United States
Environmental Protection
Agency
Great Lakes
National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
EPA 905-R94-008
August 1994
SERA Assessment and
Remediation
Of Contaminated Sediments
(ARCS) Program
BENCH-SCALE EVALUATION
OF RETEC'S THERMAL
DESORPTION TECHNOLOGY
ON CONTAMINATED SEDIMENTS
FROM THE ASHTABULA RIVER
•) United States Areas of Concern
P ARCS Priority Areas of Concern
printed on recycled paper
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x^ench-Scale Evaluation of
ReTeC's Thermal Desorption Technology on
Contaminated Sediments from the Ashtabula River
Prepared by
Michael Giordano and Evelyn Meagher-Hartzell
Science Applications International Corporation
Cincinnati, Ohio
for the
], Assessment and Remediation of Contaminated Sediments (ARCS) Program
5 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 Boulevard 12th
Chicago, IL 60604-3590
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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.
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ACKNOWLEDGEMENTS
This report was prepared by the Engineering/Technology Work Group (ETWG) as part of the Assess-
ment 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 ReTeC's Thermal
Desorption Technology on Contaminated Sediments from the Ashtabula River," EPA 905-R94-008,
Great Lakes National Program Office, Chicago, IL.
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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 is responsi-
ble for undertaking a 5-year study and demonstration program for the remediation of contaminated
sediments. GLNPO has 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 are being conducted as
part of the ARCS Program. A bench-scale study using the ReTeC Thermal Desorption 1000 Ib/hr
technology is the subject of this report. This study took place at Star Refinery in Delaware City, DE on
September 25, 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 ReTeC Holo-Flite™ Screw Processor was tested using a sediment sample obtained from
the Ashtabula River. The concentrations of the contaminants of concern in the sediment were 14.6
mg/kg PCBs and 6.1 mg/kg PAHs. The PCB and PAH concentrations of <0.6 and <2.4 mg/kg,
respectively, were found in the treated solids. This corresponds to PCB and PAH removals of >96 and
>60 percent, respectively. Since the concentrations of individual PAHs in the feed and treated solids
are very close to detection limits, significant error is associated with the calculated PAH removals. The
percent removal achieved for PAHs can be attributed to the method used to quantify the individual
PAHs, making this result an unreliable reflection of the technology's ability to remove PAHs. Metals
analyses were performed on the treated solids and untreated sediments. The data demonstrate that
except for mercury, there is no indication that the ReTeC technology effectively removes metals. The
feed and treated solids were analyzed for percent moisture, oil and grease, total organic carbon (TOC),
volatile solids, and pH. Moderate reductions were experienced for oil and grease and total volatile
solids (i.e., 56.6 percent and 44.4 percent, respectively). Because of the relatively small amount of
material treated, accurate mass balances were not possible.
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TABLE OF CONTENTS
Section Page
Disclaimer i
Acknowledgements ii
Abstract iii
List of Figures v
List of Tables vi
1.0 Executive Summary 1
2.0 Introduction 2
2.1 Background 3
2.2 Sediment Descriptions 3
2.3 Sediment Characterization 6
2.4 Technology Description 6
3.0 Treatability Study Approach 7
3.1 Test Objectives and Rationale 7
3.2 Experimental Design and Procedures 10
3.3 Sampling and Analysis 13
4.0 Results and Discussion 14
4.1 Summary of Phase I Results 14
4.2 Phase II Results , 14
4.3 Summary of Vendor Results 25
4.4 Quality Assurance/Quality Control 25
Appendix A - Thermal Treatability Testing, Ashtabula River Sediments, Great Lakes Program Office 33
Appendix B - Quality Assurance/Quality Control 79
Appendix C - Quality Assurance Project Plan 105
Appendix D - Battelle Analytical Results 151
IV
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LIST OF FIGURES
Number
1 ARCS Priority Areas of Concern 4
2 Ashtabula River Sampling Points 5
3 Process Flow Diagram 8
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LIST OF TABLES
Number
1 Summary of Total PCBs and PAHs 1
2 Mass Balance Summary 2
3 Characterization of the Ashtabula River Sediment 6
4 Parameters for Analysis of ARCS Program Technologies 10
5 Full-Scale Holo-Flite™ Screw Processor Specifications 12
6 Analytical Methods Used by ReTeC During Phase I Testing 13
7 ReTeC Analytical Matrix and Sample Identification-Ashtabula River Sediment 15
8 Optimal Operating Parameters 16
9 Total PCBs 16
10 Feed and Treated Solids PAH Concentrations 18
11 Metals Concentration in the Feed and Treated Solids 19
12 Removal Efficiencies for Other Parameters 20
13 PAH Concentrations in the Treated Solids, Water, and Oil 21
14 PCB Concentrations in the Treated Solids, Water, and Oil 21
15 Metals Concentration in the Residual Water 22
16 Residual Water Characterization Data 22
17 Solids Mass Balance 24
18 Water Mass Balance 24
19 Oil Mass Balance 25
20 PAH Mass Balance 26
VI
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1.0 EXECUTIVE SUMMARY
The ReTeC Holo-Flite™ Screw Processor was tested using sediment obtained from the
Ashtabula River. The contaminants of concern in the sediment were PCBs and PAHs. Samples of the
feed and the treated solids produced using the ReTeC technology were analyzed by Battelle Marine
Sciences Laboratory for PCB and PAH contamination. The data from these analyses are presented in
Table 1.
Table 1. Summary of Total PCBs and PAHs
(mg/kg, dry)
Parameter
Total PCBs
Total PAHs
Feed
14.6
6.1
Treated
Solids
<0.6
<2.4
%
Removal
>96
>60
The data in Table 1 indicate that PCB and PAH concentrations of <0.6 and <2.4 mg/kg,
respectively, were found in the treated solids. This corresponds to PCB and PAH removal of >96 and
>60 percent, respectively. Since the concentrations of individual PAHs in the feed and treated solids
are very close to detection limits, significant error is associated with the calculated PAH removal. The
percent removal achieved for PAHs can be attributed to the method used to quantify the individual
PAHs, making this result an unreliable reflection of the technology's ability to remove PAHs.
Metal analyses were performed on the treated solids and untreated sediments. The data
demonstrate that except for mercury, there is no indication that the ReTeC technology effectively
removes metals. The feed and treated solids were analyzed for percent moisture, oil and grease, TOC,
volatile solids, and pH. Moderate reductions were experienced for oil and grease and total volatile
solids (i.e., 56.6 percent and 44.4 percent, respectively). The results of these analyses are discussed
in more detail in Section 4.2.
Given the size of the unit employed during testing (1000 Ib/hr), the relative small amount of
material available for treatment (460 Ibs), and the relatively large amount of material trapped within the
system following treatment (approximately 107 Ibs, assuming perfect recovery), accurate mass
balances could not be calculated. To address the issue of equipment contamination fully, rough mass
balances were performed for solids, water, oils, and PAHs. As shown in Table 2, the excessively high
values obtained for oil and PAHs support suspicions of processor contamination.
1
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Table 2. Mass Balance Summary (%)
Sample Solids Water Oil PAHs
Ashtabula River 39.6 88.5 3500 3170
Small vials of the residuals from the pilot-scale 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 the pilot-scale test were sent to the analytical laboratory, Battelle
Marine Sciences Laboratory, for analysis. None of the residuals were retained and shipped to EPA for
possible further treatability studies.
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 contami-
nated 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 as part of the ARCS
Program. Information from remedial activities supervised by the U.S. Army Corps of Engineers and the
Superfund program was 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 study using the ReTeC Thermal Desorption Technology, which is the subject of this
report, took place at Star Refinery in Delaware City, DE on September 25, 1991. The specific
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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 treatability tests for the ARCS Program on
four different sediments using four treatment technologies: Thermal Desorption Technology (ReTeC),
Anaerobic Thermal Process Technology (SoilTech), Wet Air Oxidation (Zimpro Passavant), and
B.E.S.T.™ Solvent Extraction Process (RCC). This report summarizes the approach used and results
obtained during Phase I and Phase II testing of the ReTeC Thermal Desorption Technology. The
sediment tested during this evaluation technology was obtained from the Ashtabula River.
The primary objective of this portion of the study was to determine the feasibility and cost-
effectiveness of the ReTeC Thermal Desorption Technology for treating and removing PCBs and PAHs
from the Ashtabula River sediment. Based upon previous tests performed by ReTeC, it is their
experience that the data obtained from the bench-scale testing 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 the treatability studies conducted by SAIC are typical of sediments
within the Great Lakes and their tributaries. The primary contaminants in the Ashtabula River sediment
include PCBs.
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/Indiana Harbor Canal, Buffalo River, Ashtabula River, and
Saginaw River) using four different technologies. A map is provided in Figure 1 which shows the ARCS
Priority Areas of Concern. Specifics of the sample location for the Ashtabula River sediment is shown
in Figure 2.
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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
0 H 100 tK> 200
I I I I I
KLOUETER3
&EFKIQ
US ENVMONUENTM. PROTECTION MCNCV
OA£AT LMCEINATONM. PMXMAU OFFCt
Figure 1. ARCS Priority Areas of Concern.
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Ashtabula River
The sediment sample was a composite comprised of
subsamples taken throughout the Ashtabula River system
Figure 2. Ashtabula River Sampling Points
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2.2.2 Sediment Acquisition and Homogenization
Prior to conducting the treatability study using the ReTeC technology, the sediment was
homogenized and stored under refrigeration by the U.S. EPA Environmental Research Laboratory in
Duluth, MN.
Samples of the homogenized sediment were sent to SAIC by the Duluth laboratory. Ten
gallons of sediment were then transferred by SAIC to ReTeC. ReTeC used these samples to perform a
series of standard tests to determine if the samples were compatible with their process and to
determine optimum testing conditions and procedures for the treatability study (Phase I). Eleven 5-
gallon pails of the sediment were later forwarded to ReTeC by SAIC for Phase II testing.
2.3 Sediment Characterization
SAIC was responsible for the physical and chemical characterization of the raw sediment used
during the tests. Under SAIC's direction, the sediment and residuals were analyzed by Battelle Marine
Sciences Laboratory in Sequim, WA. Table 3 provides characterization data pertaining to the sediment.
Table 3. Characterization of the Ashtabula River Sediment
(mg/kg dry, unless specified)
Parameter Feed
Total PCBs 14.6
Total PAHs 6.1
Moisture, %, as received 35.6
Oil & Grease 1004
TOC, % weight 2.00
Total Volatile Solid, % 7.64
pH, S.U., as received 7.88
2.4 Technology Description
ReTeC claims to have developed a thermal desorption technology that is effective in processing
solids contaminated with organic constituents. Thermal desorption refers to the separation of
contaminants from a solid matrix through volatilization. The desorption process can be used in
conjunction with other processes such as incineration or condensation for subsequent control of the
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volatilized constituents. According to ReTeC, the technology has potential in low-temperature
applications as a pre-treatment step for subsequent biological treatment or in higher-temperature
applications as a final treatment option for waste materials. The resultant concentrated waste stream is
treated or disposed of, as appropriate.
The primary component of this thermal technology is an indirectly heated thermal
desorption/dryer system called the Holo-Flite™ Screw Processor. The Holo-Flite™ Screw Processor is
an indirect heat exchanger commonly used to heat, cool, or dry bulk solids/slurries. It consists of a
jacketed trough housing a double-screw mechanism. The rotation of the screws promotes the
movement of the material forward through the processor. The augers are arranged so that the flights
the two screws mesh, facilitating the movement of material and improving heat transfer. Heated fluid
continuously circulates through the hollow flights of the screw augers to elevate the temperature of the
soils. This fluid travels the length of the screws and returns to the heater through the center of each
shaft. To expand the surface area available for heat transfer, fluid is also circulated through the trough
jacket.
Organic material present in the sediment is volatilized and removed from the treatment
chamber by means of an induced draft fan to an off-gas control system. The atmosphere in the
treatment chamber is controlled during treatment to ensure that oxidation of the volatilized materials
does not occur. A three- stage approach is used to control the off-gas from the Holo-Flite™ Screw
Processor. Initially, entrained particulate matter is collected using a series of cyclones. The volatilized
moisture and organics are then removed using a water-cooled condenser. The remaining non-
condensable gas is then passed through a canister containing activated carbon for volatile organic
compound (VOC) control. During operation, the composition of the off-gas stream is monitored
continuously to ensure the effective operation of the treatment system.
A process flow diagram of the 1000 Ib/hr thermal desorption system which was used for Phase
II is provided in Figure 3.
3.0 TREATABILITY STUDY APPROACH
3.1 Test Objectives and Rationale
SAIC was contracted by the ARCS Program to test four technologies for 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 ReTeC
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TO
A
CONTINUOUS
MONfTORING
THC
STACK
00
CONTINUOUS
MONITORING
02
TWO-STAGE
CONDENSER
V V
COMPENSATE CONDENSATE
KEY:
SOLD SMJPUNQ LOCAHONS
LIQUID SAMPLING LOCATORS
OAS SAtlPUNC LOCATIONS
Figure 3. Process Flow Diagram
(Source: ReTeC, Inc.)
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Thermal Desorption Technology for treating and removing PCBs and PAHs from the Ashtabula River
sediment. The following objectives were critical to the success of the study:
• To record observations and data to predict full-scale performance of the ReTeC Thermal
Desorption Technology utilizing their Holo-Flite™ Screw Processor
• 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
Based upon previous tests performed by ReTeC, 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 full-scale application of the technology.
A two-phase approach was used during this study. During Phase I, SAIC sent samples of the
raw (untreated) sediments to ReTeC. These samples underwent a series of initial tests in order to
determine the optimum conditions to be used during the actual Phase II test. During Phase II, 115-
gallon pails of untreated, Ashtabula River sediment were sent to ReTeC by SAIC. Untreated sediment
and the various end products generated during the Phase II test were obtained and analyzed by SAIC.
The data generated by SAIC were used to determine treatment desorption 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 Marine Science Laboratory was subcontracted to perform all analyses for the different
treatability studies performed by SAIC (seven treatability studies utilizing four technologies on four
sediments). Assuming that the appropriate volumes of sediment and residuals were available, the
same set of parameters listed in Table 4 was analyzed during the characterization of each of the raw
sediments and end products from the different treatability tests. In addition, representatives from SAIC
observed how all Phase II testing was conducted.
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Table 4. Parameters for Analysis of ARCS Program Technologies
Parameters
TOG/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
3.2 Experimental Design and Procedures
3.2.1 Phase I
A bench-scale unit located at ReTeC's thermal treatability laboratory in Acton, MA was used
during Phase I testing. During Phase I testing, 5-gallon sediment samples were processed using the
ReTeC 100 Ib/hr system in order to determine waste-specific processing conditions for Phase II. The
process operates at temperatures ranging from 500 to 850°F with a solids content of 20 percent or
greater required. Thirty-, 60-, and 90-minute residence times were employed during Phase I testing.
Process data were collected at 10-minute intervals throughout Phase I. Using this data, ReTeC
determined that a heat transfer media temperature of approximately 600°F, with an average solids
residence time of 60 minutes, was employed during Phase I. Additionally, the carrier gas flow rate
during Phase I averaged 5 scfm, with an average temperature of approximately 1,000°F. See Appendix
A for complete data.
The data obtained by analyzing the raw sediments and treated solids for PCBs, PAHs, and
moisture were used to determine optimum solids content, processing temperatures, and residence
times to be employed during Phase II.
3.2.2 Phase II
Phase II testing is referred to as demonstration-scale testing in ReTeC's Technical Proposal of
November 1990. Because of a scheduling conflict, Phase II testing was not performed at ReTeC's
10
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thermal treatability laboratory unit in Acton, MA. In order to prevent additional delay, Phase II was
conducted at the Star Refinery in Delaware City, DE. According to ReTeC, this unit had never treated
PCB-contaminated waste; however, the processor had recently been used to treat refinery waste.
To prevent possible contamination, the unit was decontaminated prior to testing. Decontamina-
tion consisted of steam-cleaning by ReTeC. This procedure was done before the SAIC representative
arrived at the site. The unit's feed hopper and screw conveyor were inspected and were found clean
by the SAIC representative. A possible source of contamination was the hose for the condenser tank.
Visual inspection was not made of this hose.
The Phase II Holo-Flite™ Screw Processor contains two 7-inch intermeshing screw conveyors
and has the capacity to treat 1000 to 2000 Ibs/hr of material. The system uses a molten eutectic salt
as the heat transfer fluid. The salt has heat transfer characteristics similar to those of oils and provides
the capability for achieving processing temperatures in excess of 850°F. A series of electric heaters
provide 60 kw to heat the salt.
During operation, entrained particulate matter is collected and characterized using a heated
cyclone with a "cut" size of 10 um. The volatilized moisture and organics are subsequently condensed
in a two-stage system consisting of a vertically-mounted shell and tube heat exchangers cooled by a
closed-loop glycol chiller with a thermal capacity of 30 tons. A mist eliminator is used in-line after the
condenser to minimize the carryover of entrained moisture and contaminants. The remaining non-
condensable gas stream is passed through an activated charcoal unit to control VOCs prior to release
to the atmosphere. A process flow diagram of the demonstration system is provided in Figure 3.
Specifications for the system are provided in Table 5.
ReTeC conducted Phase II testing at processing conditions [temperature (975°F), screw
rotation rate (0.75 rpm), and residence time (75 min.)] determined following Phase I. Approximately
500 Ibs of Ashtabula River sediment were used during the single Phase II run. Because a significant
amount of the feed would have been lost by utilizing the bucket elevator (i.e., relative to the total
amount of material being processed), the sediment was hand-fed into the unit.
To prevent liquids present in the sediment from passing though the system with less than
optimal retention times, decanted sediment solids were initially fed into the unit to produce a "dam"
effect in the screw processor. During actual operation, dry sand may be used to create the dam effect
in the screw processor. This will keep more liquid feeds from flowing too quickly through the screw
conveyor. After the first three and a half pails of solids were added to the unit, operators began
introducing water with each scoop of solids fed into the unit. All the water associated with the original
sediment was fed through the unit. Approximately 180 Ibs of dry treated solids were generated.
11
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Table 5. Full-Scale Holo-Flite'" Screw Processor Specifications
Product Contact Parts: 316 STAINLESS STEEL
Design Pressures: Screws = 150 PSIG
Jacket = 30 PSIG
**ASME CODE CONSTRUCTION AND STAMPED**
Screw Area: 43 Sq ft
Flight Thickness: 0.25 In
Jacket Area: 17 Sq ft
Trough Volume: 4.5 Cu ft
Screws Fluid Volume: 11 Gal
Jacket Fluid Volume: 15 Gal
Rotary Joint Size: 1.25 In
Design Fluid Flow: 38 Screws-GPM
9 Jacket-GPM
Fluid Pressure Drop: 60 PSIG
Recommended Operating Pressures: Screws = 75 PSIG
Jacket = 30 PSIG MAX
The off-gases from the process were continuously monitored at the stack by ReTeC for total
hydrocarbons. The monitoring program was designed to provide emissions data during operation.
Although not covered within this report, these data may be used to characterize the airborne emissions
from the system. The monitoring system was calibrated prior to and after the completion of the test run
using commercially obtained standards. These data were not provided by ReTeC.
During Phase II, process data were collected at 15-minute intervals throughout the test run (see
Appendix A). The data included:
• Material feed rate (Ib/hr)
• Processor rotational rate (rpm)
• Transfer media temperatures in/out (°F)
• Solids residence time (min.)
• Solids temperature in/out (°F)
• Carrier gas flow rate (scfm)
• Off-gas temperature (°F)
• Mass rates of all process streams (Ib/hr).
12
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3.3 Sampling and Analysis
The Quality Assurance Project Plan is provided in Appendix B.
3.3.1 Phase I
During Phase I, the samples of the raw sediments and treated solids were collected for
analysis. The procedures used by ReTeC to characterize these samples are listed in Table 6.
Table 6. Analytical Methods Used by ReTeC During Phase I Testing
Parameter Analytical Method
PCBs (GC/ECD) EPA 8080
PAHs (GC/MS) EPA 8270
Moisture Gravimetric difference
after drying at 105°C
Analyses of the sediments were conducted for ReTeC by CEIMIC Laboratories in Narragansett,
Rl. CEIMIC has been contracted by the EPA for both organic and inorganic analysis in the Superfund
program and is a CLP contractor. In addition, CEIMIC has been approved by the Department of
Defense's NEESA and HAZWRAP programs.
3.3.2 Phase II
3.3.2.1 Test Sample Preparation
The contaminated sample from the Ashtabula River was gray-colored and contained limited
debris. The sample contained free-standing water. Since it was very difficult to homogenize the
samples with the free-standing water present, the water was decanted prior to conducting the pilot-
scale tests and was proportionally recombined with the portion used for the Phase II testing.
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 Ashtabula River sediment to SAIC's subcontract laboratory, Battelle,
in accordance with written detailed instructions supplied to the SAIC on-site representative. The
sample was representative of the material treated by the ReTeC Holo-Flite™ Screw Processor system.
This sample was obtained by decanting the standing water from the 11 pails of sediment and
compositing an equal volume of the sediment from each of the 11 5-gallon pails with a proportional
volume of the decanted water.
13
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Residuals from the ReTeC system consisted of an organic condensate, aqueous condensate,
treated solids, and gaseous by-products. After treatment, samples of these residuals were distributed
to SAIC. As specified in the Quality Assurance Project Plan (QAPP), a minimum of 300 g (dry basis) of
solid material were required in order for Battelle to be able to complete the necessary analyses. Since
approximately 177 Ibs of solids were produced, this requirement was easily met.
