) and a water phase from
the vapor recovery system, gaseous products from the combustion zone, and solid residue (tailings) that
exit the cooling zone.
Any residual liquid hydrocarbons that are not recycled back into the combustion section or
rectifying column are combined with the condensate from the rectifier for disposal. The water phase is
pumped to a water treatment facility for treatment.
Gaseous combustion products from the combustion zone (the heat source for both the retort and
preheat zones) are treated in a flue gas handling system and vented to the atmosphere. Flue gas from the
ATP cooling section passes through a cyclone and baghouse for removal of dust, and then the gas is
passed through a wet scrubber for removal of any trace particulates or acid gases prior to venting to the
atmosphere. If stack emissions data indicate a need, the gas stream can be treated with activated carbon
as a final cleanup step to remove trace hydrocarbons.
All of the solid residue (tailings) exiting the cooling zone are cooled by water addition, then
transported to an outside storage pile via screw and belt conveyors. The solids are generally eligible for
non-listed landfill disposal as discharged from the SoilTech ATP unit. SoilTech will not assume
responsibility for the samples or the disposal of residuals. SAIC will not assume responsibility for the
samples or the disposal of sample residuals. SAIC will, however, provide information to assist the generator
of the original samples for the treatability studies in disposal efforts, but will make no decisions that
ultimately determine the disposal option chosen.
72
-------
SECTION 4
4.0 FINAL REPORT
Upon completion of the bench-scale treatability test program, SoilTech will prepare a Final Report.
The Final Report will contain the following:
• SoilTech Thermal Desorption Process description, test procedures, operating parameters,
sampling locations and frequencies
• Test results discussion with analytical data
• Mass balance calculations, if applicable
• Projected full-scale system configuration and operating parameters used to treat site waste
materials
• Treatment cost estimates in dollars per unit volume of soil for each waste type, based on the
lowest cleanup level which can reasonably be achieved
• The following data will be presented in tabular form:
Initial contaminant concentrations; along with moisture contents and pH values and other
relevant data
Final analytical results for all streams generated from the thermal desorption of each
sample
Percentages of individual contaminants desorbed for each sample, as well as a calculation
of total PCBs and PAHs desorbed
Desorption efficiency for each contaminant
• Copies of log books and chromatograms, if generated.
73
-------
APPENDIX A
SoilTech's Summary of Operation Variables
74
-------
APPENDIX A
OPERATION VARIABLES
Feed Rate: The continuous feed rate of the full-scale ATP
which is currently at the Wide Beach Superfund
site is as high as 15 tons per hour. The
bench-scale tests are batch tests; therefore,
the continuous feed rate does not apply.
Rotational Speed of Kiln: The full-scale ATP can rotate at a speed of
0 to 5.5 revolutions per minute (rpm). The
bench-scale tests will be conducted at 4.5
rpm, which is a typical rate for the ATP.
Operating Temperature of Preheat Zone: The preheat zone of the full-scale
ATP is between 250 degrees Fahrenheit and 600
degrees Fahrenheit. The purpose of the
preheat zone is to dry the feed material. Due
to this the preheat temperature for the bench-
scale tests will be held at 300 degrees
Fahrenheit.
*
Operating Temperature of Reaction Zone: The temperature of the reaction
zone is the key variable in determining the
ATP's effectiveness in treating soils, sludge.
sediments, and other material. The bench-
scale tests will be conducted at three
different reaction zones temperatures as
discussed.
Pressure of Preheat and Reaction Zones: The preheat and reaction zones
of the full-scale ATP operate at a very slight
negative pressure of less than one inch of
mercury. This negative pressure is not varied
75
-------
during operation. The bench-scale tests will
be conducted at atmospheric pressure.
Rate of Heat Application: The full-scale ATP varies the rate of heat
applied through the auxiliary burners of the
combustion zone. The rate of heat application
determines the operating temperature of the
reaction and preheat zones. The rate of heat
application cannot be varied on the bench-
scale processor, and is controlled by turning
the electric heat elements on or off, either
by computer control or manually.
Rate of Clean Solids Internally Recycled: The full-scale ATP internally
recycles a portion of the cleaned solids from
the combustion zone into the reaction zone.
The recycling of clean solids is close for
thermodynamic reasons and to help increase the
thermal efficiency of full-scale processors.
The bench-scale unit does not contain any
mechanism for recycling material from the
combustion unit to the retort unit.
Flow Rate of Combustion Air: The flow rate of combustion air air helps to
control the temperature of combustion and to
control the CO and NOx emissions. The bench-
scale combustion unit does not impact the
temperature of the bench-scale retort unit,
and CO and NOx emissions are not considered.
Therefore, during bench-scale testing
sufficient combustion air is used to ensure
thorough combustion of the residual carbon-
black on the solids.
76
-------
Rate of Hydrocarbon Vapor Condensation: The full-scale ATP has a
sophisticated reflux distillation system to
recover the hydrocarbon vapor. This system
proves beneficial on sites where a recycleable
or reusable hydrocarbon is recovered. The
bench-scale units use a simple condenser and
glass reservoir for hydrocarbon recovery.
77
-------
APPENDIX C
QUALITY ASSURANCE PROJECT PLAN
FOR
GLNPO - ASSESSMENT AND REMEDIATION OF
CONTAMINATED SEDIMENT TECHNOLOGY
DEMONSTRATION SUPPORT
Revision II
February 15, 1991
Submitted to:
Lr.S. Environmental Protection Agency
Great Lakes National Program Office
230 S. Dearborn
Chicago, Illinois 60604
Submitted by:
Science Applications International Corporation
635 West Seventh Street, Suite 403
Cincinnati. Ohio 45203
EPA Contract No. 68-CS-0061, Work .Assignment No. 2-18
SAJC Proiecr No. 1-832-03-207-50
78
-------
Section No.:
Revision No.:
Date:
Page:
Q
Feh IS. 1991
1 of 2
TABLE OF CONTENTS
SECTION
1.0 INTRODUCTION
2.0 PROJECT DESCRIPTION
3.0 QUALITY ASSURANCE OBJECTIVES . . .
4.0 SAMPLE TRANSFER AND PREPARATION
PROCEDURES
5.0 ANALYTICAL PROCEDURES AND
CALIBRATION
6.0 DATA REDUCTION, VALIDATION AND
REPORTING
7.0 INTERNAL QUALITY CONTROL CHECKS
8.0 PERFORMANCE SYSTEMS AUDITS
9.0 CALCULATION OF DATA QUALITY
DUPLICATORS
10.0 CORRECTIVE ACTION
11.0 QA/QC REPORTS TO MANAGEMENT . . .
APPENDIX A - TECHNOLOGY SUMMARIES
PAGES
2
12
REVISION DATE
1 1/9/91
2 2/15/91
2 2/15/91
1 1/9/91
2 2/15/91
1 1/9/91
2 2/15/91
2 2/15/91
1/9/91
1/9/91
1/9/91
1/9/91
79
-------
QUALITY ASSURANCE PROJECT PLAN APPROVALS
QA Project Plan Title: GLNPO Assessment and Remediation of Contaminated
Sediment Technolooy Demonstration Support
Prepared by: Science Applications International Corporation (SAIC)
QA Project Category:
Revision Date: January 9. 1990
^-- / /t'
SAIC'3 -or* Assignment Manager (print,
Clyde J. Dial
SAIC's QA Manager (print)
/Date
yl4
Date
Steve Yaks-'cn
rK Group Chair (print,
Signature
Br-'an Schumacre'-
if.CS QA Officer (print;
Sizr.acure
-ate
3ene -a
IJA. ly.SL-LV, NRL 5A Officer Sprint.
iiznat-re
3,aicn Chr-ste^s
FA Tecr.nica- Project .-ianage
jave -owa*
.-r = gra= .-ianager .print;
Siznature
80
-------
DISTRIBUTION LIST:
Gene Easterly
Brian Schumacher
Tony Kizlauskas
Thomas Wagner
Clyde Dial
Steve Garbaciak
Dennis Timberlake
Steve Yaksich
David Cowgill
Gary Baker
Vic Engleman
U.S. EPA, EMSL (Las Vegas)
LOCKHEED (Las Vegas)
SAIC (Chicago)
SAIC (Cincinnati)
SAIC (Cincinnati)
U.S. COE (Chicago)
U.S. EPA, RREL (Cincinnati)
U.S. COE (Buffalo)
U.S. EPA, GLNPO (Chicago)
SAIC (Cincinnati)
SAIC (San Diego)
GLNPO - QAPjP
Section No.: Q,
Revision No.: 2.
Date:
Page:
Feb. IS. 1991
2 of 2
81
-------
GLNPO - QAPJP
Section No.: J_
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 2
1.0 INTRODUCTION
The Great Lakes National Program Office (GLNPO) leads efforts to carry out the
provisions of Section 118 of the Clean Water Act (CWA) and to fulfill U.S. obligations
under the Great Lakes Water Quality Agreement (GLWQA) with Canada. Under Section
118(c)(3) of the CWA, GLNPO is responsible for undertaking a 5-year study and
demonstration program for contaminated sediments. Five areas are specified for priority
consideration in locating and conducting demonstration projects: Saginaw Bay, Michigan;
Sheboygan Harbor, Wisconsin; Grand Calumet River, Indiana (aka: Indiana Harbor);
Ashtabula River, Ohio; and Buffalo River, New York. In response., GLNPO has initiated
an Assessment and Remediation of Contaminated Sediments (ARCS) Program. The ARCS
Program will be carried out through a management structure including a Management
Advisory Committee consisting of public interest. Federal and State agency representatives.
an Activities Integration Committee which is made up of the chairpersons of the technical
work groups, and technical work groups.
In order to obtain the broadest possible information base on which to make
decisions, the ARCS Program will conduct bench-scale and pilot-scale demonstrations and
utilize opportunities afforded by contaminated sediment remedial activities by others, such
as the Corps of Engineers and the Superfund program, to evaluate the effectiveness of those
activities. These bench-scale and pilot-scale tests will be developed and conducted under
the guidance of the Engineering/Technology (ET) Work Group for ARCS.
SAJC has been contracted to supply technical support to the ET Work Group. The
effort consists of conducting bench-scale treatabiliry studies on designated sediments to
evaluate the removal of specific organic contaminants.
82
-------
GLNPO - QAPjP
Section No.: 1_
Revision No.: 1
Date: Jan. 9. 1991
Page: 2 of 1
Sediments have been obtained by GLNPO from various sites and represent the type
of material that would be obtained for onsite treatment. The primary contaminants of these
sediments are polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons
(PAHs). Analyses to date show PCB concentrations are less than SOppm. These sediments
have been homogenized and packaged in smaller containers by EPA.
83
-------
GLNPO - QAPjP
Section No.: 2-
Revision No.: 2
Date: Feb. 13. 1991
Page: 1 of 12
2.0 PROJECT DESCRIPTION
2.1 Background
SAIC and its subcontractors will conduct seven (7) bench-scale (several liters) tests
on wet contaminated sediments using four treatment technologies.
The seven treatabiliry tests (as currently planned) will utilize sediments from 4 sites
(Saginaw River, Buffalo River, Indiana Harbor Canal, and Ashtabula River). Five
sediments have been collected from these sites by GLNPO. These samples have been
homogenized by the U.S. EPA and are being stored under refrigeration in 5 gallon
containers by EPA in Duluth. MN.
These five sediments are currently being analyzed in the U.S. EPA, Environmental
Research Laboratory in Duluth. The Duluth Laboratory is analyzing the sediments for total
organic carbon/total inorganic carbon (TOC/TIC), panicle size, density of dry material.
total sulfur, acid volatile sulfide, oil and grease (O & G), total PCBs, PAHs (10), and metals
including mercury. Table 2-1 is a summary of the data received to date.
A portion (small vial) of each residual of each treatabiliry test may be retained and
sent to the GLNPO office for "show" purposes. If available, sub-regulated quantities of the
solid and oil residuals from each test treatabiliry study may also be retained and shipped to
EPA for possible further treatment studies.
The following is a list of technologies and the proposed number of sediment samples
to be tested by each technology:
a. B.E.S.T.™ Extraction Process on three samples (Buffalo River, Indiana
Harbor, Saginaw TRP 6)
b. Low Temperature Stripping (RETEC) on one sample (Ashtabula River)
c. Wet Air Oxidation (Zimpro Passavant) on one sample (Indiana Harbor)
d. Low Temperature Stripping (Soil Tech) on two samples (Buffalo River and
Indiana Harbor)
Summaries of these technologies are included in Appendix A.
84
-------
IAIILK 2-la. Preliminary Analytical Results on ARCS Sediments
CD
tn
Description
Saginaw 221
Saginaw TRP6
Ashlabula River
Indiana Harbor
Buffalo River
Concentration (Mg/kgm)(a)
Total
I'CB
0.6
60
C
02
0.4
Total
PAH
1.2
3.1
C
96
5.6
Cu Cd
33 0.9
81 4.7
55 3.0
320 9.4
85 1.9
Ni
76
no
96
150
57
Fe(%)
1.4
09
3.7
16
39
Cr
140
200
550
540
110
Zn
240
200
240
3300
200
Pb
30
47
48
780
94
Concentration (X)(a)
roc
1.4
1.2
2.6
21
2.0
OAG
0.1
0.3
1.7
5.8
0.5
Moisture (b)
40.3
31.1
52.9
61.0
41.5
(a) Concentration In ppm and dry weight basis unless otherwise Indicated.
(b) As received basis.
TABLE 2-lh. Preliminary Particle Size Distribution (%)
Description
Buffalo River
Particle
>50u 50-20 u 20-5 u 5-2 u
19 8 12 1 290 11.8
Size (a)
2-0.2 u 0. 2-0. 08 u <0.08u
24.3 2.4 0.6
Median
Diameter, u
9.3
(a) u micarons
-------
GLNPO - QAPjP
Section NOJ 2_
Revision NOJ 2
Date: Feb. 15. 1991
Page: 3 of 12
22 Testing Program for Chemical Characterization
SAIC shall be primarily responsible for the physical and chemical characterization
of both the sediment samples prior to testing and the residuals created during the tests.
Analyses conducted by the vendors or subcontractors will not be depended on, but such data
shall be reported whenever available.
Two different sets of chemical analyses will be conducted during the performance of
the treatability tests: optimization test analyses and performance evaluation analysis. The
Phase I optimization test analyses will be conducted by the subcontractor or vendor during
the series of initial technology tests. The Phase n performance evaJuation analyses will be
conducted by SAIC (or its analytical subcontractor) on the raw sediment sample prior to the
treatability test run at optimum conditions and on the end products produced by that
particular test. These tests are described further in this section.
In order to assure objectivity and consistency of data obtained from multiple vendors
running different technology tests. SAIC shall conduct analyses as described in Table 2-2 for
characterization of the sediments and the end products of the treatability tests at optimum
conditions (Phase II).
The analyses described for the solid fraction in Table 2-2 shall be performed by
SAlC's analytical subcontractor once on a subsample taken from each sample sent to each
vendor or subcontractor for treatabiiiry tests (Phase II). This subsample will be taken at the
same time that the sample for the Phase II treatablility study is taken by the vendor. This
data will serve as the measure of the raw sediment quality for comparison to analyses of
treated end products from each technology test that may be conducted on sediments from
a particular area of concern.
Each bench-scale technology test may actually involve the performance of multiple
laboratory simulations. During the initial tests (Phase I), any analyses performed by the
86
-------
GLNfU •
Section No.: 2,
Revision No.: 2
Date: Feb. 15. 1991
Page: 4 of 12
vendor or subcontractor shall be reported, as available. For the tests run at optimum
conditions (Phase II), SAIC shall conduct the full suite of analyses, as detailed in Table 2-2,
on the end products if sufficient quantities are produced by the technology. Quotes solicited
for each technology specified that a minimum 300 grams dry basis of treated solid had to
be produced for SAICs analyses. Table 2-3 shows the apportionment of the 300 grams for
the solid analyses. The quantity of water is depended on the sediments and the individual
technologies. To do all the analyses listed in Table 2-2, and associated QC, approximately
10 liters of water are required. Table 2-4 listed specified sample volumes for each analysis,
and gives a priority to each analysis. It is possible that only the PCB and PAH analysis and
associated QC will be performed on the water samples. If any oil residue is produced, it
will be analyzed by dilution with appropriate sample cleanup steps for PCBs and PAHs.
The data generated by SAICs analyses of the untreated sediment and the treated end
products from the test at optimum conditions will be primarily relied upon to determine
treatment efficiencies. Vendor- or subcontractor-generated data will not be relied upon but
shall be reported when available.
23 Required Permits
Because of the small quantities of sediments required for the bench-scale treatabiiiry
tests, SAJC anticipates that no formal permits will be required to conduct these tests. If this
is not the case and permits (such as TSCA, RD&D or RCRA permits) are required, the
subcontractor will notify SAIC and the TPM will be notified to obtain approval for
acquisition of the permit(s).
All unused sediment samples requested by SAIC for the treatabiiiry test and all
testing residuals, except those requested by the TPM for "show" purposes and those
requested by the TPM for possible further testing, will be properly disposed of per federal
and state regulations.
87
-------
Section NOJ 2
Revision NOJ 2
Date: Feb. 15. 1991
Page: 5 of 12
TABLE 2-2
Parameters and Detection Limits for Analysis of ARCS Technologies
Parameter
TOC/TIC
Total Solids4
Volatile Solids4
Oil & Grease4
Total Cyanide
Total Phosphorus
Arsenic4
Barium4
Cadmium4
Chromium4
Copper4
Iron (total)4
Lead4
Manganese4
Mercury4
Nickel4
Selenium4
Silver4
Zinc4
PCBs (total & Aroclors)4
PAHs (16)4-5
PH
BOD5
Total Suspended Solids4
Conductivity
NOTES:
r^tf»/*tirm lirtnitc fr\r er\M
Solid*
300
1000
1000
10
0.5
50
0.1
02
0.4
0.7
0.6
0.7
5
02
0.1
2
02
0.7
02
0.02
02
full range
A r O^^ MT^M^ I 1 T^ fT llfn f
Water* Q£
1000
1000
1000
10
10
1
2
4
7
6
7
50
2
0.01
20
1
7
2
0.07 0.1
2 0.1
full range
1000
1000
full range
inr vVFAtrvn*1! T>-»^ T> T 'r- ffMr -rv^^^nlf t*l*n**1fJ
be obtainable by ICP except for As, Se, and Hg. If GFAA is used, the D.Us will be
2 mg/kgm except Hg, Cd, and Ag which will be 0.1 mg/kgm.
Detection limits for water are ppb (ug/1). The D.Us for metals should be obtainable
by ICP except for As, Se, Hg. If GFAA is used D.l_'s will be 1 ug/L except Hg
which will be 0.01 ug/L.
Detection limits for oil are ppm (mg/1).
Parameters tentatively identified for QC analyses.
Polynuclear aromatic hydrocarbons to be analyzed are the 16 compounds listed in
Table 5-2.
88
-------
GLNPO - QAPjP
Section NOJ 2.
Revision NOJ 2.
Date:
Page:
Feb. 15. 1991
6 of 12
TABLE 2-3
Solid Sample Quantities for Analyses
Parameter
TOC/TIC
Total + Volatile Solids
Oil & Grease
Total Cyanide
Total Phosphorous
Metals (except Hg)
Hg
PCBs + PAHs
PH
Subtotals
Reserve
TOTAL
Initial
Sample (g)
15
5
20
10
5
5
1
30
20
111
—
—
PC (g)
_
10
40
—
—
15
3
90(60)3
~
158(128)
-
—
Total (g)
15
15
60
10
5
20
4
90
20
269(239)
31(61)
300
OC Approach
None1
Triplicate/Control
Triplicate/Control
None2
None2
MS/Triplicate
MS/TripIicate
(3)
None4
1 For sample set II that does not have such a limited quantity of solid, The QC described in
footnote 3 will be implemented.
2 For sample set II, MS/triplicate QC will be implemented.
3 Quality control for untreated solids is Triplicate and spike and for treated solids matrix spike
and matrix spike duplicate.
For sample set n, Triplicate/Control sample QC will be implemented. The control sample
may be an EPA QC check sample, an NBS - SRM, a standard laboratory reference solution,
or other certified reference material.
89
-------
GLNPO - QAPjP
Section No.: 2.
Revision No.: 2
Date:
Page:
Feb. 15. 1991
7 of 12
TABLE 2-4
Sample Volumes Required and Priority Ranking for Water Analyses
Parameter
TOC/TIC
Volatile Solids
Oil & Grease
Total Cyanide
Total Phosphorus
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
Lead
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total & Aroclors)
PAHs (16)
PH
BOD
Total Suspended Solids
Conductivity
Priority
7
5
6
7
7
4
2
2
2
2
~>
2
2
3
2
4
2
2
1
1
7
7
5
7
Analysis
Volume, ml
25
d
1000
500
50
100
100
b
b
b
b
b
b
100
b
c
b
b
1,000
a
25
1,000
200
100
QC
Volume, ml
mm
d
2000
—
—
300
300
b
b
b
b
b
b
300
b
c
b
b
2,000
a
—
—
400
.»
QC
Approach
None (e)
Triplicate/Control
Triplicate/Control
None (f)
None (f)
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/MSD
MS/MSD
None (f)
None (f)
Triplicate/Control
None (f)
Note:
a) same aliquot as PCBs
b) same aliquot as Barium
c) same aliquot as Arsenic
e) see footnote 2, Table 2-3
0 see footnote 4, Table 2-3
same aliquot as Total Suspended Solids
90
-------
ULNKU - U/U-jf
Section No.: 2-
Revision No.: 2
Date: Feb. 15. 1991
Page: 8 of 12
2.4 Purpose of Phase I Experimental Design
The purpose of the Phase I technology experimental design is for each subcontractor
to establish a range of variables best suited for feasibly implementing their technology on
a full-scale basis (Phase n). SAIC will send a quantity (specified by the vendor) of each
sediment to the vendor to accomplish this. All data generated by the vendor during Phase
I will be supplied to SAIC for inclusion in the report for that technology. This information
will include the operating conditions/parameters, the input/output data for the contaminants
of interest to show the range of effectiveness associated with various operating conditions,
and the quantities of the input material and the various residuals resulting from the test.
The optimum set of conditions to be used for Phase II will be reported to SAIC along with
appropriate revisions to the Phase I experimental design to make it applicable to Phase II.
2.5 Purpose of Phase II Treatabilitv Test
SAIC will send another container of sediment(s) to the vendor (quantity to be
specified by the vendor). This container will not be opened until a representative of SAIC
arrives for the scheduled treatability test(s). Other observers from U.S. EPA, COE and/or
the GLNPO may also be present during the Phase II treatability test(s).
The new sample will be homogenized and a sample equivalent to a minimum of 300
gm of dry solids wiil be set aside for characterization analyses (Table 2-2) by SAIC. SAIC
will observe the treatability tests and obtain samples of process residuals for analyses (Table
2-2). The bench-scale test(s) must produce enough solid residual for all vendor
requirements and a quantity equivalent to 300 gm of dry solids for SAIC analyses. SAIC
can utilize up to 10 liters of water for analysis and 25 ml of the oil residual. The actual
quantities of water and oil that will be produced are dependent on the initial sediment and
the technology. All technologies except wet air oxidation are expected to produce an oil
residual. Also, if additional solid and/or oil residue is available, EPA may ask for these
materials to be sent to them for storage for possible future evaluation.
91
-------
GLNPO - QAPJP
Section NOJ 2.
Revision NOJ 2
Date: Feb. 15. 1991
Page: 9 of 12
All data generated by the vendor during Phase n is to be supplied to SAIC for
inclusion in the report for that technology. The vendor must stipulate in their work plan,
prior to conducting the test(s), the process locations to be sampled, the frequency and the
information being obtained.
All other residuals from both phases of the treatability study, including any untreated
sediment, will be properly disposed of by the vendor.
SAIC shall oversee the treatability test assessment(s) by vendors or subcontractors,
including all QA/QC aspects, monitoring and analysis. SAIC shall ensure compliance with
the specific experimental design during the tests conducted by vendors or subcontractors.
SAIC will make specific notes regarding the equipment being used, any pretreatment of the
sediment(s), the operation of the equipment, and any post treatment of the residuals. SAIC
personnel will pack the untreated sediment sample and the end product samples from the
Phase II test for each technology in an appropriate fashion for shipment from the vendor
or subcontractor to the laboratory SAIC is using for the analysis. Proper chain-of-custody
procedures will be developed in the QAPjP and strictly followed by SAIC personnel.
SAIC plans to take photos of the equipment while at the vendor's location for
inclusion in the report.
SAIC shall perform limited interpretation of technology test results, specifically the
development of material and energy balances. No test of air or fugitive emissions will be
done. For material balances, estimates of the mass distribution of the analytes of interest
(Table 2-2) among the residuals will be made. The term energy balance is interpreted to
mean an estimation by the vendor of the energy input into the process at a pilot- or full-
scale.
92
-------
GLNPO - QAPjP
Sectioo No.: 2.
Revision NOJ 2-
Date: FKh 1S 1991
Page: IP nf ?2
SAIC shall collect any information available from the vendor or subcontractor
concerning the actual or estimated costs of constructing and operating full-scale versions of
the technology tested.
The purpose of this project is to test five technologies for removing organic
contaminants (PCBs and PAHs) from sediments typical of locations around the Great Lakes.
GLNPO is specifying the technologies and the sediment(s) to be treated by each technology.
This study is only one part of a much larger program, and it is not necessarily intended to
evaluate the complete treatment of these sediments. Other aspects or treatment options are
being evaluated by a number of agencies, contractors, etc.
Therefore, this study is based on the following assumptions:
• The percent removal of the PCBs and PAHs from the solid residual is the
most important object of this study.
• The untreated sediments and solid residuals are the most important matrices.
• If water and oil residuals are generated by a technology, the existence of an
appropriate treatment or disposal option for these residuals is assumed.
PAHs and PCBs will be determined in these residuals as a cross check of
their fate in treating the solids.
Based on the intents of this study, the critical measurements are PAHs, PCBs, metals,
total solids, volatile solids, and oil and grease in the untreated and treated solids.
2.6 Organization and Responsibilities
A project organization and authority chart is shown in Figure 2-1. The
Environmental Monitoring Systems Laboratory (EMSL) is cooperating with GLNPO and
SAIC on this evaluation. Mr. Thomas Wagner is the SAIC Work Assignment Manager and
is responsible for the technical and budgeting aspects of this work assignment. Mr. Clyde
Dial is QA Manager and is responsible for QA oversight on this work assignment.