When aqueous condensate was drained from the unit, the initial flow contained 1 to 2 gallons of
an oily, black liquid. A sample of the first portion of this oily liquid (sample A-OR-RE-3) was analyzed
so that comparisons could be made between this sample and a sample taken after all the water and oil
had drained from the unit into a collection drum (sample A-OR-RE). Sample A-OR-RE was obtained
from the oil which collected on the surface of the water contained in the collection drum. PAH
concentrations within these samples may provide information regarding possible contamination within
the unit.
3.3.2.3 Analysis
Analyses were conducted by SAIC's subcontracted laboratory, Battelle, on the raw sediment
and the process by-products during Phase II. The number of analyses conducted on these sediments
and their residuals are listed in Table 7. Descriptions of the analytical methods employed can be found
in Appendix C.
4.0 RESULTS AND DISCUSSION
4.1 Summary of Phase I Results
ReTeC performed a series of initial tests on the raw Ashtabula River sediment to determine
specific operating parameters which would optimize the performance of the Holo-Flite™ Screw
Processor unit during Phase II testing. Following analyses of the raw sediment and residuals produced
during Phase I testing, the following parameters were evaluated relative to their effect on performance:
heat transfer media temperature, solids residence time, carrier gas flow rate, and carrier gas tempera-
ture. Table 8 briefly summarizes the operating conditions for the Phase I test.
4.2 Phase II Results
As stated previously, the concentration 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 sediment and the process residuals (i.e., treated
solids, water, and oil), as well as applicable removal efficiencies. The discussion of Phase II results
14
-------
Table 7. ReTeC Analytical Matrix and Sample Identification
Ashtabula River Sediment
Parameters
Total Solids
(Moisture)
Volatile Solids
O&G
Metals
PCBs
PAHs
TOC
Total Cyanide
Total Phosphorous
pH
BOD
Total Suspended
Solids
Conductivity
QC Sample ()
and
Method Blank
(1)
YES
(2)
YES
(2)
YES
(0)
YES
(0)
YES
(0)
YES
(0)
YES
(0)
YES
(0)
YES
(2)
YES
(1)
YES
(1)
YES
(1)
YES
Untreated
Sediment
(1)
A
(1)
A
0)
A
(1)
A
0)
A
(1)
A
(1)
A
(1)
A
(1)
A
0)
A
MS
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
Tripli-
cate
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
Treated
Solids
0)
A
(1)
A
0)
A
(1)
A
0)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
MS
0)
A
(1)
A
0)
A
(1)
A
(1)
A
(1)
A
MSD
(1)
A
0)
A
(1)
A
; rr*T=
Tripli-
cate
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
-
Water
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
0)
A
(1)
A
MS
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
(1)
A
MSD
(1)
A
(1)
A
Tripli-
cate
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
(2)
A
Oil
(1)
A
(1)
A
1 :. . .:
.:•• .,. ':.
' '.•!•:' . " •
MS
(1)
A
(1)
A
'*'•• :=.-
Tripli-
cate
""" ;
(2)
A
(2)
A
cn
(1) = Number of Analyses
A = Ashtabula River Sediment
MS = Matrix Spike
MSD = Matrix Spike Duplicate
-------
Table 8. Optimal Operating Parameters
Operating Parameter Setting
Heat Transfer Media Temperature (°F) 600
Solids Residence Time (Min.) 60
Carrier Gas Flow Rate (acFm) 9
Carrier Gas Temperature (°F) 960
concludes with an analysis of the mass balance of the media and contaminants. A complete copy of
the data generated by Battelle for the Phase II study can be found in Appendix D.
Individual PAH compounds, PCB Aroclors, and metals were quantitated 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. Where
one or more individual components are above detection limits, total concentrations are reported as the
sum of the detected values, with one exception: when a compound was detected in the feed sediment
sample but nit detected in the treated solids, the treated solids total was presented as less than the
sum of the detected values plus the detection limit of those undetected compounds that were found in
the feed material.
4.2.1 Sediments/Treated Solids
The following sections address the quality of the sediments before and after treatment. Each
section focuses upon a different contaminant type and the reductions experienced following treatment.
4.2.1.1 PCBs
Samples of the feed material and the treated solids produced using the ReTeC technology
were analyzed for PCB contamination. The data from these analyses are presented in Table 9. Total
PCBs were identified primarily as Aroclor 1248.
Table 9. Total PCBs
(mg/kg, dry)
Treated
Feed Solids % Removal
Total PCBs 14.6 <0.6 >96
16
-------
As demonstrated by these data, a PCB concentration of <0.6 mg/kg was found in the treated
solids generated from the Ashtabula River sediment. This corresponds to a PCB removal efficiency of
>96 percent.
4.2.7.2 PAHs
Feed material and treated solids were also analyzed for PAHs. As shown in Table 10, a total
PAH concentration of <2.4 mg/kg was found in the treated solids. This value corresponds to a removal
efficiency of >60 percent. The treated solids contained a relatively large amount of naphthalene, a
common constituent of refining wastes, which was not detected in the raw sediments. The presence of
naphthalene is most likely the result of trace contamination from previous testing of the ReTeC unit at
the refinery, and not a breakdown product from other, higher-molecular weight PAHs that were detected
A
in the feed sediment. Therefore the naphthalene concentration was not includejiin the calculation of the
total PAHs in the treated solids.
Generally, the low removal efficiencies obtained for the individual PAHs in the sediment can be
attributed to the low concentration of PAHs initially present in the sediment and the large errors
associated with evaluating contaminant concentrations close to analytical detection limits. The higher
removal efficiency obtained for the system (i.e., for total PAHs) may be attributed to the method used to
quantify the individual PAHs. When making comparisons between individual PAH and total PAH
removals it must be realized that since the concentrations of individual PAHs in the feed and treated
sediment are very close to analytical detection limits, it is impossible to assess accurately the percent
removal achieved by the ReTeC technology.
4.2.1.3 Total Metals
The data in Table 11 highlight the recoveries achieved for the metal contaminants present in
the untreated feed and the treated solid. As demonstrated by the percent removal listed in Table 11,
with the exception of mercury, there is no indication that the ReTeC technology effectively removes
metals. It was assumed that the metals in the solids left in the screw conveyor did not differ in
contaminant concentration from those solids that passed through the unit. There is no logical
explanation for the increase in metal concentration for copper, nickel, lead, or selenium.
4.2.1.4 Other Analyses
The feed sediment and treated solids were analyzed for percent moisture, oil and grease, TOC,
volatile organic solids, and pH as shown in Table 12. The apparent negative percent removal (-13
percent) for TOC is within the range of acceptable precision for this analysis. Four determinations (two
17
-------
Table 10. Feed and Treated Solids PAH Concentrations
(mg/kg, dry)
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 PAHs
Feed
<0.3
<0.3
<0.4
<0.4
1.4
<0.3
1.0
0.95
0.36
0.56
0.45
0.35
0.34
0.34
<0.2
0.30
6.1
Treated
Solids
0.49
<0.3
<0.5
<0.4
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.2
<0.2
<0.2
<0.2
<0.2
0.10
<2.4
Percent
Removal
NC1
NC
NC
NC
>78
NC
>70
>68
>16
>46
>55
>42
>41
>41
NC
67
>60
1 = Naphthalene in treated solids result of cross-contamination; therefore percent removal not calculated.
NC = Not Calculated
moisture and two TOC) are necessary for determining their value. There is no reason to attribute an
increase in TOC to the technology; therefore, the best interpretation of the data is that within the
limitation of the analytical procedures, there is no change in the TOC context before and after
treatment. Moderate removals of 56.6 and 44.4 percent were achieved for oil and grease and total
volatile solids, respectively, with these removal rates corresponding to total PAH removals rates but not
with total PCB removal rates; therefore the use of either oil and grease or total volatile solids as a
surrogate parameter for assessing the performance of the ReTeC process is limited.
18
-------
Table 11. Metals Concentration in the Feed and Treated Solid
(mg/kg, dry)
Silver
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Zinc
Feed
0.19
20.8
903
3.06
591
33.7
4.26
1.361
559
53.0
58.5
0.91
234
Treated
Solids
0.19
16.5
792
2.69
520
48.1
3.91
0.005
530
77.1
77.0
1.53
231
Percent
Removal
0.0
20.7
12.3
12.1
12.0
-42.7
8.2
99.6
5.2
-45.5
-31.6
-68.1
1.3
4.2.2 Oil
The concentration of PAHs and PCBs in the oil separated from the sediment can be found in
Tables 13 and 14. Final concentrations in the treated solids and water have been included for
comparison. As mentioned previously, two separate samples of the oil were submitted for analysis.
Sample A-OR-RE was collected after all the condensates had been drained from the system, while
sample A-OR-RE-3 was taken from the initial flow of organics drained from the unit. Comparisons
between the data obtained for these two samples clearly indicate that a higher degree of contamination
was present in the initial organic flow, supporting the possibility of treatment unit contamination before
processing of the ARCS sample began.
4.2.3 Water
The concentration of PAHs and PCBs in the water extracted from the sediment can also be
found in Tables 13 and 14. Metal concentrations in the water extract are listed in Table 15, while data
characterizing the treated water according to more general parameters are listed in Table 16.
19
-------
Table 12. Removal Efficiencies for Other Parameters
(mg/kg, dry, unless specified otherwise)
Contaminant
Total PCBs
Total PAHs
Moisture, % (as received)
Oil & Grease
TOC, % weight
Total Volatile Solids, %
pH, S.U. (as received)
Feed
14.6
6.1
35.6
1004
2.00
7.64
7.88
Treated
Solids
<0.6
<2.4
0.05
436
2.27
4.25
8.09
Percent
Removal
>96
>60
56.6
-13.5
44.4
4.2.4 Mass Balance
As previously stated, Phase II testing was performed using a 1000 Ib/hr Holo-Flite™ Screw
Processor. During Phase II, only 353 pounds of treated residuals (177 pounds of treated solids, 145
pounds of aqueous condensates, and 31 pounds of organic condensates), of the 460 pounds of raw
sediment introduced to the processor were collected from the system. ReTeC estimates that of the 107
Ibs of material lost, 75 Ibs were probably caught under the flights of the processor while the remaining
32 pounds of material were most likely undrained condensates. It is apparent that the size of the unit,
and the amount of material available for treatment preclude the calculation of a accurate mass balance.
Further study involving a significantly larger volume of sediment is needed to evaluate a mass balance
for the unit appropriately.
In order to fully address the issue of equipment contamination, rough mass balances were
performed for solids, water, oil, and PAHs. Because of the limitations associated with the residual
recoveries obtained during testing, these mass balances lack the level of detail found in the mass
balances presented in other treatability reports produced by SAIC under the ARCS Program.
Furthermore, since PCBs were not found within the residuals and were not suspected of contaminating
the thermal processor used during Phase II testing, a mass balance was not performed for this
parameter. It is possible the PCBs volatilized and were captured in the activated carbon unit. ReTeC
did not analyze the carbon.
20
-------
Table 13. 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
Solids
(ug/kg)
490
<300
<500
<400
<300
<300
<300
<300
<300
<300
<200
<200
<200
<200
<200
100
<2400
Residual
Water
(ug/L)
609
4.16
53.0
82.0
200
26.7
13.0
72.0
18.0
43.5
7.91
<1
10.2
1.22
1.85
5.51
<1150
Residual
Sample A-OR-RE
1070000
6860
79500
118000
264000
38600
14900
86700
22000
50000
9190
1220
12700
1450
2220
7080
1780000
Oil (ug/kg)
Sample A-OR-RE-3
2670000
11600
158000
21700
430000
61100
18200
115000
26600
56100
7890
2540
14600
2000
2220
8550
3800000
Table 14. PCB Concentrations in the Treated Solids, Water and Oil
Contaminant
Solids
(ug/kg)
Residual Residual Oil (ug/kg)
Water
(ug/L) Sample A-OR-RE Sample A-OR-RE-3
Total PCBs
<600
<20
<7000
<7000
21
-------
Table 15. Metals Concentration in the Residual Water (ug/L)
Metals
Silver
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Zinc
Water
0.002
7.37
55.6
0.61
17.3
46.5
1800
34.2
477
147
43.8
<2
202
Table 16. Residual Water Characterization Data
(mg/L, unless specified)
Contaminant Water
Total PCBs <0.020
Total PAHs <1.15
Moisture NA
Oil & Grease 564
TOC 446
Total Volatile Solids 81
Total Solids 1600
Total Suspended Solids 1400
pH, S.U., as received 8.20
NA = Not Analyzed
22
-------
The following sections address the different mass balances and those factors that influence
their closures. Tables 17 through 20 contain the data used to calculate the mass balances.
4.2.4.1 Solids
A closure of 39.6 percent was obtained for the solids initially present in the Ashtabula sediment
(see Table 17). As stated previously, a large amount of the solids (75 pounds) was most likely caught
under the screws of the processor. Given the relatively large nature of these losses, the impact of
solids suspended in either the aqueous or organic condensates is minimal and has not been accounted
for in the mass balance.
4.2.4.2 Water
The water closure obtained for the Ashtabula River sediment was comparatively good;
approximately 88.5 percent (see Table 18). Water adhering to the condensing system did not
contribute to the output water recovered. The impact of any residual water present in the treated solids
is considered negligible and has not been accounted for in the mass balance.
4.2.4.3 Oil
A closure of 3500 percent was obtained for the oil initially present in the Ashtabula River
sediment (see Table 19). This excessively high value does not take into account any oil adhering to
the interior of the condensing unit or present in air emissions. The impact of any residual oil present in
the treated solids or aqueous condensate was also considered negligible. Apparently residual
contamination, possibly from recent tests using the unit to treat refinery wastes, was present within the
processor used during the Phase II study.
4.2.4.4 PAHs
An excessively high closure of 3170 percent was realized for the PAHs introduced to the
ReTeC system. As shown in Table 20, the vast majority of the PAHs were found in the organic
condensate, further substantiating suspicions of equipment contamination. When considering the worst
case scenario for raw contaminant concentration (i.e., by adding the detection limits obtained for
individual PAHs which were not found above detection limit when determining a value for total PAHs), a
closure of 2380 was obtained. Thus, attributions justifying the excessively high closure obtained to an
underestimation of raw sediment contamination is precluded. Furthermore, closure does not take into
account oil adhering to the interior of the condensing unit or present in air emissions. The impact of
any residual oil present in the treated solids was also considered negligible.
23
-------
Table 17. Solids Mass Balance
Ashtabula River
Input
Sediment, Ibs
H2O, %
Dry Sediment, Ibs (dry)
Oil & Grease, % dry wt.
Oil, Ibs
Total Sediment Solids, Ibs (dry)
Output
Treated Solids, Ibs
Aqueous Condensate, Ibs
Total Solids, %
Solids, Ibs
Total Sediment Solids, Ibs (dry)
Recovery, %
460
35.6
296.2
0.100
0.3
295.9
117
145
0.16
0.2
117.2
39.6
Table 18. Water Mass Balance
Ashtabula River
Input
Sediment, Ibs
H2O, %
Total Input Water, Ibs
Output
Aqueous Condensate, Ibs
Oil, %
Oil, Ibs
Total Input Water, Ibs
Recovery, %
460
35.6
163.8
145
0.0565
0.1
144.9
88.5
24
-------
Table 19. Oil Mass Balance
Ashtabula River
Input
Sediment, Ibs 460
H2O, % 35.6
Dry Sediment, Ibs (dry) 296.2
Oil & Grease, % dry wt. 0.100
Total Oil, Ibs 0.3
Output
Organic Condensate, Ibs 31
Oil & Grease, % 34.0
Total Oil, Ibs 10.5
Recovery, % 3500
4.3 Summary of Vendor Results
ReTeC did not contract to provide any analyses from this test.
4.4 Quality Assurance/Quality Control
The conclusions and the limitations of data obtained during the evaluations of ReTeC's Thermal
Desorption technology are summarized in following paragraphs.
Upon review of all sample data and associated QC results, the data generated for the ReTeC
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.
pH analysis for the sediments was performed using a 1:10 soil-to-water ratio rather than the
required 1:1. These data should be used with caution.
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.
25
-------
Table 20. PAH Mass Balance
Ashtabula River
Input
Sediment, Ibs
H20, %
Dry Sediment, Ibs (dry)
Oil & Grease, % dry wt.
Oil, Ibs
Total Sediment Solids, Ibs (dry)
PAH Cone., % dry wt.
Total PAHs, Ibs
Output
Organic Condensate, Ibs
Cone. Total PAHs, %
PAHs, Ibs
Aqueous Condensate, Ibs
Cone. Total PAHs, %
PAHs, Ibs
Total PAHs Recovered, Ibs
460
35.6
296.2
0.100
0.3
295.9
6.05 x1Q-
0.0018
31
0.178
0.055
145
1.15x 10'4
0.002
0.057
Recovery, %
3170
Large unidentified peaks were observed in the PCB analyses of the untreated sediment, water
residual, and oil residual samples. Due to the high concentration of PCBs present in the untreated
sediment, the necessary dilutions eliminated any effect on data quality. For the water and oil samples,
detection limits had to be increased significantly because of these peaks. While removal efficiencies
are not affected, mass balance closures may be difficult.
Refer to Appendix B for the complete analysis related to Quality Assurance/Quality Control.
26
-------
APPENDIX A
FINAL REPORT
THERMAL TREATABILITY TESTING
ASHTABULA RIVER SEDIMENTS
GREAT LAKES NATIONAL PROGRAM OFFICE
Prepared for
SAIC
635 West Seventh Street
Cincinnati, Ohio 45203
Prepared by:
Remediation Technologies, Inc.
9 Pond Lane
Concord, Massachusetts 01742
RETEC Project^ 8-0755
Prepared by: (
Reviewed bv:
September 1992
33
-------
TABLE OF CONTENTS
NO. DESCRIPTION PAGE NO.
1.0 Introduction j_j
2.0 Technology and Equipment Description 2-1
2.1 Bench-Scale System 2-2
2.2 Pilot-Scale System .2-2
2.2.1 Material Handling 2-4
2.2.2 Thermal Processor 2-4
2.2.3 Media Heater 2-8
2.2.4 Off-Gas Control 2-10
3.0 Scope of Work 3-1
3.1 Phase I Tests 3-1
3.2 Phase II Tests 3-2
3.2.1 Process Monitoring 3-2
3.2.2 Process Stream Sampling 3-7
4.0 Presentation and Discussion of Results 4-1
4.1 Phase I Results 4-1
4.2 Phase II Results 4-2
4.2.1 Feed Material 4-2
4.2.2 Treated Material 4-2
4.2.3 Liquid Condensates 4-6
4.2.4 Mass Balance 4-10
4.2.5 Conclusions 4-10
Appendix A Phase I and II Data Sheets
34
-------
LIST OF FIGURES
NO. DESCRIPTION PAGE NO.
2-1 Holo-Flite Processor 2-3
2-2 Field-Scale Thermal Processor 2-5
2-3 Process Flow Diagram - Demonstration System 2-6
LIST OF TABLES
NO. DESCRIPTION PAGE NO.
2-1 Processor Specifications 2-7
2-2 Solids Cooler Specifications 2-9
3-1 Process Parameters of Interest 3-4
4-1 Phase I Operating Summary 4-1
4-2 Removal Efficiencies for Other Parameters 4-3
4-3 Feed and Treated Sediment PAH Concentrations 4-4
4-4 Metals Concentration in the Feed and Treated Sediment 4-4
4-5 PAH Concentrations in the Treated Sediment, Water and Oil 4-7
4-6 PCB Concentrations in the Treated Sediment, Water and Oil 4-7
4-7 Metals Concentration in the Aqueous Condensate 4-8
4-8 Aqueous Condensate Characterization Data 4-9
35
-------
1.0 INTRODUCTION
Remediation Technologies, Inc. (RETEC) was contacted to evaluate its thermal
desorption system as a treatment technology for contaminated sediments in support of the
program being conducted by the Great Lakes National Program Office (GLNPO).
The demonstration program, conducted in two phases, had the following objectives:
• Determine if thermal desorption, using RETEC's system, could effectively treat
the contaminated sediments of concern;
• Determine the material processing and handling requirements for the sediments
prior to and after the thermal treatment process;
• Determine organic contaminant removal efficiencies for each constituent of
interest (PCBs and PAHs); and
• Determine the by-product waste stream characteristics.
Phase I bench-scale testing and Phase II demonstration-scale testing, conducted from
August 1 through September 25, 1991, provided specific information related to the thermal
desorption of organic species such as polyaromatic hydrocarbons (PAHs) and polychlorinated
biphenyls (PCBs) from the contaminated sediments.
Phase I testing involved the use of RETEC's 100 Ib/hr bench-scale thermal desorption
system. Results of this phase established optimum operating parameters involving treatment
temperatures, residence times, and material handling requirements for the next phase of testing
using RETEC's 1,000 Ib/hr thermal desorption system to determine the effectiveness of
treatment at a meaningful scale.
This report provides a description of RETEC's thermal desorption technology capabilities
and summarizes the results of key operational data collected during Phase I and Phase II of the
program.
36
-------
2.0 TECHNOLOGY AND EQUIPMENT DESCRIPTION
RETEC has developed a thermal desorption technology that has been used effectively in
processing solids contaminated with organic constituents. The technology has potential, in low-
temperature applications, as a pretreatment step for subsequent biological treatment, or when
used at higher temperatures, as a final disposal option for waste materials.
Thermal desorption refers to the separation of contaminants from a solid matrix through
volatilization. The desorption process can be used in conjunction with separate processes, such
as incineration or condensation for subsequent control of the volatilized constituents.
The fact that, for some contaminants, efficient removals can be achieved at relatively low
treatment temperatures makes thermal desorption a cost-effective approach for the remediation
of solids contaminated with hazardous organic constituents.
The desorption process can be accomplished using various types of direct-fired,
incineration- or indirect-fired equipment. Applications using indirectly fired methods are
preferred in many cases since they generate a significantly smaller volume of off-gas than do
traditional incineration systems. As a result, the capital and operating costs for the system can
be reduced significantly.
RETEC's application of the technology provides for its use in a condensing mode, i.e.,
volatilized organics are condensed into a concentrated liquid stream which can subsequently be
managed on-site using biological treatment systems, or off-site at a permitted disposal facility.
The benefits of the system include capital costs that are two to three times less expensive
than more traditional thermal technologies, and permitting requirements that are significantly less
stringent than those for incineration systems.
RETEC's system is based upon the use of an established, indirectly-heated thermal
desorption/dryer system, the Holo-Flite® Screw Processor, manufactured by the Denver
Equipment Company, Colorado Springs, Colorado.
The Holo-Flite® processor is an indirect heat exchanger commonly used to heat, cool,
or dry bulk solids/slurries. The treatment system consists of a jacketed trough which houses a
double screw mechanism. The rotation of the screws promotes the forward movement of the
37
-------
material through the processor. The augers are arranged in the trough so that the flights of the
two screws mesh, facilitating the movement of material and improving heat transfer.
The processor uses a contained, non-contact circulating heat transfer fluid to elevate the
temperature of the soils. As indicated hi Figure 2-1, the heated media continuously circulates
through the hollow flights of the screw augers, travels the full length of the screws, and returns
through the center of each shaft to the heater.
2.1 BENCH-SCALE SYSTEM
RETEC's bench-scale system uses a Fin-Flite* thermal processor manufactured by the
Denver Equipment Company of Colorado Springs, CO. The system is designed to heat the
material to temperatures appropriate to volatilize the organic contaminants from the original
matrix, leaving a "clean" soil for disposal.
The processor consists of two three-inch diameter hollow augers to convey the material
and provide the principal heat transfer surface. The system circulates a synthetic oil as the heat
transfer media through the augers on a continuous basis (1.5 gpm) to achieve appropriate solids
processing temperatures. The temperature of the media is maintained using a separate 6 Kw
heater. The heat transfer media, THERMALANE 600, has a maximum operating temperature
of approximately 650°F, resulting in solids temperatures in the range of 550°F.
The system uses a proprietary inert gas handling system to improve the removal
efficiency for higher boiling organic species. Off-gases from the processor are collected in a
two-stage direct contact condenser/carbon bed assembly.
2.2 PILOT-SCALE SYSTEM
RETEC utilized its transportable demonstration system for the performance of the Phase
II testing. The system, as contained on a single 8' x 45' flatbed trailer, consists of material feed
equipment, thermal processor, indirect condensing system, and an activated carbon unit for the
control of volatile organic constituents. The system has been designed to meet Class 1 Division
2 electrical code by means of Type Z Purging of enclosures for electrical equipment and use of
38
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Agent In
Agent Out
Trough Jacket
Zoior cnange aenotes cnange in
•emoerature of neat excnange agent
• Red = Hot Blue =CooH
Holo-Flite Processor
-IGURE
2-1
39
-------
TEFC motors. RETEC's transportable demonstration system is presented in Figure 2-2. A
process flow diagram for the system is provided in Figure 2-3.
The processor uses a contained, non-contact circulating heat transfer fluid to elevate the
temperature of the solids. The heated media continuously circulates through the hollow flights
of the screw augers, travels the full length of the screws, and returns through the center of each
shaft to the heater. RETEC's pilot-scale system employs a unique heat transfer medium, a
molten salt eutectic consisting of 53% potassium nitrate, 40% sodium nitrite, and 7% sodium
nitrate. The use of this media provides the ability to achieve processing temperatures up to
850 °F to affect appropriate removals of heavier organic species and increase the efficiency in
treating more complex solid matrices. In addition to the enhanced thermal properties, the salt
eutectic provides significant aesthetic benefits; the salt melt is non-combustible; it provides no
risk of explosion; and potential vapors are non-toxic.
2.2.1 Material Handling
Generally, material to be processed is placed in a live bottom feed storage hopper
(capacity of 1.5 cubic yards). The material is sized and conveyed to a bucket elevator using
twin six-inch diameter screws with ribbon flights. The bucket elevator raises the material to a
height of 17 feet to a feed conveyor. The feed conveyor then uses a single six-inch ribbon flight
auger to convey the material to a double slide gate (air lock) to prevent the leakage of ambient
air into the processor.
The sediments dredged for the program were not amenable to the use of this equipment
because of the amount of free liquids present. The feed material had a high moisture content
and exhibited the adhesive characteristics of fine-grained material. Therefore, sediments were
fed manually into the thermal processor using the original five-gallon shipping containers.
2.2.2 Thermal Processor
The Holo-Flite® thermal processor, Model D7-10, contains two, seven-inch intermeshing
screw conveyors and has the nominal capacity to treat 0.5 ton per hour of material.
Specifications for the system are provided in Table 2-1.
40
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FIELD-SCALE THERMAL PROCESSOR
-------
FLOW DIAGRAM OF THERMAL DESORPTION SYSTEM
FIGURE
2-3
-------
TABLE 2-1
Processor Specifications
Product Contact Parts: 316 STAINLESS STEEL
Design Pressures:
Screws = 150 PSIG
Jacket = 30 PSIG
**ASME CODE CONSTRUCTION AND STAMPED'
Screw Area: 43 Sq. Ft.
Flight Thickness: 1/4 Inches
Jacket Area: 17 Sq. Ft.
Trough Volume: 4.5 Cu. Ft.
Screws Fluid Volume: 11 Gallons
Jacket Fluid Volume: 15 Gallons
Rotary Joint Size: 1 1/2 Inches
Design Fluid Flow: 38 GPM Screws
9 GPM Jacket
Fluid Pressure Drop: 60 PSIG
Recommended Operating Pressures:
Screws = 75 PSIG
Jacket = 30 PSIG MAX.
43
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The system was operated to achieve solids temperatures in the range of 500-675°F. At
these temperatures, organic constituents and moisture present in the waste material were
volatilized and drawn away under negative pressure to the off-gas control system. The pressure
inside the processor was maintained at -0.1 to -0.5 inch of water column (W.C.) to minimize
both fugitive emissions and the leakage of ambient air into the processor. Solids residence times
in the processor were set at 90 minutes.
The atmosphere in the treatment chamber was controlled during all treatment activities
to ensure that oxidation of the volatilized materials did not occur. An "inert" atmosphere was
maintained in the treatment chamber through the controlled introduction of nitrogen. RETEC
used a tube tank (commercially provided) as the inert gas source. The nitrogen was delivered
at a flow rate of 5 to 30 cfm (gas). The oxygen content in the off-gas was monitored
continuously during the operation of the treatment system using a Beckman Model 255 oxygen
analyzer.
Treated solids were fed by gravity to a second processor designed to cool the solids prior
to release to the atmosphere. The "cooling screw" was also of the Holo-Flite design and used
a single auger with chilled water as the cooling media. Specifications for this system component
are provided in Table 2-2. The cooling screw required approximately 12 gpm of water (< 90°F)
to cool the solids to a temperature of approximately 140°F. The temperature of the water was
maintained using a closed-loop chiller system. The treated solids were discharged from the
cooler through a rotary air lock into a 55-gallon storage drum.
2.2.3 Media Heater
The salt eutectic was stored/heated in an enclosed, insulated stainless steel vessel having
a capacity of approximately 600 gallons. The tank system was equipped with a continuous
containment area. The eutectic was heated electrically using 27 immersion heaters capable of
providing 1 MMBTU/hr of heating capacity to the unit and media temperatures of approximately
l,000°F. The media was delivered to the thermal processor by means of a vertical cantilever
pump with a submersible head. The pump has the capability to deliver up to 50 gpm of media
to the processor.
44
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TABLE 2-2
Solids Cooler Specifications
Product Contact Parts: 316 STAINLESS STEEL
Design Pressures:
Screws = 150 PSIG
Jacket = 30 PSIG
**ASME CODE CONSTRUCTION AND STAMPED'
Screw Area: 22 Sq. Ft.
Flight Thickness: 1/4 Inches
Jacket Area: 12 Sq. Ft.
Trough Volume: 2.6 Cu. Ft.
Screws Fluid Volume: 5.5 Gallons
Jacket Fluid Volume: 7.5 Gallons
Rotary Joint Size: 1 1/2 Inches
Design Fluid Flow: 8 GPM Screws
4 GPM Jacket
Fluid Pressure Drop: 60 PSIG
Recommended Operating Pressures:
Screws = 75 PSIG
Jacket = 30 PSIG MAX.
-------
2.2.4 Off-Gas Control
The off-gas control system was designed to accommodate an off-gas flow rate of — 150
scfm and a "worst case" moisture and organic loading of 400 Ibs/hr and 150 Ibs/hr, respectively.
Two particulate cyclones were used to remove any fine solid particles (> 10 /im) which may
have been entrained with the off-gases. Two indirect-heat exchangers, having a combined
surface area of 200 sq ft., were used to reduce the temperature of the gas leaving the processor
to approximately 120°F and condense the majority of the entrained moisture/organics. An after-
cooler (condenser #3) was placed in-line to remove the remaining moisture and volatile organics
from the off-gas stream. The exchanger was designed to achieve an exit gas temperature of
50°F. Cooling water was recirculated in a closed loop through a chiller having a capacity of
240,000 BTU/hr. Condensates were collected in two separate vessels prior to transfer from the
system. The system was driven by a variable speed rotary blower capable of developing 300
scfm of flow at a vacuum of 3 inches of Hg.
The thermal system was equipped with an activated carbon system to control non-
condensible organics prior to release to the atmosphere. The carbon system was charged with
1,500 Ibs of carbon. Volatile organic emissions from the system were monitored in the stack
on a continuous basis using the equipment described in Section 3.0 of this document.
46
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3.0 SCOPE OF WORK
RETEC conducted a series of treatability tests to evaluate the effectiveness of its thermal
desorption technology in processing contaminated sediments from the Ashtabula River as part
of the GLNPO study.
The demonstration tests were designed to characterize the influent and effluent process
streams from RETEC's thermal systems under several process conditions to determine the most
cost-effective and efficient method of operation. The results from the program were used to
validate current estimates of treatment costs.
All treatability activities, including shipment storage and disposal of samples, were
conducted in accordance with appropriate regulations. The transportation of all samples
complied with applicable shipping requirements including those of the Department of
Transportation (DOT) and the U.S. Postal Service.
RETEC provided the capability to test materials with both bench- (Phase I) and pilot-
scale (Phase II) treatment systems. In this manner, RETEC obtained meaningful data related
to the effectiveness of the technology and the composition of the effluent process streams.
3.1 PHASE I TESTS
Prior to the performance of the demonstration test program, appropriate, waste-specific
processing conditions were selected through an initial screening test conducted using RETEC's
bench-scale system. The test was conducted on a representative five-gallon sample of material
provided by SAIC. Three solids processing conditions (30, 60 and 90 minutes residence time)
were evaluated for the sample at the maximum operating temperature of the bench system,
approximately 650°F. Multiple residence times were achieved by successive 30-minute passes
of the material through the processor. Appropriate process data was collected at 10-minute
intervals throughout the tests. The recorded data included:
• material feed rate (Ib/hr);
• processor rpms;
• transfer media temperatures in/out (°F);
• solids residence time (min.);
47
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• solids temperatures in/out (°F);
• carrier gas flow rate (scfm);
• carrier gas inlet temperature (°F);
• off-gas temperature (°F); and
• mass rates of all process streams (Ib/hr).
Data sheets for the Phase I testing are provided in Appendix A.
Samples of the feed and treated solids for each residence time were collected for analysis
as discussed in Section 4.1. The results from the screening tests were appropriate to define the
system configuration, processing temperature, and approximate residence time for subsequent
testing for the Phase II program.
3.2 PHASE H TESTS
Pilot-scale testing was conducted using approximately 500 Ibs. (one 55-gallon drum) of
material. RETEC conducted this test at processing conditions defined during the Phase I testing
program. Process data was collected at 15-minute intervals throughout the test run. Treated
solids temperatures averaged 570°F, for a residence times of 90 minutes.
3.2.1 Process Monitoring
RETEC monitored all pertinent process parameters at routine intervals during the
program. Such an approach was imperative to develop appropriate data for the subsequent
design of installed equipment. The recorded data included:
• material feed rate (lb/hr);
• processor rpms;
• transfer media temperatures in/out (°F);
• solids residence time (min.);
• solids temperatures in/out (°F);
• carrier gas flow rate (scfm);
• carrier gas inlet temperature (°F);
• off-gas temperature (°F); and
• mass rates of all process streams (lb/hr).
48
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A complete list of the parameters monitored is provided in Table 3-1. Off-gas
concentrations of oxygen and hydrocarbons were recorded continuously with a strip chart
recorder. Discussions of the principal parameters monitored during Phase II testing are provided
below.
Temperature
Process temperatures were monitored at 21 locations using Type-K thermocouples
manufactured by Omega Engineering, inc. Temperature signals were transmitted to a panel-
mounted Model 115 readout, using wire insulated to withstand temperatures up to 1,000°F.
Pressure
Atmospheric pressures were monitored at seven locations within the processing system
using magnahelic gauges manufactured by the Dwyer Co. Pressures were monitored within the
headspace of the processor and across all of the principal components of the off-gas system to
ensure proper operation of the system and to help anticipate maintenance problems, such as poor
heat transfer due to paniculate "fouling."
Gas Flow Rates
The off-gas flow rate from the thermal system was monitored within the stack gas using
a hot-wire anemometer. The hot-wire measured the off-gas velocity, in feet per minute. The
actual flow rate was calculated by using the area of the stack, multiplied by the velocity to give
a flow rate of cubic feet per minute. The flow rate of inert gas into the processor dome was
monitored by use of a standard flow meter manufactured by the Dwyer Company.
Solids Feed Rate
The solids feed rate (Ib/hr) to the processor was monitored by recording the known
volume of sample material entering the unit. The untreated sediment was distributed into five-
gallon pails to ease loading of the system. The feeding was performed on a batch basis by
emptying a five-gallon pail into the feed system every ten minutes.
49
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TABLE 3-1
Process Parameters of Interest
Process Temperatures (°F)
Thermal Processor
Waste Feed^)
Treated Solids ((OUO
Transfer Media Tank
Transfer Media fin)
Transfer Media (out)
Inert Gasrm)
Solids Cooler
Treated Solids (out)
Transfer Media(in)
Transfer Media/,
1(out)
Off-Gas Treatment
Gas from Processor
Gas Exiting Cyclone
Gas Exiting Condenser
Condenser Cooling
Condenser Cooling Media(out)
Fin Fan Cooler Setpoint
Gas Entering After-cooler
Gas Exiting After-cooler
After-cooler Media(in)
After-cooler
Chiller Setpoint
50
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TABLE 3-1
Process Parameters of Interest (Continued)
Off-Gas Composition
Oxygen (exit from participate cyclone)
Total Hydrocarbons (stack)
Process Pressures (in. W.C.)
Inert Gas Delivery
Processor Headspace
Solids Cooler Headspace
Exit from Paniculate Cyclone
Exit from Condenser
Inlet to After-cooler
Inlet to Carbon Bed
Gas Flow Rates (acfm)
Inert Gas
Exit from Paniculate Cyclone
Discharge Stack
Liquid Flow Rates (gpm)
Condenser Cooling Media
After-cooler media
Solids Cooler Transfer Media
Aqueous Condensate
Organic Condensate
Solids Processing Rate (Ib/hr)
Waste Feed
feed auger rpms
processor rpms
Treated Solids
solids cooler rpms
51
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Continuous Emissions Monitoring
The continuous emissions monitoring (CEM) system, a self-contained, nitrogen-purged
cabinet on the thermal system, was designed to meet Class 1, Division 2 electrical codes.
Samples were collected from two principal locations: the exit point from the paniculate cyclone
(oxygen); and the discharge stack (total hydrocarbons). Heated sample lines carried the gas
samples to the cabinet through sample conditioning systems prior to analysis. The sample
stream conditioning systems consisted of:
• refrigerated condensers with an automatic drainage system;
• coalescing high-efficiency filters to remove oil mists, particulates, and acid
vapors; and
• membrane dryers for selective drying of the gas sample based on permeation
distillation.
Oxygen Analyzer
The oxygen monitoring system used a Beckman Model 755 oxygen analyzer to provide
continuous data related to the oxygen content of the off-gas stream. The analyzer makes
measurements based upon the determination of magnetic susceptibility of the sample gas, oxygen
being very paramagnetic, and other gases being weakly diamagnetic. The instrument provided
direct readout of oxygen concentration on a front panel meter.
The meter has a range of 0% to 100% oxygen concentration, a reproducability of ±
0.01 %, and a zero drift of ± 1 % of full scale per 24 hours. Maximum sample temperature and
pressure are 150°F and 10 psig, respectively. The sample flow rate is 250 cubic centimeters
per hour.
Total Hydrocarbon Analyzer
Total hydrocarbons were monitored in the exhaust gas from the system using a Beckman
Model 400A hydrocarbon analyzer. The analyzer continuously measured the concentration of
hydrocarbons in the gas stream using a flame ionization detector (FID).
52
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Electronic stability at maximum sensitivity is ± 1% of full scale through a sample
temperature of 30 to 110°F. Sensitivity is adjustable from 1 ppm to 2% calibrated to methane.
Recorded process data sheets for the Phase n tests are presented in Appendix A of this
document.
3.2.2 Process Stream Sampling
The field demonstration program was designed to incorporate a comprehensive sampling
and analytical program to characterize all of the influent and effluent process streams associated
with the system. Five sample streams are associated with the demonstration test equipment:
• Waste Feed;
• Treated Soil;
• Aqueous Condensate;
• Organic Condensate; and
• Process Off-Gas.
Composite samples of each of the solid and liquid streams were collected as a part of the
test program as detailed below. Appropriate aliquots of each sample were collected into
precleaned containers by SAIC and submitted for subsequent analysis.
Solid Samples
As-Received Material
RETEC pretreated the feed material by pouring off free standing liquid and stored it in
lined, covered containers before treatment. Samples of the material were obtained during the
preparation step using a grab sampling technique, SOOO (scoop). Approximately ten grab
samples were collected from the drum of material into precleaned containers and submitted to
SAIC personnel for analysis.
53
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Treated Material
Samples of the final treated material were obtained from the exit point of the solids
cooler at 15-minute intervals throughout each test and composited to form a single sample for
each test condition. The entire sample from the test run was collected into a lined 55-gallon
drum.
Liquid Samples
The aqueous and organic condensates from the test were also collected into lined 55-
gallon drums. Samples of the condensate streams were collected from a tap located in the line
leading to the sample drums. The samples were collected at 15-minute intervals and composited
into samples for analysis.
At the conclusion of the test, the collected process streams were weighed for subsequent
mass balance determinations.
The off-gases from the process stream were continuously monitored at the stack location
for total hydrocarbons. The monitoring program was designed to provide emissions data during
the operation of the thermal desorption system, and to generate information that might further
characterize the airborne emissions from the system. The monitoring system was calibrated
prior to and at the completion of each of the test runs using commercially obtained standards.
54
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4.0 PRESENTATION AND DISCUSSION OF RESULTS
RETEC performed bench- (Phase I) and pilot- (Phase II) scale testing of its thermal
desorption technology on contaminated sediments from the Ashtabula River. Results of the
program are presented in detail in the following sections.
4.1 PHASE I RESULTS
RETEC performed a series of bench-scale tests on the raw Ashtabula River sediment to
determine specific operating parameters which would optimize the performance of the thermal
desorption technology during pilot-scale testing (Phase II). Process parameters during Phase I
testing were analyzed and evaluated relative to their effect on treatment performance. Table 4-1
briefly summarizes the operating conditions for the bench-scale test.
TABLE 4-1
Phase I Operating Summary
OPERATING PARAMETERS
Heat transfer media temperature (°F)
Solids residence time (min.)
Carrier gas flow rate (acfm)
Carrier gas temperature (°F)
600
60
5
1,000
Waste feed for the bench-scale tests had PCB concentrations of 11.6 mg/kg and a
moisture content of 48%. The analysis of residuals associated with a residence time of 60
minutes indicated that PCB concentrations had been reduced to < 0.5 mg/kg. The moisture
content of the material had been reduced to less than 1 %. Concentrations of PAHs in the waste
feed were not detected. Data sheets for the Phase I tests are included in Appendix A.
55
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4.2 PHASE H RESULTS
RETEC's pilot-scale demonstration system was used to evaluate further the effectiveness
of thermal desorption on the contaminated river sediments. The test provided the opportunity
to process sediments with a treatment technology which resembles a design and operating
condition typical of larger full-scale treatment systems.
The pilot test was performed on September 25, 1991. Residence time for the pilot-scale
test was set at 90 minutes in order to ensure appropriate removal rates. The following sections
address the quality of the sediments before and after treatment.
4.2.1 Feed Material
Approximately 500 Ibs. of Ashtabula River sediments was received. A composite sample
was collected and analyzed for PCBs, PAHs, metals, oil and grease, total organic carbon, total
volatile solids, moisture content and pH. Data from these analyses are presented in Tables 4-2
through 4-4. Percent moisture of the feed material was 35.6%. Total PCB and PAH
concentrations were 14.6 and 6.05 mg/kg, respectively. Oil and grease content was measured
at 1,000 mg/kg dry weight.