93
-------
ni urn WORKGROUP
US liP
ri«»l:<:i MANAIil-.li
SMC.
n:.< IINICAI
II S I:PA QA MANAfinU
-------
GLNPO - QAPjP
Section NOJ 2-
Revision NOJ
Date: Feb. 15. 1991
Page: 12 of 12
2.7 Schedule
The Phase I experimental designs are scheduled for mid to late February 1990, and
the Phase n Treatability Tests are scheduled for March and April 1991.
95
-------
GLNPO - QAPjP
Section No.: JJ_
Revision No.: 2_
Date: Feb. 15. 1991
Page: Iof2
3.0 QUALITY ASSURANCE OBJECTIVES
3.1 Precision. Accuracy. Completeness, and Method Detection Limits
Objectives for accuracy, precision, method detection limits, and completeness for the
critical measurements of solids are listed in Table 3-1. Accuracy (as percent recovery) will
be determined from matrix spike recovery for PAHs, PCBs and metals, and from laboratory
control samples (certified reference material- CRM) for the remaining analyses. Precision
(as relative standard deviation) will be determined from the results of triplicate analyses for
PAHs, PCBs, solids (total, volatile and/or suspended), oil and grease, and metals. Matrix
spike and matrix spike duplicate analyses will be used for treated solids for PCBs and PAHs.
The completeness will be determined from the number of data meeting the criteria in Table
3-1 divided by the number of samples that undergo performance evaluation analyses.
3.2 Representativeness and Comparability
Representativeness and Comparability are qualitative parameters. The sediment
samples have already been collected and have been reported to be representative of the
areas to be remediated. The data obtained in this program will be comparable because all
the methods are taken from a standard EPA reference manual and all the analyses will be
conducted at the same laboratory. Reporting units for each analysis are specified in Section
6 of this document and are consistent with standard reporting units in this program.
3.3 Method Detection Limits
The target detection limits (TDLs) were specified by GLNPO (Table 2-2). Based on
the analytical methods appropriate for the analyses and the amount of samples specified in
the methods, the detection limits listed in Table 3-1 should be achievable. Generally the
instrument detection limits are defined as 3 times the standard deviation of 15 blanks or
standards with a concentration within a factor of 10 of the EDL.
96
-------
TABLE 3-1. Quality Assurance Objectives for Critical Measurements
(Sediments and Treated Solids)
CD
Parameter
Tout Solids
Volatile Solids
Oil & Grease
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
Lead ,
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total
& Aroclors (e)
PAHs (T«ble 5-2)
Method (a)
160.3
160.4
9071
3050/7060
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
3050/6010
7471
3050/6010
3050/7740
3050/6010
3050/6010
3540 or
3SSO/8080
3540 or 3550/
8270 or 8 100
Accuracy (b)
(as % recovery)
80-120
80-120
80-120
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-115
85-1 15
85-115
70-130
70-130
Precision (c)
%
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Method
Detection Limit (d)
(mg/kgm)
1000
1000
10
O.I
0.2
0.4
0.7
0.6
0.7
5
0.2
O.I
2
0.2
0.7
0.2
0.02
0.2
Completenest
%
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
00
90
90
(a) References are to 'Methods for Chemical Analysis of Water and Wastes'. EPA/600/4-79/020 or Test Methods for
Evaluating Solid Waste*. SW-846. 3rd. Ed.
(b) Determined from MS or MS/MSD analyses for metals, PAHs. and PCBs; others determined from
laboratory control samples.
(c) Determined as relative percent standard deviation of triplicate analyses, except PAHs and PCBs
in treated solids where MS/MSD will be used.
(d) See Footnotes I and 2 of Table 2-2
(e) Detection limits based on extraction of 30 gram samples.
-------
GLNPO - QAfjf
Section No j 4_
Revision
Date: Jan. 9. 1991
Page: 1 of 4
4.0 SAMPLE TRANSFER AND PREPARATION PROCEDURES
As described in Section 2, SAIC will receive a number of 5 gallon containers of
previously homogenized sediments from the U. S. EPA in Duluth, Minnesota. The number
of containers of each sediment is dependent on the final determination by GLNPO of which
sediments will be tested by the various technologies. Only if smaller portions of sediments
are requested by the vendors will these containers be opened by SAIC. If smaller portions
are required, SAIC will resuspend the solids and water within an individual container by
rolling, tumbling, and stirring of the contents. The final stirring will be in the original
containers using a metal stirrer as would be used to mix a 5 gallon container of paint. The
metal stirrer is appropriate because metals are not the primary constituents of concern in
these treatability tests.
The Chain of Custody Record shown in Figure 4-1 will be completed for each cooler
shipped to the subcontractor or vendor that will conduct the optimization and performance
evaluation tests. The samples obtained from the vendor for analysis will be labeled as
shown in Figure 4-2. The labels will document the sample I.D., time and date of collection,
and the location from where the sample was taken. The amount/type of preservative that
was added will also be recorded.
SAIC personnel will pack and ship the untreated sediment and the end product
samples (residuals) from the optimum conditions test for each technology. The amount of
preservative will be recorded. Samples will be labeled (see Figure 4-2) and shipped by
overnight delivery service to the laboratory in coolers containing ice. If "blue ice" is used
in the coolers, samples will be initially cooled with regular ice prior to being packed in the
coolers with blue ice. The Chain of Custody Record (Figure 4-1) will be completed for each
cooler shipped to the laboratory.
98
-------
GLNPO - UAFjP
Section NOJ 4
Revision NOJ j
Date:
Page:
Jan. 9. 1991
2 of 4
Solid, sediment and oil samples require no preservative other than cooling to 4° C.
The appropriate types of containers (solid and liquids), holding times, and preservatives for
water samples are listed in Table 4-1.
TABLE 4-1. Sample Containers, Preservation and Holding Times
Parameter
TOC
Solids (Total,
Volatile &
Suspended
Oil and Grease
Total Cyanide
Container
P,G
P,G
G
P.G
Preservation of Water Samples
Cool 4° C, H2SO4 to pH < 2
Cool 4° C
Cool 4° C, H2SO4 to pH < 2
Cool 4° C, NaOH to pH > 12
Holding Time
28 days
7 days
28 days
14 days
Total Phosphorous P,G
Metals P,G
(except Cr VI)
Cr (VI) P,G
PAHs & PCBs
BOD5
PH
Conductivity
G teflon
lined cap
P,G
P,G
P,G
0.6g Ascorbic acid
Cool 4° C, H2SO4 to pH < 2
HNO3 to pH < 2
Cool 4° C
Cool 4° C, store in dark
Cool 4° C
Cool 4° C
28 days
6 months except Hg
(Hg 28 days)
24 hours
Extract within 7 days
Analyze within 40 days
48 hours
Performed immediately
28 days
99
-------
' Sctonc* Application*
Inttmttloatl Corporation
O
O
Chofn-of-Cusfody Record
Date Page oL
St*xn«nlNo
Name '
Address
Phone Number
Project Name
Job/PO. No
Simptof (StgniMe) (Printed Name)
•tamwyRe
y«M>
B»inp»i No
CM*
RetnquUtwo-By
•r—
IMJ-IIU..M
Caapssf
RtHnqutalwdBir
•w—
•*«-«—
c-w
Tk*i*
Ottt
Tim*
O»lt
Flvnt
CM/Zw*
Requested Piiamelen
—
ruc^.,
*»•«««
c-**,
R«^dBy
"""*"
r.ij-jri i
&«-,
DIM
Tkno
Oil*
Ttm»
—
N
O
O
F
C
O
N
T
A
N
E
n
s
—
—
T*W Nunkve e« CMtokwn:
1 F» ou> lomi UJiniliim mar> let «h»did
t (
t
4
I
1
9
I
t
^^rs-r0--'
umotf
ntlma
mtoiei
w«w
«M«
Oreua
matyM
ogMhi
mine
Ion ConxjIiH M *n*n
bW«MO>IOM
•pplciDle pmemwvi
n Irom one umphng locallort
Phone
Contact Nun*
OBSERVATIONS. COMMENTS.
SPECIAL INSTRUCTIONS
CtahnMI
t» «M UK (Ml. fc«M «•). OH Mm
Hi* TJJ not
IM« OMAWgi (M«. IMMn V* tliei
So""** 1 IN
flmmo
Sctenco AppMcMfoni *tfwnMlo>M> CorporaWon • «H w»i m S»M S.*.
-------
GLNI*U -
Section NOJ
Revision NOJ J.
Date: Jan. 9. 1991
Page: 4 of 4
635 W. 7th Street. Suite 403, Cincinnati, OH 45203
Sample No.:
Sample Location/DatefTime:
Project Location/No.:
Analysis:
Collection Method: Purge Volume:
Preservative:
Comments:
Collector's Initials
Figure 4-2. Example Sample Label
101
-------
GLNPO - QAPjP
Section NOJ £.
Revision NOJ 2
Date: Feb. 15. 1991
Page: 1 of 3
5.0 ANALYTICAL PROCEDURES AND CALIBRATION
Analytical procedures for all critical measurements are referenced in Table 3-1. The
non-critical measurements are for any residual water and oil remaining after the
performance evaluation tests and some additional analyses on the solid samples. The EPA
procedures are specified in Table 5-1.
The required calibration for all analyses are specified in the methods and will be
followed. All instruments will be calibrated as specified in the methods prior to performing
any analysis of the samples. Internal QC checks, including initial calibration and continuing
calibration checks, for the critical measurements are listed in Table 7-1.
Table 5-2 contains the minimum list of the sixteen PAHs that must be determined
by either analytical method. Additional compounds may be included, but none of these
sixteen may be deleted from the target list
The laboratory is responsible for maintaining a preventive maintenance program
consistent with manufacturers recommendations for all instruments required for this
program. In addition, they are responsible for having a sufficient supply of routine spare
parts necessary for the operation of the analytical equipment in order to complete the
analysis in a timely fashion.
102
-------
GLNPO - QAPjP
Section No: 1
Revision NOJ 2.
Date:
Page:
Feb. 15. 1991
2 of 3
TABLE 5-1
Analytical Methods for Critical and Non-critical Measurements
Methods*
Parameter
Solid
Water
Oil
TOC
Total Solids
Volatile Solids
Oil and Grease
Total Cyanide
Total Phosphorous
Arsenic
Mercury
Selenium
Other Metals
PCBs
PAHs
PH
BOD
Total Suspended Solids
Conductivity
9060
1603
160.4
9071
9010
3652
3050/7060
7471
3050/7740
3050/6010
3540 or
3550/8080
3540 or 3550/
8270 or 8100b
9045
NA
NA
NA
9060
NA
160.4
413.1
9010
3652
7060
7470
7740
3010/6010 (7760 Ag)
3510 or
3520/8080
3510 or 3520/
8270 or 8100"
9040
405.1
1602
9050
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
3580/8080
3580/8270
NA
NA
NA
NA
(a) References are to "Methods for Chemical Analysis of Water and Wastes", EPA/600/4-
79/020 or 'Test Methods for Evaluating Solid Waste", SW-846, 3rd. Ed.
(b) Where options for methods are given,-Either is acceptable if the detection limits given
in Table 2-2 can be achieved.
NA - Not analyzed
103
-------
GLNI'O - QAPjP
Section NOJ JL.
Revision No- 2
Date: Feb. 15. 1991
Page: 3 pf 3
TABLE 5-2
List of PAHs*
Acenaphthene Chiysene
Acenaphthylene Dibenzo(aTh)anthracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Inden(1^3-cd)pyrene
Benzo(b)fluoranthene Naphthalene
Benzo(k)fluoranthene Phenanthrene
Benzo(ghi)perylene Pyrene
PAH analyses must detennine these 16 compounds at a minimum.
104
-------
GLNPO - QAPjP
Section NOJ £_
Revision NOJ 1
Date: Jan. 9. 1991
Page: 1 of 1
6.0 DATA REDUCTION, VALIDATION AND REPORTING
Data will be reduced by the procedures specified in the methods and reported by the
laboratory in the units also specified in the methods. The work assignment manager or his
designer will review the results and compare the QC results with those listed in Table 3-1.
Any discrepancies will be discussed with the QA Manager.
All data will be reviewed to ensure that the correct codes and units have been
included. All organic and inorganic data for solids will be reported as mg/kgm except TOC,
oil & grease (O&G), moisture and iron that will be reported as percent and pH that will
be reported in standard pH units. All metals and organics in water samples will be reported
as ug/1. TOC, solids (suspended and volatile), O&G, cyanide, phosphorus, and BOD will
be reported as mg/1. Conductivity will be reported as umhos/cm and pH as standard pH
units. After reduction, data will be placed in tables or arrays and reviewed again for
anomalous values. Any inconsistencies discovered will be resolved immediately, if possible,
by seeking clarification from the sample collection personnel responsible for data collection,
and/or the analytical laboratory.
Data Tables in the report will be delivered in hard copy and on discs. The discs will
be either in Lotus files or WordPerfect 5.1 files.
105
-------
GLNPO - QAPjP
Section No.: 2
Revision No.: 2
Date: Feb. 15. 1991
Page: 1 of 7
7.0 INTERNAL QUALITY CONTROL CHECKS
The internal QC checks appropriate for the measurement methods to be utilized for
this project are summarized in Table 7-1. These items are taken from the methods and the
QC program outlined in Section 3 of this QAPjP.
For the GLNPO program, the following QC measures and limits are employed:
on-going calibration
checks
method blanks
matrix spikes
replicates
beginning, middle, and end of sample set for metals, pH,
TOC/TIC, total cyanide, and total P
mid-calibration range standard
± 10% limit unless otherwise stated
± 0.1 pH unit for pH
± 10 umhos/cm for conductivity at 25° C
beginning, every 12, and end of sample set for PCBs and
PAHs
mid calibration range standard
± 10% limit
one per sample set for PCBs and PAHs
< MDL limit unless otherwise stated
beginning, middle and end for metals, TOC/TIC, total
P, total cyanide, and pH
beginning, middle and end for conductivity with
acceptance limits of < 1 umho/cm
one per sample set
1 to 1.5 times the estimated concentration of sample
±15% limit for metals; ± 30% for PCBs and PAHs
triplicate analyses
RSD i 20% unless otherwise stated
one per sample set
± 0.1 pH unit for pH
± 2 umhos/cm for conductivity
106
-------
CJUMitJ - UATJJT
Section Nou J_
Revision NOJ 2
Date: Feb. 15. 1991
Page: 2 of 7
QC sample - - minimum of one per sample set
(CRM) - ± 20% of known CRM
- ± 0.1 pH unit for pH
- ± 1 umhos/cm for conductivity
surrogate spikes - added to each sample
(PCBs and PAHs only) - ± 30% recovery
The surrogate for PCB analysis is tetrachlorometaxylene and the internal standard is 1,2,3-
trichlorobenzene.
Table 7-2 shows an analytical matrix that will be completed for each technology
tested. For example, consider the case of a bench scale treatability test of (1 kilogram)
Indiana harbor sediment by low temperature stripping. Based on the data presented in
Table 2-la and assuming complete separation and recovery of oil, water, and solid, a 1
kilogram sample of untreated sediment will produce 58 grams of oil, 610 ml of water, and
332 grams of dry treated solids. For the purpose of this program, this sample set consists
of 1 untreated solid, 1 treated solid, and the water and oil generated by the process. Table
7-3 is a completed analytical matrix for this test Table 7-3 is based on Tables 2-2 and 2-4
and the QC approach described in this QA plan. The analysis of the water sample in this
example is severely limited by the relatively small amount of sample obtained.
Table 7-4 is a matrix summarizing the anticipated samples to be analyzed for this
project. The sets for each technology (see section 2.1) are:
I B.E.S.T.
n ReTec
III Wet Air Oxidation
IV Soil Tech
The Soil Tech process will process treated soils at two distinct points. Therefore,
four treated solids are produced from the two untreated sediments.
107
-------
TABLE 7-1. Internal QC Checks for Measurements
o
oo
Parameter
Solids
(Total &
Volatile
Oil & Grease
Metals
Metals
PCBs(b)
PAHs
Method (a)
160.3
160.4
I
9071
6010
7000
series
8080
8270 or
8iOO
Initial
Calibration
Balance
(Yearly)
See Above
2 points
4 points
5 points
S points
Calibration
Checks
Balance
Each Day
See Above
Every 10th
Sample
Every 10th
Sample
Every 10th
Sample
Every 12
Hours
Method
Blank
Yes
Yes
Yes
Yes
Yes
Yes
MS/MSD
NA
NA
MS only
MS only
Yes (treated)
MS only (untreated)
Yes (treated)
MS only (untreated)
Triplicate
Sample
Analysis
Yes
Yes
Yes
Yes
NA (treated)
Yes (untreated)
NA (treated)
Yes (untreated)
QC
Sample
Yes
Yes
Yes
Yes
Yes
Yes
Surrogate
Spikes
NA
NA
NA
NA
Yes
Yes
(a) References are to "Methods for Chemical Analysis of Water and Wastes', EPA/600/4-79/020
or "Test Methods for Evaluating Solid Waste". SW-846. 3rd. Ed.
(b) Second column confirmation of positive results is required.
NA - Not Applicable
ffffl
p.
*
3
-n
~J
-------
TABLE 7-1. Internal QC Checks for Measurements (continued)
o
-------
TAm.fi 7-2. Analytical Matrix
QC Simple
tnd
Method Blink
If
2?
P. S
8
-------
Ill
H
33
SJ
U)
rn
X
Bl
1
5°
T66I Si
-------
TABUi 7-4. Analytical and QC Sample Matrix for GLNPO Treatabilily Studies (numbers of samples)
SAMPLE SET
SETI
Untreated S.
Treated S.
Wiler
Oil
SET IV
Untreated S.
Treated S.
Water
Oil
SBTH
Untreated S.
Treated S.
Water
Oil
SETHI
Untreated S.
Treated S.
Water
TOTALS
Solida
Water
Oil
roc/r/c
(•) QCft>)
3
3
2
4
I
1
1
16
1
-
/
3
2
3
-
5
3
TOTAL
SOUDS
S QC
2
1
1
1
16
3
3
2
3
2
20
VOL
SOLIDS
S QC
2
1
1
16
3
3
2
3
3
2
20
3
OA O
S QC
2
1
1
1
16
3
3
2
3
3
2
20
3
TOTAL
Y A HIDE
S QC
2
1
1
1
16
i
-
-
3
3
3
-
6
3
TOTAL
PtIOS
S QC
3
2
1
1
1
16
i
-
-
3
3
3
-
6
3
METALS
S QC
3
2
1
1
1
16
i
3
3
3
3
3
3
3
24
3
PCBs
S QC
3
3
3
2
2
2
16
7
6
2
1
3
3
3
3
2
2
3
3
2
2
20
6
9
PAH
S QC
3
3
3
2
2
2
16
7
6
2
1
3
3
2
1
3
3
2
2
3
3
2
2
20
6
9
PH
S QC
3
2
4
1
1
1
1
1
16
I
-
-
3
2
3
-
i
3
BOD
S QC
-
-
1
-
I
-
-
3
-
3
TSS
S QC
-
-
1
-
I
-
-
3
-
3
COM)
S QC
-
-
I
-
!
-
-
1
.
3
(a) Number of original iimplet.
(b) Number of quality control samples. A *3* represents two additional replicate* (triplicate determination) and a (pike or control
(ample analysis resulting in an additional three QC analyse!. A *2* represents matrix (pike/matrix (pike duplicate analysis
scheme resulting in an additional two QC antlytes. A "I" indicates a blink spike or other control simple analysis resulting
in one additional QC analysis.
(c) Treited ind unlreited tolids does not apply, ind only one control simple per set will be analyzed.
-------
GLNPO - QAPjP
Section No.: JL
Revision No.: 2
Date: Feb. 15. 199L
Page: 1 of 1
8.0 PERFORMANCE AND SYSTEM AUDITS
The laboratory will perform internal reviews by the QA officer or a designee. These
reviews should include, as a minimum, periodic checks on the analysts to assess whether they
are aware of and are implementing the QA requirements specified in the ARCS QA
program.
The laboratory will be prepared to participate in a systems audit to be conducted by
the SAIC QA Officer or his designee and/or ARCS QA Officer.
The vendors of the various technologies have all been advised that a number of
representatives from SAIC, GLNPO, and other organizations will be present during
Phase II of the treatability studies. Thus the ARCS QA officer can be present during
Phase II of anv or all of the treaiabilirv studies.
113
-------
GLNPO -
Section No.: JL
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 3
9.0 CALCULATION OF DATA QUALITY INDICATORS
9.1 Accuracy
Accuracy for PAHs, PCB and metals will be determined as the percent recovery of
matrix spike samples. The percent recovery is calculated according to the following
equation:
%R = 100% xC'"_^ _
Q
where
%R = percent recovery
C, = measured concentration in spiked sample aliquot
C0 = measured concentration in unspiked sample aliquot
C, = actual concentration for spike added
Accuracy for the other critical measurements will be determined from laboratory
control samples according to the equation:
% R = 100% l
C,
where
%R = percent recovery
C_, = measured concentration of standard reference material
C, = actual concentration for standard reference material
9.2 Precision
Precision will be determined from the difference of percent recovery values of MS
and MSDs for PAHs and PCBs or triplicate laboratory analyses. The following equations
will be used for all parameters:
114
-------
GLNPO - QAPjP
Section NOJ J
Revision No.: J
Date:
Page:
Jan. 9. 1991
2 of 3
When 2 values are available:
[C, - CJ x 100%
[Q + CJ/2
where
RPD = Relative percent difference
Cj = The larger of two observed values
Q = The smaller of the two observed values
When more than 2 values are available:
S =
N
I
i = 1
2 _
i
N i
N
I X
= 1
N - 1
where
S = standard deviation
Xi = individual measurement result
N = number of measurements
Relative standard deviation may also be reported.
will be calculated as follows:
RSD = 100 ^
If so, it
115
-------
GLNPO - UAf jr
Section No.: £.
Revision No.: 1
Date: Jan. 9. 1991
Page: 3 of 3
where
RSD = relative standard deviation, expressed in percent
5 = standard deviation
X = arithmetic mean of replicate measurement.
9.3 Completeness
Completeness will be calculated as the percent of valid data points obtained from the
total number of samples obtained.
% Completeness = VDP x 100
TOP
where
VDP = number of valid data points
TDP = total number of samples obtained.
116
-------
GLJVPO - (JAfjf
Section No.: 10
Revision No.: 1
Date: Jan. 9 1991
Page: 1 of 2
10.0 CORRECTIVE ACTION
Corrective actions will be initiated whenever quality control limits (e.g., calibration
acceptance criteria) or QA objectives (e.g., precision, as determined by analysis of duplicate
matrix spike samples) for a particular type of critical measurement are not being met.
Corrective actions may result from any of the following functions:
• Data Review
• Performance evaluation audits
• Technical systems audits
• Interlaboratory/interfield comparison studies
All corrective action procedures consist of six elements:
• Recognition that a Quality Problem exists
• Identification of the cause of the problem
• Determination of the appropriate corrective action
• Implementation of the corrective action
• Verification of the corrective action
• Documentation of the corrective action
For these treatabiliry studies after initial recognition of a data quality problem, the
data calculation will be checked first. If an error is found, the data will be recalculated and
no further action will be taken. If no calculation error is found, further investigation will
be conducted. Depending on the cause and the availability of the appropriate samples.
reanalysis or flagging of the original data will be utilized.
117
-------
GLNPO - QAPjf
Section No.: 10
Revision No.: 1__
Date: Jan. 9. 1991
Page: 2 of 2
All corrective action initiations, resolutions, etc. will be implemented immediately and
will be reported in Sections One and Two (Difficulties Encountered and Corrective Actions
Taken, respectively) in the existing monthly progress reporting mechanisms established
between SAIC, EPA-RREL, GLNPO, AND THE ARCS QA officer and in the QA section
of the final report. The QA Manager will determine if a correction action has resolved the
QC problem.
118
-------
GLNPO - QAPjP
Section No.: 11
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of l
11.0 QA/QC REPORTS TO MANAGEMENT
This section describes the periodic reporting mechanism, reporting frequencies, and
the final project report which will be used to keep project management personnel informed
of sampling and analytical progress, critical measurement systems performance, identified
problem conditions, corrective actions, and up-to-date results of QA/QC assessments. As
a minimum, the reports will include, when applicable:
• Changes to the QA Project Plan, if any.
• Limitations or constraints on the applicability of the data, if any.
• The status of QA/QC programs, accomplishments and corrective actions.
• Assessment of data quality in terms of precision, accuracy, completeness,
method detection limit, representativeness, and comparability.
• The final report shall include a separate QA section that summarizes the data
quality indicators that document the QA/QC activities that lend support to
the credibility of the data and the validity of the conclusions.
For convenience, any QA/QC reporting will be incorporated into the already well-
established monthly progress reporting system between SAIC and EPA-RREL for all TESC
Work Assignments. In addition, copies of monthly reports will be sent to the ARCS QA
officer. Any information pertaining 10 the above-listed categories will be reported under
Sections One through Three (Difficulties Encountered, Corrective Actions Taken, and
Current Activities, respectively) in the monthly reports.
119
-------
GLNPO - QAPjP
Section No.: Appendix A
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 3
APPENDIX A
TECHNOLOGY SUMMARIES
120
-------
GLNPO - QAJ
Section No.:
Revision No.:
Date:
Page:
V
Appendix A
1
Jan. 9. 1991
2 of 3
Process Descrition
The B.E.S.T.™ process is a patented solvent extraction technology utilizing triethylamine
as the solvent. Triethylamine is an aliphatic amine that is produced by reacting ethyl
alcohol and ammonia. The key to success of the B.E.S.T.™ process is triethylamine's
property of inverse miscibility. At temperatures below 65°F, triethylamine is completely
soluble with water. Above this temperature, triethylamine and water are only partially
miscible. The property of inverse miscibility can be utilized since cold triethylamine can
simultaneously solvate oil and water.
The B.E.S.T.™ process produces a single phase extraction solution which is a homogeneous
mixture of triethylamine and the water and oil (containing the organic contaminants, such
as PCBs, PNAs, and VOCs) present in the feed material. In cases where the extraction
efficiencies of other solvent extraction systems are hindered by emulsions, which have the
effect of partially occluding the solute (oil containing the organic contaminants),
triethylamine can achieve intimate contact at nearly ambient temperatures and pressures.
This allows the B.E.S.T.™ process to handle feed mixtures with high water content without
penalty in extraction efficiency. This process is expected to yield solid, water, and oil
residuals.
Low Temperature Stripping
Low-temperature stripping (LTS) is a means to physically separate volatile and semivoJatile
contaminants from soil, sediments, sludges, and filter cakes. For wastes containing up to
10% organics or less, LTS can be used alone for site remediation.
LTS is applicable to organic wastes and generally is not used for treating inorganics and
metals. The technology heats contaminated media to temperatures between 200-1000°F,
driving off water and volatile contaminants. Offgases may be burned in an afterburner,
condensed to reduce the volume to be disposed, or captured by carbon adsorption beds.
For these treatability studies, only processes that capture the contaminants driven off will
121
-------
Section NOJ Appendix A
Revision NOJ 1
Date: Jan. 9. 1991
Page: 3 of 3
be considered. The process (for these treatability studies) is expected to yield solid, water,
and oil residuals.
Wet Air Oxidatiop
Wet air oxidation is a process that accomplishes an aqueous phase oxidation of organic or
inorganic substances at elevated temperatures and pressures. The usual temperature range
varies from approximately 350 to 600°F (175 to 320°C). System pressures of 300 psig to well
over 300 psig may be required. However, testing has been done at temperatures exceeding
the critical point for water to limit the amount of evaporation of water, depending on the
desired reaction temperature. Compressed air or pure oxygen is the source of oxygen that
serves as the oxidizing agent in the wet air oxidation process. This process is expected to
yield only solid and water residuals.
122
-------
APPENDIX D
SoilTecn, Inc.
94 Inverness Terrace East - Suite 100
Englewood. Colorado 80112
Phone: (303) 790-1410
Fax. (303) 799-0186
AprilS, 1992
90-426-30
Ms. Evelyn Hartzel
Science Applications International Corporation
635 West Seventh Street, Suite 403
Cincinnati, OH 45203
Response to Comments
Great Lakes National Program Testing
Dear Ms. Hartzel:
As requested on April 3, 1992, presented in this letter is our response to Science
Applications International Corporation's (SAIC) inquiries on Phase I and II bench-scale
testing by SoilTech ATP Systems, Inc. (SoilTech) of two Great Lakes tributary
sediment samples. You requested that we make a supplemental letter report to SAIC
to state the method of selecting Phase II test conditions and revisions (if any) to the
experimental design.
Prior Activities
SoilTech conducted bench-scale tests on sediments from the Buffalo River and Indiana
Harbor to evaluate the SoilTech Anaerobic Thermal Processor (ATP) Technology's
ability to remove polycyclic aromatic hydrocarbons (PAHs) and poiychlorinated
biphenyls (PCBs) from the samples by anaerobic thermal desorption. Phase I testing,
completed on July 18, 1991, was conducted to identify optimum conditions for
Phase II testing. Phase II testing was completed on August 20, 1991. Phase I
samples and test products were analyzed by SoilTech's contract laboratory to obtain
guidance data, while Phase I! samples were independently analyzed by a separate
laboratory under subcontract to SAIC. In September 1991, SoilTech reported to SAIC
on the test results, excluding the Phase II sample analyses. The Phase II analytical
data and partial assessment were forward to SoilTech in a letter dated
March 20, 1992 from Mr. Thomas Wagner, Project Manager for SAIC.
123
-------
Ms. Evelyn Hartzel April 9, 1992
As stipulated in the contract Statement of Work, SoilTech reported Phase I data that
comprised:
1. Operating conditions/parameters,
2. Input/output data for the contaminants of interest to show the range of
effectiveness associated with various operating conditions, and
3. Quantities of the input material and the various residuals resulting from the
test.
The September 1991 report also included SoilTech's Phase II data on operating
conditions and material quantities. We did not have access to Phase II analytical
results for that report.
Determination of Phase II Test Conditions
This section describes the selection of Phase II test conditions from Phase I data.
The Phase I test results (refer to tables in the September 1991 report) showed that
the range of operating conditions of the full-scale SoilTech ATP System will reduce
all of the detected PAHs from cumulative levels of about 123 parts per million (ppm)
[Buffalo River sample] and 481 ppm (Indiana Harbor sample), achieving uniformly
nondetectable levels at practical quantitation limit (PQL) values of only 1 ppm for all
species.
Therefore, the Phase II test temperatures were selected to span the actual range of
higher system temperatures in the full-scale system. We made no changes in the
experimental design used in Phase I. Because of the high moisture content of the feed
samples (approximately 42 to 60 percent on average), the test temperatures were
started at preheat zone conditions to boil off the moisture at rates that would not
over-pressure the test system. Temperatures were then raised to the retort zone
conditions.
This procedure corresponded to using starting temperatures of about 443 °F and
586 °F and raising the samples to top temperatures of 1,210 °F and 1,177 °F,
respectively, as shown below. The low Phase II test temperatures reflect realistic
values in the hot end of the preheat zone of the SoilTech ATP Processor. The high
Phase II temperatures correspond to maximum discharge temperatures from the retort
zone, where the limit of contaminant distillation is reached.
-------
Ms. Evelyn Hartzel April 9, 1992
Phase I Reaction Zone Test Phase II Reaction Zone Test
Sample Name Temperatures. °F Temperature. °F
Buffalo River 777-786; 443-1210
950-966;
1150-1135
Indiana Harbor 741-778; 586-1177
969-981;
1175-1154
Operation Variables
In our discussion about supplemental reporting, reference was made to Appendix A
(Operation Variables) of the original SoilTech proposal for this project. The variables
described are for the full-scale process system, and for testing purposes we are
interested primarily in temperature as a control parameter. The discussion in Appendix
A briefly indicates the limitations in the parallels between the bench and full-scale
units. A copy of Appendix A is enclosed.
However, as we discussed last Friday, it may be useful to SAIC to roughly quantify
those operating variables. Therefore, the following text briefly summarizes the
potential full-scale operating parameters.
1. Feed Rate: In their as-received condition, the wet sediments would limit the
feed rate of the commercial SoilTech ATP Unit. Therefore, we anticipate
that a full-scale remediation project would entail dewatering the sediments
to achieve cost-effective production rates. We have evaluated this option
in other projects involving lake or river sediment feed sources. Pending
more complete data on the sediment physical characteristics, the existing
SoilTech ATP Unit may approach its design operating rate of 10 tons per
hour with dewatering incorporated into the scope of the ATP System under
a site-specific remedial design.
2. Rotational Speed of the Kiln: The nominal operating speed range may vary
from about 3.5 revolutions per minute (rpm) to 5 rpm. The speed depends
principally on balancing the vacuum system controls, heat transfer
efficiency, and feed rate.
3. Operating Temperatures: The temperatures in the preheat zone would rise
to about 600 °F at the hot end. Temperatures in the retort zone can range
125
'Oil
-------
Ms. Evelyn Hartzel April 9, 1992
from as low as 900 °F to roughly 1,200 °F. Temperature is kept as low as
possible, consistent with quality-control of the decontamination process, to
optimize the sediment processing rate. (The test temperatures in this
project were selected to show optimal decontamination effectiveness. Rate
optimization would entail further sediment characterization and shakedown
testing at the start of full-scale remediation.)
4. Pressures of Preheat and Reaction Zones: These "distillation" zones are
maintained at a minimal controllable vacuum (i.e., just below atmospheric
pressure). This is determined in the early phases of full-scale operation, and
controlled automatically thereafter.
5. Rate of Heat Application: Heat generation is regulated by automatic control
of fuel addition and combustion air injection. Nominal peak rates are about
10 million BTU per hour. The rate of heat generation is adjusted to
maximize feed processing rates, while holding numerous other process
variables within system design range.
6. Rate of Clean Solids Internally Recycled: After decontamination in the
preheat and retort zones, the treated solids pass through the combustion
zone where they are heated to about 1,300 °F to 1,400 °F. These clean,
heated solids are recycled back into the retort zone as the primary heat
transfer mechanism, at a rate projected to be about three times the solid
flowrate entering the retort zone.
7. Flow Rate of Combustion Air: Combustion air flow will be automatically
regulated to meet the heat demand of the process. The flow is governed
according to real-time measurements of flue gas composition, with principal
attention to carbon monoxide and trace hydrocarbons.
8. Rate of Hydrocarbon Vapor Condensation: The rate of hydrocarbon
condensation depends on the contamination levels of the feed material and
the sustainable net plant feed rate. The analytical data for the Phase I and
Phase II samples showed total organic loadings (including natural organics)
in the feed, in the range of about 1 to 7 weight percent, with one value of
12.3 percent. The test runs demonstrated that between 2 and 1 1 percent
of the feed hydrocarbons may be recovered as oily liquid product.
Costs
The contract Statement of Work/Experimental Design made a very brief statement
that SAIC would report "cost estimates as provided by the vendor or subcontractor."
126
-------
Ms. Evelyn Hartzel April 9, 1992
However, no further definition of a costing basis was ever made. To provide you with
a reference cost value for your report, we suggest comparing similar applications
evaluated by SoiiTech. For processing other Great Lake sediments containing similar
levels of PAHs and PCBs, SoiiTech has previously estimated "hopper to hopper" costs
of about $180 per ton for a 10 ton-per-hour plant setup. Major factors in this
estimated cost are the condition and properties of the feed sediment in terms of
moisture, total contamination, and soil characterization. Pending an engineering
evaluation of these parameters, the above cost should be recognized as being very
preliminary, and possibly varying substantially either up or down.
Please note these costs pertain to the restricted scope of soil/sediment processing,
exclusive of other project functions that may be characterized as common
infrastructure elements (i.e., general site control and management, construction of
utilities and equipment pads, site health and safety control, excavation and materials
management, performance testing, permitting, etc.). However, these elements will
be substantially similar for remediation using any large-scale process system to treat
the sediments. Therefore, the hopper-to-hopper processing estimate may be a useful
component of an overall cost estimate.
Conclusion
We have addressed your request for the description of the determination of Phase II
test parameters from the Phase I results. I have also provided extra information to
enhance the use of the SoiiTech ATP test results in your composite technology study.
Finally, enclosed are two technical papers on SoiiTech ATP Technology and
performance that may also support your review of technologies for sediment
remediation.
If I can be of further assistance, please call me at 303/790-1747.
Very truly yours,
Martin Vorum
Project Supervisor
MV/df
Enclosures
127
-------
APPENDIX A
OPERATION VARIABLES
Feed Rate: The continuous feed rate of the full-scale ATP
which is currently at the Wide Beach Superfund
site is as high as 15 tons per hour. The
bench-scale tests are batch tests; therefore,
the continuous feed rate does not apply.
Rotational Speed of Kiln: The full-scale ATP can rotate at a speed of
0 to 5.5 revolutions per minute (rpm). The
bench-scale tests will be conducted at 4.5
rpm, which is a typical rate for the ATP.
Operating Temperature of Preheat Zone: The preheat zone of the full-scale
ATP is between 250 degrees Fahrenheit and 600
degrees Fahrenheit. The purpose of the
preheat zone is to dry the feed material. Due
to this the preheat temperature for the bench-
scale tests will be held at 300 degrees
Fahrenheit.
Operating Temperature of Reaction Zone: The temperature of the reaction
zone is the key variable in determining the
ATP's effectiveness in treating soils, sludge,
sediments, and other material. The bench-
scale tests will be conducted at three
different reaction zones temperatures as
discussed.
Pressure of Preheat and Reaction Zones: The preheat and reaction zones
of the full-scale ATP operate at a very slight
negative pressure of less than one inch of
mercury. This negative pressure is not varied
128
SoiiTech
-------
during operation. The bench-scale tests will
be conducted at atmospheric pressure.
Rate of Heat Application; The full-scale ATP varies the rate of heat
applied through the auxiliary burners of the
combustion zone. The rate of heat application
determines the operating temperature of the
reaction and preheat zones. The rate of heat
application cannot be varied on the bench-
scale processor, and is controlled by turning
the electric heat elements on or off, either
by computer control or manually.
Rate of Clean Solids Internally Recycled: The full-scale ATP internally
recycles a portion of the cleaned solids from
the combustion zone into the reaction zone.
The recycling of clean solids is close for
thermodynamic reasons and to help Increase the
thermal efficiency of full-scale processors.
The bench-scale unit does not contain any
mechanism for recycling material from the
combustion unit to the retort unit.
Flow Rate of Combustion Air: The flow rate of combustion air air helps to
control the temperature of combustion and to
control the CO and NOx emissions. The bench-
scale combustion unit does not impact the
temperature of the bench-scale retort unit,
and CO and NOx emissions are not considered.
Therefore, during bench-scale testing
sufficient combustion air is used to ensure
thorough combustion of the residual carbon-
black on the solids.
129
SoilTech
-------
Rate of Hydrocarbon Vapor Condensation: The full-scale ATP has a
sophisticated reflux distillation system to
recover the hydrocarbon vapor. This system
proves beneficial on sites where a recycleable
or reusable hydrocarbon Is recovered. The
bench-scale units use a simple condenser and
glass reservoir for hydrocarbon recovery.
130
SoilTech
-------
SAIC GLNPO (CF *3611
CONVENTIONALS IN UNTREATED SEDIMENT
SOIL TECH
REVISED
2/26/92
MSLCoda
MDL
Sponsor ID
% Moisture
001%
PH
NA
% Total
Volatile Solid
0001%
Oil & Grease
(mg/kg)
20 0
TOG
% weight
0 007
Total Cyanide
(mg/kgl
02
Total Phosphorus
(mg P/kg>
0.002
68 22%
NA
NA
41 51%
8.14
NA
NA
7.82
5.07%
5.07%
5.19%
1580%
11743
9786
7093
94956
1.78%
NA
NA
18.98%
83
NA
NA
16 7
1508
NA
NA
2391
NA
NA
0%
20 U
0.014%
361-18. Rep 1 B US-ST. Rep 1
361-18. Rep 2 BUS ST. Rep 2
361-18. Hep 3 B US ST. Hep 3
36H9 i us sr
Method Blank
STANDARD REFERENCE MATERIAL
MESS 1 SHM
In-house Concensus Value
MATRIX SPIKE RESULTS
Amount Spiked
361-19
361-19 + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-18. Rep 1
361-18. Rep 2
361-18. Rep 3
RSD%
NA - Not analyzed
U = B&low detection limit
~ TOC value lor MbSS determined based on past In-house analyses. Not a statistical determination.
NOTE: All Cuiwuntionul msults aiu itipoilui) on a dry woiylil basis.
02 U
0.005
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2 2
23
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
4086
2391
5975
3584
68%
•o
tj
m
z
0
X
in
68.22%
NA
NA
NA
8.30
NA
NA
NA
5.07%
5.07%
5.19%
1%
11743
9786
7093
24%
1 .78%
NA
NA
NA
83
NA
NA
NA
1508
NA
NA
NA
-------
SAIC GLNPO (CF #361)
SOIL TECH
REVISED
2/26/92
CONVENTIONALS IN TREATED SEDIMENT
MSLCode Sponsor ID
MDL
361-14 B-TS-ST-R
361-15 I-TS-ST-R
361-16. Rep 1 B-TS-S1-C. Rep 1
361-16, Hep 2 B-TS-ST-C. Hep 2
361-16, Rep 3 B-1S-SC-C, Rep 3
361-17 ITSSI-C
Method Blank
STANDARD REFERENCE MATERIAL
MESS 1 SRM
In house Concensus Value "
MATRIX SPIKE RESULTS
Amount Spiked
Sample
Sample •*• Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-16, Rep 1
361-16, Rep 2
361 16, Hep 3
RSD%
% Moisture
0 0 1 %
0 05%
001% U
001%
001%
NA
0 02%
NA
NA
NA
NA
NA
NA
NA
NA
001%
NA
NA
NA
PH
NA
9 95
9.78
10 72
NA
NA
9 96
NA
NA
NA
NA
NA
NA
NA
NA
10.72
NA
NA
NA
% Total
Volatile Solid
0 001%
014%
1.45%
0 03%
0.03%
0.03%
0 28%
0%
NA
NA
NA
NA
NA
NA
NA
0 03%
0 03%
0 03%
0/0
Oil & Grease
(mg/kg)
0 10
434
672
302
388
246
732
20 U
NA
NA
361-16
4220
302
5313
5011
1 1 9%
302
388
246
23%
TOG
% weight
0 007
0 14%
2 08%
001% U
NA
NA
0 34%
0014%
2 1
2 3
NA
NA
NA
NA
NA
001 U
NA
NA
NA
Total Cyanide
(mg/kg)
0 001
1 6
0 3
02
NA
NA
0 7
02 U
NA
NA
361-14
154 5
1 6
143 1
141 5
92%
0 2
NA
NA
NA
Total Phosphorus
(mg P/kg)
0 001
215
653
93
NA
NA
205
0 005
NA
NA
NA
NA
NA
NA
NA
93
NA
NA
NA
NA = Not analyzed
U - Below detection limit
= TOC value lor MESS determined based on past in-house analyses.
NOTE. All Conventional losullb are tupoitud on a dry wuight basis
Not a statistical determination.
-------
CO
SAICGLNPO (CF »361)
UETALS IN UNTREATED SEDIMENT
(Concenlialons In ug/g dry wolghl)
MSLCode Sponsor 10
MOL (I)
361 IB. Rep 1 B US ST, Rep 1
361 18, Rep 2 B US ST. Hop 2
361 18. Rep 3 B US ST. Hup 3
361 19 1 US SF
Molliod Blank (2)
STANDARD REFERENCE MATERIAL
1646 SRM
carlllUd
vuluu
MATRIX SPIKE RESULTS
Amount Splkod
361 IB "
361 18 » Spike
Amount Recovered
Purcenl ftucovery
REPLICATE ANALYSIS
361-18. Hep 1 B US ST. Rup 1
361-18, Rep 2 B US SI, Hop 2
361 18. Rep 3 B US ST, Hop 3
RSO%
SOIL TECH
Ag
AA
0 007
0 29
0 28
0 28
5 15
002
0 11
N;
tc
2
0 28
2 73
2 45
1 22%
0 23
0 28
0 28
1%
As
Mf
2 5
130
12 5
14 4
13 0 U
NA
1 1 2
1 1 6
il 3
NA
NA
NA
NA
NA
13 0
12 5
14 4
V/o
Ba
Mt
43
401
391
397
288
NA
384
M;
NO
NA
HA
NA
NA
NA
401
391
397
1%
Cd
A*
0006
2 10
1 88
1 97
733
001
0 39
036
1007
2
1 98
3 88
1 00
95%
2 10
1 88
1 97
5%
Cf
»»
33
123
137
121
1086
NA
68
76
13
NA
NA
NA
NA
NA
123
137
121
7%
Cu
Xlt
55
750
73 5
700
2560
NA
21 9
IB
±3
NA
NA
NA
NA
NA
750
73 5
70 0
4%
%Fe
»F
0 26
4 58
4 52
4 58
184
NA
3 44
3 35
10 1
NA
NA
NA
NA
NA
4 58
4 52
4 58
1%
H9
CV»A
0 0003
0 422
0 485
0 513
1.590
000013
0 066
0 063
10 012
1 990
0 473
2 312
1 84
92%
0 422
0 4B5
0 513
10%
Ml
»v
56
694
692
714
2040
NA
363
375
120
NA
NA
NA
NA
NA
694
692
714
2%
Nl
Of
7 5
450
43 2
450
95 0
NA
298
32
13
NA
NA
NA
NA
NA
450
43 2
45 9
3%
Pb
ar
6 2
107 5
107 3
108 0
789 0
NA
28 3
282
11 8
NA
NA
NA
NA
NA
107 5
107 3
108 0
0 34%
REVISED
2/26/02
Sa
AA
0 22
0 74
062
0 74
5 65
0 22 U
0 74
NC
NC
2 74
0 70
5 37
4 67
170%
0 74
0 62
0 74
10%
Zn
»f
7 8
190 8
186 2
191 7
3100 0
NA
122. B
138
16
NA
NA
NA
NA
NA
190 B
186 2
191 7
2%
U - Below detection limit
NA - Not analyzed
- Mean ol triplicated sample
NS - Not spiked
(I) NOTE. MDLs lor XRF determined using 15 tops ol SRM Dolocllon limits
listed lur Individual samplus aiu jciual Inslrumunl Doluciion I units (IUI s)
|2) NOTE. All molals uala Is bljnK cuiiuclud
-------
CO
SAIC GLNPO (CF »361)
METALS IN TREATED SEDIMENT
(Concenlralons in ug/g dry woighl)
MSLCode Sponsor ID
MD1. (1)
361-14 B TS ST R
361 15 1 TS ST H
361-16, Rep 1 B TS ST C, Rep 1
361 16. Rop 2 BTSSTC. Rep 2
36116. Hop 3 BTSSfC. Hop 3
361 17 1 TS Sf C
Muttiod Blank (2)
STANDARD REFERENCE MATERIAL
1646 SRM
certified
vilus
MATRIX SPIKE RESULTS
Amount Spiked
361 16 *
361 16 t Spike
Amount Rucovured
Puiconl Recovery
REPLICATE ANALYSIS
361 16, Hep 1 B TS ST C. Rep 1
361 16, Rep 2 B TS ST C. Hup 2
361 16. Hup 3 B IS ST C. Rop 3
RSO%
SOIL TECH
Ag
AA
0 007
0 065
0 521
0 085
0 088
0 OD7
0 262
0 020
0 109
rC
1C
2
0 03
2 39
2 30
1 1 b%
0 085
0 088
0 097
7%
As
HI
2 5
3 3
1 8 U
1 9
1 7
2 3
2 5
NA
10 6
11 6
11 3
NS
KB
NS
ML;
NS
1 9
1 7
2 3
15V.
Ba
»f
43
82
42
66
59
57
53 4
NA
3t)4
N3
N3
NS
NS
NS
It.
NS
66
59
57
7%
Cd
AA
0 006
0 299
1 006
0 205
0 226
0 206
0 503
0 006
0 39
0 36
1007
2
0 22
2 31
2 09
105%
0 205
0 226
0 206
6%
Cr
»f
33
25
1 16
27
45
24
84
NA
77
76
13
NS
NS
NS
re
NS
27
45
24
35%
Cu
Mt
5 5
16 9
34 5
18 8
19 2
20 5
40 4
NA
21 5
18 0
±3
NS
NS
NS
NS
NS
18 8
19 2
20 5
5%
%Fe
Mt
0 26
0 94
2 03
0 70
0 75
0 75
1 60
NA
3 47
3 35
10 1
NS
NS
NS
NS
NS
0 70
0 75
0 75
4%
Hg
CVAA
0 0003
0 00030 U
0 00030 U
0 00030 U
0 00029 U
0 00030 U
0 00030 U
0 00013
0 066
0 063
10 012
1 972
0 00030
1 826
1 8257
93%
0 00030 U
0 00029 U
0 00030 U
NA
Mi
XI 1
56
149
215
96
90
89
161
NA
360
375
120
NS
NS
NS
NS
NS
96
90
89
57.
Nl
»«-
7 5
8 5
17 0
7 5
tt 6
9 6
21 6
NA
32 3
32
13
NS
NS
US
NS
NS
7 5
11 6
9 6
21%
Pb
at
6 2
20 4
87 5
19 6
18 5
16 9
77 3
NA
30 3
28 2
11 8
NS
NS
NS
NS
NS
19 6
18 5
16 9
7%
REVISED
2/26/92
Se
AA
0 22
0 22 U
0 22 U
0 22 U
0 22 U
0 22 U
0 22 U
0 22 U
0 78 U
l£
rC
2 71
0 22 U
2 35
2 35
87%
0 22 U
0 22 U
0 22 U
NA
Zn
>w
7 8
38 3
339 0
37 9
35 3
35 8
244 0
NA
128 3
138
±6
NA
NA
NA
NA
NA
37 B
35 3
35 8
4%
U - Below detection limit
NA - Not analysed
- Moan of Implicated samplu
NS - Not splkod
(1) NOTE MDLs lor XRF dulormlned using 15 (tips ol SUM Duluclion limits
liblud loc Individual samples aiu actual liiMiuimml Uutuclion I will:, (HJIs)
(2) NOTE. All mulals dala ib blank couutluJ
-------
CO
en
SAIC GLNPO (CF »361)
PAH IN UNTREATED SEDIMENT
1 ow Moloculnr Wolnhl PAHi (HQ/O *y wnlgtil)
SOIL TECH
Nnphlhuloiw Aconiiplilliyloiio Aconnphlhoiio
MSL Cod* 3|>oiuior ID
3fll-ia, Rop t B US ST. Rop t
381-18. Mop 2 B US ST, Rup 2
301-18. Rop 3 B US ST. Rup 3
361-18 1 US ST
Molhod Blank 0
STANDARD REFERENCE MATERIAL
8RM NI3TI041
ctrlllUd vilu*
MATRIX SPIKE RESULTS
Amount Spiked
361 IB 1
381-18 + Spike
Amount Rocovoiod
Potconl Rocovory
REPLICATE ANALYSES
361-18, Rop 1 B US ST, Rop 1
361-18. (top 2 B US SI. Hup 2-
381 18. Hop 3 B US ST. Mop 3
ieo%
70
87
100
4108
40 U
364
hC
7602
00
2020
1022
26% '
70
87
160
54%
00 U
37 U
40 U
2050
60 U
64
N2
7602
66 U
3826
3020
60V.
00 U
37 I)
40 U
41%
101 U
06
02 U
4014
72 U
00 U
M:
7602
03 U
4167
4167
64V.
101 U
OS
02 U
24%
Revised
2/12/92
Fluoruno Plioniinlhrona Anlhinconu
144
140
102
4424
64 U
63
NC
7002
160
6033
6076
70V.
144
140
102
13%
1040
000
1057
15023
42 U
660
577
7602
1035
7782
6727
or/.
1040
ooa
1057
3%
604
648
646
4050
47 U
164
202
7602
661
7207
6846
oa%
504
548
545
9%
t ' Moan ol Ulplloalud lumplo
U . Oulow dolucllon Ilinlli
NC . Not codlllod
- Valuo oulalda ol Inluinul QC llmlu (40 120%)
-------
SA1C OLNPO (CF »36I)
PAH IN UNTREATED SEDIMENT
Hlqh Maliiciilm Wnlnlil PAIIt (nq/q (try wulqhl)
MSI Coclu Sponsor 10
361-18. Rup 1 B US ST, Hep 1
361-18, Hop 2 B US ST, Hap 2
361-18, Hap 3 B US ST, Hup 3
361-10 i-us-sr
Malhod Blank 6
STANDARD REFERENCE MATERIAL
SRM NISTI041
_^ ctrlllUd vilut
CO
05 MATRIX BPIKE RESULTS
Amount Splkod
361-18 «
391-18 t Splku
Amounl Rocovoiud
Puicunl Rucovury
REPLICATE ANALYSES
301-18. Rup 1 B US ST. Rup 1
331-13, Hup 2 Q US ST, Hup 2
391-18, Hop 3 B US ST, Hop 3
HUTU.