4.2.2 Treated Material
A single composite sample of the treated material was analyzed for the same parameters
as the initial feed material. Results of the analyses calculated removal efficiencies summarized
in Tables 4-2 through 4-4. PCBs detected in the initial feed of 14.6 mg/kg were reduced to less
than 0.6 mg/kg. This corresponds to a removal efficiency of >96%.
As shown in Table 4-3, a total PAH concentration of 0.58 mg/kg was found in the
treated sediment. This value corresponds to a removal efficiency of 90.4 percent. The principal
contaminant in the treated solids, naphthalene, was not detected in the as-received sediments,
but is a common constituent of petroleum refining wastes. Therefore, the presence of
naphthalene may be the result of trace contamination from previous testing at a petroleum
refinery.
-------
Generally, the low removal efficiencies obtained for the individual PAHs in the sediment
can be attributed to the low concentration of PAHs initially present in the sediment and the large
errors associated with evaluating contaminant concentrations close to analytical detection limits.
The high removal efficiency obtained for the system (i.e., for total PAHs) may be attributed to
the method used to quantify the individual PAHs. When making comparisons between individual
PAH and total PAH removals, it must be realized that, since the concentrations of individual
PAHs in the feed and treated sediments are very close to analytical detection limits, it is
impossible to accurately assess the removal efficiencies effectively.
The data in Table 4-4 highlight the recoveries achieved for the metal contaminants
present in the untreated feed and the treated sediment. As demonstrated by the percent removals
listed in Table 4-4, with the exception of mercury, there is no indication that this technology is
effective at removing metals.
The feed sediment and treated solids were analyzed for percent moisture, oil and grease,
TOC, volatile organic solids, and pH as shown in Table 4-2. Although moderate removals of
56.6% (oil and grease) and 44.4% (volatilize organic solids) were achieved, these removals do
not closely correspond to total PAH or PCB removal efficiencies and is believed to be from the
contamination of residuals from past treatment demonstrations at petroleum refineries. Percent
moisture in the sediments was removed at a rate of 97.2%. The TOC concentration increased
from 2.00 to 2.27% because of the weight reduction of the treated material versus the feed.
TABLE 4-2
Removal Efficiencies for Other Parameters
(mg/kg, dry, unless specified differently)
CONTAMINANT
Total PCBs*
Total PAHs
Moisture, % (as received)
Oil & Grease
TOC, % weight
Total Volatile Solids, %
pH, S.U. (as received)
FEED
14.8
6.05
35.6
1004
2.00
7.64
7.88
TREATED
SEDIMENT
<0.6
0.58
<1
436
2.27
4.25
8.09
%
REMOVAL
>98
90.4
97.2
56.6
-13.5
44.4
Identified primarily as Aroclor 1248
57
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TABLE 4-3
Feed and Treated Sediment PAH Concentrations
(mg/kg, dry)
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k) fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(a, h)anthracene
Benzo(g,h,i)perylene
Total PAHs
FEED
<0.3
<0.3
<0.4
<0.4
1.378
<0.3
1.037
0.949
0.358
0.559
0.448
0.348
0.337
0.335
<0.2
0.303
6.05
TREATED
SEDIMENT
0.485*
<0.3
<0.5
<0.4
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.2
<0.2
<0.2
<0.2
<0.2
0.097
0.58
%
REMOVAL
NC
NC
NC
NC
>78.1
NC
>70.9
>68.3
>16.1
>46.3
>55.1
>42.3
>40.3
>39.7
NC
68.7
90.4
NC = Not Calculated.
* Potentially the result of residual contamination
58
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TABLE 4-4
Metals Concentration in the Feed and Treated Sediment
(rag/kg, dry)
Silver
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Zinc
FEED
0.19
20.8
903
3.06
591
33.7
4.26
1.361
559
53.0
58.6
0.91
234
TREATED
SEDIMENT
0.19
16.6
792
2.69
520
48.1
3.91
0.005
530
77.1
77.0
1.53
231
%
REMOVAL
0.0
20.7
12.3
12.1
-12.0
-42.7
8.2
99.7
5.2
-45.5
-31.6
-68.1
1.3
59
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4.2.3 Liquid Condensates
Liquid condensates were collected from the off-gas condensing system during the
treatment process. A two-phase condensate of water and oil was drained from the system.
The concentration of organics in the soil separated from the sediment can be found in
Tables 4-5 and 4-6. Final concentrations in the treated sediment and water have been included
for comparison. There are two columns for constituent levels in the oil phase. Oil, was a
sample collected of the first oil condensate from the off-gas condensing system. This first
"sludge" was very viscous and dark in color. The second oil, Oil2, was a much lighter color
oil which exited the condensing system after Oil,. The analyzed results indicate that Oil, has
a much higher contaminant concentration than Oil2. Upon further investigation, Oil, is
reminiscent of condensates collected during the thermal treatment of oily petroleum refinery
wastes. It is believed that constituent concentrations in Oil[ condensate are residues from past
treatment demonstrations at petroleum refineries and, in fact, was the last program conducted
before the Ashtabula River program.
Oil2 is more indicative of a lighter condensate from a material that contains low oil and
grease and high moisture content, such as the sediments from the Ashtabula River.
Water
The concentration of PAHs and PCBs in the water extracted from the sediment can also
be found in Tables 4-5 and 4-6. Metal concentrations in the water extract may be found in
Table 4-7, while data characterizing the treated water according to more general parameters can
be found in Table 4-8.
60
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TABLE 4-5
PAH Concentrations in the Treated Sediment, 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
Indeno(l,2,3 -cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g , h , i)perylene
Total PAH
SEDIMENT
(ug/kg)
485
<300
<500
<400
<300
<300
<300
<300
<300
<300
<200
<200
<200
<200
<200
97
582
WATER
(ug/L)
609
4.16
53.0
82.0
200
26.7
13.0
72.0
18.0
43.5
7.92
<1
10.2
1.22
1.85
5.51
1150
OILi
(ug/kg)
1,070,000
6,860
79,500
118,000
264,000
38,600
14,900
86,700
22,000
50,000
9,190
1,220
12,700
1,450
2,220
7,080
1,780,000
OIL,
(ug/kg)
2,670,000
11,600
158,000
21,700
430,000
61,100
18,200
115,000
26,600
56,100
7,890
2,540
14,600
2,000
2,220
8,500
3,800,000
TABLE 4-6
PCB Concentrations in the Treated Sediment, Water and Oil
CONTAMINANT
Total PCBs
SEDIMENT
(ug/kg)
<600
WATER
(ug/L)
<20
OIL2
(ug/kg)
< 7,000
OIL,
(ug/kg)
<7,000
61
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TABLE 4-7
Metals Concentration in the Aqueous Condensate (ug/L)
Silver
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Zinc
WATER
0.002
7.37
55.6
0.61
17.3
46.5
1,800
34.2
477
147
43.8
<2
202
62
-------
TABLE 4-8
Aqueous Condensate Characterization Data
(mg/L, unless specified differently)
CONTAMINANT
WATER
Total PCBs
Total PAHs
Moisture
Oil & Grease
TOC
Total Volatile Solids
Total Solids
Total Suspended Solids
pH, S.U. as received
< 0.020
1.15
NA
564
446
81
1,600
1,400
8.20
63
-------
4.2.4 Mass Balance
As previously stated, Phase II testing was performed using a full-scale, 1,000 Ib/hr Holo-
Flite® thermal processor. During Phase II, only 353 pounds of treated residuals (177 pounds
of treated solids, 145 pounds of aqueous condensates, and 31 pounds of organic condensates),
out of the 460 pounds of raw sediment introduced to the processor, were collected from the
system. This calculates into a mass balance of 76.7%. RETEC estimates, of the 107 Ibs of
material not accounted for, 75 Ibs. of solids were retained in the void spaces of the processor,
and approximately 32 pounds (four gallons) of water were most likely retained in the condensate
receiving vessels. It is apparent that the size of the unit, as compared to the amount of material
available for treatment, precludes the calculation of a meaningful mass balance. Further study,
involving a significantly larger volume of sediment, is needed in order to appropriately evaluate
a mass balance for the unit.
4.2.5 Conclusions
A review of the results provide for the following conclusions related to material
composition, material handling, effectiveness of treatment and process conditions.
Material Composition
The as-received material had an average moisture content of 35.6%. Solids were
primarily silts and clays and were very cohesive. The material contained relatively low levels
of organic contamination. The oil and grease concentration was 0.1 %. PCBs and total PAHs
were present at 14.8 and 6.05 mg/kg, respectively.
Material Handling
Due to the high moisture content, the sediments could not be fed through the existing
material handling system. Feeding was performed on a batch basis by emptying a five-gallon
pail of sediment into the feed chute every ten minutes. The sediment was generally free of
debris or oversized material which would adversely affect the processing of the sediment during
full-scale operations. RETEC recommends investigating alternative methods to feed the
processor, such as a positive displacement pump designed to handle high solids content.
64
-------
Performance of the Technology
RETEC's process was successful in treating the Ashtabula River sediments for both waste
minimization and organic contaminant removal.
The most dramatic effect of treatment is the mass/volume reduction of the treated solids.
The mass reduction was 23.2%, primarily due to the removal of moisture. Moisture was
reduced by 97% in the treated solids, demonstrating that the technology can provide an effective
means of dewatering sediment.
Total PCS and PAH concentrations in the feed material were removed by greater than
98 and 90%, respectively. Oil and grease, as well as total volatile solids concentrations were
also reduced. It is believed that residual contamination from previous testing at petroleum
refineries were the cause of the lower removal rates.
Due to the limited scale of this test program (500 Ibs. of feed) and the size of RETEC's
demonstration unit (1,000 Ib/hr), it is difficult to define processing parameters with much detail.
Further, with the low concentration of contaminants in the feed, a single batch-type test is not
representative of the technology's full capabilities. RETEC recommends the performance of a
larger scale test program designed to evaluate processing data under steady state operating
conditions and varying treatment parameters.
65
-------
APPENDIX A
Phase I and II Data Sheets
66
-------
54IC. AsnbaU Bi
DATE:
SHIFT START TIME:
SHIPTENDTIME:
9/25
-J
AIR MONITORING
O2%
TUG PPM
MOISTURE CONTENT * TOTAL
WASTE FEED
Tltl-ATlin SOU
LEVEL OP PRODUCT
OIL
WATER
SALT DRIP RATE
PROCESSOR dpm
AVO.
10| 104 86 108 118 102 12 113 123 11.4 11 11.4 10(3
2I9J 214 200 198 180 172 183 204 293 470 317 293 2452
I I
1 1
1
| 60 1 60 1 60 1 50 1 45 1 45 1 50 1 40 1 40 30 20 1 20 1 4333
SAMPLE COLLECTION
TIMEOI'SAMPI INO
TYFB OP SAMI'IJ!
# OP SAMPLES
AMOUNTOPEAal SAMPLE
DESTINATION
-------
t 541/r SY.51EM
03
5A|C,A!nbu|. Bi«t5{dime.i!> _._ .. __ ......
EBOigCT * H80-755-400
I) All:.
iiiiii-r siAur iiME:
SIMFTENDTIME:
OFF O AS FLOW RATES
STACK O AS Vl-.l OCITY («f|2m)
SI ACKGAS I'l OWKA'IF. Ulan)
SYSTEM PRESSURES
PKOCI-SSOK lll-ADSI'Ari; (IN II2O)
COOI 1NU III. All M'ACI: [IN II2O|
I'RE-CYC 1 ONI: *l
I'KE-CY< 1 ONI: *2
1 W M
I'OSr-C'YCI ONL *2
PRE-1IXI
I'OST-IIXI l'ic> dr,i|>
PRE-IIX2
I'OST-IIXZ I'fcs JH^
PRE-IIXil'rci dioj)
I'OSr-IIXi
lllOWIjjl (|,il|8)
STACK (in II.! II]
Bl OWI.K bP ll£
9«S
6 ".(10
-04
0
(1 5
n
i
u
0
0
6
5500
8500
-0 3
0
OS
0
0
0
0
0
6
-0 1
n
0 5
0
u
0
n
0
6 5
7500
-04
0
OS
0 5
0
0
0
0
82
1500
-04
0
1 5
1
0
0
0
1
10
1500
9000 1500
___"__; "~_:
blower
off AVO.
9000
650 0 1 600 0
1
00
691 6
AVO.
-01
0
1 7
1
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0
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1
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-04
0
2 5
1 5
0
1
0
2
124
-05
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II 9
-OS
0
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104
-05
0
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77
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0
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0
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0
77
0
0
0
0
0
0
0
0
0
-034
0
0191
03
0
0 166
0
0451
1066
-------
VO
BeTtC'S MgBl^E SALT SYSTEM
5A|C.AHibuji Rjvsf Stjimenli._.
DAJE:
SHIFT START TIME:
SHIFT END TIME:
9/25
SJCSIEHELQJV BATES AMfi-EBE§s.l)BES_
COOUNO WATER PLOW RATES
CONDENSER HX1 PRESSURE PSI
CONDENSER 11X2 PRESSURE PSI
CONDENSER 11X3 PRESSURE PSI
COOUNO SCREW PRESSURE PSI
COOIJNG SCREW FLOW OPM
SYSTEM Fl OW Cil'M
100
100
100
100
20
160
100
100
100
100
20
160
too
100
100
too
20
160
100
100
100
100
20
160
100
100
100
100
20
160
100
100
100
100
20
160
100
100
100
too
20
160
100
100
100
too
20
160
100
100
100
too
20
160
100
100
100
100
20
160
100
100
100
too
20
160
100
100
100
100
20
160
*VO.
100
100
100
too
20
160
NITROGEN FLOW RATES
PLOW TO PROCESSOR SCPM
COOUNG SCREW SCFM
TYPE Z PURGE *1 SCFM
*2 SCPM
43SCHM
»4 SCFM
*SSCPM
NITROGEN REMAIINO IN 1120
TANK CAPACITY IN 112)
120
20
100
100
60
10
90
10
90
BO
90
SO
90
10
90
10
90
|
»
)
6
5
6
3
2
TOTAL
AVQ.
7.5J3
7013
180
-------
SALT SYSTEM.
EBQJECJ Si ll»Qr?53rJQ9
DATE:
START FEED
FINISH PEED
•9/25
GAS TEMPERATURES
N2 TEMP OUT OF HEATERS
PRE -CYCLONE TEMP #1
PRE -CYCI ONE TEMP #2
POST- CYCLONE #1
POST-CYCLONE #2
IN1ETHXI GAS TEMP
oimimixi OASTEMP
INI ETIIXK2ASTI-MI'
ODTI ETIIX2 OASTKMP
INI.ETIIX3 TASTEMP
OUTLET 11X3 OASTEMP
STACK OAS TEMP
1026
699
616
461
«35
468
65
43)
65
75
63
76
1026
729
622
507
455
507
66
455
64
75
62
77
1021
716
665
520
505
520
64
305
64
75
62
77
1031
714
632
520
511
520
66
5IS
65
73
62
71
1029
606
629
411
542
411
70
542
69
73
63
II
1030
467
624
315
544
3(5
67
544
69
73
61
to
1027
340
556
218
509
211
73
509
74
74
64
to
1030
326
522
271
461
J71
71
468
72
74
62
79
1031
474
527
346
452
346
71
452
64
73
60
79
1033
510
540
410
432
410
69
432
64
74
62
71
1032
632
545
442
421
442
67
421
63
74
61
71
989
551
512
3»7
375
397
65
175
64
76
64
78
AVO.
1026
5695
5825
4195
471.3
4I»5
67.83
471 1
6641
74.08
62.16
7841
COOUNO WATER TBMPS
CONDENSER HX1IN
CONDENSER 11X3 OUT/HXI IN
CONDENSER IIXI OUT/IIX2IN
CONDENSER 11X2 OUT/COOLINO SCW It-
COOUNO SCREW OUT
Clllll EH SUT POINT
60
60
61
60
60
61
61
60
59
60
60
60
60
61
62
61
63
63
65
64
61
61
62
64
63
64
65
65
62
62
63
63
60
61
60
60
61
62
62
61
61
61
60
62
62
62
62
61
AVO.
(1
(1.5
61.11
61.75
-------
l£Q^ MQB!i,g_SALT_SY§IEM_
DATE:
START FEED
FINISH FEED
CREW
TREATMENT OOAL
EST SALT TEMP
EST. SOIL TEMP
975
700
P.BQCJS.SQB_ DATA;
WASTE FEED CONVEYOR SPEED_
PROCESSOR RPM
REMDENCI: TIME
COOUNO SCREW RPM
RESIDENCE TIME
NA
90m In
ERR
Sun Feed® Il.l3im
Fluih FceUla! l2.4Upra
SOLIDS •} E MPER ATURES
TIMt
TEMP IN
TEMP OUT RIOHT
TEMP OUT LEFT
COOIJNO SCREW OUT
1105
676
614
69
1120
570
529
69
1135
567
511
69
1150
534
565
70
1205
52»
542
70
1220
532
561
75
1235
560
573
14
1250
546
572
10
1315
542
564
132
1330
519
tn
147
1345
599
651
154
1400
675
tit
163
AVO.
1234
5765
5116
915
SALT TEMPERATURES
BATH TEMP - SAI T TANK
TEMP IN RIOHT
TEMP IN I EFT
TEMP OUT RIOHT
TEMP OUT LtFT
SET POINT TEMP
977
975
973
960
962
976
976
974
972
956
957
976
974
973
969
952
9)2
976
97 J
972
969
949
930
976
970
967
964
934
934
976
961
964
961
926
925
976
970
961
959
919
915
976
969
960
95»
924
921
976
972
967
965
942
942
976
974
973
970
933
954
976
970
975
973
951
959
976
970
971
971
95)
960
976
AVO.
9720
9696
967
9431
9442
976
-------
ro
DATASHEET
RETEC'S HliNCII-SCAI.fi THERMAL DESORPTION SYSTEM
DATE:
PROJECT #:
Cl MINT.
WASTE TYPE:
TREATMENT GOAL:
TEST RESULTS
8/1/91
H80-755
SAIC
Sediment - PCB
Hi - Temperature Trealment
MIN. TO HOIM'ER EMPTY:
MATERIAL IN (I hs):
MATERIAL OUT (l.bs):
DENSITY (I .b/cu.fl.):
FEED RATE (I.b/hr):
MASSREDUCHON%:
20
3.125
2.875
-------
u>
DATASHEET
KEIF'S HENCH-SCALE Tl
DATIi:
PROJECT #: ! !§?_:: 755
CLIENT: SAIC
WASTE TYPE: Sediment
TREATMENT GOAL: 1 li - Temperature Treatment
EBQEQSED TEST CjjNij JTJONJ^
RESIDANCETIME:
MATERIAL TEMPERATURE:
CARRIER GASTEMPERATURH
MEDIA TEMPERATURE:
550
loop
650
TEST START 11ME:
4:10
HOPPER EMPTY TIME:
TEST END TIME:
ENGINEER: Mike Gardner
4:30
5:00
TIME
OILTEMPIN
OJLITiMPOyT
HEAD SPACE TEMP
CARRIER GAS TEMP
OEF GAS TEMP
SOILTEMPIN
4:10
J07
J30
499
976
512
300
4:20
666
J30
J83
982
296
290
4:30
611
J32
J77
986
286
325
4:40
613
J62
981
287
410
4:50
_612
532
467
982
302
450
5:00
532
471
987
296
489
AVG.
620.1666
531.5
476^
982.3333
296.5
300
392.8
-------
DATASHEET
RETECS HENCII-SCALE THERMAL DESORPTION SYSTEM
DATE:
PROJECT #:
CLIENT:
WASTE TYPE:
TREATMENT OOAL:
TEST RESULTS
MIN. TO HOPPER EMPTY.
MATERIAL IN (Lbs):
MATERIAL OUT (Lbs):
DENSITY (Lb/cu.fl.):
FEED RATE (Lb/hr).
MASSREDUCnON%:
8/1/91
H80-75S
SAIC
Sediment - PCB
Treatment
15
4.125
3.12
16.5
-------
-J
Ul
DATASHEET
UETECS HENCII-SCALE THERMAL DESORPTION SYSTEM
DATE:
PROJECT*:
CLIENT:
WASTE TYPE:
TREATMENT GOAL:
PROPOSED TEST CONDITIONS
8/1/91
H80-755
SAIC
Sediment
Hi - Temperature Trcalment
RESIDANCETIME: JO (^0 minutes
MATERIAL TEMPERATURE: 500
CARRIER GAS TEMPERATURE: 1000
MEDIA TEMPERATURE: 600
TEST START TIME:
3:20
HOPPER EMPTY TIME:
TEST END TIME:
ENGINEER: Mike Gardner
3:35
4:05
TIME
OIL TEMP IN
OIL TEMP OUT
HEAD SPACE TEMP
CARRIER GAS TEMP
OFF GAS TEMP
SOILTEMI'lN
SOIL TEMP OUT
3:20
606
526
509
964
299
160
3:30
599
526
519
971
300
160
3:40
601
525
516
967
303
347
3:50
607
531
490
972
308
439
3:55
601
532
501
976
308
500
4:05
603
534
494
976
310
496
AVG.
602.8333
529
504.8333
971
304.6666
160
445.5
-------
-0
DATASHEET
RETECS IJENCII-SCALE THERMAL DESORPT1ONSYSTEM
DATE:
PROJECT #:
CLIENT:
WASTE TYPE:
TREATMENT GOAL:
8/1/91
H80-755
SAIC
Sediment
Hi Temp Treatment
RESIDANCE TIME: 30 minutes
MATERIAL TEMPERATURE: 500
CARRIER GAS TEMPERATURE: 1000
MEDIA TEMPERATURE:
650
'niST START TIME: 2:15
HOPPER EMPTY TIME: 2:50
TEST EN D TIM E: \. 15
ENGINEER: Mike Gardner
TIME
OIL TEMP IN
OIL TEMP OUT
HEAD SPACE TEMP
CARRIER GAS TEMP
OFF GAS TEMP
SOILTEMPIN
SOIL TEN POUT
2:15
608
530
547
958
169
75
2:25
593
519
518
965
280
75
2:35
595
509
455
966
288
75
383
2:45
596
509
406
968
281
75
421
2:55
597
510
285
964
269
460
2:05
606
523
440
969
273
440
3:10
607
530
476
964
281
450
AVG.
600.2857
518.5714
446.7142
964.8571
263
75
430.8
-------
DATASHEET
RETEC'S Ill-NCI I-SCALE THERMAL DESORPTION SYSTEM
DATE:
PROJECT #:
CLIENT:
WASTE TYPE:
TREATMENT GOAL:
TEST RESULTS
MIN. TO HOPPER EMPTY:
MATERIAL IN (Lbs):
MATERIAL OUT (Lbs):
DENSITY (Lb/cu.fl.):
FEED RATE (Lb/hr):
MASS REDUCTION %:
8/1/91
H80-755
SAIC
Sediment - PCB
_lli - Temperature Treatment
40
10.9
4.125
16.35
•4*78440 Lei \ 7p
Feed Note: Gray - Fine grained saturated sediment with slight organic and sulide odor, free liquid.
-------
APPENDIX B
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, TOC, total cyanide, and total phosphorus. If water
and oil residuals were generated by a technology, then polynuclear aromatic hydrocarbons (PAHs) and
polychlorinated biphenyls (PCBs) were determined as a check on their fate resulting from in treating the
sediments. In addition, for the ReTec water residual sample, total suspended solids and conductivity
analysis were performed. 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
analyte(s) used to document the accuracy of a method in a given sample matrix. For matrix spikes,
recovery is calculated as follows:
79
-------
%R = C|'C° x 100
C,
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):
RRD = (C, - C2) x 100
(C, + C2) / 2
where: C-, = the larger of two observed values
C2 = the smaller of two observed values
80
-------
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 ReTec treatability studies, one of two samples collected as
contamination checks of the system was broken during sample shipment. 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.
81
-------
ANALYTICAL QUALITY 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 ReTec technology evaluation.
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-labelled 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 ReTec 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.) All samples were acceptable
with respect to the guidelines used for surrogate recoveries.
As required by the QAPP, triplicate analyses of the Ashtabula River untreated sediment (A-US-RE)
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 RSDs with
the exception of benzo(k)fluoranthene fell within the control limits specified. The lack of precision
for benzo(k)fluoranthene can be attributed to concentrations near analytical detection limits. All matrix spike
recoveries fell within specified control limits.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MD) analysis was
performed for the treated Ashtabula River sediment (A-TS-RE). These results are presented in Table QA-3.
Recoveries for benzo(g,h,i)perylene were slightly outside the specified accuracy control limits. Due to the
minimal quantity of this compound found in the sample, the total PAH concentration is minimally affected.
82
-------
TABLE QA-1. PAH SURROGATE RECOVERIES
Sample
A-US-RE, Rep. 1
A-US-RE, Rep. 2
A-US-RE, Rep. 3
Method Blank
A-TS-RE
Method Blank
A-WR-RE
Method Blank
A-OR-RE, Rep. 1
A-OR-RE, Rep. 2
A-OR-RE, Rep. 3
A-OR-RE3
Method Blank
d8-Naphthalene
58
72
74
97
74
77
29 *
79
72
61
72
71
23 •
d10-Acenaphthalene
70
76
80
91
78
80
61
77
81
68
80
109
26 *
d12-Perylene
93
95
100
71
61
94
51
66
94
80
89
90
72
Control Limits
40- 120
I
I
I
40- 120
I
40- 120
I
40- 120
I
I
I
I
• Outside Control Limits
(1) Insufficient sample remained for reanalysis of water residuals
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed on the Ashtabula River water residual (A-WR-RE). These results are presented in Table QA-4.
Due to the high concentrations of PAHs found in this water samples, many of the spiking levels were too
low. Only those recoveries obtained from spike greater than half of the sample concentration are presented.
The recovery problem observed for benzo(b)fluoranthene could not be identified. Due to the high
concentrations of the other 15 PAHs analyzed, total PAH concentration should be minimally affected. As
this matrix is noncritical, removal efficiencies are not affected.
The QAPP specified that triplicate analyses and a matrix spike be performed on the Ashtabula River
oil residual (A-OR-RE). These results are summarized in Table QA-5. Due to the high concentrations of
naphthalene and phenanthrene found, spiking levels were too low for accurate recovery determinations.
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
83
-------
TABUE QA-2. PAH REPUCATE AND SPIKE RESULTS FOR B-US-ST
Compound
Replicate 1
dry ppb
Replicate 2
dry ppb
Replicate 3
dry ppb
RSD
Precision
Control Limits
Mean
Recovery
Accuracy
Control Limits
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,l)perytene
300U
300U
400U
400U
1420
300U
1120
1010
393
585
437
368
384
333
200U
346
222
300U
400U
300U
1340
300U
971
905
324
520
385
265
300
285
200U
283
243
200U
300U
247
1380
171
1020
927
356
571
522
410
326
387
88
277
NC
NC
NC
NC
1380
NC
1040
949
358
559
448
348
337
335
NC
303
NC 20 58 40- 120
NC
NC
NC
2.8
NC
7.6
6.1
10
6.1
15
21*
13
15
NC
13
71 I
69
76
78
82
88
87
91
86
85
84
89
89
92
61
NC = Not Calculated
U = Undetected
-------
TABLE QA-3. PAH MS/MSD RESULTS FOR A-TS-RE
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Ruorene
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
(%)
52
60
73
73
79
75
82
82
78
77
74
74
68
57
66
38 *
MSD
Recovery
(%)
46
53
68
69
76
71
79
78
73
75
70
70
60
47
56
35
Accuracy Precision
Control Control Limits
RPD Limits (%)
(%)
12 40-120 20
12 | I
7.1 I I
5.6 |
3.9 | |
5.5 | I
3.7 | |
5.0 I I
6.6
2.6 | I
5.6 | I
5.6 | |
12 I
19
16 I
8.2
* Outside Control Limits
in Table QA-6. No recovery was obtained for anthracene as the certified value was less than the analytical
detection limit achieved.
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 sediment and water samples. No
corrections were performed for method blanks as no consistent significant contamination problems were
observed.
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.
One surrogates, tetrachloro-m-xylene, was 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
85
-------
to be <25 percent. Calibrations were verified after every ten samples;
TABLE QA-4. PAH MS RESULTS FOR A-WR-RE
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Ruorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a)anthracene
Chrysene
Benzo (b)f luoranthene
Benzo (k)fluoranthene
Benzo (a)pyrene
lndeno(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
IS = Inappropriate Spiking
NC = Not Calculated
MS Recovery
IS
61
IS
IS
IS
IS
IS
IS
IS
IS
10
73
IS
53
64
38
Concentration
MSD
Recovery
IS
48
IS
IS
IS
IS
IS
IS
IS
IS
-6
67
IS
52
62
25
Accuracy Precision
Control Control Limits
RPD Limits (%)
NC Not Specified Not Specified
24 | |
NC |
NC | |
NC | |
NC | |
NC | |
NC |
NC | |
NC |
NC | |
7.1 | |
NC |
1.9 | |
3.2 | |
41 |
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 Discnssinn
Surrogate recoveries for all PCB samples for the ReTec demonstration are summarized in Table QA-7.
Water sample could not be quantified due to unidentified coeluting peaks. All samples were acceptable with
respect to the surrogate criteria used with the exception of the water residual. The surrogate recovery for
the presence of these peaks also resulted in significantly increased Aroclor detection limits (approximately
25 to 50 times higher than the method blank).
86
-------
TABLE QA-5. PAH REPLICATE RESULTS FOR A-OR-RE
Compound
Napthalene
Acenaphthylene
Acenapthene
Fluorene
Phenanthrene
Anthracene
Flouranthene
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
Replicate 1
ppb
964000
6300
73300
112000
241000
35400
13700
79300
20200
46400
8830
1000U
12000
1340
1940
6290
Replicate 2
ppb
1010000
6670
76000
111000
254000
37500
14400
64000
21400
48100
8660
1000U
11900
1500
2060
6660
Replicate 3
ppb
1130000
7140
83500
122000
278000
40200
15600
90000
23100
52000
9430
2000U
13300
2000U
2510
7570
Mean
1040000
6700
77600
115000
258000
37700
14500
84600
21500
48800
8970
NC
12400
NC
2170
6910
RSD
(%)
8.4
6.2
6.8
5.5
7.2
6.4
6.6
6.4
6.8
5.9
4.5
NC
6.3
NC
14
9.3
Precision
Control Recovery
Limits (%) (%)
Not Specified IS
| 83
| 96
| 104
I is
| 99
| 106
| 110
| 100
| 102
| 84
| 92
| 93
| 93
| 98
| 66
Accuracy
Control
Limits (%)
Not Specified
I
I
I
I
I
I
I
I
I
I
I
I
I
I
|
IS = Inappropriate Spiking Concentration
-------
TABLE QA-6. PAH SRM RESULTS
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Ruorene
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
Recovery Control Limits
(%) (%)
NC 80-120
NC |
NC |
NC |
90 |
0 * |
87 |
92 |
82 |
NC |
99 |
142 * |
78 * |
98 |
NC |
75 * |
NC
Not Certified
Outside Control Limits
As required by the QAPP, triplicate analyses of the Ashtabula River untreated sediment (A-US-RE)
were performed to assess precision. These results fell within specific guidelines and are summarized in
Table QA-8. A matrix spike using Aroclor 1254 was performed on the same sample to assess accuracy; no
recovery could be determined due to residual Aroclor 1248 peaks.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed for the treated Ashtabula River sediment (A-TS-RE). These results are presented in Table QA-9.
Both the recoveries and RSD were acceptable.
As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed on the Ashtabula River water residual (A-WR-RE). Due to the presence of unidentified coeluting
peaks, recoveries could not be determined.
The QAPP specified that triplicate analyses and a matrix spike be performed on the Ashtabula River
oil residual (A-OR-RE). These results are summarized in Table QA-10.
88
-------
TABLE QA-7. PCB SURROGATE RECOVERIES
Sample
A-US-RE, Rep. 1
A-US-RE, Rep. 2
A-US-RE, Rep. 3
Method Blank
A-TS-RE
Method Blank
A-WR-RE
Method Blank
A-OR-RE, Rep. 1
A-OR-RE, Rep. Z
A-OR-RE, Rep. 3
A-OR-RE3
Method Blank
Tetrachloro-m-xylene
(%)
101
109
113
102
91
102
NQ
20 *
108
93
100
96
35 *
Control Limits
(%)
40- 120
1
1
1
40-120
I
40- 120
I
I
I
I
I
* Outside Control Limits
NQ = Not quantifiable due to unidentified coeluting peaks
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 190% was
obtained. This can be attributed to a certified value near the analytical detection limit.
Method blanks were extracted and analyzed with each set of samples extracted. No PCBs were
found in any of the method blanks.
Early eluting large peaks were present in the untreated sediment, water residual, and oil residual.
These peaks did not correspond to any Aroclor pattern and were therefore not quantified. Their presence,
however, did create some QA/QC problems as have been discussed.
89
-------
TABLE QA-8. PCB REPLICATE RESULTS FOR A-TS-flE
u
NC
U
NC
NS
U
NC
NS
Aroclor
1242
1248
1254
1260
= Undetected
= Not Calculated
PCB
Aroclor 1254
= Undetected
= Not Calculated
= Not Spiked
Aroclor
1242
1248
1254
1260
= Undetected
= Not Calculated
= Not Spiked
Replicate 1 Replicate 2 Replicate 3 RSD
ppb dry ppb dry ppb dry Mean (%)
200 U 200 U 200 U 200 U NC
14400 13900 15600 6.0
100 U 100 U 100 U 100 U NC
100 U 100 U 100 U 100 U NC
TABLE QA-9. PCB MS/MSD RESULTS FOR A-TS-RE
Accuracy Control
MS Recovery MSO Recovery Limits
(%) (%) RPD (%}
78 76 2.6 40 - 120
* Outside Control Limits
TABLE QA-10. PCB REPLICATE AND SPIKE RESULTS FOR A-OR-RE
Precision
Control
Replicate 1 Replicate 2 Replicate 3 RSD Limits
(Ppb) (ppb) (ppb) Mean (%) (%)
2000 U 2000 U 2000 U 2000 U NC Not Specified
2000 U 2000 U 2000 2000 U NC |
1000 U 1000 U 1000 U 1000 U NC |
1000 U 1000 U 1000 U 1000 U NC |
Precision
Control
Limits
(%)
20
20
20
20
Precision
Guideline Limits
(%)
20
Accuracy
Recovery Control
(%) Limits
NS Not Specified
NS |
73 |
NS |
-------
METALS
Metals Procedures - Sediments
Sediments were prepared for metals analysis by freeze-drying, blending, and grinding. Sedmerts
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.
Metals Procedures - Water
The water sample was analyzed for all metals but Ba and Hg using direct injection flame atomic
absorption (FLAA). Barium was analyzed using ICP/MS; Hg was analyzed using cold vapor AA (VCAA).
Metals QC Results and Discussion
Triplicate analyses of the Ashtabula River untreated sediment (A-US-RE), treated sediment (A-TS-RE),
and water residual (A-WR-RE) were performed to assess precision. Matrix spikes were analyzed for the
same samples to assess accuracy. Results are summarized in Tables QA-11, 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 11, QA-12, and QA-13. An RSD result for mercury was outside limits are due to concentrations
near the analytical detection limits. Some recoveries for silver and selenium were outside limits, but due to
the low concentrations found, data should be minimally affected.
One solid NIST certified standard reference material (SRM) was digested and analyzed with the
sediment samples for XRF, GFAA, and CVAA analyses. These results are presented in Table QA-14. One
aqueous NIST SRM was digested and analyzed with the water samples; results are also presented in Table
QA-l4. No reason for zero recovery for Se was identified; matrix spike recovery was good.
Method blanks were digested and analyzed for the metals analyzed by GFAA, CVAA, and FUV\
(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.
91
-------
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). Water samples were extracted with freon and analyzed
gravimetrically as described in Method 413.1 from the same reference above.
Oil and Grease QC Results and Discussion
The untreated Ashtabula River sediment, (A-US-RE) and treated sediment (A-TS-RE), and water residual
(A-W-RE) were analyzed for oil and grease in triplicate. Results are presented in Table QA-15. RPD results
for A-TS-RE fell slightly outside specified guidelines; data is not significantly impacted.
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. Waters were
analyzed using Method 160.4; a volume of sample was dried and then ignited at 550°C. The loss of weight
on ignition was then determined.
92
-------
TABLE QA-11. METALS REPUCATE AND SPIKE RESULTS FOR A-US-RE
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
0.1B
20.9
892
3.02
568
33.9
4.14
1.362
537
49.5
56.7
0.87
228
Replicate 2,
ppm dry
0.19
20.0
906
304
624
34.6
4.32
1.337
573
549
57.9
0.99
237
Replicate 3,
ppm dry
0.20
21.4
910
3.12
561
32.6
4.32
1.387
566
54.7
60.6
0.87
238
Mean
0.19
20.8
903
3.06
591
33.7
4.26
1.361
559
53.0
58.5
0.91
234
Precision
RSD Control Limits Recovery
(%) (%) (%)
5.3 20 124*
3.4
1.0
1.7
5.3
3.0
2.4
1.9
3.4
5.8
3.6
7.6
2.0
NS
NS
97
NS
NS
NS
95
NS
NS
NS
175*
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-12. METALS REPUCATE AND SPIKE RESULTS FOR A-TS-RE
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
0.19
15.3
789
2.74
494
477
365
0.005
520
73.3
75.2
1.60
223
Replicate 2,
ppm dry
0.18
16.5
811
2.67
514
44.6
3.92
0.006
533
80.7
768
1.49
227
Replicate 3,
ppm dry
0.19
17.6
775
2.67
552
52.0
3.97
0.003
538
77.7
78.9
1.49
243
Mean
0.19
16.5
792
2.69
520
48.1
391
0.005
530
77.1
77.0
1.53
231
Precision
RSD Control Limits Recovery
(%) (%) (%)
31 20 118*
7.0
2.3
1.5
5.7
7.7
1.5
33*
1.8
4.8
2.4
4.2
4.6
NS
NS
100
NS
NS
NS
97
NS
NS
NS
172*
NS
Accuracy
Control Limits
(%)
85 - 115
—
—
85- 115
—
—
—
85- 115
—
—
—
85- 115
—
NS - Not Spiked
U = Undetected
(1) Result in Percent for Fe
Outside Control Limits
-------
TABLE QA-13. METALS REPUCATE AND SPIKE RESULTS FOR A-WR-RE
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
NS =
U =
Method
FLAA
FLAA
ICP/MS
FLAA
FLAA
FLAA
FLAA
CVAA
FLAA
FLAA
FLAA
FLAA
FLAA
Not Spiked
Undetected
Replicate
ppb
0.003
7.37
55.2
072
17.9
47.6
1790
35.7
482
152
43.8
2U
202
*
1 , Replicate 2.
ppb
0.001 U
7.53
56.0
0.56
17.9
45.9
1760
34.6
489
152
43.B
2U
195
Outside Control Limits
Replicate 3,
ppb
0.001 U
7.22
556
0.54
16.2
45.9
1860
32.3
459
136
43.8
2U
208
Mean
NC
7.37
556
0.61
17.3
46.5
1800
34.2
477
147
43.8
2U
202
Precision Accuracy
RSD Control Limits Recovery Control Limits
(%) (%) (%) (%)
NC 20 56' 85-
2.1
0.7
16
5.7
2.1
2.8
5.1
1.2
6.3
0
NC
3.2
87
90
84*
84*
95
90
106
I 91
86
1 B?
| 102
| 104
115
I
I
I
I
I
-------
TABLE QA-14. METALS SRM RECOVERIES
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
Sediment SRM
NC
96.6
NC
111
93.4
92.2'
99.4
103
93 1
972
105
NC
89.9
Water SRM Control Limits
93.7 80 - 120%
103 |
99.2 |
105 |
100 |
87.0 |
99.5 |
96.2 |
106 |
85.1 |
104 |
0 I
93.4 |
* Outside Control Limits
NC = Not Certified
TABLE QA-15. OIL AND GREASE REPLICATES AND SPIKE RESULTS FOR
A-US-RE, A-TS-RE, AND A-WR-RE
Sample
A-US-RE. ppm dry
A-TS-RE, ppm dry
A-WR-RE, ppm
Replicate 1
919
563
560
Replicate 2
1080
357
560
Replicate 3
1010
389
574
RSD
Mean (%)
1000 8.0
436 25*
564 1 .4
Precision
Control
Limits
(%)
20
20
NS = Not Spiked
Total Volatile Solid QC Results and Discussion
The Ashtabuia River untreated sediment (A-US-RE), treated sediment (A-TS-RE), and water residual A-
WR-RE) were analyzed for TVS in triplicate. Results are summarized in Table QA-16. All RSDs fell within
specified control limits.
96
-------
TABLE QA-16. TVS REPLICATES FOR A-US-RE, A-TS-RE, AND A-WR-RE
Sample
A-US-RE, %
dry
A-TS-RE, %
dry
A-WR-RE, ppm
Replicate 1
7.54
4.30
1400
Replicate 2
7.39
4.33
1400
Replicate 3
7.99
4.13
1400
Mean
7.64
4.25
1400
RSD
(%)
4.1
2.5
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 1:10 ratio rather than the required 1:1 ration and mixed prior to pH determination. These
results should be used with caution. Water samples were analyzed for pH using SW-846 Method 9040.
Replicate pH results are presented in Table QA-1 7.
TABLE QA-1 7. pH REPLICATE RESULTS
Sample
A-US-RE, SU
A-TS-RE, SU
A-WR-RE, SU
Replicate 1
7.84
8.07
8.15
RSD Control Limits
Replicate 2 Replicate 3 Mean (%) (%)
7.91 7.88 7.88 0.4 Not Specified
8.07 8.14 8.09 0.5
8.24 8.20 8.20 0.6
Total Organic Carbon (TOO
Sediment and water samples were analyzed for TOC using SW-846 Method 9060. Two SRMs were
analyzed with the sediments, yielding recoveries of 95.6 percent and 100 percent. Replicate TOC results
are presented in Table QA-18.
97
-------
TABLE QA-18. TOO REPLICATE RESULTS
Sample
A-TS-RE, %
dry
A-WR-RE, ppm
Replicate 1
2.33
428
Replicate 2
2.27
452
Replicate 3
2.21
458
Mean
2.27
446
RSD Control Limits
(%) (%)
2.6 Not Specified
3.6 |
Total Cyanide
Sediment and water samples were analyzed for cyanide by SW-846 Method 9010. For the sediments,
approximately 5 g of sediment was distilled; the distillate was analyzed spectrophotometrically. Replicate
and spike results for cyanide are presented in Table QA-19.
Total Phosphorus
Sediment and water samples were analyzed for phosphorus by EPA Method 365.2. For
sediments.Approximately 1 g of sediment was digested; the digestate was analyzed spectrophotometrically.
Replicate and spike results for phosporus are presented in Table QA-20.
Total Solids
Sediment and water samples were analyzed for total solids using EPA Method 160.3. Replicate results
are presented in Table QA-21.