Fluoiun-
UlilMU
1734
1436
1417
33062
32 U
1114
1220
7802
1620
0660
0031
104V.
1734
J438
1417
12%
Py(an«
SOIL TECIt
Bomo(a)
Cliiyaunu
FUvliOd
2/12/02
Indono
Baruo(b)- Bumo (k)- Uoiuo(u) (1.2.3.cd)- Olboruo(a li>- Buiua(g.li.l)
QlilliidCiliHi lluoi.mllionu MiioiunlluliMi
1628
1347
1336
30807
33 U
1034
IOBO
7602
1437
0006
7580
00%
1620
1347
1336
12%
744
620
607
10030
32 U
481
650
7602
663
6002
0220
10/%
744
620
607
12%
670
733
674
26130
31 U
703
to
7602
702
7403
8641
86%
070
733
674
14%
705
610
661
20043
23 U
766
700
7002
626
0046
7421
00%
706
010
601
12%
506
413
307
13763
20 U
603
444
7002
436
6036
6400
03V.
600
413
307
14V.
pyiofm
61 7
543
404
20660
28 U
600
670
7002
651
7400
6057
00%
017
643
404
1 1%
pyiunu ttnihiucuiw purylonu
488
424
376
16162
24 U
408
660
7602
420
7701
7382
00%
400
424
376
13%
1 10
105
07
6637
30 U
141
to
7602
104
0360
0257
107V.
110
IOC
07
6V.
382
327
207
14472
23 U
421
518
7602
336
6601
6256
61V.
302
327
207
13%
I • Muun ol Ulpllculud imnplu
U - Dulow dulucllon Ilinlli
NC . Not collided.
- Valua uulaldo ol Inlumul QC llmlu (40 120"/.)
-------
SMC GLNPO (Cf »361)
PAIt IN UNTREATED SEDIMENT
SOIL TECH
Rovlsod
21 I 2/92
MSLCodo
Sponsor ID
SunofliiUi Rncovniy V.
DO Nuph- DlO Aconuph-
Iliiiloiui Ilialono
D12 Porylonu
361-16. Hop I
361-18. Rap 2
361 18. Hop 3
361-16
B US ST, Rop I
B US ST. Hop 2
B US ST, Rop 3
i-us-sr
21% *
18% •
45%
37% '
39% '
46%
60%
67%
100%
105%
01%
06%
Molhod Blank- 0
20% •
30%
60%
STANDARD REFERENCE MATERIAL
SHM NIST1041
20% •
47%
74%
O3
-g
MATRIX &PIKE RESUL18
381-18
391-16
SpIKo
20%
26%
61%
66%
102%
00%
REPLICATE ANALYSES
B US ST. Rop 1
D US ST. Hop 2
BUS Sf, Hop 3
301-18, flop 1
361-18. Hop 2
361-16, Rep 3
• • Valu* outelde of Internal QC llmllt (40-120%)
NA « Nut nppllcutlo
2t% '
10% •
45%
53%
30% '
40%
60%
30%
109%
105%
or/.
8%
-------
CO
CD
SAIC GLNPO (CF »38I)
PAH IN TREATED SEDIMENT
low Mgjociilnr Wulph! PAH; |nq/g dry wl)
SOIL TECH
2/12/02
MSI Coda Sponsor 10
381-14 B-TS-ST-H
381-16 I-TS-ST-R
381 18 B-TS-ST-C
381 17 1 TS SI C
Molhod Blank 6
STANDARD REFERENCE MATERIAL
SRM NIST1041
ctrlllUd vilu*
MATRIX BPIKE RESULTS
Amount Splkod
301-10
381-18 * Splhu
Amount Rocovorod
Porcunl Rucovury
Amount Splkod
381-18
301-18 + Splko DUP
Amount Rooovurod
Poiconl Rucovory
Nuphlhuluno Acumiphlliyliino Ac<>iui|>lilliuiio
J 7 U
27
12U
1 1 1
40 U
364
NC
2302
12 U
006
066
40%
2600
12 U
1128
1128
46V.
22 IJ
17 U
16 U
10 U
60 U
54
rc
2302
1C U
1260
1260
6J%
2600
16 U
1277
1277
61%
20 U
21 U
10 tl
24 U
72 U
60 U
hC
2302
10 U
1220
1220
61%
2600
10 U
I20E
1206
61%
FluoruiKj Plmrturilhruiio AnUirnciinu
26 (1
20 1)
10 U
25
64 U
63
NO
2302
10 U
1430
MOO
00%
2600
10 U
1620
1620
01%
17 U
26
16
125
42 U
550
577
2302
16
1770
1704
74%
2600
16
2000
2074
UJV.
21 U
ia u
1 4 U
25
47 U
164
202
2302
1 4 U
2030
2030
OG%
2600
1 4 U
2462
2<162
UD%
U - Bolow dolocllon Ilinlla
NC - Not corllllud
• - Valuu oulsldu Internal QC limit! (40 120%)
-------
SAIC QLNPO (CF »381)
PAH IN TREATED SEDIMENT
SOIL TECH
Ravliod
2 / I 2 / U 2
MSL Coda
Sponsor ID
Fluor an-
lliune
Pyrana
Bonjo(a)
anlluacoriu
Chryaona
Bonio(b)-
Mtioiiinllionu
Bonzo (k)-
Ihioniiilhoiio
Bonio(a)-
pytonu
Indono
pyionu
Olbomo(a h)-
anlhrncuno
Bonto(a h.l)
porylunu
CD
361-14
361-16
361-16
381-17
B-T3-ST H
I-TS-ST-H
B-TS-&T-C
I-TS-ST-C
Malhod Blank 6
STANDARD REFERENCE MATERIAL
SRM NIST1841
vilu*
MATRIX SPIKE RESULTS
Amount SplKod
361-16
361-16 t Splka
Amount Rocovotod
Puiconl Racovory
Amount Splkod
381-16
381-16 t Splka DUP
Amount Rucouurud
Percent Recovery
32 U
It 14
2302
11 u
2408
2408
104%
2500
I 1 U
3255
3255
1 J0% '
33 U
1034
1000
2302
11 U
2383
2363
00%
2600
11 U
3005
3005
124% '
10 U
14 U
13 U
16 U
32 U
481
6SO
2302
13 U
2760
2780
110%
2500
13 U
3676
3076
155% '
16 U
12 U
11 U
14 U
31 U
703
NC
2302
1 1 U
2240
2240
04%
2500
11 U
3163
3163
127% *
16 U
11 U
10 U
13 U
23 U
708
700
2302
10 U
2641
2641
110%
2600
10 U
3750
3750
150% *
12U
0 U
8 U
10 U
20 U
603
444
2302
0 U
2202
22U2
ou%
2500
0 U
3150
3150
1 26% '
18 U
12 U
1 t U
14 U
28 U
600
070
2302
1 1 U
2306
2306
100%
2500
1 1 U
3356
3358
134V. '
14 U
1 1 U
to u
12 U
24 U
400
600
2302
10 U
2642
2642
110%
2600
10 U
3004
3804
152% •
16 U
12 U
10 U
14 U
30 U
141
hC
2302
10 U
2030
2030
1 2 J% '
2600
10 U
4254
4254
170% '
23 U
421
616
2302
0 U
2100
2100
02%
2500
8 U
3154
3154
126% '
U . Billow doiocilon llmli*
NC - Nol oodlllod
• . Valuu oulildo Inlomul QC Ilinlli (40-120%).
-------
SAIC QLNPO (CF *36I)
PAH IN TREATED SEDIMENT
MSLCoda Sponioi ID
381-14 B-TS-8T R
381-18 1 T3 ST-R
381-18 B-TS-ST-C
381-17 I-T3-8T-C
Molhod Blank 8
BTANDAHD REFERENCE MATERIAL
SRM NIST1841
MATRIX SPIKE RESULTS
381-18
381 18 t Splka
381-18
391-18 * SpIKo DUP
SOIL TECH
flovliod
21 1 2/92
SurtoQnto Rocovory •/.
08 Noph- 010 Aconnph-
Ihulono llialuno
10% • 27% '
63% 78%
65% 60%
43% 60%
20V. ' 38V. '
20% ' 47V.
65% 68%
42% 6-1%
65% 86%
47% 63%
012 Porylono
60%
30%
113%
77%
60%
74%
113%
1 00%
113%
144%
• . Vnluoi ounldo ol Inlornol QC llmlli (40 120V.)
NA - Not applicable
-------
SAIC GLNPO (CF »301)
PAH IN WATER
low Moloculnr WolQhl PAHl (nn/L)
M3L Coda Sporwor ID
301-20 B WR-ST
301-21 1 WR-ST
Molhod Blink 7
MATRIX SPIKE RESULTS
Amounl Spiked
Blank-7
Blank 7 . Splko
Amount Rocoverod
Puicenl Recovery
Nnphlhnlono
1131040 D
401814 D
260 U
26000
260 U
0047
6047
36V. '
SOIL
AconuphUiylono
00007 D
107200 D
276 U
26000
276 U
10024
10024
40Y.
TECH
Aconiiphlhnno
07600 D
106607 D
306 U
26000
306 U
10260
10260
41V.
Fluorono
104647 D
nooeo D
340 U
26000
340 U
11000
1 1808
47V.
Phonnnlhrono
201400 D
203333 D
230 U
26000
230 U
16202
16202
a iv.
Reviled
2/12/02
Amhmcono
130330 D
120163 D
260 U
26000
260 U
10041
16041
6U%
D - Sample axlracl diluted 1:10 and re run
U - Below dolecllon limits.
NC - Not corllllod
• - Value oulilde ol Inlornal QC llmlli (40-120%)
-------
SAIC QLNPO (CF 1381)
PAH IN WATER
Hlflh Molecular Wojohl PAM« (mi/Q dry wol(jhl>
MSL Cod* Sponsor 10
381-20 B-WR-ST
381-21 I-WH-ST
Molhod Blank 7
MATRIX SPIKE RESULTS
Amount Splkad
Blank-7
Blank 7 t Splka
Amount Rocovuiod
Puiconl Rucovary
Fluor nn-
Ihono
132786 0
261017 D
176 U
26000
176 U
22732
22732
01%
Pyrono
110501 D
230400 0
181 U
25000
181 U
22303
22303
00%
BOIL TECH
Bonio(a)-
nillhiaCOIH)
42842 0
102064 D
177 U
25000
177 U
28433
28433
106%
Chryiono
64133 D
134048 D
171 U
25000
171 U
24443
24443
OU%
Oomo(b)
Itiioinnlliano
38214
00000
127
25000
127
24360
24360
07%
Incluno
Boruo(k) Bonio(u)- (I.Z.l.c.d)- Dlbomo(a.ti)-
Iliiorunihono
D 1B5180
D 61817 D
U 1 1 1 U
25000
U 1 11 U
22607
22607
00%
pyioito
30003 0
73060 0
143 U
25000
143 U
23230
23230
03%
pyionu
1004 0
30052 D
131 U
25000
131 U
23847
23847
06%
BriUirucimo
2173 0
12300 D
188 U
25000
188 U
30176
30)76
121% *
n»vlt«d
21 1 2/02
Banio(o.li.l)-
poiylono
12882 06
27002 DO
142
25000
142
221 17
21076
Ou%
D - 8«mpl» •xlraci diluted 1:10 and ro-run.
B - Analyle dotoctod In blank ui loclalod wim »amplo
U « Bolow dolocllon llmll*
NC - Not carlllled
• . Value oultldo ol Imornal QC llmlti (40 120%)
-------
-
co
SAIC QLNPO (CF »381)
SOIL TECH
Revised
211 2/02
PAH IN WATER
MSLCodu
301-20
301-21
Sponsor 10
Simoqnlo Recovery %
D8 Naph-
Ilialunu
B-WR-ST 8)2%
I-WH-ST 126V.
010 Aconaph-
Ihalono
118V.
13<% '
012 Poiylone
67%
100%
Molhod Blink-7
10% '
00%
Bl«nk 7
Dlank-7 •» Spike
18% '
22% '
10% '
27% '
00%
00%
' - Vilu* oulildo ol Inlomal QC llmlli (40 120%)
NA - Not applicable
-------
SAICGLNPO (CF »361)
PAH IN OIL
Low Molecular Wukjhl PAHs (no/ml)
Sample
MSL Coda Sponsor ID Density (a/ml)
361-22 R B-OR-ST 05731
361 23, Rop 1 1 OR ST. Rap t 0 9120
361 23. Hop 2 lORSf. Rop 2 09120
36123. Rep 3 1 OR ST. Hap 3 09120
Mothod Blank 1
Molliod Blank R
OIL CONCENTRATIONS ON X OIL BASIS
low Molecular Weight PAHs (ug*q oil)
•/. on
MSL Code Sponsor ID (%)
361-22 R B-OR-ST 1 38
361 23, Rep 1 1 OR ST. Rep 1 3 06
36123. Rep 2 IORST. Rup 2 306
361 23, Rep 3 1 OR ST. Hup 3 306
MATRIX SPIKE RESULTS
Amount Spiked
361 22 R
35! 22 < SplK.s
Amount Recovered
Percent Rocovary
REPLICATE ANALYSES
361-23. Rep 1 1 OR ST. Rep 1
361 23, Rep 2 1 OR ST. Hop 2
361 23. Hep 3 1 OR ST. Hop 3
RSO%
SOIL TECH
Naphthalene
17581
47100
57400
30500
11178 LI
370 U
Naphthalene
2225494
1688172
2057348
1093100
50000
17581
75400
57819
lib"/.
47100
57400
30500
30%
Acenaphlhylone
720
3580
3590
2820
1902 U
397 U
Acenaphlhytene
91182
128315
128674
101075
SOOOO
720
39800
39080
78%
3580
3590
2820
U%
Acenaphlhene
632 U
4240
4050
3350
2675 U
559 U
Acenaphlhene
80009
151971
145161
120072
50000
632 U
40400
40400
81%
4240
4050
3350
12%
Fluor one
5150
22900
21100
20700
2241 U
468 U
Fluor ene
651849
820789
756272
741935
50000
5150
55100
40950
100%
22900
21 100
20700
9'/.
Phonanlhrene
14371
49800
44500
47900
1312 U
274 U
Phenanthrene
1819101
1784946
1594982
1716846
50000
14371
71000
56629
1 1 3%
49800
44500
47900
&•/.
Revised
2/24/92
Anthracene
4334
17400
15500
16900
1489 U
311 U
Anthracene
548619
623656
555556
605735
50000
4334
47200
42866
867.
17400
15500
16900
6Y.
R - Re extracted sample ruMilb
U - Bulow dutuclion limits
• . Value outside ol inlurnal QC limits (40 120%)
-------
-p.
tn
SAIC GLNPO (CF i361)
PAH IN OIL
High Molecular Weight PAHs (rig/ml)
SOIL TECH
Sample
Donaly
MSL Code Sponsor ID (g/inl)
36122 H BOHST 0
361 23, Rep t 1 OR ST, Rep 1 0
361 23, Rep 2 (ORSr, Hop 2 0
361 23. Rep 3 1 OR ST, Hep 3 0
Method Blank- 1
Method Blank R
5731
9120
9120
9120
Fliwraii
Ihuiio
5810
30800
27100
28400
898 U
187 U
Pyrene
4963
31500
27700
26900
895 U
187 U
Benzo(a)-
anlhiacone
2203
23700
20800
21400
845 U
176 U
Chrysene
Benzo(b)-
Benzo (k)-
Duoranlhene luoranlhuoe
3216
27900
24400
25200
805 U
168 U
2614
23500
20500
20700
645 U
135 U
360
10200
9160
9300
529 U
110 U
Benzo(a)-
pyrene
954
17500
15300
15600
688 U
144 U
Indeno Dibonzo
(l.2,3.c.d) (a.h)dnlhra-
pyiene
451
6480
8300
6440
707 U
148 U
cene
172
5300
4460
4710
694 U
145 U
R*vls»d
2/26/92
Benzo(g.h.l)-
perytone
377
10400 B
9190 B
9410 B
1430
83 U
OIL CONCENTRATIONS ON % OIL BASIS
Hlqh Molecular Weight PAHs (ug/kgotl)
•/.Oil
MSL Code Sponsor ID
361 22 R B OR ST
361 23. Rep 1 1 OR ST, Rep t
361 23. Rep 2 1 OH ST. Rep 2
361 23. Hep 3 I-OH-ST. Hop 3
MATRIX SPIKE RESULTS
Amounl Spiked
361 22 R
361 22 t Spike
Amounl Recovered
Percent Recovery
REPLICATE ANALYSES
381 23, Rep t 1 OR ST. Rep 1
361 23. Hep 2 1 OR ST. Rep 2
361 23. Hep 3 1 OH ST. Rep 3
RSD%
1*1
1 3b
306
306
306
Fluoian
Ihune
73S400
1103043
971326
1017921
60000
5810
69200
53300
10/%
30800
27100
28400
T-/.
Pyrene
628214
1129032
992832
1035842
50000
4963
56400
51437
10J%
31500
27700
26900
TV-
Benzo(a)-
anthracena
278923
848462
745520
767025
60000
2203
56000
53797
108%
23700
20800
21400
TV.
Chrysene
407053
1000000
874552
903226
SOOOO
3216
53500
50284
101%
27900
24400
25200
/%
Benzo(b)-
fluoranlhene
330892
842294
734767
741935
50000
2614
50300
47686
95%
23500
20500
20700
U;'_
Benzo (k)-
luoranihene
45601
365591
328315
333333
60000
360
45200
44840
90%
10200
9160
9300
O;',
Beruo(a)-
oyrene
120782
627240
548387
559140
50000
954
47300
46346
93%
17500
15300
15600
7%
Indeno
(1.2.3.c.d)
pyrena
57111
339765
297491
302500
60000
451
46300
45840
92%
9480
8300
8440
7%
Dlbenzo
(a.h) anthra-
cene
21785
189964
159857
168817
50000
172
60100
58028
118%
5300
4460
4710
IM.
B0lUO(g.h.l)-
perytena
47671
372760
320301
337276
60000
377
43300
42923
86%
10400
9190
9410
A/.
R - Re exlractud tamplu rusulls
U - Aiulylu dutuclud In inulhud lilanh dbsoclalod will) l>jiu|ilu
I) - Bulow duluulon Iliniis
• - Valuo oulsldo ol Inkirnal QC limits (40
-------
SAIC GLNPO (CF »36I)
SOIL TECH
Revised
2/24/92
PAH IN OIL
MSLCoda
Sponsor ID
Surrogate Recovery %
08 Naph- 010 Acenaph- 012 Petylene
Itialone lhalene
38122 R
361 23. Rep 1
361 23. Rep 2
361 23, Rep 3
Mulhod Blank 1
Meltiod Blank R
B-OR-ST
I OR ST. Rep 1
I OR ST. Rep 2
I OR ST. Rep 3
29%'
35% '
41%
22%'
60%
35% '
36%'
58%
64%
45%
64%
42%
79%
121% '
103%
106%
73%
49%
OIL CONCENTRATIONS ON % OIL BASIS
MSL Code
Sponsor ID
Surrogate Recovery %
08 Naph- 010 Acenaph-
thalone thalone
012 Perylene
361 22 R
361 23. Rup 1
361 23. Rep 2
361 23. Rep 3
B OR ST
I OR ST. Rep 1
I OR ST. Hop 2
I OR ST, Hop 3
MATRIX SPIKE RESULTS
29% •
35% •
41%
22% •
36% '
58%
54%
45%
79%
121% '
103%
106%
361-22
361 22
R
• Spike R
29% '
69%
36% '
78%
79%
87%
REPLICATE ANALYSES
361 23. Rep 1 I OR ST. Rep 1
361 23, Rop 2 I OH ST. Hop 2
361 23. Rep 3 I OR ST. Hop 3
RSD%
R - Re extracted sample rusiills
• - Value oulsido ol Internal QC limits (40 120%).
NA - Not applicable
35% '
41%
22%
30%
58%
54%
45%
13%
121%
103%
106%
91/.
-------
RE-PROCESSED RESULTS (1/92)
PCBs IN UNTREATED SEDIMENT
Concentrations in ug/kg dry wuighl
SOIL TECH
SAIC GLNPO (CF #361)
2/12/92
MSL Code Sponsor ID
361-18. Rep 1 B US ST. Rep 1
361-18. Hop 2 B-US-Sr. Hop 2
361-18, Hop 3 11 US-Sf. Hop 3
361-19 IUS-SF
Blank-5
STANDARD REFERENCE MATERIAL
SRM-3 (MS 2)
certified value
MATRIX SPIKE RESULTS
Amount Spiked
361-18 #
361-18 + Spike
Amount Recovered
Percent Recovery
Amount Spiked
Blank-5
Blank-5+ Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-18. Rep 1 B US ST. Rep 1
361-18. Rep 2 BUS SI. Hep 2
361-18. Rep 3 BUS ST. Hop 3
RSD%
Aroclor
1242
200 U
200 U
200 U
200 U
200 U
40 U
N3
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
200 U
200 U
200 U
0%
Aroclor Aroclor Aroclor
1248 1254 1260
329 100U 100U
320 100 U 100 U
365 100 U 100 U
10728 100 U 100 U
200 U 109 100 U
40 U 69 E 20 U
N3 111 N3
NS 7692 NS
NS 100 U KB
NS 6262 NS
NS 6262 NS
NS 81% NS
NS 5000 NS
NS 109 NS
NS 3846 NS
NS 3737 NS
NS 75% NS
Tetrachloro- Oclachloro-
m-Xylene naphthalene
71.0% 97.6%
82.3% 95.7%
83.7% 84.4%
91 .5% 69.9%
90.7% 83.8%
65.2% 93.7%
N3 N3
NA NA
79.0% 92.6%
121.8%' 89.9%
NA NA
NA NA
NA NA
90.7% 83.8%
91 .5% 80.6%
NA NA
NA NA
329 100U 100U 71.0% 97.6%
320 100U 100U 823% 95.7%
365 100U 100U 83.7% 844%
7% 0% 0%
9% 8%
U = Below detection limits
E = Value estimated, no rocognuable Aroclor patlurn
NC = Not corliliod
U - Moan ot replicated sainplu
* - Vdluo oulbidu mlumal GC Inmlb (40 120%)
NS - Not i>pikod NA - Nol u(i()lii-jl)lo
-------
co
RE-PROCESSED RESULTS (1/92)
PCBs IN TREATED SEDIMENT
Concentrations In ug/kg dry weight
SOIL TECH
SAIC GLNPO (CF #361)
2/12/92
% Surrogate Recovery
MSL Code Sponsor ID
361-14 B-TS-ST R
361-15 1 TS-ST-R
361-16 B-TS-ST-C
361-17 1 TS-SF-C
Blank-5
STANDARD REFERENCE MATERIAL
SRM3 (IIS-2)
certified value
MATRIX SPIKE RESULTS
Amount Spiked
361-16
361-16 + Spika
Amount Recovered
Percent Recovery
Arnouni Spiked
361 16
361-16 + Spike DUP
Amount Recovered
Percent Recovery
Aroclor Aroclor Aroclor Aroclor
1242 1248 1254 1260
200 U
200 U
200 U
200 U
200 U
40 U
hC
NS
NS U
NS U
he
NS
NS
NS
NS
NS
NS
200 U 100 U 100 U
200 U 100 U 100 U
200 U 100 U 100 U
200 U 100 U 100 U
200 U 109 100 U
Tetrachloro- Octachloro-
m-Xylene naphthalene
45.7% 92.2%
86.8% 80 2%
81 .7% 85.6%
75.2% 76.4%
90.7% 83.8%
40U 69E 20U 65.2% 93.7%
N3 111 hC
NS 2392 NS
N3 NC
NA NA
200 U 100U 100U 81.7% 85.6%
200 2111 NS
NS 2111 NS
NS 88% NS
hS 2500 NS
NS 100 U NS
NS 2813 NS
NS 2813 NS
NS 113% NS
68 6% 86.6%
NA NA
NA NA
NA NA
81 .7% 85.6%
76.3% 117.7%
NA NA
NA NA
U = Below detection limits.
E = Value estimated, no recognizable Aroclor pattern.
NC = Not certified
NS = Not spiked
NA = Not applicable
-------
(D
RE-PROCESSED RESULTS (1/92)
PCBs IN WATER
Concentrations
MSI.
361-20
361-21
Code
(D)
(D)
In ug/L
Sponsor ID
B WR-ST
I-WH-ST
SOIL TECH
SAIC GLNPO (CF #361)
Aroclor Aroclor Aroclor Aroclor
1242 1248 1254 1260
2 U 66 CE 1 U 1 U
2 U 64 CE 1 U 1 U
REVISED
2/26/92
% Surrogate Recovery
Tetrachloro- Octachloro-
m-Xylene naphthalene
N/A (1) N/A
N/A N/A
0 2 U
02 U
Blank-2
MATRIX SPIKE RESULTS
Amount Spiked
Blank-2
Blank-2 + Spike
Amount Recovered
Percent Recovery
D =» Samples diluted 1:20 and re run.
E " Values calculated based on external standard method.
Due to RT drift and lack ol STDS, only one peak per aroclor was quantified.
N/A - Not available.
(1) Due to dilution and RT drill, surrogates were not quantifiable.
U m Below detection limits.
NS - Not spiked.
NA = Not applicable.
* = Value outside of Internal QC limits (40-120%).
0 1 U
0.1 U
22 4%
191.1%
NS
N3
NS
NS
NS
NS
NS
NS
NS
NS
50.0
72.0
0 1 U
72 0
144%
NS
NS
NS
NS
NS
NA
22 4% '
35.8% *
NA
NA
NA
191.1%
143.7%
NA
NA
-------
en
o
RE-PROCESSED RESULTS (1/92)
PCBs IN OIL
Concentrations In ug/L
MSL Coda
361-22
361-23.