Total Suspended Solids
Water samples were analyzed for total suspended solids using EPA Method 160.2. Replicate results
are presented in Table QA-22.
Conductivity
Water samples were analyzed for conductivity using SW-846 Method 9050. Replicate results are
presented in Table QA-23.
BOD
BOD was requested for the water sample using EPA Method 405.1. The holding time was exceeded
at the laboratory and the analysis was not performed.
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TABLE QA-19. CYANIDE REPLICATE AND SPIKE RESULTS
Sample
A-US-RE, ppm dry
A-TS-RE, ppm dry
AWR-RE, ppm
NA = Not Analyzed
U = Undetected
NC = Not Calculated
NS = Not Spiked
Sample
A-US-RE, ppm dry
A-TS-RE, ppm dry
A-WR-RE, ppm
NS = Not Spiked
Sample
A-US-RE, %
A-TS-RE, %
A-WR-RE, ppm
Precision
Control
RSD Limits Recovery
Replicate 1 Replicate 2 Replicate 3 Mean (%) (%) (%)
1.1 2.0 1.5 1.5 29 Not Specified NS
2.1 2.1 NA 2.1 NC | 93
0.004 0.006 0.004 U NC NC | 96
TABLE QA-20. PHOSPHORUS REPLICATE AND SPIKE RESULTS
Precision
Control
RSO Limits Recovery
Replicate 1 Replicate 2 Replicates Mean (%) (%) (%)
1200 1440 1220 1280 11 Not Specified NS
2290 2070 2060 2140 6.1 | 106
0.439 0.488 0.401 0.443 9.9 | 97
TABLE QA-21. TOTAL SOLIDS REPLICATE RESULTS
RSO
Replicate 1 Replicate 2 Replicate 3 Mean (%)
38.2 37.8 31.0 35.6 11
20.5 25.5 25.5 23.8 12
1600 1500 1700 1600 6.3
Accuracy
Control
Limits
Not Specified
I
I
Accuracy
Control
Limits
Not Specified
I
I
Precision
Control
Limits
(%)
20
20
Not Specified
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TABLE QA-22. TOTAL SUSPENDED SOLIDS REPLICATE RESULTS
Sample
RSD
Replicate 1
Replicate 2 Replicate 3
Mean
Precision
Control
Limits
A-WR-RE, ppm
70
85
88
81
12
Not Specified
TABLE QA-23. CONDUCTIVITY REPLICATE RESULTS
Sample
RSD
Replicate 1
Replicate 2 Replicate 3
Mean
Precision
Control
Limits
A-WR-RE, .uhoa/cm
2.49
2.37
2.31
2.39
3.8
Not Specified
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.
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
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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 PCB 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 rts 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.
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.
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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
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.
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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 for the critical organic
parameters were performed within these holding times (from the time of sample receipt). PAH analysis of
the water extract was performed approximately 12 days past the 40 day holding time. PCB analysis of the
water extract was performed approximately 40 days past the 40 day holding time. Due to the noncritical
nature of the water sample, removal efficiencies are not affected. Holding times for solids, TOC, cyanide,
and phosporus were exceeded slightly.
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.
PAHs/PCBs
Analyses of PAH and PCB extracts for the sediments were performed approximately 12 and 40 days
past the 40 day holding time, respectively. As both untreated and treated sediment extracts were analyzed
similarly, relative removal efficiencies should not be affected.
CONCLUSIONS AND LIMITATIONS OF DATA
Upon review of all sample data and associated QC results, the data generated for the ReTec 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.
pH analyses for the sediments were performed using a 1:10 soil:water ration rather than the required
1:1. This data should be used with caution.
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,
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then detection limits become a factor. Removal efficiency demonstration may be limited by the sensitivity
of the analytical methods.
Large unidentified peaks were observed in the PCB analyses of the untreated sediment, water residual,
and oil residual samples. Due to the high concentration of PCBs present in the untreated sediment, the
necessary dilutions eliminated any affect on data quality. For the water and oil samples, detection limits had
to be increased significantly because of these peaks. While removal efficiencies are not affected, mass
balance closures may be difficult.
As discussed previously, the analytical laboratory used several specialized methods when analyzing
samples from the ReTec 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.
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The following Data Verification Report is an attachment to
Appendix B. Page numbering resumes with Appendix C at page 105.
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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
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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 Oow temperature
stripping), ZIMPRO (wet air oxidation), and Soil Tech Oow 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.
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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 treatabiliry 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);
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and (4) conventionals, including percent moisture, pH, percent total volatile, oil and grease, total
organic carbon (TOC), total cyanide, and total phosphorus. Analyses of metals and
conventionals 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 conventionals
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 b'mit 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.
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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 _>.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.
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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 QA7QC 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 SO
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 SO 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 fiags 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
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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 ConkJing 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
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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,
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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
D.Ex.3. 1 •
12-QDo
0-A, B, C, D, P0 S,
0-A, B, Q D, PO S,
6-A,CoD, S,
15-A, C6
12-C. Po S,
14-Ao P0
14-AoPo
17-B2 D0
17-D0 S2
ZIMPRO
12-CoDo
3-A, B, Q D, S,
0-A,B,CoD,P0S,
3-A, Bo Q D, S,
6-A, B, C6 D, S,
12-C4 P0S,
14-A^ P0
HA P0
14-A, B: D0
M-RjD.S.S,
Soil Tech
12-CoDo
0-A,B,CoD,P0S,
0-A,B,CoD,P0S,
6-A, C0 D, S,
6-A, Bj C4 D, S0
12-C4 PO S,
ll-AoP0S0
14-Afl P0
14-A, B2 D0
17-D0 S,
RETEC
12-QD.
3-A, B, C, D, S,
3-A,B,C.D,S,
6-A, Cp D, S,
9-A, D0 C4 So
9-C.D0P0S,
8-AoD.P.So
11-AoD.So
H-A.BjDoS,
20-D0
Treated
Sediments
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
12-QDo
0-A, B, Q D, P0 S,
0-A, B, C, D, P0 S,
6-A, 0, D, S,
15-A, C4
12-C6P0S,
14-AoPo
14-Ao PO
14-B, D0 P,
14-D0 P, S7
12-QDo
0-A,B,CoD,P0S,
3-A,B,CoD,S,
3-A,BoCoD9S,
6-A, Bj C6 D, S,
12-C4 Po S,
14-Ao Po
14-A« P0
11-A.BjDoP,
17-D0 S,
12-QDo
3-A, B, Q D, S,
0-A,B,CoD,P0S,
6-A,CoD,S,
9-A, B, C4 D,
12-C4P0S,
14-Ao PO
14-Ao PO
14-B,D0P,
14-D0 P, S,
12-CoD.
3-A, 8,0,0,5,
3-A,B,C,D,S,
6-A,C,D,S,
frA.C.D.P.So
12-C.D.S,
ll-AoD,P0
14-Ao D,
14-A, B, DO
20-Do
-------
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
**
**
••
**
*«
*«
**
**
**
«*
U-^DoP,
H-AoDoP.S,
**
«*
•*
«*
**
•*
««
«>
**
**
14-Bj D0 P0
17-Dp S,
*•
**
*«
•*
*«
*«
»»
**
«*
•*
5-A, B, D0 P0 S,
s.
17-D0P0
20 |
.... — _|
**
3-A, B, 0, D, S,
6-A,CoD,S,
6-A, Co D, S,
6-A,CoD,S,
12-A, C6 D0
9-A, C6 D0 S,
14-AoD0
14-A^Do
9-A,C.D,S,
5-AoBjDoPoS,
s.
11-A.DoP.S,
Oil residue
PCBs
PAHs
11-A.BjDoS,
11-A0BID0S2
*
*
17-BjDo
14-B2 D0 S,
11-BjDoPoS,
17-B, D0
* 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 noj in an addition to the calculated point scores since these analyses were
not applicable to the methodologies used by the laboratory (Table 2).
-------
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
10
Untreated
Sediments
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
PCBs
PAHs
D.d> 1 •
20
8
8
6
17
17
20
20
20-B,
20-Sj
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-B, P,
I7-P, S2
ZIMPRO
20
8
8
6
8-B:D,S,
17
20
20
17-A, B,
14-Bj S, S,
Soil Tech
20
8
8
6
11-B.D,
17
20
20
17-A.B,
20-S,
RETEC
20
8
8
6
17
17
17-P,
20
17-A, B,
23
20
8
8
6
8-B, D, S,
17
20
20
14-A, Bj P,
20-S,
20
8
8
6
11-B,D,
17
20
20
17-B, P,
20-S;
20
8
8
6
9-P,
17
20
20
17-A, B,
"
-------
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-B,
17-P, S,
**
•*
•*
**
**
**
*•
««
«*
**
**
20-B,
20-S2
**
•*
**
**
**
9*
**
«*
**
»»
**
14-A, B, S,
23
20
8
8
6
17
17
20
20
14
6
6
20-B,
14-A, P, S,
Oil residue
PCBs
PAHs
14-A, B, S,
17-8,5,
«
*
20-B,
17-B, S,
20-B,
20-B,
* 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. PCB 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. PCB 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 TOC 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 ber.zo(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,
accnaphthylene 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.
-------
NOTE
Appendix A - Laboratory Submitted Data Summary Sheets
and
Appendix D - ARCS Data Verification Templates by Parameter
are not included with 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
BO = no information available
Bj = reagent blank value exceeded MDL
B, = blanks are not applicable
C = Calibration Problem
Co = no information available
C, = initial calibration problem
Cj = on-going calibration problem
C5 = no information on initial calibration
C4 = no information on on-going calibration
C, = on-going calibration is not applicable
D = Detection Limit Problem
D0 = no information available
D, = detection limit exceeded
D, = detection limit is not applicable
-------
H = Holding Times Exceeded
P = Precision Problem
P0 = no information available
P, = precision limit for analytical replicate exceeded the QA/QC
requirements
Pj = 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
-------
APPENDIX C
QUALITY ASSURANCE PROJECT PLAN
FOR
GLNPO - ASSESSMENT AND REMEDIATION OF
CONTAMINATED SEDIMENT TECHNOLOGY
DEMONSTRATION SUPPORT
Revision II
February 15, 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, Suite 403
Cincinnati, Ohio 45203
EPA Contract No. 68-CS-0061, Work Assignment No. 2-18
SAJC Project No. 1-832-03-207-50
105
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Revision No.: 2.
Date:
Page:
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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
2
REVISION DATE
1
7
1
3
2
1
3
1
2
2
1
2
2
1
1
1
1
1/9/91
2/15/91
2/15/91
1/9/91
2/15/91
1/9/91
2/15/91
2/15/91
1/9/91
1/9/91
1/9/91
1/9/91
106
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QUALITY ASSURANCE PROJECT PLAN APPROVALS
QA Project Plan Title: GLNPO Assessment and Remediation of Contaminated
Sediment Technology Demonstration Suooort
Prepared by: Science ADD7Tcations Internationa? Corporation (SAIC)
QA Project Category: II
Revision Date: January 9, 1990
,1
SAlC's Work Assignment Manager (print)
Clyde J. Dial
SAlC's QA Manager (print)'
Steve Yaksicn
JU.'PQ 'Jons, Croup Chair (print)"
Brian Schumacher
ARCS QA Officer (print)
3ene Easterly
IPA, ISSL-LV, NRD QA Officer (print;
Signature
Signature
Signature
/T3ate
Date
Date
Ralph Chr-'stensen
£?A Technical Project Manager (print;
Signature
Dave Cowgill
ogram Manager (print;
Signature
107
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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
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Revision No.: 2
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2 of 2
108
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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.
SAIC has been contracted to supply technical support to the ET Work Group. The
effort consists of conducting bench-scale treatability studies on designated sediments to
evaluate the removal of specific organic contaminants.
109
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Date: Jan. 9. 1991
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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 50 ppm. These sediments
have been homogenized and packaged in smaller containers by EPA.
no
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GLNPO - QAPjP
Section No.: jj_
Revision No.: 2
Date: Feb. 15. 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 treatability 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 treatability 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 treatability 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.
Ill
-------
TABLE 2-la. Preliminary Analytical Results on ARCS Sediments
Description
Saginaw22l
Saginaw TRP6
Ashtabula River
Indiana Harbor
Buffalo River
Concentration (Mg/kgm)(a)
Total
PCB
0.6
6.0
C
0.2
0.4
Total
PAH
1.2
3.1
C
96
5.6
Cu
33
81
55
320
85
Crf
0.9
4.7
3.0
9.4
1.9
Ni
76
110
96
150
57
Fe(%)
1.4
09
3.7
16
3.9
Cr
140
200
550
540
110
Zn
240
200
240
3300
200
Pb
30
47
48
780
94
Concentration (%)(•)
roc
1.4
1.2
2.6
21
2.0
OAG Moisture (b)
0.1 40.3
0.3 31.1
1.7 52.9
5.8 61.0
0.5 41.5
(a) Concentration In ppm and dry weight basis unless otherwise indicated.
(b) As received basis.
TABLE 2-1 b. Preliminary Particle Size Distribution (%)
Description
Buffalo River
Particle Size (a)
>SOu 50-20 u 20-5 u 5-2 u 2-0.2 u 0.2-0.08 u <0.08u
19.8 12.1 29.0 11.8 24.3 2.4 0.6
Median
Diameter, u
9.3
Is)
(a) u micarons
-------
GLNPO - QAPjP
Section No.: 2.
Revision No.: 2-
Date: Feb. IS. 1991
Page: 3 of 12
22 Testing Program for Chemi^l 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 II performance evaluation 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
SAIC's analytical subcontractor once on a subsample taken from each sample sent to each
vendor or subcontractor for treatability 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
113
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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 H), 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 SAIC's 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 SAIC's 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.
2.3 Required Permits
Because of the small quantities of sediments required for the bench-scale treatability
tests, SAIC 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 treatability 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.
114
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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
BODS
Total Suspended Solids4
Conductivity
NOTES:
* T""}^f ^^ti/iri Kmt*f fs\v «*./-k1*
Soft*1
300
1000
1000
10
0.5
50
0.1
0.2
0.4
0.7
0.6
0.7
5
0.2
0.1
2
0.2
0.7
0.2
0.02
0.2
full range
si f i-i*-f* ^-^Y^TVI / m n l\rrt /*
Water*
1000
1000
1000
10
10
1
2
4
7
6
7
50
2
0.01
20
1
7
2
0.07
2
full range
1000
1000
full range
l^*» iirAirvn+ 1 "T ~V+ « ll
Gift
0.1
0.1
1 T f fr\ V •M^ y^ ^ n 1 A ^-l.^«i.lrJ
be obtainable by ICP except for As, Se, and Hg. If GFAA is used, the D.L.'s 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.L's 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.
115
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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 (%)
..
10
40
—
—
15
3
90(60)3
—
158(128)
—
—
Total fg)
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/Triplicate
(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.
4 For sample set II, 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.
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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
1
5
6
7
7
4
2
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
_.
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 (0
None (f)
Triplicate/Control
None (f)
Note:
a) same aliquot as PCBs
b) same aliquot as Barium
c) same aliquot as Arsenic
d) same aliquot as Total Suspended Solids
e) see footnote 2, Table 2-3
f) see footnote 4, Table 2-3
117
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GLNPO - QAPjP
Section No.: 2.
Revision No.: 2
Date: Feb. 15. 1991
Page: 8 of 12
2.4 Purpose of Phase I Experimental Desim
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 II). 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 Treatability 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 will 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.
118
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GLNPO - QAPjP
Section No.: 2_
Revision No.: 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.
119
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GLNPO - QAPjP
Section No.: 2.
Revision No.: 2
Dale: Feb. 15. 1991
Page: 10 of 12
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 pan 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.
120
-------
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GLNPO - QAPjP
Section No. i.
Revision NOJ i.
Date:
Page:
Feb. 15. 199L
11 of 12
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121
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GLNPO - QAPJP
Section No.: 2
Revision No.:
Date:
Page:
2
Feb. 15. 1991
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.
122
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GLNPO - QAPjP
Section No.: 2_
Revision No.: 2
Date: Feb. IS. 1991
Page: 1 of 2
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 IDL.
123
-------
TABLE 3-1. Quality Assurance Objectives Tor Critical Measurements
(Sediments and Treated Solids)
Parameter
Total Solids
Volatile Solids
Oil & Grease
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
l^ad ,
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total
ft Aroclors (e)
PAHs (Table 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
3550/8080
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
85-115
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
0.1
2
0.2
0.7
0.2
0.02
0.2
Completeness
%
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
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.
2>OX>*a
« 611.5
-------
GLNPO - QAPjP
Section No.: 4_
Revision No.: 1
Date: Jan. 9. 199L
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.
125
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GLNPO - QAPJP
Section No.: 4
Revision No.: 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 davs
Total Phosphorous P,G
P,G
Metals
(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
126
-------
' Setone* AppHctllon*
Inlfmttlontl Corporation
An Empinyvfl Owntfd Conipjny
Chafn-of-Cusfody Record
Dale Page ol_
ro
-o
Phone Number
Project Name
Job/P.O. No.
OBSERVATIONS. COMMENTS
SPECIAL INSTRUCTIONS
Onctovll
Vvou^t MTOfi md InNW
l>l«Ooo*U*> CMM.-lklMii. V» Bin
I «0| 01-000
3 BiqmO tntr*n Ming EPA
numb** only Contu* •<• pre)Ml QAPf> to
Intlructtora
too (MiMfi T»*iM. m irua
on* umpkng localkm
togritw Do not M kx*v«Ju«»y
Sctenc* AppHctnont fntfmrtlonil Corpormllon • 6J5 lV»
Si*» «03 Cior«m«i( DM <5JO3
Figure 4-1. Chain of Custody Record
-------
GLNPO - QAPjP
Section No.: 4.
Revision No.: 1_
Date: Jan. 9. 1991
Page: 4 of 4
635 W. 7th Street. Suite 403. Cincinnati, OH 45203
Sample No.:
Sample Location/Date/Time:
Project Location/No.:
Analysis:
Collection Method: Purge Volume:
Preservative:
Comments:
Collector's Initials
Figure 4-2. Example Sample Label
128
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GLNPO - QAPjP
Section No.: £_
Revision No.: 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
pans necessary for the operation of the analytical equipment in order to complete the
analysis in a timely fashion.
129
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GLNPO - QAPjP
Section No.: £
Revision No.: 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
160.3
160.4
9071
9010
365.2
3050/7060
7471
3050/7740
3050/6010
3540 or
3550/8080
3540 or 3550/
8270 or 8100"
9045
NA
NA
NA
9060
NA
160.4
413.1
9010
365.2
7060
7470
7740
3010/6010 (7760 Ag)
3510 or
3520/8080
3510 or 3520/
8270 or 8100b
9040
405.1
160.2
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
130
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GLNPO - QAPjP
Section No.: .5.
Revision No.: 2
Date: Feb. 15. 1991
Page: 3 of 3
TABLE 5-2
List of PAHs'
Acenaphthene Chrysene
Acenaphthylene Dibenzo(a,h)antbracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Inden(l,23-cd)pyrene
Benzo(b)fluoranthene Naphthalene
Benzo(k)fluoranthene Phenanthrene
Benzo(ghi)perylene Pyrene
PAH analyses must determine these 16 compounds at a minimum.
131
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GLNPO - QAPJP
Section No.: £_
Revision No.: 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.
132
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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 z 20% unless otherwise stated
one per sample set
± 0.1 pH unit for pH
± 2 umhos/cm for conductivity
133
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GLNPO - QAPjP
Section No.: 2.
Revision No.: 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.
II ReTec
III Wet Air Oxidation
IV Soil Tech
The Soil Tech process wiD process treated soils at two distinct points. Therefore,
four treated solids are produced from the two untreated sediments.
134
-------
TABLE 7-1. Internal QC Checks for Measurements
Ul
Parameter
Solids
(Total &
Volatile
Oil & Grease
Metals
Metals
PCBs (b)
PAHs
Method (a)
160.3
160.4
9071
6010
7000
series
8080
8270 or
8100
Initial
Calibration
Balance
(Yearly)
See Above
2 points
4 points
5 points
5 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
?. O
-------
TABLE 7-1. Internal QC Checks for Measurements (continued)
CO
0>
Parameter
PH
Conductivity
Cyanide
Phosphorous
TOC/TIC
Method (a)
9045/9040
9050
9010
365.2
9060
Initial
Calibration
2 points
1 point
7 points
9 points
3 points
Calibration
Checks
Every 10th
Sample
Every 15th
Sample
Every 15th
Sample
Every 15th
Sample
Every 15th
Sample
Method
Blank
NA
NA
Yes
Yes
Yes
MS/MSD
NA
NA
NA
NA
NA
Triplicate
Sample
Analysis
NA
NA
NA
NA
NA
QC
Sample
Yes
Yes
Yes
Yes
Yes
Surrogate
Spikes
NA
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.
NA - Not Applicable
-------
TABLE 7-2. Analytical Matrix
U)
QC Sample
•fid
Method Bltnk
s> -J
-------
TABLE 7-3. Hxample
LO
o>
tnmeters
oUl Solids
Moisture)
olstile Solids
Petals
AH.
TOC
total Cyanide
ToUl Phosphorous
BOD
Total Suspended
Solids
Conductivity
QC Simple
tnd
Method BItnk
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Untreated
Sediment
\
MS
Tripli-
cate
Tntted
Solids
I
MS
MSD
Tripli-
cate
>VV" *,
Water
MS
MSD
'ripli-
ctto
Oi/
MS
Tripli-
cate
IS,
•o n
«I
O
-------
TABLE 7-4. Analytical and QC Sample Matrix for GLNPO Treatability Studies (numbers of samples)
SAMPLE SET
SETI
Untreated S.