361-23,
361-23,
Blank-1
Rep 1
Rep 2
Hep 3
Oil
Sponsor ID
B-OR ST
I-OR-ST. Rep 1
I OR ST. Rep 2
I-OR-ST. Hep 3
Sample
Density (g/ml)
0 5731
0 9120
0.9120
0 9120
Aroclor
1242
2000
2000
2000
2000
2000
U
U
U
U
U
SOIL TECH
SAIC GLNPO (CF #361)
Aroclor
1248
2000 U
2392
2044
2080
2000 U
Aroclor
1254
1000
1000
1000
1000
1000
U
U
U
U
U
Aroclor
1260
1000 U
1000 U
1000 U
1000 U
100 U
% Surrogate
Tetrachloro-
m-Xylene
60 6%
81.1%
70.4%
75.7%
48 6%
REVISED
2/26/92
Recovery
Oclachloro-
naphlhalene
1128%
105.6%
88.7%
91.8%
96.7%
PCB CONCENTRATIONS ON % OIL BASIS
Concentrations In ug/kg oil
MSL Coda
361 22
361-23, Rep 1
361-23. Rep 2
361-23. Rep 3
Sponsor ID
B OR ST
I-OR-ST. Rep 1
I OH ST, Rep 2
I-OR-ST. Hop 3
% Oil
(%)
1 38
3.06
3.06
3 06
Aroclor
1242
2531650
71685 U
716850
71685 0
Aroclor
1248
253165 U
85720
73247
74552
Aroclor
1254
1265B2U
358420
358420
358420
Aroclor
1260
% Surrogate
Telrachloro
m-Xylene
1 26582 U 606%
358420 ai.1%
35842 VJ 70.4%
35842 O 75.7%
Recovery
Oclachloro-
naphthalene
1128%
105.6%
88.7%
91.8%
MATRIX SPIKE RESULTS
Amount Spiked MS NS 50000 NS NA
361-22 NS NS 1000 U NS 599%
361-22 + Spike NS NS 42895 NS 96.3%
Amount Recovered NS NS 42895 NS NA
Percent Recovery NS NS 86% NS NA
REPLiCATE ANALYSES
361-23. Rep 1 I-OR-ST, Rep 1 2000 U 2392 1000 U 1000 U 81.1%
361-23. Rep 2 I OR ST. Rep 2 2000 U 2044 1000 U 1000 U 70.4%
361-23, Hep 3 I-OR ST, Hop 3 2000 U 2080 1000 U 1000 U 75.7%
RSD% NA NA NA NA 7%
U - Below detection limits
NS = Not spiked.
NA = Not applicable.
= Value outside ol inlumal QC limits (40-120%)
NA
124.4%
88.8%
NA
NA
105.6%
88.7%
91.8%
9%
-------
SAIC GLNPO (CF *361)
CONVENT1ONALS IN UNTREATED SEDIMENT
SOIL TECH
ADDENDUM
2/14/92
MSLCode
361-25. Rep t
361 25, Rep 2
361 25, Rep 3
Sponsor ID
SAND. Rep 1
SAND, Rep 2
SAND. Rep 3
% Moisture
1 51%
1 00% U
1.42%
% Total
pH Volatile Solid
5 68
5.B5
5.77
006%
NA
NA
Oil & Grease
(mg/hg)
250
297
264
IDC Total Cyanide Total Phosphorus
% weight (mg/kg) (mg P/kg(
001% U
NA
NA
0.1 U
0.1 U
0.1 U
10
1 1
9
Method Blank
NA
6.06
0%
1.1
0.009%
0.004 U
0.036
STANDARD REFERENCE MATERIAL
MESS 1 SHM NA NA NA
In house Concensus Value ' NA NA NA
REPLICATE ANALYSES
361 25. Rep 1
361 25, Hep 2
361 25. Rep 3
NA
NA
2 2
2 3
NA
NA
NA
NA
RSD%
1 51%
1 00% U
1 42%
4%
5.68
5 85
5 77
1%
0 06%
NA
NA
NA
250
297
264
9%
001% U
NA
NA
NA
0.1 U
0 1 U
01 U
0%
10
11
9
10%
NA - Not analyzed
U = Below detection limit
-- TOC value lor MESS determined based on past In house analyses.
NOTE: All Conventional results aru reported on a dry weight basis.
Not a statistical determination.
-------
SAIC GLNPO (CF »361)
METALS IN UNTREATED SEDIMENT
(Concentrations In ug/g dry weight)
Ag As Ba Cd
MSLCode Sponsor ID AA NF »r AA
MX 0007 25 43 0006
361-25 SAND 0 007 U 0 80 U 79U 0.01
Method Blank 0 020 NA NA 0 006 U
STANDARD REFERENCE MATERIAL
1646 SRM 0 114 112 425 0 401
cirlllltd tC 1)6 N3 0 36
valuo tC 11 3 1C 1007
Ol
to
SOIL TECH ADDENDUM
2/14/92
Cr Cu %Fe Hg Mn Nl Pb
Of Mf Hf CVAA «H- WF Xtf
33 55 026 00003 56 75 62
12 U 651 006 0.0003 U 113 1811 1.7U
NA NA NA 000133 NA NA NA
71 166 333 0065 349 311 295
76 18 3 35 0 063 375 32 28 2
13 13 101 10012 120 13 It B
So Zn
AA ttf
0 22 78
0 22 U 5 33
0 22 U NA
087 124
1C 138
hC 16
U - Below detection limits
NA - Not analyzed
NC - Not ceitlllod
NOTE: All metals results are blank corrected
-------
SAICGLNPO (CF 1361)
PAH IN UNTREATED SEDIMENT
Low Molecular Weight PAHs (nq/9 dry welghl)
MSL Code Sponsor ID
361-25 SAND
Blank a
STANDARD REFERENCE MATERIAL
SHM NIST1B41
ctrlllUd vilu*
SOIL TECH ADDENDUM
2/14/92
Naphthalene Acenaphlhylone Acanaphthene Fhiorene Phenanlhiene Anthracene
165U 199 U 304 U 261 U 177U 194U
193 U 232 U 355 U 305 U 206 U 226 U
871 190 U 291 U 250 U 521 I85U
hC N2 r-C N3 577 202
tn
CO
U - Below detection limits
NC - Not certified
* - Value outside ol Internal QC limits (40 120%)
-------
RE-PROCESSED RESULTS (1/92)
SOIL TECH
PCBs IN UNTREATED SEDIMENT SAIC GLNPO (CF #361 )
Concentrations in ug/kg dry weight
Aroclor Aroclor Aroclor Aroclor
MSLCode Sponsor ID 1242 1248 1254 1260
361-25 SAND 200 U 200 U 100 U 100 U
Blank-8 200 U 200 U 100 U 100 U
STANDARD REFERENCE MATERIAL
SRM-7 (HS-2) 200 U 200 U 221 100.0 U
certified value N3 N3 111 (s£
ADDENDUM
2/14/92
% Surrogate
Recovery
Telrachloro-
m-Xylene
87.0%
102.1%
84.7%
NC
U = Below detection limits
NC = Not certilied
-------
Oeatfeiie
Pacific Northwest Division
Marine Sciences Laoorjior^
439 West Sequim Bjv Koou
Scouim Wjsninuion OUjaJ
12061 683-4151
April 6, 1992
Ms. Evylyn Hertzell
SAIC
635 W. 7th Street
Cincinnati, Ohio 45203
Dear Evylyn:
Enclosed are revised PCB and PAH data tables for the oil samples from the Soil
Tech project. The density values were re-measured and the value for B-OR-ST
appears to have been incorrect on the original tables. A slightly different
value for I-OR-ST is also provided; however, it is not significantly different
from the original data reported.
If you have any additional comments or questions, please call me at 206/681-
3654.
Sincerely,
Lisa F. Lefkovitz
Research Scientist
rat
Enclosures
Twenty-five yean ofscjence
for OOt ata the Atonftwesr
155
-------
01
05
SAIC GLNPO (CF »361)
PAH IN OIL
Low Molecular Weight PAHs (ng/ml)
Sample
MSL Code Sponsor ID Density (g/ml)
361 22 R B OH ST 1 17
361 23. Rep 1 1 OR ST. Rep 1 1 13
361 23. Rep 2 1 OH ST. Hop 2 113
361 23, Rep 3 1 OH ST. Hop 3 1 13
Method Blank 1
Method Blank R
OIL CONCENTRATIONS ON % OIL BASIS
Low Molaculai Weigh! PAHs (ug/kg oil)
%Oll
MSL Code Sponsor ID (%)
361 22 H B-OR-ST 1 38
361 23, Hep 1 1 OR ST, Rep 1 3 06
361 23, Rep 2 1 OH ST. Hop 2 306
361 23. Rep 3 1 OR ST. Rep 3 306
MATRIX SPIKE RESULTS
Amount Spiked
361 22 R
361 22 t Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361 23. Rep 1 1 OR ST. Rep 1
361 23, Rep 2 IOHST, Hop 2
361 23, Hop 3 1 OR ST, Hup 3
HSO%
SOIL TECH
Naphthalene
17581
47100
57400
30500
11178 U
370 U
Naphthalene
2225494
1688172
2057348
1093190
50000
17581
75400
57819
116%
47100
57400
30500
3O%
Acenaphlhylene
720
3580
3590
2820
1902 U
397 U
Acenaphlhylene
01182
128315
128674
101075
60000
720
30800
39080
78%
3580
3590
2820
13%
Acenaphthene
632 U
4240
4050
3350
2675 U
559 U
Acenaphthene
80000
151971
145161
120072
50000
632 U
40400
40400
81%
4240
4050
3350
12%
Fluor ene
5150
22900
21100
20700
2241 U
468 U
Fluorene
651840
820789
756272
741935
50000
5150
55100
49950
100%
22000
21100
20700
9V.
Phenanlhrene
14371
49800
44500
47900
1312 U
274 U
Phenanlhrene
1810101
1784946
1594982
1716846
50000
14371
71000
56629
113%
40800
44500
47900
6%
R*vli«d
4/3/02
Anthracene
4334
17400
15500
16900
1489 U
31 1 U
Anthracene
548610
623656
555556
605735
50000
4334
47200
42866
86%
17400
15500
16900
ev.
R - Re extracted sample results
U - Below detection limits
-------
cn
•vl
SAIC GLNPO (CF »361)
High Molecular Weigh! PAHs (ng/ml)
Sample
Donsily
MSL Code Sponsor ID (g/tnl)
361 22 H B-OR-ST 1 17
361 23. Rep 1 1 OR ST. Rep 1 113
361 23. Rep 2 1 OR ST. Rep 2 113
361 23. Rep 3 1 OR ST. Rep 3 1)3
Method Blank 1
Method Blank R
OIL CONCENTRATIONS ON X OIL BASIS
High Molecular Weight PAHs (ug*g oil)
V. Oil
MSL Code Sponsor ID (%)
361-22 R B OH-ST 1 36
361-23. Rep 1 IOHST. Rep 1 306
361-23, Rep 2 t-OR-ST. Rep 2 3 06
361 23, Rep 3 1 OR ST. Rep 3 3 06
MATRIX SPIKE RESULTS
Amount Spiked
361 22 R
361 22 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-23, Rep 1 1 OR ST. Rep 1
361-23. Rep 2 1 OR ST. Rep 2
361 23, Rep 3 1 OR ST. Rep 3
RSD%
SOIL TECH
Fluorarv
Ihuiia
5810
30800
27100
28400
898 U
187 U
Fluoran-
Ihuno
735400
1103943
971326
1017921
SOOOO
S810
59200
53390
107%
30800
27100
28400
7%
Pyrene
4963
31500
27700
28900
895 U
187 U
Pyrene
628214
1129032
992832
1035842
50000
4963
66400
51437
103%
31500
27700
28900
7%
Beruo(a)
anthracene
2203
23700
20800
21400
845 U
176 U
Benzo(a)-
anthracene
278923
840462
745520
767025
60000
2203
56000
53707
108%
23700
20800
21400
7%
Chrysene
Benzo(b)-
Benzo (k)-
tluoranlhene fluoranlhene
3216
27900
24400
25200
805 U
168 U
Chrysene
407053
1000000
874552
903226
50000
3216
53500
50284
101%
27900
24400
25200
7%
2614
23500
20500
20700
645 U
135 U
Benio(b)-
Huoranlhene
330802
842294
734767
741935
50000
2614
50300
47686
95%
23500
20500
20700
8%
360
10200
9160
9300
520 U
110 U
Benzo (k)-
luoranlhene
45601
365591
328315
333333
50000
360
45200
44840
90%
10200
9160
9300
6%
Benzo(a)-
pyrene
954
17500
15300
15600
688 U
144 U
Beruo(a)
pyrene
120782
627240
548387
£59140
60000
054
47300
46346
93%
17500
15300
15600
7%
Indeno
(1.2,3.c.d)
pyrene
451
9480
8300
8440
707 U
148 U
Indeno
(1,2.3.c.d)
pyrene
57111
330785
207401
302509
SOOOO
451
46300
45840
92%
0480
8300
8440
7%
Dibenzo
a.h) anlhra-
cane
172
5300
4460
4710
694 U
145 U
Dlbenzo
(a.h) anthra-
cene
21785
189064
159857
168817
50000
172
50100
58928
118%
5300
4460
4710
9%
R*vli*d
4/3/92
Benzo(g.h,i)-
perylune
377
10400 B
0100 B
9410 B
1430
83 U
B»nzo(g.h.i)-
perylene
47671
372760
320391
337276
SOOOO
377
43300
42023
86%
10400
0100
0410
7%
R - Re-extracted sample results
U - Below doloction limits
-------
en
CO
SAIC GLNPO (CF
PAH IN OIL
MSLCoda
361-22 R
361-23, Rep 1
361-23, Rep 2
361 23, Rep 3
Method Blank- 1
Method Blank R
•361)
Sponsor ID
B-OR-ST
I-OR-ST.
I-OH-ST.
I-OH-ST.
Rep 1
Rep 2
Rep 3
SOIL TECH
R*vli*d
4/3/82
Surrogate Recovery %
08 Naph- 010 Acenaph-
Ihalene thalene
29% ' 36%'
35% ' 58%
41% 54%
22% ' 45%
60% 64%
35% * 42%
012 Perylene
79%
121%
103%
106%
73%
49%
OIL CONCENTRATIONS ON % OIL BASIS
MSL Coda
Sponsor ID
Surrogate Recovery %
08 Naph- 010 Acenaph
lhalene thalene
012 Perylene
361-22 R
381 23. Rep 1
361 23, Rep 2
361 23, Rep 3
B-OR-ST
I-OH-ST. Rep 1
I OR ST. Rep 2
I OH ST, Rep 3
29% '
35% '
41%
22% '
36%'
58%
54%
45%
79%
121% '
103%
106%
MATRIX SPIKE RESULTS
361 22
361 22
Spike R
29% '
69%
36% '
78%
79%
87%
REPLICATE ANALYSES
361-23. Rep 1
361 23. Rop 2
361 23. Rep 3
I OR ST. Rep 1
I OR ST, Rep 2
I OH ST, Rep 3
RSD%
35% '
41%
22% '
30%
58%
54%
45%
13%
121%
103%
106%
9%
R - Re extracted sample results
• - Value outside ol Internal QC limits (40-120%)
-------
en
to
RE-PROCESSED RESULTS (1/92)
PCBt IN OIL
Concentrations In ug/L
SOIL TECH
SAIC-GLNPO (CF #361)
REVISED
4/3/92
Sample
MSL Code Sponsor ID Density (g/ml)
361-22 B OR ST 1.17
361-23, Rep 1 I-OR-ST. Rep 1 1.13
361-23. Rep 2 I-OR-ST. Rep 2 1.13
361-23. Rep 3 I-OR-ST, Rep 3 1.13
Blank-1 Oil
PCB CONCENTRATIONS ON % OIL BASIS
Concentrations in ug/kg oil
%Oil
MSL Code Sponsor ID (%)
361-22 BOR-ST 1.38
361-23. Rep 1 1 OR-ST, Rep 1 3.06
361-23. Rep 2 I-OR-ST. Rep 2 3.06
361-23, Rep 3 I-OR-ST. Rep 3 3.06
MATRIX SPIKE RESULTS
Amount Spiked
361-22
361-22 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-23. Rep 1 I-OR-ST. Rep 1
361-23, Rep 2 I-OR-ST, Rep 2
361-23, Rep 3 I-OR-ST, Rep 3
RSD%
Aroclor
1242
2000 U
2000 U
2000 U
2000 U
2000 U
Aroclor
1242
253165
71685
71685
71685
NS
NS
NS
NS
NS
2000 U
2000 U
2000 U
NA
Aroclor
1248
2000 U
2392
2044
2080
2000 U
Aroclor
1248
253165
85720
73247
74552
NS
NS
NS
NS
NS
2392
2044
2080
NA
Aroclor Aroclor
1254 1260
1000 U 1000 U
1000 U 1000 U
1000 U 1000 U
1000 U 1000 U
1000 U 100 U
Aroclor Aroclor
1254 1260
126582 126582
35842 35842
35842 35842
35842 35842
50000 NS
1000U NS
42895 NS
42895 NS
86% NS
Tetrachloro-
m-Xylene
60.6%
81.1%
70.4%
75.7%
48.6%
% Surrogate
Tetrachloro-
m-Xylene
60.6%
81.1%
70.4%
75.7%
NA
59.9%
96.3%
NA
NA
1000U 1000U 81.1%
1000 U 1000 U 70.4%
1000U 1000U 75.7%
NA NA
7%
Oclachloro-
naphthalene
1 1 2 8%
105.6%
88.7%
91.8%
96.7%
Recovery
Octachloro-
naphthalene
112.8%
105.6%
88.7%
91.8%
NA
124.4% '
88.8%
NA
NA
105.6%
88.7%
91.8%
9%
U - Below detection limits.
NS - Not spiked.
NA « Not applicable.
= Value outside of internal QC limits (40-120%).
-------
APPENDIX F
QUALITY ASSURANCE/QUALITY CONTROL
In order to obtain data of known quality to be used in evaluating the different technologies for the
different 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 different technologies, the following measurements were identified in the QAPP as critical
- PAHs, PCBs, metals, total solids, oil and grease and volatile solids in the untreated and treated sediments.
Other parameters analyzed in the sediments included pH, TOO, total cyanide, and total phosphorus. If water
and oil residuals were generated by a technology, then polynudear aromatic hydrocarbons (PAHs) and
polychlorinated biphenyls (PCBs) were determined as a check on their fate resulting from in treating the
sediments. Each of these measurements and the associated quality control (QC) data will be discussed in
this section.
Also included in this section are a discussion of the QC results, modifications and deviations from
the QAPP, and the results of a laboratory audit performed. Any possible effects of deviations or audit
findings on data quality are presented.
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 section; specific results for accuracy and precision are summarized in later sections.
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 (%R).
Accuracy was determined during this project using matrix spikes (MS) and/or standard reference
materials (SRMs). Matrix spikes are aliquots of sample spiked with a known concentration of target
anaiyte(s) used to document the accuracy of a method in a given sample matrix. For matrix spikes,
recovery is calculated as follows:
160
-------
%R = C| ' °° x 100
where: C, = measured concentration in spiked sample aliquot
C0 = measured concentration in unspiked sample aliquot
C, = actual concentration of spike added
An SRM is a known matrix spiked with representative target analytes used to document laboratory
performance. For SRMs, recovery is calculated as follows:
%R = Cm x 100
C,
where: Cm = measured concentration of SRM
C, = actual concentration of SRM
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 SRMs.
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 (RPD):
(C1 + C2) / 2
where: C, = the larger of two observed values
C2 = the smaller of two observed values
161
-------
When the number of replicates is three or greater, precision is determined using the relative standard
deviation (RSD):
RSD = S x 100
where: S = standard deviation of replicates
X = mean of replicates
Precision was determined during this project using triplicate analyses for those samples suspected
to be high in target analytes (i.e., untreated sediments). Matrix spike and matrix spike duplicate (MSD)
analyses were performed on those samples suspected to be low in target analytes (i.e., treated sediments).
A 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.
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 Soil Tech treatability studies, no samples were lost due to field or
analytical problems. Though all guidelines for QA objectives were not met, all data generated was deemed
useable.
Representativeness
Representativeness refers to the 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 reported to be representative of the areas to be remediated.
Samples of untreated and treated sediment and residuals were taken by SAIC personnel during Phase II of
these tests. Samples were shipped under chain-of-custody to Battelle Marine Sciences Laboratory in
Sequim, Washington. Therefore, the data is representative of material actually treated.
Comparability
Comparability expresses the extent with which one data set can be compared to another. As will
be discussed in more detail in the section Modifications and Deviations From the QAPP, the data generated
are comparable within this project and within other projects conducted for the ARCS Program. However,
because specialized procedures were used in some instances, the data may not be directly comparable to
projects outside the ARCS Program.
162
-------
ANALYTICAL QUALJTY CONTROL
The following sections summarize and discuss analytical procedures and the results of the QC
indicators of accuracy and precision for each measurement parameter for the Soil Tech technology
evaluation. Please note that replicate results for treated solids are not corrected for the dilution effect of the
sand added prior to treatment.
PAHs
PAH Procedures
Sediments and waters were extracted and analyzed using modified SW-846 procedures as described
in the section Modifications and Deviations From the QAPP. Oils were diluted 1:10 in hexane. Three
isotopically-Jabelled PAH surrogates were added to all samples and blanks prior to extraction. Daily mass
tuning was performed using decafluorotriphenylphosphine (DFTPP) to meet the criteria specified in Method
8270. The instrument was calibrated at five levels for the sixteen PAHs. The RSD of the response factors
for each PAH was required to be <25 percent. Calibrations were verified every 12 hours for each PAH;
criteria for % difference from the initial calibration was <25 percent for each PAH. An internal standard,
hexamethyl benzene, was added prior to cleanup and was used to correct PAH
concentrations for loss during cleanup and extract matrix effects. Quantification was performed using
Selective Ion Monitoring (SIM).
PAH QC Results and Discussion
Surrogate recoveries for all PAH samples for the Soil Tech demonstration are summarized in Table
QA-1. If more than one of the three surrogates fell outside the control limits used, corrective action
(reanalysis) was necessary. (This criteria was not applied by Battelle to method blanks.) Surrogate
recoveries were generally low for samples and method blanks, indicating a possible analytical problem rather
than matrix effects. An investigation indicated possible problems with the evaporator used to concentrate
the extracts. In summary, low surrogate recoveries indicate that PAH target concentrations may be biased
somewhat low. Since both the untreated and treated sediments were affected similarly, relative removal
percentages should be valid.
As required by the QAPP, triplicate analyses of the Buffalo River untreated sediment (B-US-ST) were
performed to assess precision. These results are summarized in Table QA-2. A matrix spike was performed
on this same sample to assess accuracy; these results are included in Table QA-2. All RSD and spike
recoveries with the exception of naphthalene fell within the control limits specified. The lack of precision
for naphthalene can be attributed to concentrations near analytical detection limits. The low recovery
163
-------
TABLE QA-1. PAH SURROGATE RECOVERIES
Sample
B-US-ST, Rep. 1
B-US-ST, Rep. 2
B-US-ST, Rep. 3
I-US-ST
Method Blank
B-TS-ST-R
B-TS-ST-C
I-TS-ST-R
I-TS-ST-C
Method Blank
B-WR-ST
I-WR-ST (1)
Method Blank
B-OR-ST
I-OR-ST, Rep. 1
I-OR-ST, Rep. 2
I-OR-ST, Rep. 3
Method Blank
Method Blank
d 8- Naphthalene
21 *
18 *
45
37 *
28 *
18 *
55
63
43
28 *
612 *
125 *
16 *
29 •
35 *
41
22 *
60
35 *
d 1 0-Acenaphthalene
39 *
46
68
67
38 *
27 *
66
76
59
38 •
118
134 *
18 *
36 *
58
54
45
64
42
d12-Perylene
109
105
91
86
68
60
113
30 *
77
68
67
108
80
79
121 *
103
106
73
49
Control Limits
40- 120
I
I
I
I
40- 120
I
I
I
I
40- 120
I
I
40- 120
I
I
I
I
* Outside Control Limits
(1) Insufficient sample remained for reanalysis of water residuals
obtained for naphthalene is probably due to the volatility of this light hydrocarbon. Due to the minimal
quantity of naphthalene present, the total removal efficiencies are not affected.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MD) analysis was
performed for the treated Buffalo River sediment combustor solids (B-TS-ST-C). These results are presented
in Table QA-3. Several RPDs and recoveries were consistently outside the guidelines specified in the QAPP.
As no target PAHs were found in this sample, the data is unaffected.
164
-------
TABLE QA-2. PAH REPLICATE AND SPIKE RESULTS FOR B-US-ST
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anlhracene
Benzo(g,h,i)perylene
Replicate 1
dry ppb
70
BOU
100U
144
1050
594
1730
1630
744
679
705
506
617
46B
110
382
Replicate 2
dry ppb
67
40U
65
148
999
546
1440
1350
626
733
610
413
543
424
105
327
Replicate 3
dry ppb
160
SOU
70U
182
1060
545
1420
1340
587
674
561
387
494
375
97
297
Mean
99
NC
NC
158
1040
561
1530
1440
653
762
625
435
551
429
104
335
Precision Accuracy
RSD Control Limits Recovery Control Limits
(%) (%) (%) (%)
54* 20 25* 40 - 120
NC
NC
13
3.2
5.0
12
12
12
14
50
54
76
87
86
104
98
107
86 |
12 | 96 |
14 | 83 |
11 | 89 |
13 | 96 |
6.3 | 107 |
13 | 81 |
NC = Not Calculated
U = Undetected
-------
TABLE QA-3. PAH MS/MSD RESULTS FOR B-TS-ST-C
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo (b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo (a.h)anthracene
Benzo(g,h,i)perylene
MS Recovery
(%)
40
53
51
60
74
85
104
99
116
94
110
96
100
110
123 *
92
MSD Accuracy Precision
Recovery Control Control Limits
(%) RPD Limits (%)
(%)
45
51
51
61
83
98
130
124
155
127
150
126
134
152
170
126
12 40-120 20
3.8 |
0 I
1.7 |
11 I
14 |
22 ' |
22 . |
29 * |
* 30 |
31 * I |
27 - | |
29 * |
32 - | |
32 * | |
31 * I |
* Outside Control Limits
Due to the minimal amount of water generated by the Soil Tech process, no PAH QC analyses were
performed on this matrix.
The QAPP specified that triplicate analyses and a matrix spike be performed on the Buffalo River oil
residual (B-OR-ST). This sample was spiked but triplicate analyses were performed on the Indiana Harbor
oil residual (I-OR-ST). These results are summarized in Tables QA-4 and QA-5, respectively.
One certified National Institute of Science and Technology (NIST) standard reference material (SRM) was
extracted and analyzed with the sediment samples. The recoveries for this standard are summarized in
Table QA-6.
Method blanks were extracted and analyzed with each set of samples extracted. Insignificant quantities
of benzo(g,h,i)perylene were detected in the blanks analyzed with the water and oil samples. No corrections
were performed for method blanks as no consistent significant contamination problems were observed.
166
-------
TABLE QA-4. PAH MS RESULTS FOR B-OR-ST
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Ruorene
Phenanthrene
Anthracene
Ruoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
MS Recovery Control Limits
116 Not Specified
78
81
100
113
86
107
103
108
101
95
90
93
92 |
118 |
86 |
PCBs
PCB Procedures
Sediments and waters were extracted and analyzed using modified SW-846 procedures as described
in the section Modifications and Deviations From The QAPP. Oils were diluted 1:10 in hexane. Two
surrogates, tetrachloro-m-xylene and octachloronaphthalene, were added to all samples and blanks prior
to extraction. The gas chromatograph (GC) employed electron capture detection (ECD) and was calibrated
at three levels for each of four Aroclors (1242, 1248,1254, 1260). The RSD of the response factors for each
Aroclor was required to be <25 percent. Calibrations were verified after every ten samples; criteria for
percent difference from the initial calibration was <25 percent. An internal standard,
dibromooctafluorobiphenyl, was added prior to cleanup and was used to correct PCB concentrations for
loss during cleanup and extract matrix effects. Quantification of Aroclors was performed on two columns
(DB-5, primary and 608, confirmation) as a confirmation of their presence.
PCB QC Results and Discussion
Surrogate recoveries for all PCB samples for the Soil Tech demonstration are summarized in Table QA-7.
If both recoveries fell outside the control limits used, correction action (reanalysis) was necessary.
All samples were acceptable with respect to the surrogate criteria used.
167
-------
TABLE QA-5. PAH REPUCATE(a) RESULTS FOR I-OR-ST
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(l ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Replicate 1
ppb
1700000
128000
152000
821000
1780000
624000
1100000
1130000
849000
1000000
842000
366000
627000
340000
190000
373000
Replicate 2
ppb
2060000
129000
145000
756000
1590000
556000
971000
993000
746000
875000
735000
328000
548000
297000
160000
329000
Replicate 3
ppb
1090000
101000
120000
742000
1720000
606000
1020000
1040000
767000
903000
742000
333000
559000
303000
169000
337000
Mean
1610000
119000
139000
773000
1700000
595000
1030000
1050000
787000
926000
773000
342000
578000
313000
173000
346000
RSD Control Limits
30 Not Specified
13
12
54
57
5.9
6.5
6.6
70
7.1
7.8
5.9
7.4 |
7.4 |
8.9 |
6.7 |
(a) Replicate results represent values after correction for percent oil concentration.
-------
TABLE QA-6. PAH SRM RESULTS
Compound
Naphthalene
Acenaphthyrlene
Acenaphthene
Ruorene
Phenanthrene
Anthracene
Ruoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo (k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,c.d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Recovery Control Limits
NC 80-120
NC
NC
NC
95
81
91
96
87
NC
98
136 *
75 *
88
NC
82 |
NC = Not Certified
Outside Control Limits
As required by the QAPP, triplicate analyses of the Buffalo River untreated sediment (B-US-ST) were
performed to assess precision. These results are summarized in Table QA-8. A matrix spike using Aroclor
1254 was performed on the same sample to assess accuracy; these results are included in Table QA-8.
Results were within specified guidelines.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed for the treated Buffalo River sediment combustor solids (B-TS-ST-C). These results are presented
in Table QA-9. The RPD was outside guideline limits; however, no Aroclor 1254 was found in the sample and
the data is not impacted. Matrix spike recoveries were acceptable.
Due to the minimal amount of water generated by the Soil Tech process, no PCB QC analyses were
performed on this matrix.
The QAPP specified that triplicate analyses and a matrix spike be performed on the Buffalo River
oil residual (B-OR-ST). This sample was spiked but triplicate analyses were performed on the Indiana Harbor
oil residual. These results are summarized in Tables QA-10 and QA-11, respectively.
169
-------
TABLE QA-7. PCB SURROGATE RECOVERIES
Sample
B-US-ST, Rep. 1
B-US-ST, Rep. 2
B-US-ST, Rep. 3
I-US-ST
Method Blank
B-TS-ST-R
B-TS-ST-C
I-TS-ST-R
I-TS-ST-C
Method Blank
B-WR-ST
I-WR-ST
Method Blank
B-OR-ST
I-OR-ST, Rep. 1
I-OR-ST, Rep. 2
I-OR-ST, Rep. 3
Method Blank
Tetrachloro-m-xylene
(%)
71
82
84
92
91
46
82
87
65
75
NO
NQ
22 *
61
81
70
76
49
Octachloronaphthalene
(%)
98
96
84
70
84
92
86
80
94
76
NQ
NQ
191 *
113
106
89
92
97
Control Limits
(%)
40- 120
I
I
I
I
40- 120
I
I
I
I
40- 120
I
I
40- 120
I
i
I
I
* Outside Control Limits
NQ = Not Quantifiable due to necessary sample dilutions
170
-------
TABLE QA-8. PCB REPLICATE AND SPIKE RESULTS FOR B-US-ST
u =
NC =
NS =
Aroclor
1242
1248
1254
1260
Undetected
Not Calculated
Not Spiked
Precision Accuracy
Replicate 1 Replicate 2 Replicate 3 RSD Guideline Limits Recovery Control Limits
ppbdry ppb dry ppb dry Mean {%) (%) (%) (%)
200 U 200 U 200 U 200 U NC 20 NS —
329 320 365 338 7.0 20 NS —
100 U 100 U 100 U 100 U NC 20 B1 40 - 120
100 U 100 U 100 U 100 U NC 20 NS —
* Outside Control Limits
TABLE QA-9. PCB MS/MSD RESULTS FOR B-TS-ST-C
Accuracy Control Precision
MS Recovery MSD Recovery Limits Guideline Limits
PCB (%) (%) RPD (%) (%)
Aroclor1254 88 113 25* 40-120 20
U
NC
NS
= undetected * Outside Control Limits
not calculated
= not spiked
-------
TABLE QA-10. PCB MS RESULT FOR B-OR-ST
PCS
MS Recovery
Control Limits
Aroclor 1254
86
Not Specified
TABLE QA-11. PCB REPLICATE RESULTS FOR I-OR-ST
Aroclor
1242
1248
1254
1260
Replicate 1
(PPb)
80000 U
85700
40000 U
40000 U
Replicate 2
(PPb)
80000 U
73200
40000 U
40000 U
Replicate 3
(PPb)
80000 U
74600
40000 U
40000 U
Mean
80000 U
77800
40000' U
40000 U
RSD
NC
8.8
NC
NC
Precision
Control
Limits
20
20
20
20
U = Undetected
NC = Not Calculated
One standard reference material (SRM) certified by the National Research Council of Canada (NRCC)
for Aroclor 1254 was extracted and analyzed with the sediment samples. A recovery of 62.2% was obtained.
Method blanks were extracted and analyzed with each set of samples extracted. Minimal quantities of
Aroclor 1254 were found in the blank analyzed with the sediment samples. As no Aroclor 1254 was present
in either sediment, the data is not impacted.
METALS
Metals Procedure
Sediments were prepared for metals analysis by freeze-drying, blending, and grinding.
Sediments for Ag, Cd, Hg, and Se were digested using nitric and hydrofluoric acids. The digestates
were analyzed for Ag, Cd, and Se by graphite furnace atomic absorption (GFAA) by SW-846 Method 7000
series using Zeeman background correction. The digestates were analyzed for mercury by cold vapor AA
(CVAA) using SW-846 Method 7470.
Sediments for As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were analyzed by energy-diffusive X-Ray
fluorescence (XRF) following the method of Sanders (1987). The XRF analysis was performed on a 0.5 g
aliquot of dried, ground sediment pressed into a pellet with a diameter of 2 cm.
172
-------
Metals QC Results and Discussion
Triplicate analyses of the Buffalo River untreated sediment (B-US-ST) and treated sediment combustor
solids (B-TS-ST-C) were performed to assess precision. Matrix spikes were analyzed for the same samples
to assess accuracy. Results are summarized in Tables QA-12 and QA-13. It should be noted that the
sediments were not spiked for XRF analysis as spiking is not appropriate for that analysis.
Accuracy and precision results for metals were acceptable with only a few minor exceptions, as shown
in Tables QA-12 and QA-13. RSD results outside limits are due to concentrations near the analytical
detection limits. These exceptions have little, if any, impact on data quality and project results.
One NIST certified standard reference material (SRM) was digested and analyzed twice with the
sediment samples for XRF, GFAA, and CVAA analyses. These results are presented in Table QA-14.
Method blanks were digested and analyzed for the metals analyzed by GFAA and CVAA. (Method
blanks are not applicable to XRF analysis). If analyte was detected in the method blank, blank correction
was performed. Minimal amounts of some metals were detected; data quality is not affected.
OIL AND GREASE
Oil and Grease Procedures
Sediment samples were extracted with freon using Soxhlet extraction according to SW-846 Method
9071. The extract was analyzed for oil and grease by infra-red (IR) as outlined in Method 418.1 (Methods
for Chemical Analysis of Water and Wastes, 1983).
Oil and Grease QC Results and Discussion
Both the untreated Buffalo River Sediment and treated combustor solids (B-US-ST and B-TS-ST-C) were
analyzed for oil and grease in triplicate. In addition, a matrix spike was performed for B-TS-ST-C. Results
are presented in Table QA-15. RPD results fell slightly outside specified guidelines; data is not significantly
impacted. Matrix spike recovery was acceptable.
TOTAL VOLATILE SOLIDS
Total Volatile Solid Procedures
Sediments were analyzed for total volatile solids (TVS) following the procedures in Method 160.4
(Methods for Chemical Analysis of Water and Waste, 1983) modified for sediments. An aliquot of sediment
was dried and then ignited at 550°C. The loss of weight on ignition was then determined.
173
-------
TABLE QA 12. METALS REPUCATE AND SPIKE RESULTS FOR B-US-ST
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe(1)
Hg
Mn
Ni
Pb
Se
Zn
Method
GFAA
XRF
XRF
GFAA
XRF
XRF
XRF
CVAA
XRF
XRF
XRF
GFAA
XRF
Replicate 1 ,
ppm dry
0.29
13.0
401
2.10
123
750
458
0.422
694
45.0
108
0.74
191
Replicate 2,
ppm dry
026
125
391
1.88
137
735
452
0.485
692
432
107
062
186
Replicate 3,
ppm dry
0.28
14.4
397
1.97
121
70.0
4.58
0.513
714
45.9
108
0.74
192
Mean
0.28
13.3
396
1.98
127
72.8
456
0.473
700
44.7
108
0.70
190
Precision
RSO Control Limits Recovery
(%) (%) (%)
2.0 20 122*
7.4
1.3
5.6
6.9
3.5
0.8
10
1.7
3.1
0.3
10
1.7
NS
NS
95
NS
NS
NS
92
NS
NS
NS
170*
NS
Accuracy
Control Limits
(%)
85- 115
-
—
85- 115
-
—
—
85- 115
—
—
—
85- 115
—
NS - Not Spiked
(1) Results in Percent for Fe
Outside Control Limits
-------
TABLE QA-13. METALS REPLICATE AND SPIKE RESULTS FOR B-TS-ST-C
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe(1)
Hg
Mn
Nl
Pb
Se
Zn
Method
GFAA
XRF
XRF
GFAA
XRF
XRF
XRF
CVAA
XRF
XRF
XRF
GFAA
XRF
Replicate 1,
ppm dry
0.085
1.9
66
0.205
27
16.8
0.70
0.0003 U
96
75
196
0.3 U
37.9
Replicate 2,
ppm dry
0.088
1.7
59
0.226
45
19.2
0.75
0.0003 U
90
11.6
18.5
0.3 U
353
Replicate 3,
ppm dry
0.097
2.3
57
0.206
24
20.5
0.75
0.0003 U
69
9.6
16.9
0.3 U
35.8
Mean
0.090
2.0
61
0.212
32
19.5
0.73
0.0003 U
92
9.6
18.3
0.3 U
36.3
Precision
RSO Control Limits Recovery
(%) (%) (%)
6.9 20 115
15
7.8
5.6
35*
4.6
3.9
NO
4.1
21*
7.4
NC
3.8
NS
NS
105
NS
NS
NS
93
NS
NS
NS
87
NS
Accuracy
Control Limits
(*)
85- 115
—
—
85- 115
—
—
—
85- 115
—
—
—
85- 115
NS - Not Spiked
U = Undetected
NC = Not Calculated
(1) Result in Percent for Fe
* Outside Control Limits
-------
TABLE QA-14. METALS SRM RECOVERIES
Metal
Afl
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
SRM-1
NC
96.6
NC
108
89.5
122*
103
105
96.8
93.1
100
NC
89.0
SRM-2 Control Limits
NC 80 - 120%
91.4 |
NC |
108 |
101 |
119 |
104 |
105 |
96.0 |
101 |
107 |
NC |
93.0 |
* Outside control limits.
NC = not certified.
TABLE QA-15. OIL AND GREASE REPLICATES AND SPIKE RESULTS FOR
B-US-ST AND B-TS-ST-C
Sample
B-US-ST
B-TS-ST-C
Replicate 1,
ppm dry
11700
302
Replicate 2,
ppm dry
9790
388
Replicate 3, RSD
ppm dry Mean (%)
7090 9540 24*
246 312 23*
Precision
Control
Limits
(%)
20
20
Recovery
(%)
NS
119
Accuracy
Control
Limits
(%)
80- 120
NS = Not Spiked
Total Volatile Solid QC Results and Discussion
Both the Buffalo River untreated sediment and treated combustor solids (B-US-ST and B-TS-ST-C) were
analyzed for TVS in triplicate. Results are summarized in Table QA-16. Both RSDs fell within specified
control limits.
176
-------
TABLE QA-16. TVS REPUCATES FOR B-US-ST AND B-TS-ST-C
Sample
B-US-ST
B-TS-ST-C
Replicate 1,
%dry
5.07
0.03
Replicate 2,
%dry
5.07
0.03
Replicate 3,
%dry
5.19
0.03
Mean
5.11
0.03
RSD
(%)
1.4
0
Control Limits
(%)
20
20
OTHER ANALYSES
Sediment samples were analyzed for pH using SW-846 Method 9045. Sediment and water were
combined in a 1:1 ratio and mixed prior to pH determination.
Total Organic Carbon (TOO
Sediment samples were analyzed for TOC using SW-846 Method 9060. Two SRMs were analyzed with
the sediments, yielding recoveries of 95.6 percent and 91 .3 percent.
Total Cyanide
Sediment samples were analyzed for cyanide by SW-846 Method 9010. Approximately 5 g of sediment
was distilled; the distillate was analyzed spectrophotometrically. A matrix spike was analyzed for B-TS-ST-R;
a recovery of 91.6 percent was obtained.
Total Phosphorus
Sediment samples were analyzed for phosphorus by EPA Method 365.2. Approximately 1 g of sediment
was digested; the digestate was analyzed spectrophotometrically. A matrix spike was analyzed for B-US-ST;
a recovery of 87.7 percent was obtained.
AUDIT FINDINGS
An audit of the Battelle-Marine Sciences Laboratory was conducted on September 25 and 26, 1991.
Participants included EPA, GLNPO, and SAIC personnel. The path of a sample from receipt to reporting
was observed specifically for samples from these bench-scale treatability tests. Two concerns were
identified in the organic laboratory: 1) the preparation, storage, record -keeping, and replacement of
standards is not well-documented; and 2) the nonstandard procedures used to extract, clean up and analyze
samples needs to be documented with reported data.
177
-------
During the audit, the use of nonstandard procedures was discussed. It was concluded that data
comparability within this project and within the ARCS program should not be an issue, as the Battelle
laboratory has performed all analyses to date. However, comparability to data generated outside the ARCS
program is not possible.
MODIFICATIONS AND DEVIATIONS FROM THE QAPP
Laboratory activities deviated from the approved QAPP in two areas-analytical procedures and quality
assurance (QA) objectives. Specific deviations and their effect on data quality are discussed in this section.
ANALYTICAL PROCEDURES
The Assessment and Remediation of Contaminated Sediments (ARCS) Program was initiated by the
Great Lakes National Program Office (GLNPO) to conduct bench-scale and pilot-scale demonstrations for
contaminated sediments. To date, all laboratory analyses performed in support of the ARCS Program have
been done at the Battelle-Marine Sciences Laboratory (MSL) in Sequim, Washington. Standard procedures
used by Battelle-MSL often do not follow those procedures identified in SW-846 and the QAPP. While these
nonstandard procedures yield results of acceptable quality, comparability with analyses performed outside
the ARCS Program is not possible.
PAH Analysis
• Samples were co-extracted with PCS samples using a modified SW-846 extraction procedure which
entailed rolling of the sample in methylene chloride and an additional clean-up step using high pressure
liquid chromatography (HPLC). An internal standard, hexamethyl benzene, was added prior to this
clean-up step to monitor losses through the HPLC. Final results were corrected for the
recovery of this internal standard. A second internal standard, d12-phenanthrene, was added prior to
analysis; however, no corrections were made based on its recovery. Neither of these internal standards
are specified in Method 8270.
SW-846 Method 8270 was modified to quantify the samples using Selective Ion Monitoring (SIM) Gas
Chromatography/Mass Spectrometry (GC/MS). This modification results in improved detection limits.
Three isotopically-labelled PAH compounds were used as surrogates rather than those recommended
in Method 8270. Recoveries of these compounds should better represent the recoveries of target PAHs.
178
-------
PCB Analysis
• Samples were extracted using the modified extraction procedures as described for the PAH analysis.
An internal standard, dibromooctafluorobiphenyl, was added prior to the HPLC clean-up to monitor
losses. Final results were corrected for the recovery of this standard. A second internal
standard, 1,2,3-trichlorobenzene (required by QAPP) was added prior to analysis; however, no
corrections were made based on its recovery.
Quantification of PCBs was not done on a total basis as required by SW-846 Method 8080 but by
quantifying four peaks for each Aroclor and averaging these results. Peaks were considered valid if the
peak shape was good, if there was no tailing, and if there was little or no coelution with other peaks.
A definite Aroclor pattern was necessary for quantification of PCBs.
A three-point calibration for each peak was used instead of the five-point calibration required by Method
8080. This modification should have minimal effect on data quality.
• The surrogate required by the QAPP, tetrachloro-m-xylene, was used. A second surrogate,
octochloronaphthalene, was also added to monitor extraction efficiency.
Metals Analysis
Nine of the 13 metals analyzed for sediment samples were measured by energy-diffusive X-Ray
fluorescence (XRF) - As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. This procedure yields a total metals
concentration instead of the recoverable metals determined by SW-846 methods.
Sediments for Ag, Cd, Hg, and Se were subjected to an acid digestion using nitric and hydrofluoric
acids. This digestion again yields total rather than recoverable metals.
Oil and Grease
Oil and grease extracts for sediments were analyzed using infrared (IR) detection rather than the
gravimetric procedures specified in the QAPP. This should have no effect on data quality.
QUALITY ASSURANCE OBJECTIVES
Many of the guideline QA objectives and internal QC checks criteria guidelines specified in the QAPP
(particularly for organic analyses) are not routinely achievable by standard or nonstandard methods. To
avoid excessive reanalyses (both costly and time-consuming), some acceptance criteria established
179
-------
internally by Battelle were used for this project. These internal limits are adequate for use in determining
whether or not project results are valid.
PAH Analysis
Both surrogate and matrix spike objectives for PAHs were specified in the QAPP to be 70-130%. For
surrogates, Battelle actually used internal limits of 40-120%, with one of the three surrogates out of limits
being acceptable. If more than one surrogate did not fall within 40-120%, reanalysis was required. For
matrix spikes, internal limits of 40-120% were also used; no reanalyses however, were performed based
on exceedences of these limits.
• Limits for continuing calibration checks were specified as ± 10% in the QAPP; limits of ±25% were used.
PCB Analysis
• Both surrogate and matrix spike objectives for PCBs were specified in the QAPP to be 70-130%. For
surrogates, Battelle actually used internal limits of 40-120%. If both surrogates exceeded these limits,
re-extraction was performed. For matrix spikes, internal limits of 40-120% were also used; no
reanalyses, however, were performed if these limits were exceeded.
Limits for continuing calibration checks were specified as ± 10% in the QAPP; limits of ± 25% were used.
Metals Analysis
• Samples analyzed by XRF cannot be spiked. Therefore, no measure of sample accuracy was obtained
for those metals previously identified as being analyzed by XRF. An SRM was analyzed, providing a
means to measure method accuracy for eight of the nine metals determined by XRF (all but Ba).
SAMPLE HOLDING TIMES
Water Samples
The QAPP specified holding times for water samples only. All water extractions and analyses for the
critical parameters were performed within these holding times (from the time of sample receipt).
Sediment/Oil Samples
Though holding times for organics in sediment and oil samples were not specified in the QAPP, the
referenced SW-846 methods do require that extractions be done within 14 days and that the analysis of the
extracts be performed within 40 days after extraction. Any analyses exceeding these criteria for the critical
parameters will be discussed below.
180
-------
PAHs/PCBs
Initial dilutions of all oil residuals were performed 6 to 8 days past the method specified holding times.
Due to the noncritical nature of these analyses, exceeding these holding times has no effect on technology
removal efficiency results.
CONCLUSIONS AND LIMITATIONS OF DATA
Upon review of all sample data and associated QC results, the data generated for the Soil Tech
treatability study has been determined to be of acceptable quality. In general, QC results for accuracy and
precision were good and can be used to support technology removal efficiency results.
In some cases, the demonstration of removal efficiency for PAHs and PCBs may be limited if relatively
small amounts of these compounds are present in the untreated sediments. If minimal amounts are present,
then detection limits become a factor. Removal efficiency demonstration may be limited by the sensitivity
of the analytical methods.
Due to the minimal quantity of oil generated by the process, it was necessary to rinse the oil collection
vessel with methylene chloride in order to create a sample for analysis. The oil/methylene chloride mixture
was analyzed as received for PAHs, PCBs, and percent oil. Results for PAHs and PCBs were then corrected
for the concentration of oil determined. As these oil concentrations were approximately one and three
percent for the two sediments tested, error could have been introduced in making these corrections. Oil
results for PAHs and PCBs should be used with caution.
As discussed previously, the analytical laboratory used several specialized methods when analyzing
samples from the Soil Tech treatability study. These same methods, however, have been used in analyzing
all samples generated to date in support of the ARCS Program. Therefore, while the data generated for the
Soil Tech treatability study may not be comparable to data generated by standard EPA methods, it is
comparable to data generated within the ARCS Program.
181
-------
Data Verification Report For Assessment and
Remediation of Contaminated Sediment Program
Report Number 8
(SAIC, Bench-Scale Tests)
By
M. J. Miah, M. T. Dillon, and N. F. D. O'Leary
Lockheed Environmental Systems and Technologies Company
980 Kelly Johnson Drive
Las Vegas, Nevada 89119
Version 1.0
Work Assignment Manager
Brian A. Schumacher
Exposure Assessment Research Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193
Environmental Monitoring Systems Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Las Vegas, Nevada 89193
-------
ABSTRACT
Data submitted by the Science Applications International Corporation
(SAIC) of Cincinnati, Ohio, have been verified for compliance of the QA/QC
requirements of the Assessment and Remediation of Contaminated Sediment
(ARCS) program. This data set includes results from bench-scale technology
demonstration tests on wet contaminated sediments using four treatment
technologies, namely, B.E.S.T. (extraction process), RETEC (low temperature
stripping), ZIMPRO (wet air oxidation), and Soil Tech (low temperature
stripping). The primary contaminants in these sediments were polychlorinated
biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs). In addition,
metal contents and conventionals (% moisture, pH, % total volatile solids, oil and
grease, total organic carbon (TOC), total cyanide, and total phosphorus) in these
sediments were also considered for this project. The objective of the bench-scale
technology demonstration study was to evaluate four different treatment
techniques for removing different organic contaminants from sediments. Both
treated and untreated sediment samples were analyzed to determine treatment
efficiencies.
A total of seven sediment samples from four different areas of concerns
(Buffalo River, Ashtabula River, Indiana Harbor, and Saginaw River) were
analyzed under the bench-scale technology demonstration project. The samples
from these areas of concern (AOCs) were collected by the Great Lakes National
Program Office (GLNPO) in Chicago, IL, and sample homogenization was
performed by the U. S. EPA in Duluth, MN. SAIC was primarily responsible
for the characterization of the sediment samples prior to testing and for the
residues created during the test. The solid fraction analyses were performed by
SAIC's analytical subcontractor Battelle-Marine Sciences Laboratory of Sequim,
Washington, and Analytical Resources Incorporated of Seattle, Washington.
The submitted data sets represent analyses of untreated sediments, as well
as solid, water, and oil residues obtained by using different treatments. The
verified data set is divided into several parameter groups by sampled media. The
data verifications are presented in parameter groups that include: metals, PCBs,
conventionals, and PAHs.
The results of the verified data are presented as a combination of an
evaluation (or rating) number and any appropriate data flags that may be
applicable. The templates used to assess each individual analyte are attached in
case the data user needs the verified data of a single parameter instead of a
parameter group.
-------
INTRODUCTION
The bench-scale technology demonstration project was undertaken to evaluate the
efficiencies of four techniques used for the removal of specific contaminants from wet sediments
collected from designated Great Lakes areas of concern. Four different sediment treatment
techniques, namely, B.E.S.T (Basic Extraction Sludge Technology), RETEC, ZIMPRO, and Soil
Tech were considered for evaluation. B.E.S.T. is a solvent extraction process, RETEC and Soil
Tech are low temperature stripping techniques, and ZIMPRO is a wet air oxidation technique.
Wet sediments were collected by the Great Lakes National Program Office (GLNPO) from four
Great Lakes sites, namely, the Buffalo River in New York, the Saginaw River/Bay (referred to
as Saginaw River throughout the following discussions) in Michigan, the Grand Calumet
River/Indiana Harbor (referred to as Indiana Harbor throughout the following discussions) in
Indiana, and the Ashtabula River in Ohio. The four techniques were used to treat the sediment
samples from these four sites. The sediment samples represent the sediment that would be
obtained for on-site treatment.
The B.E.S.T. process is a patented solvent extraction technology that uses the inverse
miscibility of triethylamine as a solvent. At 65° F, triethylamine is completely soluble in water
and above this temperature, triethylamine and water are partially miscible. This property of
inverse miscibility is used since cold triethylamine can simultaneously solvate oil and water.
RETEC and the Soil Tech (low temperature stripping) are techniques to separate volatile and
semivolatile contaminants from soils, sediments, sludges and filter cakes. The low temperature
stripping (LTS) technology heats contaminated media to temperatures between 100 -200° F,
evaporating off water and volatile organic contaminants. The resultant gas may be burned in
an afterburner and condensed to a reduced volume for disposal or can be captured by carbon
absorption beds. For these treatability studies, only the processes that capture the driven off
contaminants were considered. The ZIMPRO (wet air oxidation) process accomplishes an
aqueous phase oxidation of organic and inorganic compounds at elevated temperatures and
pressures. The temperature range for this process is between 350 to 600° F (175 to 320° C).