Treated S.
Water
Oil
SETIV
Untreated S.
Treated S.
Water
Oil
sern
Untreated S.
Treated S.
Water
Oil
SET in
Untreated S.
Treated S.
Water
TOTALS
Solids
Water
Oil
Tocmc
*•) QC(b)
3
3
2
4
1
1
1
1
1
16
1
-
/
3
2
3
-
5
3
TOTAL
SOLIDS
S QC
3
2
4
1
1
1
1
16
2
3
2
3
2
3
2
20
VOL
SOUDS
S QC
3
2
4
1
1
1
1
1
16
1
2
3
2
3
2
3
3
2
20
3
OAO
S QC
3
2
4
1
1
1
1
1
16
1
2
3
2
3
2
3
3
2
20
3
TOTAL
CYANIDE
S QC
3
2
4
1
1
1
1
1
16
1
-
_
3
3
3
-
6
3
TOTAL
PHOS
S QC
3
2
4
1
1
1
1
1
16
1
-
_
3
3
3
-
6
3
METALS
S QC
3
2
4
1
1
1
1
1
16
1
3
3
3
3
3
3
3
3
24
3
PCBs
S QC
3
3
2
4
2
i
16
7
2
1
3
2
1
1
3
2
2
3
3
2
2
20
6
PAH
S QC
3
3
2
4
2
•y
16
7
2
1
3
2
1
i
3
2
2
3
3
2
2
20
6
pH
S QC
3
2
4
1
1
1
1
t
16
1
-
-
3
2
3
-
5
3
BOD
S QC
-
-
1
-
1
-
-
3
-
3
TSS
S QC
-
-
1
-
1
-
-
3
-
3
COND
S QC
-
-
1
-
1
-
-
3
-
3
(a) Number of original samples.
(b) Number of quality control samples. A *3* represents two additional replicates (triplicate determination) and a spike or control
sample analysis resulting in an additional three QC analyses. A "2" represents matrix spike/matrix spike duplicate analysis
scheme resulting in an additional two QC analyses. A *l* indicates a blank spike or other control sample analysis resulting
in one additional QC analysis.
(c) Treated and untreated solids does not apply, and only one control sample per set will be analyzed.
-------
GLNPO - QAPJP
Section No.: £_
Revision No.: 2
Date: Feb. 15. 1991
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 any or all of the treatability studies.
140
-------
GLNPO - QAPjP
Section No.: £_
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% xCj 'C°
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% i
C,
where
%R = percent recovery
Cm = 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:
141
-------
GLNPO - QAPjP
Section No.: 9
Revision No.: .1
Date: Jan. 9. 1991
Page: 2 of 3
When 2 values are available:
RPD = [C, - Cj x 100%
[C, + CJ/2
where
RPD = Relative percent difference
Cj = The larger of two observed values
C~2 = The smaller of the two observed values
When more than 2 values are available:
S =
N
I
i = 1
2 _
I
N
N
I X
i = 1
N - 1
where
S = standard deviation
X, = individual measurement result
N = number of measurements
Relative standard deviation may also be reported. If so, it
will be calculated as follows:
RSD = 100
X
142
-------
GLNPO - QAPjP
Section No.: JL
Revision No.: J_
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.
143
-------
GLNPO - QAPJP
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 treatability 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.
144
-------
GLNPO - QAPjP
Section No.: JJ
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.
145
-------
GLNPO - QAPjP
Section No.: 11
Revision No.: 1
Date: Jan. 9. 1991
Page: 1 of 1
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 to 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.
146
-------
GLNPO - QAPjP
Section No.:
Revision No.: J.
Date: Jan. 9. 1991
Page: 1 of 3
APPENDIX A
TECHNOLOGY SUMMARIES
147
-------
GLNPO - QAPjP
Section No.: Appendix A
Revision No.: 1
Date: Jan. 9. 1991
Page: 2 of 3
B.E.S.T.™ Process Description
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 semivolatile
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
148
-------
GLNPO - QAPjP
Section No.: Appendix A
Revision No.: 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 Oxidation
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.
149
-------
APPENDIX D
BATTELLE DATA
151
-------
SAIC GLNPO (CF *361) RETEC
CONVENTIONALS IN UNTREATED SEDIMENT
MSLCode
361-37.
361-37.
361-37.
Rep 1
Rep 2
Rep 3
% Tola! Oil & Grease TOG Total Cyanide
Sponsor ID % Moisture pH Volatile Solid (mg/kg) % weight (mg/kg)
A US RE. Rep 1 38.20% 7.84 7.54 919 2.00% 1.1
A US RE, Rep 2 37.78% 7.91 7.39 1083 NA 2.0
A US-HE. Rep 3 30.96% 7.88 7.99 1011 NA 1.5
REVISED
2/14/92
Total Phosphorus
(rng P/kg)
1196
1443
1217
Method Blank
NA
6.06
0%
1.1
0.009%
0.004 U
0.036
STANDARD REFERENCE MATERIAL
ui
NA
NA
7.54
7.39
7.99
4%
NA » Not analyzed
U - Below detection limit
' - TOO value lor MESS delermlned based on past In-house analyses.
NOTE: All Conventional results are reported on a dry weight basis.
MESS 1 SRM
In-hous* Concensus Value '
NA
NA
NA
NA
REPLICATE ANALYSES
361-37, Rep 1
361 37, Rep 2
361-37. Rep 3
A US RE, Rep 1
A US RE, Rep 2
A US RE. Rep 3
RSD%
38.20%
37.78%
30.96%
11%
7.84
7.91
7.88
0%
NA
NA
919
1083
1011
8%
2.2
2.3
2.00%
NA
NA
NA
NA
NA
1.1
2.0
1.5
29%
NA
NA
1196
1443
1217
11%
Not a statistical determination.
-------
U1
U)
SAIC GLNPO (CF #361)
RETEC
REVISED
2/14/92
CONVENTIONALS IN TREATED SEDIMENT
MSL Code Sponsor ID
MDL
361 41. Rep 1 ATS RE, Rep 1
361-41. Rep 2 A TS RE, Rep 2
361-41. Rep 3 ATS RE, Rep 3
Method Blank
STANDARD REFERENCE MATERIAL
MESS 1 SRM
In-house Concensus Value '
MATRIX SPIKE RESULTS
Amount Spiked
Sample 36! 41*
Sample + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361 41. Rep 1
361-41. Rep 2
361-41. Rep 3
RSD%
% Moisture
20.46%
25.50%
25.50%
NA
NA
NA
NA
NA
NA
NA
NA
20.46%
25.50%
25 50%
12%
PH
8.07
8.07
8.14
6.06
NA
NA
NA
NA
NA
NA
NA
8.07
8.07
8 14
05%
% Total
Volatile Solid
4.30%
4.33%
4.13%
0%
NA
NA
NA
NA
NA
NA
NA
4.30%
4.33%
4.13%
3%
Oil & Grease
(mg/kg)
563
357
389
1.1
NA
NA
NA
NA
NA
NA
NA
563
357
389
25%
TOG
% weight
2.33%
2 27%
2.21%
0.008
2.3
2.3
NA
NA
NA
NA
NA
2.33%
2.27%
2.21%
3%
Total Cyanide
(mg/kg)
2.1
NA
2.1
0.004 U
NA
NA
88.6
2.1
84.3
82.2
93%
2.1
NA
NA
NA
Total Phosphorus
(mg P/kg)
2293
2071
2058
0.036
NA
NA
3993
2141
6368
4227
1 06%
2293
2071
2058
6%
NA = Not analyzed
U = Below detection limit
= TOG value lor MESS determined based on past in-house analyses. Not a statistical determination.
# = Mean for replicated sample.
NOTE: All Conventional results are reported on a dry weight basis.
-------
Ul
SAIC GLNPO (CF *361)
CONVENTIONALS IN WATER
RETEC
REVISED
3/6/92
MSLCode
Total
Sponsor ID % Moisture pH Solids
(mg/L)
Total
Volatile
Solids
(mg/L)
Total
Suspended
Solids
(mg/L)
Oil &
Grease
(mg/L)
TOG
(mg/L)
Total
Cyanide
(mg/L)
Total
Phosphorus
(mg P/L)
Conductivity
(umho/cm)
361 33. Rep 1 A WR RE, Rep 1
361 33. Rep 2 A WR HE, Hep 2
361 33, Rep 3 A WR RE. Rep 3
361 35, Rep 1 A WR HE. Rep t
361 35, Rep 2 A WR RE. Rep 2
361 35, Rep 3 A WR RE, Rep 3
361 36. Rep 1 A WR RE, Rep 1
361 36. Rep 2 A WR RE. Rep 2
361 36, Rep 3 A WR RE, Rep 3
Method Blank
MATRIX SPIKE RESULTS
Amount Spiked
Sample A WR RE #
Sample t Spike
Amount Recovered
% Recovery
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NS
NS
NS
NS
NS
NA
NA
NA
NA
NA
NA
8.15
8.24
8.20
6.06
NS
NS
NS
NS
NS
NA
NA
NA
NA
NA
NA
1600
1500
1700
10 U
NS
NS
NS
NS
NS
NA
NA
NA
NA
NA
NA
1400
1400
1400
tou
NS
NS
NS
MS
NS
NA
NA
NA
NA
NA
NA
70
85
88
2.0 U
NS
NS
NS
NS
NS
NA
NA
NA
560
560
574
NA
NA
NA
1.0 U
Blank Spike
68.5
1.0 U
62
62
90 5%
NA
NA
NA
427.7
452.5
457.9
NA
NA
NA
0.84
40.0
446.0
511 8
65.8
164.4%
0.004
0.006
0.004 U
NA
NA
NA
NA
NA
NA
0.004 U
0.207
0.005
0.203
0 198
95.7%
NA
NA
NA
0.439
0.488
0.401
NA
NA
NA
0.012
0.4
0.443
0.830
0.387
96.8%
NA
NA
NA
NA
NA
NA
2.49
2.37
2.31
0.34
NS
NS
NS
NS
NS
REPLICATE ANALYSES
361-33, Rep 1
361 33, Rep 2
361 33, Rep 3
361-35. Rep 1
361-35. Rep 2
361-35. Rep 3
361-35. Rep 1
361-35, Rep 2
361 35, Rep 3
A WR RE, Rep 1
A WR RE. Rep 2
A WR RE, Rep 3
RSD%
A WR RE, Rep 1
A WR RE. Rep 2
A WR RE, Rep 3
RSD%
A WR RE, Rep 1
A WR RE. Rep 2
A WR RE. Rep 3
RSO%
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
8.15
8.24
8.20
0.6%
1600
1500
1700
6.3%
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1400
1400
1400
0.0%
NA
NA
NA
NA
NA
NA
NA
NA
70
85
88
11.9%
NA
NA
NA
NA
560
560
574
1.4%
NA
NA
NA
NA
NA
NA
NA
NA
427.7
452.5
457.9
3.6%
NA
NA
NA
NA
0.004
0.006
0.004 U
24.7%
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.439
0.488
0.401
9.9%
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.49
2.37
2.31
3.8%
NA - Not analyzed
U - Below detection limit
- TOC value lor MESS determined based on past In-house analyses.
* > Mean lor replicalud samplu
Not a statistical determlnallon.
-------
Ul
Ul
SAICGLNPO (CF *36I)
METALS IN UNTREATED SEDIMENT
RETEC
REVISED
2/14/B2
(Concentrations In ug/g dry weight)
MSLCode Sponsor ID
MX
361-37. Rep 1 A US HE, Rep 1
361 37. Rep 2 A US HE, Hop 2
361-37. Rep 3 A US RE. Rap 3
Method Blank
STANDARD REFERENCE MATERIAL
1648 SRM
c»rlllUd
vulua
MATRIX SPIKE RESULTS
Amount Spiked
361 37 *
361 37 t Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-37. Rep 1 A US RE, Rep 1
361 37, Rep 2 A US HE. Hup 2
361-37. Hep 3 A US RE. Hop 3
RSD%
Ag
AA
0007
0 18
0 19
0 20
0020
0114
N3
rC
2
0 19
2 67
2 48
124%
0 18
0 19
0 20
3V.
As
»f
25
20 9
20 0
21 4
NA
11 2
11 6
11 3
NS
MS
MS
MS
NS
20 9
200
21 4
3Vo
Ba
»*
43
892
906
010
NA
425
tc
NC
NS
M3
MS
NS
N3
892
906
910
1%
Cd
AA
0 006
302
3 04
3 12
0 006 U
0 401
0 36
1007
2
3 06
5 00
1 94
S/Vo
3 62
3 04
3 12
2%
Cr
**
33
588
624
561
NA
71
76
±3
NS
MS
NS
he
N3
sea
624
561
91/.
Cu
Vf
5 5
33 9
34 6
32 6
NA
16 6
18
13
NS
NS
NS
NS
NS
33 9
34 6
32 6
3%
%Fe
»»
0 26
4 14
4 32
4 32
NA
3 33
3 35
10 1
NS
NS
NS
NS
NS
4 14
4 32
4 32
2%
Hg
CVAA
0 0003
1 362
1 337
1 383
000133
0065
0 063
±0012
1 979
1 361
3 246
1 89
95%
1 362
1 337
1 383
2%
Ml
HI
56
537
573
566
NA
349
375
120
NS
NS
NS
NS
NS
537
573
566
3%
Ni
WF
7 5
49 5
54 9
54 7
NA
31 1
32
±3
NS
NS
NS
NS
NS
49 5
54 9
54 7
6%
Pb
XRF
6 2
56.7
57 9
60 8
NA
29 5
28 2
It 8
NS
NS
N3
NS
NS
56 7
57 9
60 8
4%
Se
AA
0 22
0 87
0 99
0 87
0 22 U
0 87
rc
NC
2 73
0 91
5 70
4 79
1 75%
0 87
0 99
087
8%
Zn
WF
78
228
237
238
NA
124
138
16
NS
NS
NS
NS
NS
22C
23'
23(
2V
U - Below detection limits
NA - Not analyzed
NC - Not cerlihud
NS - Not spikud
I - Mean ol triplicated sample
NOTE All inuuli ru&ulls .HO blank corructud
-------
(Jl
CTi
SAICGLNPO (CF «J61)
METALS IN TREATED SEDIMENT
HETEC
REVISED
2/14/92
(Concentrations in ug/g dry weight)
MSLCode Sponsor 10
WX
361 41, Rep 1 A TS RE. Rep 1
361 41, Rop 2 A TS RE. Hop 2
36141, Hop 3 ATS RE, Rop 3
Method Blank
STANDARD REFERENCE MATERIAL
1646 SHM
oilllUd
vulu*
MATRIX SPIKE RESULTS
Amount Spiked
361 41 *
361 41 t Spike
Amount Rocovored
Percent Recovery
REPLICATE ANALYSES
361 41, Rep 1 A TS RE. Hop 1
361 41. Hep 2 A TS RE. Rop 2
361 41, Hop 3 A IS HE, Hup 3
RSO%
Ag
AA
0007
0 19
0 10
0 19
0020
0117
N;
hC
2
0 19
2 54
2 35
1 1 U%
0 19
0 IB
0 19
4%
As
>of
2 5
153
16 5
17 6
MA
It 2
11 6
it 3
NS
us
N3
NS
NS
15 3
16 5
17 6
/%
Ba
Ml-
43
789
611
775
NA
425
tc
NC
NS
NS
NS
NS
NS
789
81 1
775
2Jt
Cd
AA
0 006
2 74
2 67
2 67
0 006 U
041
0 36
1007
2
2 69
4 70
201
100%
2 74
267
2 67
2%
Cr
»f
33
494
514
552
NA
71
76
i3
NS
NS
NS
NS
NS
494
514
552
6%
Cu
*>r
5 5
47 7
44 6
52 0
NA
16 6
18
13
NS
NS
NS
NS
NS
47 7
44 6
52 0
a-/.
%Fo
Nf
0 26
3 85
3 92
3 97
NA
333
3 35
10 1
NS
NS
NS
NS
NS
385
3 92
3 97
27.
Hg
CVAA
0 0003
0 005
0 006
0 003
0 00133
0 066
0 063
10 012
1 978
0 005
1 927
1 92
97%
0 005
0 006
0 003
33%
Ml
wt
56
520
533
538
NA
349
375
120
NS
NS
NS
NS
NS
520
533
538
2%
Nl
*f
7 5
73 3
80 7
77 7
NA
31 1
32
13
NS
US
NS
NS
NS
73 3
80 7
77 7
9X,
Pb
»r
6 2
75 2
76 8
78 9
NA
29 5
28 2
11 8
NS
NS
NS
NS
NS
75 2
76 80
78 90
27.
Se
AA
0 22
1 60
1 49
1 49
0 22 U
0 87
N3
rc
2 73
1 53
6 22
4 69
172%
1 60
1 49
1 49
4%
Zn
at
7 8
223
227
243
NA
124
138
16
NS
NS
NS
NS
NS
223
227
243
9%
U - Below detection limits
NA - Not analyzed
NC . Not certified
NS . Not spiKuJ
0 - Moan ol triplicated sample
NOTE All metals results are blank corrected
-------
SAIC GLNPO (CF »361)
METALS IN WATER
RETEC
REVISED
2/14/92
MSLCode
MX
Sponsoi ID
A9
AA
0001
As
AA
003
Ba
ICPlMS
0 1
Cd
AA
0 002
Cr
AA
0 15
Cu
AA
0015
Fa
AA
00
Hg
CVAA
0 0003
Ml
AA
22 6
Ni
AA
0051
Pb
AA
0031
Se
AA
1 12
Zn
AA
2 528
Ul
-4
361-34. Rep 1 A WR RE. Rap 1
361-34, Rep 2 A WR RE. Rap 2
361 34. Hop 3 A WR RE. Rep 3
Method Blank
STANDARD REFERENCE MATERIAL
1643C
c*rllll«d
v»lu«
1641b
orlllUd
v»lu»
MATRIX SPIKE RESULTS
Amount Spiked
361-34 *
361 34 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-34, Hep 1 A WH RE. Rep 1
361 34. Rep 2 A WR RE. Rup 2
361-34, Rep 3 A WR RE. Rup 3
BSO%
0003
0 001 U
0001 U
0003
2 07
2 21
10 30
NA
NA
NA
10
0 001 U
b 61
5 61
56%
0003
0 001 U
0 001 U
6U%
737
7 53
7 22
003 U
84 62
82 1
±1 2
NA
NA
NA
90
7 3733
8b 55
78 177
a/%
7 37
7 53
7 37
1%
55 2
56 0
55 6
NA
49 2
496
±3 1
NA
NA
NA
42 9
55 6
94 4
3d 8
90%
55 2
56 0
556
1%
0 72
0 56
0 54
001
12 86
1220
±1 0
NA
NA
NA
to
061
900
8 39
84%
0 72
0 56
0 54
16%
17 9
17 9
16 2
3 6
19 0
19 0
±06
NA
NA
NA
89 a
17 4
93 3
75 9
B4%
17 9
17 9
16 2
6%
U - Below detection limns
NA - Not analyzed
NC - Not corliliutl
NS - Not spikud
« - Moan ol triplicated samplo
NOTE All iiiuldls rusulls Jiu blank couuclud
476
45 9
45 9
0 053
19 4
22 3
126
NA
NA
NA
20
46 5
65 5
19 0
95%
47 6
45 9
45 9
2%
1786
1763
1657
259
106 4
106 9
±30
NA
NA
NA
1765
1602
33B5
1SU2 9
90%
1786
1763
1857
3%
35 7
34 6
32 3
0004
NA
NA
NA
1461 7
1520 0
1400
48 5
34 2
85 7
51 5
106%
35 7
34 6
32 3
Ki
481 6
489 1
459 0
37.6
37 2
35 1
12 2
NA
NA
NA
97 0
476 6
564.4
87 B
91%
481 6
489 \
459 0
3%
151.7
151 7
136 5
009
51 6
60 6
±73
NA
NA
NA
20
146 6
163 8
17 2
86%
151 7
151 7
136 5
6%
43 8
438 .
43 8
004
36 8
35 3
±09
NA
NA
NA
20
43 8
61 3
17 5
87%
43 8
43 8
43 8
0%
1.12 U
1 12 U
1 12 U
1 12 U
1 12 U
12 7
±07
NA
NA
NA
42 86
1 12 U
43 90
4390
102%
1 12 U
1 12 U
1 12 U
OY.
201 7
195 4
208.0
17 4
690
73 S
±09
NA
NA
NA
888 8
201.7
1122 0
920 3
104%
201.7
IBS. 4
208 0
3%
-------
Ul
03
SAIC GLNPO (CF »361)
PAH IN UNTREATED SEDIMENT
Low Molecular Welghl PAHs (ng/g dry weight)
MSL Code Sponsor ID
361-37. Rep t A US HE. Rep 1
361 37, Rop 2 A US RE. Rap 2
361-37. Hep 3 A US HE. Hop 3
BLANKS
STANDARD REFERENCE MATERIAL
SRMNIST1941
c*rllll«d valu*
MATRIX SPIKE RESULTS
Amount Spiked
361 37 «
361 37 » Spiko
Amount Rocovoiod
Percent Recovury
REPLICATE ANALYSES
361 37. Hep 1 A US RE. Rop 1
361 37. Rop 2 A US RE. Hop 2
361 37. Hap 3 A US HE. Hop 3
RSD%
RETEC
REVISED
2/14/92
Naphthalene Acanaphlhytone Acenaphthene
21 1 U
222
243
193 U
871
NC
4673
233
2019
2919
6«,
21 1 U
222
243
7%
254 U
224 U
134 U
232 U
190 U
tc
4673
204 U
3S09
3509
75V.