System pressure of 300 psi to well over 300 psi may be required. In this process, air or pure
oxygen is used as an oxidizing agent.
Samples for the technology demonstration projects were obtained by GLNPO (Chicago,
Illinois) and were analyzed by Battelle-Marine Sciences Laboratory (Battelle-MSL, Sequim, WA)
and by Analytical Resources Incorporated (Seattle, WA). To evaluate the bench-scale
technologies, the sample analyses were divided into four parts: (1) raw untreated sediment
samples, (2) treated sediments, (3) water residues, and (4) oil residues. The amount of residues
available for the analyses depended upon the corresponding sediment samples and on the
individual technology used to treat those sediment samples.
The analyses of sediment and residue parameters for these projects were divided into four
different categories: (1) metals, including Ag, As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se,
and Zn; (2) polychlorinated biphenyls (PCBs); (3) polynuclear aromatic hydrocarbons (PAHs);
-------
and (4) conventional including percent moisture, pH, percent total volatile, oil and grease, total
organic carbon (TOC), total cyanide, and total phosphorus. Analyses of metals and
conventional were performed on treated and untreated sediment samples only for B.E.S.T.,
ZIMPRO, and Soil Tech, while for the RETEC process, analyses of metals and conventional
were performed on treated and untreated sediment samples as well as water residue samples.
No oil residues were produced by the ZIMPRO technique (wet air oxidation treatment
technique), while in the other three techniques, oil residues were analyzed after appropriate
sample cleanup steps for PCBs and PAHs.
QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS
The objective behind all quality assurance and quality control (QA/QC) requirements is
to ensure that all data satisfy predetermined data quality objectives. These requirements are
dependent on the data collection process itself. Under the bench-scale technology demonstration
project, QA/QC requirements were established for:
1. Detection limits,
2. Precision,
3. Accuracy,
4. Blank analyses,
5. Surrogate and matrix spike analyses, and
6. Calibration
a) initial
b) ongoing.
Four parameter groups analyzed in the sediment and water residue phases were of interest
in the bench-scale technology demonstration project. These groups included: (a) metals, (b)
PCBs, (c) PAHs, and (d) conventionals. The conventionals included: percent moisture, pH,
percent total volatile, oil and grease, TOC, total cyanide, and total phosphorus. In addition,
total solids, total suspended solids, and conductivity were included in the conventionals group
for RETEC conventional analyses. The analyses for metals and conventionals were performed
for solids only, except for RETEC, where metals and conventionals were analyzed in solid and
water residue phases. Parameter groups analyzed in the oil residue phase are PCBs and PAHs.
The objective of these analyses was to characterize samples both before and after each treatment
was applied.
The detection limits for metals, PCBs, PAHs, and conventionals (where appropriate)
were defined as, three times the standard deviation for 15 replicate analyses of a sample with
an analyte concentration within a factor of 10 above the expected or required limit of detection.
Individual parameter detection limits are presented in the approved quality assurance project plan
for SAIC on file at the Great Lakes National Program Office in Chicago, IL.
-------
Precision requirements were based on analytical triplicate analyses for all parameters of
sediment samples and treated residues, at the rate of 1 per 20 samples. The results of the
triplicate analyses provided the precision for the analytical laboratory. An acceptable limit was
the coefficient of variation less than or equal to 20 percent. The precision requirement was
established for all variable types in this project. For treated sediments, the relative percent
difference (RPD) between the matrix spike and matrix spike duplicate was used as a measure
of precision with an acceptance limit of less than 20% .
Accuracy was defined as the difference between the expected value of the experimental
observation and its "true" value. Accuracy in this project was required to be assessed for each
variable type using analysis of certified reference materials, where available, at the rate of 1 per
20 samples. Acceptable results must agree within 20 percent of the certified range. Since no
PCBs and PAHs were expected to be detected in the treated sediment, matrix spikes and matrix
spike duplicate analyses were required during the analyses of treated sediment for the organic
parameters. Matrix spike analyses were used as a measure of accuracy for treated sediment
analyses, with an acceptance limit of ±30% from the known value.
Matrix spikes were required to be used at a rate of 1 per 20 samples and to be within
plus or minus 15 percent of the spiking value for metals and 70 to 130 percent of the spiking
value for organics (PCBs and PAHs).
Surrogate spike analyses were only required for each sample in organic analyses. The
acceptable limits for the surrogate recovery was between 70 and 130 percent of the known
concentration.
The observed values should have been less than the method detection limit for each
parameter for method blanks (run at the beginning, middle, and end of each analytical run).
The ongoing calibration checks were required at the beginning, middle, and end of a set
of sample analyses for all variable types. The maximum acceptable difference was .+ 10% of
the known concentration value in the mid-calibration range. Initial calibration acceptance limits,
for metals, was the J> 0.97 coefficient of determination for the calibration curve, while a %RSD
of the response factors of less than or equal to 25% was required for organics.
RESULTS AND DISCUSSION
The ARCS QA program was formally adopted for use when SAIC received final approval
from the GLNPO on May 31, 1991. An evaluation scale, based upon the QA program
developed for the ARCS program, was developed to evaluate the success of the data collection
process in meeting the QA/QC requirements of the ARCS program. The following section
discusses how to interpret the data verification results.
-------
The Verification Process and Evaluation Scale
For verification purposes, the data set from each technology was divided into 4 different
sample media as follows:
1. Untreated sediment,
2. Treated sediment,
3. Water residue, and
4. Oil residue.
The verification process included QA/QC compliance checking for accuracy, precision,
matrix spike analysis, surrogate spike analysis, blank analysis, detection limits, initial and
ongoing calibration checks, and holding times as well as checks on calculational correctness and
validity on a per parameter/analyte basis. Compliance checks were performed to ensure that the
QA/QC measurements and samples: (a) met their specified acceptance limits; (b) had reported
results that were supported by the raw data; and (c) were analyzed following good laboratory
practices, where checking was possible. Upon completion of the verification process, a final
rating was assigned for each of the individual categories. The final ratings are presented as a
combination of a number value and a flag list.
The numerical value for the rating of a given parameter was assigned based upon the
successful completion of each required QA/QC sample or measurement. The QA/QC samples
were broken down into four different sample groups, namely, accuracy, precision, blanks, and
spike recoveries. A fifth category was included for QA/QC measurements to address the
successful completion of instrument calibrations (both initial and ongoing) and the determination
of method detection limits. If the laboratory successfully met the acceptance criteria of 50
percent or more of the parameters in a given QA/QC sample group, then the laboratory received
the full value for that category. For example, if 50 percent or more of the reagent blanks for
the metals in sediment analyses had measured values below the method detection limit, then
three points were awarded for that category, assuming reagent blanks were the only blank
samples analyzed by the laboratory. The individual point values for each QA/QC sample type
or measurement and the minimum acceptance levels for each category are presented in Appendix
B. The final numerical rating presented for each parameter category is the summation of the
point values from each of the five categories.
Along with each numerical rating, a list of appropriate flags has been attached to the final
rating value (Appendix C). The flag indicates where discrepancies exist between the laboratory
data and the acceptance limits of the required QA program. Different flags are presented for
each category of QA sample (accuracy, precision, blanks, and spike recoveries) and for the
QA/QC measurements (instrument calibration and detection limit determination). The flags have
a letter and subscript configuration, such as A,. The letter of the flag represents the category
of the discrepancy while the subscript designates the form of the discrepancy. For example, the
A flags indicate discrepancies in the use of accuracy checking samples, such as reference
materials or standards. A flag with a subscript of 1 indicates that the laboratory failed to meet
-------
the acceptance criteria. Using the example of the A, flag, this flag would then indicate a failure
of the laboratory to meet the QA/QC requirements for the use of reference materials in their
appraisal of accuracy. A flag with the subscript 0 indicates that no information was received
(or no standards were available in the case of accuracy) from the analytical laboratory, and
therefore, no points could be allotted towards the final calculated rating value for that particular
category. It should be noted that the 0 flag does not necessarily indicate that the analytical
laboratory did not perform the QA/QC analyses, only that no information was received from the
laboratory.
The subscript 9 flag indicates that the sample category or QA/QC measurement is not
applicable to that particular parameter or parameter group (Appendix C). For example, an S,
flag indicates that a matrix spike for that given parameter or analyte is not applicable, such as
was the case for percent moisture. Where subscript 9 flags occur, an adjustment to the passing
and maximum scores (to be discussed) for a parameter group was made and will be reported in
the appropriate tables.
A complete presentation of the QA/QC rating factors (point values by sample type) and
the various data flags and their subscripts are presented in Appendices B and C, respectively.
A more complete discussion of the rating scale can be found in the report submitted to the
RA/M workgroup by Schumacher and Conkling entitled, "User's Guide to the Quality
Assurance/Quality Control Evaluation Scale of Historical Data Sets."
Individual parameter flags are presented in the templates found in Appendix D. The
objective of the presentation of the individual flag templates is to help the data user make a
determination regarding the useability of the data set for any given purpose and to provide the
data user with a means to assess any individual parameter that may be of specific interest.
The Interpretation and Use of the Final Verified Data Rating Values
The data verification scale was developed to allow for the proper rating of the verified
data and the subsequent interpretation and evaluation of the ratings. Two different
interpretations can be made using the ratings provided in this report, namely, the actual or "true"
rating and the potential rating. The first interpretation is based upon the formal ARCS QA
program, while the second interpretation scale is based upon the "full potential" value of the
submitted data set. In the following sections, each interpretation of the results will be discussed.
Data Interpretation Based upon the Formal ARCS OA Program
For each of the four parameter categories, the data were initially verified for QA/QC
compliance following the requirements specified in the signed QAPP submitted by SAIC and the
ARCS QAMP on file at the GLNPO in Chicago, Illinois.
Table 1 provides the verified data ratings for each variable class for the four different
technologies studied based on the current ARCS QA program. The ratings of these variable
-------
classes are presented to provide the data user with a means for comparing the ARCS QA
program-based verified results with other data sets, using the same or similar parameters, that
were generated prior to and after the initiation of the formal ARCS QA program.
Table 2 provides the data user with the full compliance and acceptable scores presented
for each parameter group based upon the current ARCS QA program. The full compliance score
represents the numerical rating value if all required QA/QC samples and measurements were
performed by the analytical laboratory and successfully met all the QA/QC requirements of the
ARCS QA program. An acceptable score is lower than the full compliance score and accounts
for laboratory error that can be reasonably expected during an analysis of multiple samples.
Any final rating value less than the acceptable score indicates that problems were identified in
the data that could adversely effect the quality of the data. The acceptable score was set at 60
percent of the full compliance score. To determine the percentage of QA/QC samples and
measurements successfully analyzed for a given parameter versus the number analyzed following
the complete ARCS QA protocols, divide the numerical rating received by the full compliance
score. An acceptable data set, in this case, has a rating of 60 percent or greater.
In some cases, all the QA/QC requirements may not be applicable (e.g., matrix spikes
for percent solids are not applicable). If this is the case, a flag with the subscript 9 was used,
and the full compliance and acceptable scores were adjusted by lowering the score on appropriate
number of points for nonrequired sample type, as identified in Appendix B. An example of this
situation is % moisture, as indicated in Table 1, the subscript 9 flag has been applied to
accuracy, blank, detection limit, and spike samples. Therefore, the full compliance and
acceptable scores (Table 2) are only based upon the possible points for the successful completion
of the remaining QA/QC samples that have cumulative points value of 8 (Appendix B).
Data Interpretation Based upon the" Potential* Value of the Data Set
A second interpretation scale has been presented to allow the data user to establish the
"full potential" value of the submitted data set. The numerical value and associated flags
presented in the first interpretation can be considered as an absolute rating for that data set or
parameter. These ratings were based upon all the data submitted to Environmental Monitoring
Systems Laboratory - Las Vegas (EMSL-LV) and to Lockheed for review by the analytical
laboratory. If one or more parameter or parameter groups qualifying flags had the subscript of
5, 6, 9, or 0 (Appendix C), the required information was not available or not applicable at the
time of sample analysis, and consequently was not included during the data verification and
review process. The equivalent point value(s) for each individual sample type may be added to
the reported point sum to give the data user the full potential value of the data set. This process
assumes that if the "missing" QA/QC samples or measurements were performed, the results
would fall within the ARCS QA program specified acceptance limits. For example, if the point
value (including qualifying flags) for the metals was 6-Bo C0 D0 S0, then the data user could
potentially add 14 points to the score since the blank analyses, spike information, detection limit,
-------
and calibration (initial and ongoing) information was not available for verification. The resulting
data would then have a rating of 20.
TABLE 1. Verified Data Ratings Based on the Current ARCS QA Program
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
!>
-------
TABLE 1. Verified Data Rating Based on the Current ARCS Program
(Continued)
Water
residue
Metals
% Moisture
PH
Total
Suspended
Solids
%TVS
Total Solids
Oil and grease
TOC
Total cyanide
Total
phosphorus
Conductivity
PCBs
PAHs
**
**
**
*«
**
**
**
**
**
**
14-B2 D0 P0
H-AoDoP.S,
**
**
**
*«
**
**
**
«*
**
**
14-83 D0 P0
17-D0 S2
**
**
**
**
**
**
**
**
**
**
5-A, 83 D0 P0 S,
se
17-D0 P0
20
**
3-A, 8, Co D, S,
6-A, CoD, S,
6-A, Co D9 S,
6-A, Co D9 S,
12-A,C6D0
9-Ao C6 D0 S9
14-Ao D0
14-Ao D0
9-AoC.D.S,
S-AoBjDoPoS,
S6
ll-A.DoP.S,
Oil residue
PCBs
PAHs
H-A.BjDoS,
H-AoRjDoSj
*
*
17-Bj D0
U^DoSj
H-BjDoPoS,
17-B2 Do
* No oil residue was produced by this treatment
** Analyses were not conducted for this treatment
-------
TABLE 2. Full Compliance and Acceptable Scores Based on the Current ARCS QA Program
Variable Class
Metals in Treated Sediment
Metals in Untreated Sediment
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
Conductivity
Suspended Solids
Total Solids
PAHs
PCBs
Full Compliance
20
20
8
8
9
17
17
20
20
14
9
9
23
23
Acceptable
12
12
5
5
6
11
11
12
12
9
6
6
14
14
Table 3 presents the verified data ratings for each variable class in the four technologies
based on their full potential value. All data qualifying flags with the subscripts 5, 6, 9, or 0
have been removed. The appropriate point values for each of the 5, 6, or 0 flags (Appendices
B and C) were added to the final rating scores for each parameter or parameter group. In
contrast, the removal of the subscript 9 flags resulted in an adjustment to the full compliance and
acceptable scores, and npj in an addition to the calculated point scores since these analyses were
not applicable to the methodologies used by the laboratory (Table 2).
-------
10
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
PCBs
PAHs
B.Iii«o> 1 •
20
8
8
6
17
17
20
20
20-83
20-S2
ZIMPRO
20
8
8
6
8-8,0,5,
17
20
20
17-A,B2
14-Bj S, S2
Soil Tech
20
8
8
6
11-B2D,
17
20
20
17-A, B2
20-S2
RETEC
20
8
8
6
17
17
17-P,
20
17-A.B,
23
Treated
Sediments
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
PCBs
PAHs
20
8
8
6
17
17
20
20
17^ P,
17-P, S2
20
8
8
6
8-B2 D, S,
17
20
20
H-A.B.P,
20- Sj
20
8
8
6
11-B2D,
17
20
20
17-8, P,
20-S2
20
8
8
6
9-P,
17
20
20
17-A, B,
23
-------
11
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
(continued)
Water
residue
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
Conductivity
Suspended Solids
Total Solids
PCBs
PAHs
»*
**
**
**
**
**
**
**
**
**
**
20-83
17-P,S2
**
**
**
**
**
**
**
**
**
**
**
20^
20-S2
**
**
**
**
*«
**
*»
**
**
**
**
14-A, 62 S,
23
20
8
8
6
17
17
20
20
14
6
6
20-B2
14-A, P, S,
Oil residue
PCBs
PAHs
14-A, B2 S,
n-B^
*
*
20-B2
17-8282
20-Bj
20-83
* No oil residue was produced by this treatment
** Analyses were not conducted for this treatment
To evaluate the data using the values presented in Table 3, the final ratings should be
compared to the full compliance and acceptable scores presented in Table 2. The data user
should bear in mind that these values are only the potential values of the data set and assumes
that the "missing" QA/QC data could have been or were performed successfully by the
laboratory. Any value falling below the acceptable value presented in Table 2 clearly indicates
that major QA/QC violations were identified and the data should be used with a great deal of
caution by the data user.
-------
12
Data Verification Results for Bench-scale Technology Demonstration Project
B.E.S.T.
The B.E.S.T. technology was evaluated by analyzing sediment samples and their treated
residues (treated sediments, water residues, and oil residues) for metals, conventionals, PCBs
and PAHs. PCB and PAH analyses were performed for sediments, water, and oil residues. The
metals and conventional analyses were performed for the sediment samples only.
In the majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten
of the thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, Pb, and Zn) satisfied
ARCS specified QA/QC requirements for accuracy. Four of the thirteen metal analyses (Cd,
Hg, Se, and Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine
metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of
the XRF analyses, results from blank sample analyses were not applicable. Both initial and
ongoing calibration for Cd, Hg, Se, and Ag analyses met the ARCS QA/QC specifications for
both treated and untreated sediments, while for the remaining nine metals (As, Ba, Cr, Cu, Fe,
Mn, Ni, Pb, and Zn) calibration information was not available. Detection limits information for
metal analyses in treated and untreated sediments were not available for verification except for
Cd, Hg, Se, and Ag where detection limits were satisfactory. The precision information for the
metal analyses in treated sediment was not available for Se, but was satisfactory for the
remaining elements, with the exception of Hg, where precision information did not satisfy
QA/QC requirements. The precision information for the metal analyses in untreated sediment
was not available for Se, but was satisfactory for the remaining twelve metal (Ag, As, Ba, Cd,
Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) analyses. The matrix spike information for both treated
and untreated sediment analyses were satisfactory for Cd, Hg, and Se, were unsatisfactory for
Ag, while the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed
by XRF techniques. In all of the XRF analyses, results from matrix spike analyses were not
applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
phosphorus. In the remaining four conventional analyses, accuracy was not applicable. In both
sediments, five of the seven conventionals (%TVS, oil and grease, TOC, total cyanide, and total
phosphorus) satisfied QA/QC requirements for blank analyses, and the blank information was
not applicable for moisture, pH, and TVS. Both initial and ongoing calibration information was
satisfactory for all conventional analyses in both treated and untreated sediments except for
moisture and pH where calibration information was not available and for TOC and oil and grease
where ongoing calibration information was not available. Detection limits were satisfactory for
four (oil and grease, TOC, total cyanide, and total phosphorus) of the seven conventional
-------
13
analyses in treated and untreated sediments, and were not applicable for moisture, pH, and TVS.
The precision information was satisfactory for two (%TVS, oil and grease) of the seven
conventional analyses in treated and untreated sediments. No precision information was
available for the remaining five conventional analyses in treated or untreated sediments. The
matrix spike information for both treated and untreated sediment analyses were satisfactory for
oil and grease, total cyanide, and total phosphorus, while for the remaining four conventional
analyses the matrix spike information was not applicable.
In treated sediments, untreated sediments, and water residues, the accuracy objective for
PCBs was satisfactory for Aroclor 1254 analyses only and could be used to represent the whole
PCB group. No accuracy information was available for the remaining three Aroclor analyses.
In oil residues, accuracy information was not satisfactory for PCB analyses. In both sediments
and in both residues, PCB analyses did not satisfy ARCS specified QA/QC requirements for
blank analyses indicating potential contamination at the laboratory. Initial and ongoing
calibration was satisfactory for all PCB analyses in both treated and untreated sediments as well
as in water and oil residues. Detection limit information were not available for PCB analyses
in treated and untreated sediments and for water and oil residues. In the untreated sediments,
the precision information was satisfactory for Aroclors 1242 and 1254, and no precision
information was available for Aroclors 1248 and 1260. In the treated sediments, the precision
information was not satisfactory for Aroclor 1254, and no precision information was available
for Aroclors 1242, 1248, and 1260. In water residues, no precision information was available
for any of the Aroclors. In oil residues, the precision information was; satisfactory for Aroclor
1248, and no precision information was available for Aroclors 1242, 1254, and 1260. The
matrix spike for Aroclor 1254 was satisfactory for both sediment and water residue analyses and
could be used to represent the whole PCB group. The matrix spike for Aroclor 1254 was
unsatisfactory for the analyses of oil residue. In both sediment or residue analyses, no matrix
spike information was available for Aroclors 1242, 1248, and 1260. The surrogate spike
recoveries were satisfactory for PCB analyses in both sediments and residues.
In eight of sixteen PAH analyses of treated and untreated sediments, the accuracy
objective was satisfactory. No accuracy information was available for six PAHs (naphthalene,
acenaphthylene, acenaphthene, fluorene, chrysene, and dibenzo(a,h)anthracene) analyses in both
treated and untreated sediments. The accuracy objective was not satisfactory for benzo(k)
fluoranthene and benzo(a)pyrene in treated or untreated sediments. No accuracy information was
available for any of the PAH analyses in water and oil residues. In treated and untreated
sediments, and in water residues, PAH analyses satisfied ARCS specified QA/QC requirements
for blank analyses. In all cases of oil residues, the blank analyses exceeded the MDL indicating
potential contamination at the laboratory. Initial and ongoing calibration limits for PAH analyses
met the ARCS QA/QC specifications for both treated and untreated sediments and water and oil
residue analyses. Detection limit information was not available for PAH analyses in treated and
untreated sediments, nor for water and oil residues. In untreated sediments and oil residues, the
precision information was satisfactory for all PAH analyses, except for acenaphthene in untreated
sediment, and naphthalene in oil residues where no precision information was available. In
treated sediments, the precision information was satisfactory for fluorene, phenanthrene, and
-------
14
anthracene but was unsatisfactory for the remaining PAH analyses. In water residues, no
precision information was available for PAH analyses except for benzo(g,h,i)pyrene where
precision was unsatisfactory. The matrix spike information was satisfactory for twelve of sixteen
PAH analyses in treated sediment and for eight of the sixteen analyses in untreated sediment and
in water and oil residues. Surrogate recoveries were not satisfactory for PAHs in either
sediment and residue analyses.
ZIMPRO
The ZIMPRO technology was evaluated by analyzing sediment samples, treated
sediments, and water residues for metals, conventionals, PCBs, and PAHs. PCS and PAH
analyses were performed for both sediment and water residues. The metals and conventional
analyses were performed for the both sediment samples only.
In the majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten
of the thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, and Zn) satisfied ARCS
specified QA/QC requirements for accuracy. Four of the thirteen metal analyses (Cd, Hg, Se,
and Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine metals (As,
Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of the XRF
analyses, blank sample analyses are not applicable. Both initial and ongoing calibration for Cd,
Hg, Se, and Ag analyses met the ARCS QA/QC specifications for both treated and untreated
sediments while for the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn),
calibration information was not available. Detection limit information for metal analyses in
treated and untreated sediments was not available for verification except for Cd, Hg, Se, and
Ag where the detection limits were satisfactory. The precision for the metal analyses in treated
sediment was not satisfactory for As, but was satisfactory for the remaining elements. The
precision information for the metal analyses in untreated sediment was satisfactory for all
elements. The matrix spike information for both treated and untreated sediment analyses were
satisfactory for four (Cd, Hg, Se, and Ag) of the thirteen elements while the remaining nine
metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of
the XRF analyses, results from matrix spike analyses were not applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
phosphorus. In the remaining four conventional analyses, accuracy was not applicable. In both
sediments, three of the seven conventionals (TOC, total cyanide, and total phosphorus) satisfied
QA/QC requirements for blank analyses. The blank information was unsatisfactory for oil and
grease, was not available for %TVS, and the blank information was not applicable for moisture
and pH. Both initial and ongoing calibration information was satisfactory for all conventional
analyses in both treated and untreated sediments except for % moisture, pH, and TVS where
calibration information was not available, and for TOC and oil and grease, where ongoing
-------
15
calibration information was not available. Detection limits were satisfactory for three (TOC,
total cyanide, and total phosphorus) of the seven conventional analyses in treated and untreated
sediments. Detection limits were unsatisfactory for oil and grease analyses in treated and
untreated sediments and were not applicable for %moisture, pH, and %TVS. The precision
information was satisfactory for pH, %TVS, and oil and grease analyses in treated, and for
%moisture, %TVS, and oil and grease analyses in untreated sediment. No precision information
was available for % moisture, TOC, total cyanide, and total phosphorus analyses in treated
sediment and for pH, TOC, total cyanide, and total phosphorus analyses in untreated sediments.
The matrix spike information for both treated and untreated sediment analyses were satisfactory
for total cyanide and total phosphorus, were unsatisfactory for oil and grease while for the
remaining four conventional analyses the matrix spike information was not applicable.
The accuracy objective was unsatisfactory for the PCB analyses in treated and untreated
sediments for Aroclor 1254. No accuracy information was available for the remaining three
Aroclor analyses in treated and untreated sediments. In water residue, the accuracy objective
for PCBs was satisfactory for Aroclor 1254 analyses only and could be used to represent the
whole PCB group. No accuracy information was available for the remaining three Aroclor
analyses in water residues. In water residues and in both treated and untreated sediments, the
blank analyses exceeded the detection limits specified in the QAPP indicating potential
contamination at the laboratory. Initial and ongoing calibration was satisfactory for all PCB
analyses in both treated and untreated sediments as well as in water residues. Detection limits
information were not available for PCB analyses in treated and untreated sediments, nor in the
water residues. In untreated sediment analyses, most PCB observations were below the
instrument detection limits, therefore it was not possible to calculate meaningful precision
information for PCB Aroclors, with the exception of Aroclor 1248 analyses, where precision
information satisfied QA/QC requirements. No precision information was available for PCB
analyses in treated sediments, except for Aroclor 1254 in treated sediment where it did not
satisfy QA/QC requirements. In the water residue, no PCB precision information was available.
The matrix spike for Aroclor 1254 was satisfactory for both sediments, and the water residue
analyses and could be used to represent the whole PCB group. The matrix spike information
for sediments and water residue analyses for Aroclor 1242, 1248, and 1260 were not available
for verification. The surrogate recoveries were satisfactory for PCB analyses in sediment and
residue analyses.
In ten of the sixteen PAH analyses in treated sediment and nine of the sixteen PAH
analyses in untreated sediments, the accuracy objective was satisfactory. No accuracy
information was available for six PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene,
chrysene, and dibenzo(a,h)anthracene) analyses in treated and untreated sediment. The accuracy
objective was not satisfactory for benzo(k)fluoranthene in untreated sediment. Accuracy
information in water residue was unsatisfactory for naphthalene, acenaphthylene, acenaphthene,
phenanthrene, and benzo(a)pyrene. Accuracy was satisfactory for the rest of the PAH analyses
in water residues. In treated sediments and water residues, PAH analyses satisfied ARCS
specified QA/QC requirements for blank analyses. In all cases of untreated sediment analyses,
the blank analyses exceeded the detection limit specified in the QAPP. Calibration limits for
-------
16
PAH analyses met the ARCS QA/QC specifications for both treated and untreated sediments,
and also for water residue analyses. Detection limits information were not available for PAH
analyses in treated and untreated sediments, nor for the water residues. The precision
information was satisfactory for PAH analyses in both sediments except for naphthalene,
acenaphthylene, acenaphthene, fluorene, and benzo(a)pyrene analyses in treated sediment and
for naphthalene, acenaphthene, phenanthrene, and benzo(a)pyrene in water residue, where
precision was unsatisfactory. The matrix spike information was satisfactory for fifteen of the
sixteen PAH analyses in treated sediment, for five of the sixteen analyses in untreated sediment
and for eleven of the sixteen analyses in water residues. Surrogate recoveries were not
satisfactory for PAHs in the sediment and residue analyses.
SOIL TECH
The Soil Tech technology was evaluated by analyzing sediment samples and their treated
residues (treated sediments, water residues, and oil residues) for metals, conventionals, PCBs,
and PAHs. PCS and PAH analyses were performed for sediment and residues. The metals and
conventional analyses were performed for the sediment samples only.
In the majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of the thirteen metals analyzed, accuracy
information was not available for Ba, Se, and Ag. Four of the thirteen metal analyses (Cd, Hg,
Se, and Ag) satisfied QA/QC requirements for blank analyses, while the remaining nine metals
(As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed by XRF techniques. In all of the
XRF analyses, blank sample analyses are not applicable. Both initial and ongoing calibration
for Cd, Hg, Se, and Ag analyses met the ARCS QA/QC specifications for both treated and
untreated sediments while for the remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and
Zn), calibration information was not available. Detection limits information for metal analyses
in treated and untreated sediments were not available for verification except for Cd, Hg, Se, and
Ag where detection limits were satisfactory. The precision information for the metal analyses
in treated sediment was not available for Se and Hg but was satisfactory for the remaining
elements with the exception of Cr, where precision information did not satisfy the QA/QC
requirements. The precision information for the metal analyses in untreated sediment was
satisfactory for all metal analyses. The matrix spike information were satisfactory for four (Cd,
Hg, Se, and Ag) of the thirteen elements for treated sediments and two (Cd, Hg) of the thirteen
elements for untreated sediments. The matrix spike information were unsatisfactory for Se and
Ag analyses in untreated sediments. The remaining nine metals (As, Ba, Cr, Cu, Fe, Mn, Ni,
Pb, and Zn) were analyzed by XRF techniques. In all of the XRF analyses, results from matrix
spike analyses were not applicable.
Of the seven conventional analyses, the accuracy information in both treated and
untreated sediments was satisfactory for TOC and was not available for total cyanide, and total
phosphorus. In the remaining four conventional analyses, accuracy was not applicable. In both
sediments, four of the seven conventionals (%TVS, TOC, total cyanide, and total phosphorus)
-------
17
satisfied QA/QC requirements for blank analyses, and the blank information was not applicable
for moisture and pH, while blank analyses was not satisfactory for oil and grease. Both initial
and ongoing calibration information was satisfactory for all conventional analyses in both treated
and untreated sediments, except for % moisture, pH, and %TVS where calibration information
was not available. Ongoing calibration information was not available for TOG and oil and
grease. Detection limits were satisfactory for three (TOC, total cyanide, and total phosphorus)
of the seven conventional analyses in treated and untreated sediments. Detection limits were
unsatisfactory for oil and grease and were not applicable for %moisture, pH, and %TVS. The
precision information was satisfactory for % moisture, %TVS, and oil and grease in treated
sediments. The precision information was satisfactory for %TVS, and oil and grease in treated
sediments. No precision information was available for the remaining conventional analyses in
treated or untreated sediments. The matrix spike information were satisfactory for oil and
grease, total phosphorus, and total cyanide in treated sediment analyses and for total phosphorus
in untreated sediment analyses. The matrix spike information were not available for oil and
grease and total cyanide in untreated sediment analyses. While for the remaining four
conventional analyses, the matrix spike information was not applicable.
The accuracy objective was satisfactory for the PCB analyses in treated sediments and
in oil residue analyses for Aroclor 1254 only and could be used to represent the whole PCB
group. The accuracy objective was unsatisfactory for the PCB analyses in untreated sediments
and in water residue analyses for Aroclor 1254. No accuracy information was available for the
remaining three Aroclor analyses in sediment or residue analyses. In both residues and in both
treated and untreated sediments, the blank analyses exceeded the detection limits specified in the
QAPP, except for Aroclor 1260 in oil residue. Initial and ongoing calibration was satisfactory
for all PCB analyses in both treated and untreated sediments, as well as in both water and oil
residues. Detection limit information was not available for PCB analyses in both sediments and
residues. In untreated sediment analyses, most PCB observations were below the instrument
detection limits, therefore, it was not possible to calculate meaningful precision information for
PCB Aroclors, with the exception of Aroclor 1248 analyses, where precision information
satisfied QA/QC requirements. No precision information was available for PCB analyses in
treated sediment, except for Aroclor 1254, where it did not satisfy QA/QC requirements. No
precision information was available for PCB analyses in oil and water residues, except for
Aroclor 1248 in oil residue, where precision was satisfactory. The matrix spike for Aroclor
1254 was satisfactory for both sediments and the oil residue analyses and could be used to
represent the whole PCB group. The matrix spike for Aroclor 1254 was unsatisfactory for the
water residue analyses, and the matrix spike information for both sediment and residue analyses
for Aroclor 1242, 1248, and 1260 were not available for verification. The surrogate recoveries
were satisfactory for PCB analyses in sediment and residue analyses, except for water residue
where surrogate information was not available.
In eight of sixteen PAH analyses in treated and untreated sediments, the accuracy
objective was satisfactory. No accuracy information was available for six PAHs (naphthalene,
acenaphthylene, acenaphthene, fluorene, chrysene, and dibenzo(a.h)anthracene) analyses in both
treated and untreated sediments. The accuracy objective was not satisfactory for benzo(k)
-------
18
fluoranthene in treated or untreated sediments nor for benzo(g,h,i)perylene in untreated
sediment. Accuracy information was satisfactory for the PAH analyses in water and oil
residues. In treated and untreated sediments and water residues, PAH analyses satisfied ARCS
specified QA/QC requirements for blank analyses. In all cases of oil residues, the blank
analyses exceeded the MDL. Calibration limits for PAH analyses met the ARCS QA/QC
specifications for both treated and untreated sediments as well as water and oil residue analyses.
Detection limit information was not available for PAH analyses in treated and untreated
sediments nor for water and oil residues. In untreated sediment and oil residues, the precision
information was satisfactory for all PAH analyses, except for acenaphthene and acenaphthene
in untreated sediment, and naphthalene in oil residues, where no precision information was
available. In treated sediments, the precision information was satisfactory for naphthalene,
acenaphthylene acenaphthene, fluorene, phenanthrene, and anthracene, and was unsatisfactory
for the remaining PAH analyses. In water residues, no precision information was available for
any of the PAH analyses. The matrix spike information was satisfactory for twelve of sixteen
PAH analyses in treated sediment, and for thirteen of the sixteen analyses in untreated sediment
and ten of the sixteen analyses in water and all analyses in oil residues. Surrogate recoveries
were unsatisfactory for PAHs in either sediment and oil residue analyses but were satisfactory
in water residue.
RETEC
The RETEC technology was evaluated by analyzing sediment samples and their treated
residues (water residues and oil residues) for metals, conventionals, PCBs and PAHs. PCB and
PAH analyses were performed for sediment and residues. The metals and conventional analyses
were performed for both sediment samples and water residues.
In a majority of the cases studied, the accuracy objective was satisfactory for the metal
analyses in treated and untreated sediments. Of thirteen metals analyzed, accuracy information
was not available for Ba, Se, and Ag. In both treated and untreated sediments, ten of the
thirteen metal analyses (As, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Hg, and Zn) satisfied ARCS specified
QA/QC requirements for accuracy. The accuracy objective was satisfactory for all metal
analyses in water, except for Se, where accuracy did not satisfy QA/QC requirements. Four of
the thirteen metal analyses (Cd, Hg, Se, and Ag) satisfied QA/QC requirements for blank
analyses. The remaining nine metal analyses (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn) were
analyzed by XRF techniques. In all of the XRF analyses, blank sample analyses are not
applicable. In water residue, blank analyses were satisfactory for all metals except for Fe, Mn,
and Se, where blank analyses exceeded the detection limits specified in the QAPP, and for Ba,
where no information regarding blank analyses was available. Both initial and ongoing
calibration met the ARCS QA/QC specifications for Cd, Hg, Se, and Ag for both treated and
untreated sediments, and for all metals in water residue analyses. While in both treated and
untreated sediments the remaining nine metals (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn),
calibration information were not available. Detection limits information for metal analyses in
treated and untreated sediments were not available for verification, except for Cd, Hg, Se, and
-------
19
Ag, where detection limits were satisfactory. Detection limits for metal analyses in water
residue were satisfactory, except for Mn, Se, and Zn, where detection limits exceeded the
QA/QC requirements. The precision information for the metal analyses in treated and untreated
sediments, and in water residue was satisfactory for all elements, except for Hg in treated
sediment, and Se and Hg in water residue analyses, where precision information did not satisfy
QA/QC requirements. The matrix spike information for treated sediment analyses were
satisfactory for Cd, Hg, and Ag, and was not satisfactory for Se. The matrix spike information
for untreated sediment analyses were satisfactory for Cd and Hg, and was not satisfactory for
Se and Ag. The remaining nine metals (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn) were
analyzed by XRF techniques for treated and untreated sediment. In all of the XRF analyses,
matrix spike analyses are not applicable. The matrix spike information for water residue
analyses was satisfactory for all metals except for Ag where matrix spike information did not
satisfy QA/QC requirement.
Of the seven conventional analyses in both treated and untreated sediments, accuracy
information was satisfactory for TOC, and was not available for total cyanide, or total
phosphorus. In the remaining four conventional analyses accuracy was not applicable. Of ten
conventional analyses in water residue, accuracy information was not available for TOC, total
cyanide, total phosphorus, and conductivity. In the remaining seven conventional analyses
accuracy was not applicable. In both treated and untreated sediments and in water residue
analyses, %TVS, oil and grease, TOC, total cyanide, and total phosphorus satisfied QA/QC
requirements for blanks. Also, the blank information was satisfactory for total solids and total
suspended solids in water residue analyses. The blank information was not applicable for the
remaining conventional analyses in sediment and water residue analyses. Both initial and
ongoing calibration information was satisfactory for all conventional analyses in both sediment
and water residue, except for % moisture (in sediment), pH, and TVS, TSS, TS where
calibration information was not available, and for TOC and oil and grease, where ongoing
calibration information was not available. Detection limit information was not available in both
treated and untreated sediments and in water residue for oil and grease, TOC, total cyanide, and
total phosphorus, and was not applicable for the remaining conventional analyses. In treated
sediment, the precision information was not satisfactory for oil and grease and no precision
information was available for total cyanide. In untreated sediment, the precision information
was not satisfactory for total cyanide, and no precision information was available for TOC. The
precision information was satisfactory for the remaining five conventional analyses in treated and
untreated sediments. In water residue, the precision information was satisfactory for all the
conventionals, except for moisture, where no precision information was available. The matrix
spike information was not available for oil and grease, and was satisfactory for total cyanide and
total phosphorus in treated sediment analyses. The matrix spike information was not available
for oil and grease, total cyanide, and total phosphorus in untreated sediment analyses. The
matrix spike information was satisfactory for oil and grease, total cyanide, and total phosphorus
in water residue analyses. The matrix spike information for the remaining conventional analyses
was not applicable for sediment and water residue analyses.
-------
20
The accuracy objective was unsatisfactory for the PCB analyses in treated sediments,
untreated sediments, and oil residue for Aroclor 1254 and could be used to represent the whole
PCB group. No accuracy information was available for the remaining three Aroclor analyses
in treated and untreated sediments. No accuracy information was available for PCB analyses
in water residues. In both sediments and residues, the blank analyses exceeded the detection
limits specified in the QAPP. Both initial and ongoing calibration for PCB analyses met the
ARCS QA/QC specifications for both treated and untreated sediments, as well as for water and
oil residues. Detection limit information was not available for PCB in either sediments or
residue analyses. The precision information for the PCB analyses in treated and untreated
sediment was satisfactory for Aroclor 1254. In all remaining analyses, precision information
was not available. The matrix spike was satisfactory for Aroclor 1254 in treated sediment and
in oil residue analyses, and could be used to represent the whole PCB group. The matrix spike
information was not available for the remaining Aroclors in treated sediment and oil residues.
The matrix spike information was not available for PCB analyses in untreated sediment and in
water residues. The surrogate recoveries were satisfactory for PCB analyses in sediment and
residue analyses.
In ten of the sixteen PAH analyses in treated sediments and in seven of the sixteen PAH
analyses in untreated sediments, the accuracy objective was satisfactory. No accuracy
information was available for six PAHs (naphthalene, acenaphthylene acenaphthene, fluorene,
chrysene, dibenzo(a,h)anthracene) analyses in treated and untreated sediment. The accuracy
objective was not satisfactory for benzo(k)fluoranthene, benzo(a)pyrene, and benzo(g,h,i)
perylene in untreated sediment. Accuracy information was satisfactory for fourteen of the
sixteen PAH analytes in oil residue. Accuracy information was unsatisfactory for PAH analyses
in water residue, except for benzo(k)fluoranthene, indeno(l,2,3,c,d)pyrene,
dibenzo(a,h)anthracene. The blank analyses for the PAHs in treated and untreated sediment was
satisfactory in all cases except for acenaphthylene, acenaphthene, fluorene, phenanthrene, and
anthracene. In water residues, all PAH analyses satisfied ARCS specified QA/QC requirements
for blank analyses. In all oil residues, the blank analyses exceeded the detection limit specified
in the QAPP. Both initial and ongoing calibration information for PAH analyses met the ARCS
QA/QC specifications for both treated and untreated sediments, and also for water and oil
residue analyses. Detection limit information was not available for PAH analyses in either
sediments or residues. The precision information was satisfactory for PAH analyses in treated
sediments, except for benzo(k)fluoranthene, where precision did not satisfy QA/QC
requirements. The precision information was satisfactory for PAH analyses in untreated
sediments except for acenaphthylene and acenaphthene, where precision information was not
available, and for benzo(k)fluoranthene, where precision did not satisfy QA/QC requirements.
The precision information was satisfactory for PAH analyses in oil residue, except for
benzo(k)fluoranthene, where precision information did not satisfy QA/QC requirements. In
water residue, precision was unsatisfactory for PAH analyses except for benzo(k)fluoranthene,
indeno(l,2,3,c,d)pyrene, and dibenzo(a,h)anthracene, where precision was satisfactory. The
matrix spike information was satisfactory for ten of the sixteen PAH analytes in treated
sediment, for fourteen of the analytes in untreated sediment, for thirteen of the analytes in oil
residues, and for three of the analytes in water residues. Surrogate recoveries were satisfactory
-------
21
for PAHs in both treated and untreated sediments as well as for oil and water residue analyses.
Summary
Based on the compliance with the ARCS QA/QC requirements, SAIC was capable of
supplying acceptable results for metals, conventionals, PCBs, and PAHs. The results received
for all four technologies satisfied ARCS QA/QC requirements.
An examination of results of the bench scale technology demonstration data set indicates,
that SAIC could have successfully provided acceptable data for all parameters. The data user
should be aware that some QA/QC discrepancies were identified, as indicated by subscript 1 and
2 flags in Table 3.
-------
APPENDICES A and D
are not included in this report.
Copies are available from GLNPO upon request.
-------
APPENDIX B
QA/QC Sample Rating Factors
-------
CATEGORY
RATING FACTORS
CATEGORY
SCORE ACCEPTABILITY LEVEL
Accuracy
Precision
Certified Reference Material = 3
Analytical Replicate = 3
Acceptable = 3
Acceptable = 3
Spike Recovery
Blanks
Miscellaneous
Matrix Spike = 3
Surrogate Spike (organics) = 3
Blanks = 3
Instrument Calibration (initial) = 3
Instrument Calibration (on going) = 2
Instrument Detection Limit = 3
Acceptable = 3
(organics) = 6
Acceptable = 3
Acceptable = 3
-------
APPENDIX C
Data Verification Flags
-------
A = Accuracy Problem
A0 = no standard available/no information available
A, = accuracy limit for the reference materials exceeded
A, = accuracy is not applicable
B = Blank Problem
B0 = no information available
Bj = reagent blank value exceeded MDL
B^ = blanks are not applicable
C = Calibration Problem
C0 = no information available
C, = initial calibration problem
Cj = on-going calibration problem
Cs = no information on initial calibration
C6 = no information on on-going calibration
G, = on-going calibration is not applicable
D = Detection Limit Problem
D0 = no information available
D, = detection limit exceeded
D9 = detection limit is not applicable
-------
H = Holding Times Exceeded
P = Precision Problem
P0 = no information available
PI = precision limit for analytical replicate exceeded the QA/QC
requirements
P3 = MSD exceeded the QA/QC requirement
P9 = precision is not applicable
S = Spike Recovery Problem
S0 = no information available on spike
$! = limit of matrix spike recovery exceeded
S2 = limit of surrogate spike recovery exceeded
S5 = no information available on matrix spike recovery
S6 = no information available on surrogate spike recovery
S9 = spike recovery not applicable
-------
19
Ag, where detection limits were satisfactory. Detection limits for metal analyses in water
residue were satisfactory, except for Mn, Se, and Zn, where detection limits exceeded the
QA/QC requirements. The precision information for the metal analyses in treated and untreated
sediments, and in water residue was satisfactory for all elements, except for Hg in treated
sediment, and Se and Hg in water residue analyses, where precision information did not satisfy
QA/QC requirements. The matrix spike information for treated sediment analyses were
satisfactory for Cd, Hg, and Ag, and was not satisfactory for Se. The matrix spike information
for untreated sediment analyses were satisfactory for Cd and Hg, and was not satisfactory for
Se and Ag. The remaining nine metals (As, Ba, Cr, Cu, Fe, Pb, Mn, Ni, and Zn) were
analyzed by XRF techniques for treated and untreated sediment. In all of the XRF analyses,
matrix spike analyses are not applicable. The matrix spike information for water residue
analyses was satisfactory for all metals except for Ag where matrix spike information did not
satisfy QA/QC requirement.
Of the seven conventional analyses in both treated and untreated sediments, accuracy
information was satisfactory for TOC, and was not available for total cyanide, or total
phosphorus. In the remaining four conventional analyses accuracy was not applicable. Of ten
conventional analyses in water residue, accuracy information was not available for TOC, total
cyanide, total phosphorus, and conductivity. In the remaining seven conventional analyses
accuracy was not applicable. In both treated and untreated sediments and in water residue
analyses, %TVS, oil and grease, TOC, total cyanide, and total phosphorus satisfied QA/QC
requirements for blanks. Also, the blank information was satisfactory for total solids and total
suspended solids in water residue analyses. The blank information was not applicable for the
remaining conventional analyses in sediment and water residue analyses. Both initial and
ongoing calibration information was satisfactory for all conventional analyses in both sediment
and water residue, except for % moisture (in sediment), pH, and TVS, TSS, TS where
calibration information was not available, and for TOC and oil and grease, where ongoing
calibration information was not available. Detection limit information was not available in both
treated and untreated sediments and in water residue for oil and grease, TOC, total cyanide, and
total phosphorus, and was not applicable for the remaining conventional analyses. In treated
sediment, the precision information was not satisfactory for oil and grease and no precision
information was available for total cyanide. In untreated sediment, the precision information
was not satisfactory for total cyanide, and no precision information was available for TOC. The
precision information was satisfactory for the remaining five conventional analyses in treated and
untreated sediments. In water residue, the precision information was satisfactory for all the
conventionals, except for moisture, where no precision information was available. The matrix
spike information was not available for oil and grease, and was satisfactory for total cyanide and
total phosphorus in treated sediment analyses. The matrix spike information was not available
for oil and grease, total cyanide, and total phosphorus in untreated sediment analyses. The
matrix spike information was satisfactory for oil and grease, total cyanide, and total phosphorus
in water residue analyses. The matrix spike information for the remaining conventional analyses
was not applicable for sediment and water residue analyses.
-------
20
The accuracy objective was unsatisfactory for the PCB analyses in treated sediments,
untreated sediments, and oil residue for Aroclor 1254 and could be used to represent the whole
PCB group. No accuracy information was available for the remaining three Aroclor analyses
in treated and untreated sediments. No accuracy information was available for PCB analyses
in water residues. In both sediments and residues, the blank analyses exceeded the detection
limits specified in the QAPP. Both initial and ongoing calibration for PCB analyses met the
ARCS QA/QC specifications for both treated and untreated sediments, as well as for water and
oil residues. Detection limit information was not available for PCB in either sediments or
residue analyses. The precision information for the PCB analyses in treated and untreated
sediment was satisfactory for Aroclor 12S4. In all remaining analyses, precision information
was not available. The matrix spike was satisfactory for Aroclor 1254 in treated sediment and
in oil residue analyses, and could be used to represent the whole PCB group. The matrix spike
information was not available for the remaining Aroclors in treated sediment and oil residues.
The matrix spike information was not available for PCB analyses in untreated sediment and in
water residues. The surrogate recoveries were satisfactory for PCB analyses in sediment and
residue analyses.
In ten of the sixteen PAH analyses in treated sediments and in seven of the sixteen PAH
analyses in untreated sediments, the accuracy objective was satisfactory. No accuracy
information was available for six PAHs (naphthalene, acenaphthylene acenaphthene, fluorene,
chrysene, dibenzo(a,h)anthracene) analyses in treated and untreated sediment. The accuracy
objective was not satisfactory for benzo(k)fluoranthene, benzo(a)pyrene, and benzo(g,h,i)
perylene in untreated sediment. Accuracy information was satisfactory for fourteen of the
sixteen PAH analytes in oil residue. Accuracy information was unsatisfactory for PAH analyses
in water residue, except for benzo(k)fluoranthene, indeno(l,2,3,c,d)pyrene,
dibenzo(a,h)anthracene. The blank analyses for the PAHs in treated and untreated sediment was
satisfactory in all cases except for acenaphthylene, acenaphthene, fluorene, phenanthrene, and
anthracene. In water residues, all PAH analyses satisfied ARCS specified QA/QC requirements
for blank analyses. In all oil residues, the blank analyses exceeded the detection limit specified
in the QAPP. Both initial and ongoing calibration information for PAH analyses met the ARCS
QA/QC specifications for both treated and untreated sediments, and also for water and oil
residue analyses. Detection limit information was not available for PAH analyses in either
sediments or residues. The precision information was satisfactory for PAH analyses in treated
sediments, except for benzo(k)fluoranthene, where precision did not satisfy QA/QC
requirements. The precision information was satisfactory for PAH analyses in untreated
sediments except for acenaphthylene and acenaphthene, where precision information was not
available, and for benzo(k)fluoranthene, where precision did not satisfy QA/QC requirements.
The precision information was satisfactory for PAH analyses in oil residue, except for
benzo(k)fluoranthene, where precision information did not satisfy QA/QC requirements. In
water residue, precision was unsatisfactory for PAH analyses except for benzo(k)fluoranthene,
indeno(l,2,3,c,d)pyrene, and dibenzo(a,h)anthracene, where precision was satisfactory. The
matrix spike information was satisfactory for ten of the sixteen PAH analytes in treated
sediment, for fourteen of the analytes in untreated sediment, for thirteen of the analytes in oil
residues, and for three of the analytes in water residues. Surrogate recoveries were satisfactory
-------
21
for PAHs in both treated and untreated sediments as well as for oil and water residue analyses.
Summary
Based on the compliance with the ARCS QA/QC requirements, SAIC was capable of
supplying acceptable results for metals, conventionals, PCBs, and PAHs. The results received
for all four technologies satisfied ARCS QA/QC requirements.
An examination of results of the bench scale technology demonstration data set indicates,
that SAIC could have successfully provided acceptable data for all parameters. The data user
should be aware that some QA/QC discrepancies were identified, as indicated by subscript 1 and
2 flags in Table 3.
-------
APPENDICES A and D
are not included in this report.
Copies are available from GLNPO upon request.
-------
APPENDIX B
QA/QC Sample Rating Factors
-------
CATEGORY
RATING FACTORS
CATEGORY
SCORE ACCEPTABILITY LEVEL
Accuracy
Precision
Spike Recovery
Blanks
Miscellaneous
Certified Reference Material = 3
Analytical Replicate = 3
Matrix Spike = 3
Surrogate Spike (organics) = 3
Blanks = 3
Instrument Calibration (initial) = 3
Instrument Calibration (on going) = 2
Instrument Detection Limit = 3
Acceptable
Acceptable
Acceptable
(organics)
= 3
= 3
= 3
= 6
Acceptable = 3
Acceptable = 3
-------
APPENDIX C
Data Verification Flags
-------
A = Accuracy Problem
AO = no standard available/no information available
A, = accuracy limit for the reference materials exceeded
A, = accuracy is not applicable
B = Blank Problem
B0 = no information available
BZ = reagent blank value exceeded MDL
B, = blanks are not applicable
C = Calibration Problem
C0 = no information available
C, = initial calibration problem
Q = on-going calibration problem
C5 = no information on initial calibration
C6 = no information on on-going calibration
€9 = on-going calibration is not applicable
D = Detection Limit Problem
D0 = no information available
DI = detection limit exceeded
D9 = detection limit is not applicable
-------
H = Holding Times Exceeded
P = Precision Problem
P0 = no information available
PI = precision limit for analytical replicate exceeded the QA/QC
requirements
P3 = MSD exceeded the QA/QC requirement
P9 = precision is not applicable
S = Spike Recovery Problem
S0 = no information available on spike
S| — limit of matrix spike recovery exceeded
S2 = limit of surrogate spike recovery exceeded
S5 = no information available on matrix spike recovery
S6 — no information available on surrogate spike recovery
S9 = spike recovery not applicable
------- |