254 U
224 U
134 U
NA
389 U
344 U
206 U
355 U
291 U
NO
4673
313 U
3548
3548
76%
389 U
344 U
206 U
NA
Fluorene Phenanlhrene Anthracene
334 U
295 U
247
305 U
250 U
NC
4673
292 U
3827
3827
82%
334 U
295 U
247
15%
1417
1341
1376
206 U
521
577
4673
1378
5020
3642
78%
1417
1341
1376
3%
24B U
218 U
171
226 U
IBS U
202
4673
212 U
4048
4048
87%
248 U
218 U
171
18%
U - Below detection limits
NC - Not certified
» - Moan ol detected values
NA - Not applicable
-------
(Jl
VD
SAIC GINPO (Cf »361)
PAH IN UNTREATED SEDIMENT
High Molecular Walghl PAHs (ng/g dry weigh!)
MSL Code Sponsor 10
361 37, Rep 1 A US RE. Rep \
361 37. Rep 2 A US RE, Rep 2
361 37, Rep 3 A US HE. Rep 3
Method Blank
STANDARD REFERENCE MATERIAL
SRM NIST1941
ctrUIUd v»lu»
MATRIX SPIKE RESULTS
Amount Spiked
361 37»
361-37 t Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-37, Rep 1 A US RE. Rep 1
361 37. Hop 2 A US RE, Rup 2
361 37, Rep 3 A US HE. Rup 3
RSOX
Flu « an
Ihena
1124
071
1015
167 U
1065
1220
4673
1037
5136
4099
68%
1 124
971
1015
tr/o
Pyrena
RETEC
REVISED
2/14/02
Indeno
Baruo(a)- Chrysena Beruo(b)- Benzo(k)- Benzo(a)- (1.2.3.c.d) Dioenzo(a,h)- Beruo(g.h.l)-
anltuacune
1014
905
027
175 U
004
1080
4673
949
4992
4043
87%
1014
905
927
6%
393
324
356
167U
454
550
4673
358
4592
4234
91%
393
324
356
10%
lluoianttiene lluoranlhane
585
520
571
166 U
668
N2
4673
559
4581
4022
86%
585
520
571
6%
437
385
522
127 U
771
780
4673
448
4401
3953
85%
437
385
522
15%
368
265
410
117 U
620
444
4673
348
4265
3917
84%
368
265
410
21%
pyrene
384
300
326
145 U
525
670
4673
337
4489
4152
89%
384
300
326
13%
pyrene anihiacarw pervlene
333
285
387
121 U
558
560
4673
335
4473
4138
89%
333
285
387
15%
138 U
122 U
88
126 U
113
rc
4673
88
4423
4335
03%
138 U
122 U
88
22%
348 B
283 B
277 B
118
387
516
4673
303
3145
2842
61%
348
283
277
13%
U - Below detection limits
B - Analyle delected in blank associated wilh sample
NC - Not ceililied
* - Moan ol delected values
-------
SAIC GLNPO (CF »361)
PAH IN UNTREATED SEDIMENT
MSL Coda Sponsor ID
361 37, Rep 1 A US RE. Rep 1
361 37. Rep 2 A US RE. Rep 2
361 37. Rep 3 A US RE, Rep 3
HETEC
| Surrogate
Recovery %
08 Naph- D10 Acenaph-
Ihdlono lhalene
58%
72%
74%
70%
76%
80%
REVISED
2/1 4/92
D12 Perylene
93%
95%
100%
Method Blank
STANDARD REFERENCE MATERIAL
SRM NIST1941
carllllad value
MATRIX SPIKE RESULTS
Amount Spiked
361 37 *
361 3/ t Spike
Amount Recovered
Poicont Recovery
REPLICATE ANALYSES
97%
77%
91%
80%
71%
94%
NA
68%
58%
NA
NA
NA
75%
68%
NA
NA
NA
96%
86%
NA
NA
361 37, Rep 1
361 37. Rep 2
361-37. Rep 3
A US-RE. Rep 1
A US RE. Rep 2
A US RE, Rep 3
RSD%
58%
72%
74%
13%
70%
76%
60%
7%
93%
95%
100%
4%
» - Moan ot delected values.
-------
o\
SAICGLNPO(CF #361)
PAH IN TREATED SEDIMENT
Low Molecular Weigh! PAHs fug/kg dry wl)
MSL Code Sponsor ID
361-41 ATS RE
Method Blank
STANDARD REFERENCE MATERIAL
SRM NIST1941
certified valu*
MATRIX SPJKE RESULTS
Amount Spiked
361-41
361-41 + Spike
Amount Recovered
Poicent Recovery
Amount Spiked
361 41
361-41 * Spike DUP
Amount Recovered
Percent Recovery
RETEC
REVISED
3/6/02
Naphthalene Acenaphlhylene Acenaphlhene
485
193U
871
NS
4167
485
26S1
2166
52%
3676
485
2158
1673
46%
280 U
232 U
190 U
NC
4167
280 U
2514
2514
60%
3676
280 U
1930
1930
53%
429 U
355 U
291 U
N3
4167
429 U
3056
3056
73%
3676
429 U
2488
2488
68%
Fluorene Phenanlhrene Anttuacene
368 U
305 U
250 U
NC
4167
368 U
3050
3050
73%
3676
368 U
2533
2533
69%
249 U
206 U
521
577
4167
249 U
3286
3286
79%
3676
249 U
2808
2808
76%
273 U
226 U
185 U
202
4167
273 U
3121
3121
75%
3676
273 U
2624
2624
71%
U - Below detection limits
NC - Not certified
* - Value outside internal QC limits (40 120%)
-------
CTi
SAIC GLNPO (CF K361)
PAH IN TREATED SEDIMENT
High Molecular Welghl PAHs (nq/g dry waiqhlj
RETEC
REVISED
3/6/82
MSL Coda
361 41
Method Blank
Sponsoi ID
A-TS-RE
Fluoiart-
Ihanu
202 U
167 U
Pyrena
211 U
1 75 U
Beruo(a)-
anlhiacene
201 U
167 U
Chrysene
201 U
166 U
Beruo(b)
lluoianlhona
153
127
Banio (K)
rhioranlherte
U 142 U
U 117 U
Beiuo(a)-
pyrene
175 U
145 U
Indeno
(1.2.3,c.d)
pyrena
146
121
Diberuo(a.h)-
amhiacene
U 152
U 126
Benzo(g.h.l)-
peiylene
U 97 B
U 1 18
STANDARD REFERENCE MATERIAL
SRM NIST1941
certified value
MATRIX SPIKE RESULTS
Amount Spiked
361 41
361-41 < Spike
Amount Recovered
Percent Recovery
Amount Spiked
361 41
361 41 t Spike DUP
Amount Recovered
Percent Recovery
B - Analyte delected In blank associated with sample
U - Below detection limits
NC - Not cedilled
* > Value outside Internal OC limits (40 120%)
1065
1220
4167
202 U
3418
3418
82%
3676
202 U
2905
2905
79%
994
1080
4167
211 U
3413
3413
82%
3676
211 U
2875
2875
78%
454
550
4167
201 U
3270
3270
78%
3676
201 U
2603
2693
73%
668
NC
4167
201 U
3228
3228
77%
3676
201 U
2740
2740
75%
153 U
127 U
771
780
4167
153 U
30B5
3085
74%
3676
153 U
2564
2564
70%
142 U
117 U
629
444
4167
142 U
3076
3076
74%
3676
142 U
2568
1568
43%
175 U
145 U
525
670
4167
175U
2819
2819
68%
3876
175 U
2219
2218
60%
146 U
121 U
558
569
4167
146 U
2370
2370
57%
3676
146 U
1715
1715
47%
152 U
126 U
113
tc
4167
152 U
2761
2761
66%
3676
152 U
2061
2061
56%
387
516
4167
07 B
1683
1586
38% '
3676
97 B
1278
1278
35% '
-------
O\
CJ
SAIC GLNPO (CF
PAH IN TREATED
MSLCoda
361 41
Method Blank
*361)
SEDIMENT
Sponsor ID
A-TS-RE
RETEC
I Surrogate
Recovery %
D8 Naph- 010 Acenaph-
thalene lhalene
74%
97%
78%
91%
REVISED
3/6/92
D12 Perylene
61%
71%
STANDARD REFERENCE MATERIAL
SRMNIST1941
carllllcd valua
MATRIX SPIKE RESULTS
Amount Spiked
361 41
361 41 t Spike
Amount Recovered
Percent Recovery
Amount Spiked
361-41
361-41 + Spike DUP
Amount Recovered
Percent Recovery
* - Values outside of internal QC limits (40-120%)
NA - Not applicable
77%
80%
94%
NA
74%
61%
NA
NA
NA
74%
57%
NA
NA
NA
78%
69%
NA
NA
NA
78%
65%
NA
NA
NA
61%
63%
NA
NA
NA
61%
58%
NA
NA
-------
SAICGLNPO (CF »36t)
RETEC
REVISED
2114/92
PAH IN WATER
MSL Code Sponsor ID
361-40 A-WH-RE
Method Blank
Naphthalene Acenaphlhylene Acenaphthene Fluorene Phenanlhrene Anihracena
608612 4156 52962 61969 199962 26748
266 U 320 U 491 U 421 U 285 U 312 U
ON
MATRIX SPIKE RESULTS
Amount Spiked
361 40
361-40 + Spike
Amount Recovered
Percent Recovery
Amount Spiked
361 40
361-40 + Spike DUP
Amount Recovered
Percent Recovery
U - Below detection limits.
NC - Not certified
* - Value outside of Internal QC limits (40 120%).
4673
608612
720383
111771
2392% *
4808
608612
556144
52468
-1091%'
4673
4156
7029
2873
61%
4808
4156
6478
2322
48%
4673
52962
56095
3133
67%
4808
52962
46387
-6575
-137% '
4673
81969
84485
2516
54%
4808
81969
70724
-11245
-234% *
4673
199962
199620
-342
-7% '
4808
199962
166182
-33780
-703% *
4673
26748
30162
3414
73%
4808
26748
26103
-645
-13%
-------
SAIC-GLNPO (CF «36I)
PAH IN WATER
High Molecular Weight PAHs (ng/L)
MSLCode
361-40 A
Method Blank
Sponsor 10
WRRE
Fluoian-
Ihene
12973
231 U
Pyrem Beruo(a)-
anlhracene
72041 18027
242 U 230 U
RETEC
Chrysene Beruo(b)-
Huoranlhene
43493 7909
230 U 175
Benzo (k)-
Auoranlhene
907 U
U 162 U
Benzo(a)-
pyrane
10220
200 U
Indeno
(1,2.3.c.d) D
pyiene
1220
167 U
REVISED
2/14/92
iberuo(a.h)- Benzo(g.h.i|
anlhracene perylene
1849 5509
174 U 131
-
B
MATRIX SPIKE RESULTS
Amount Spiked
361-40
361-40 + Spike
Amount Recovered
Percent Recovery
Amount Spiked
361-40
361-40 t Spike DUP
Amount Recovered
Percent Recovery
U - Below detection limits
B - Analyte delected in blank associated with sample.
NC . Not certified
• . Value outside of Inlernal QC limits (40 120%)
4673
12973
15517
2544
54%
4808
12973
16432
3459
72%
4673
72041
72662
821
18%
4808
72041
61907
-10134
211%*
4673
18027
20566
2539
54%
4808
18027
17618
208
-4%'
4673
43493
44535
1042
22% '
4808
43493
38457
-5036
- 1 05% •
4673
7909
8383
474
10% •
4808
7909
7542
367
-8% '
4673
907 U
4315
3408
73%
4808
907 U
4136
3229
67%
4673
10220
13057
2837
61%
4808
10220
11561
1341
26% '
4673
1220
3691
2471
53%
4808
1220
3721
2501
52%
4673
1849
4863
3014
64%
4808
1849
4820
2971
62%
4673
5500
7268
1760
38%
4808
SS09
6706
1197
25%
-------
SAIC GLNPO (CF #361)
PAH IN WATER
RETEC
MATRIX SPIKE RESULTS
REVISED
2/14/92
1 Surrogate Recovery %
MSL Code Sponsor ID
361 40 A-WR-RE
Method Blank
D8 Naph-
thalene
29% '
79%
010 Acenaph-
Ihalene
61%
77%
012 Perylene
51%
66%
CTi
CTi
Amount Spiked
361 40
361 40 + Spike
Amount Recovered
Percent Recovery
Amount Spiked
361 40
361 40 + Spike DUP
Amount Recovered
Percent Recovery
NA
29% '
57%
NA
NA
NA
29% '
57%
NA
NA
NA
61%
63%
NA
NA
NA
61%
64%
NA
NA
NA
51%
53%
NA
NA
NA
51%
56%
NA
NA
• - Value outside ol internal QC limits (40-120%)
NA - Not applicable
-------
RE-PROCESSED RESULTS (1/92)
PCBs IN UNTREATED SEDIMENT
Concentrations in ug/kg dry weight
MSL Code Sponsor ID
361-37. Rep 1 A US-RE. Rep 1
361-37, Rep 2 A US RE. Rep 2
361-37. Rep 3 A US-RE. Rep 3
Blank-8
Aroclor
1242
200 U
200 U
200 U
200 U
Aroclor
1248
14400
13900
15600
200
RETEC
SAIC-GLNPO(CF#361)
Aroclor Aroclor
1254 1260
100U 100U
100U 100U
100U 100U
U 100U 100U
% Surrogate
Recovery
Tetrachloro-
m-Xylene
100.7%
108.8%
113.1%
102.1%-
2/14/92
OTHER (1)
25000
24000
20000
NA
STANDARD REFERENCE MATERIAL
SRM-7 (HS-2)
certified value
MATRIX SPIKE RESULTS
Amount Spiked
361-37 *
361-37 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-37. Rep 1
361-37, Rep 2
361-37, Rep 3
A US RE, Rep 1
A US RE. Hep 2
A US RE. Rop 3
200 U
200 U
RSD%
(1) Numerous early eluling large peaks not corresponding to Aroclor pattern;
qauntities estimated based on average Aroclor response taclor.
(2) Residual peaks from presence of Aroclor 1248 masked 1254 spike.
U = Below detection limits
* = Value outside of internal QC limits (40-120%).
NC = Not cenihed.
0 = Mean of replicated sample.
NS = Not spiked NA ^ Not applicable.
221
111
100 U
84.7%
NA
NA
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
4673
100 U
NA(2)
NA(2)
NA(2)
NS
NS
NS
NS
NS
NA
107.5%
102.6%
NA
NA
NA
NA
NA
NA
NA
200 U
200 U
200 U
0%
200 U
200 U
200 U
0%
14400
13900
15600
6%
100 U
100 U
100 U
0%
100.7%
1 08 8%
113.1%
6%
NA
NA
NA
NA
-------
RE-PROCESSED RESULTS (1/92)
RETEC
3/5/92
oo
PCBs IN TREATED SEDIMENT
Concentrations in ug/kg dry weight
MSLCode Sponsor ID
361-41 A-TS-RE
Blank-8
STANDARD REFERENCE MATERIAL
SRM 7 (HS-2)
certified value
MATRIX SPIKE RESULTS
Amount Spiked
361 41
361 -4U Spike
Amount Recovered
Percent Recovery
Amount Spiked
361-41 DUP
361-41 + Spike DUP
Amount Recovered
Percent Recovery
Aroclor
1242
200 U
200 U
200 U
N3
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Aroclor
1246
200
200
200
N3
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
SAIC-GLNPO (CF #361)
Aroclor Aroclor
1254 1260
U 100 U
U 100 U
U 221
111
4167
100 U
3232
3232
78%
3676
100 U
2789
2789
76%
100 U
100 U
100 U
N3
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
% Surrogate
Recovery
Telrachloro-
m Xylene
91 .4%
102.1%-
84.7%
N3
NA
91 .4%
81.3%
NA
NA
NA
91 .4%
81.8%
NA
NA
OTHER (1)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
U m Below detection limits.
* « Value outside ol internal QC limits (40-120%).
NC a Not certified.
NS = Not spiked. NA - Not applicable.
-------
RE-PROCESSED RESULTS (1/92)
PCBs IN WATER SAMPLES
Concentrations in ug/L
MSLCode Sponsor ID
361-40 AWR-RE
Blank-9
RETEC
SAIC-GLNPO(CF#361)
Aroclor Aroclor Aroclor Aroclor
1242 1248 1254 1260
5U 5U 5U 5U
02 U 02 U 0.1 U 0.1 U
% Surrogate
Recovery
Telrachloro-
m-Xylene
NA(2)
20.2%'
3/5/92
OTHER (1)
10 to 20
NA
MATRIX SPIKE RESULTS
Amount Spiked
361-40
361-40 + Spike
Amount Recovered
Percent Recovery
Amount Spiked
361-40 DUP
361-40 t Spike
Amount Recovered
Percent Recovery
(1) Numerous early eluting large peaks not corresponding to Aroclor pattern;
qauntities estimated based on average Aroclor response (actor.
(2) Not available; peaks were not quantified due to coeluting unidentified peaks.
(3) Spikes were not recovered due to high background interference.
U - Below detection limits.
NS - Not spiked. NA > Not applicable.
NS
he
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
5
5 U
NA(3)
NA(3)
NA(3)
5
5 U
NA(3)
NA(3)
NA(3)
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
-4
O
RE-PROCESSED RESULTS (1/92)
PCBs IN OIL SAMPLES
Concentrations in uq/L
MSLCode
Sample
Sponsor ID Density (g/ml)
361-38. Rep 1 A-OR-RE. Rep 1
361-38. Rep 2 A-OR RE. Rep 2
361-38. Rep 3 A OR-RE, Rep 3
361-39 A-OR RE3
Blank-10
OIL CONCENTRATIONS ON % OIL BASIS
Concentrations in
MSLCode
361-38. Rep 1
361-38. Rep 2
361-38. Rep 3
361-39
ug/kg oil | %
Sponsor ID ('
A-OR-RE, Rep 1
A OR-RE. Rep 2
A-OR RE. Rep 3
AOR-RE3
0.9762
0.9762
0.9762
O.B985
Oil
/.)
33.97
33.97
33.97
48.61
Aroclor
1242
2000 U
2000 U
2000 U
2000 U
2000 U
Aroclor
1242
6030 U
6030 U
6030 U
4579 U
SAIC
Aroclor
1248
2000 U
2000 U
2000 U
2000 U
2000 U
Aroclor
1248
6030 U
6030 U
6030 U
4579 U
RETEC
-GLNPO(CF#361)
Aroclor
1254
1000 U
1000U
1000 U
1000 U
1000 U
Aroclor
1254
3015 U
3015 U
3015 U
2289 U
Aroclor
1260
1000 U
1000U
1000 U
1000 U
1000 U
Aroclor
1260
3015 U
3015 U
3015 U
2289 U
% Surrogate
Recovery
Tetrachloro-
m-Xylene
107.5%
93.0%
99.5%
96.3% •
34.8% '
% Surrogate
Recovery
Tetrachloro-
m-Xylene
107.5%
93.0%
99.5%
96.3%
3/5/92
OTHER (1)
-150000
NA
NA
-100000
NA
OTHER (1J
-150000
NA
NA
-100000
MATRIX SPIKE RESULTS
Amount Spiked
361-38 #
361-38 -i- Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-38, Rep 1
361-38. Rep 2
361-38. Rep 3
A OR-RE. Rep 1
A-OR-RE. Rep 2
A OR-RE. Rep 3
NS
NS
NS
NS
NS
2000 U
2000 U
2000 U
0%
NS
NS
NS
NS
NS
2000 U
2000 U
2000 U
0%
50000
1000 U
36700
36700
73%
1000U
1000 U
1000 U
0%
NS
NS
NS
NS
NS
1000U
1000 U
1000 U
0%
NA
100.0%
107.5%
NA
NA
107.5%
93.0%
99.5%
7%
(1) Numerous early eluting large peaks not corresponding to Aroclor pattern;
qauntities estimated based on average Aroclor response factor.
U = Below detection limits.
• - Value outside ol internal QC limits (40-120%).
NA - Not applicable. NS = Not spiked.
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
SAIC GLNPO (CF »36t)
PAH IN OIL
Low Molecular Weight PAHs (ng/ml)
MSL Code Sponsor ID
361-38. Rep 1 A OR RE, Rep 1
361-38, Rep 2 A OR RE. Rep 2
361-38, Rep 3 A OR RE, Rep 3
361-39 A-OR-RE3
Method Blank
RETEC
Sample
Denisty (g/ml)
0 9762
09762
0 9762
0 8985
Naphthalene
963952
1009533
1131802
2396562
3121 U
Acenaphlhylene
6302
6673
7136
10398
3753 U
Acenaph thane
73327
75953
83482
141580
5755 U
Fluorenu
112104
110830
122398
195290
4940 U
Phenanthrene
241457
253511
277739
386564
3339 U
REVISED
3/6/92
Anthracene
35429
3745ft
40202
54906
3659 U
OIL CONCENTRATIONS ON % OIL BASIS
Low Molecular Weight PAHs (ug/kg oil)
MSL Coda Sponsor ID
361-38, Rep 1 A OR RE, Rep 1
361-38. Rep 2 A OR RE. Rep 2
361 38. Rep 3 A OR RE, Rep 3
361-39 AORRE3
MATRIX SPIKE RESULTS
Amount Spiked
361 38 «
361-38 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
% Oil
fM
33 97
3397
33 97
48 61
361 -38, Rep 1 A OH RE, Rep 1
361-38. Rep 2 A OH RE, Rop 2
361-38, Rep 3 A OH RE. Rop 3
RSD%
Naphthalene
2921067
3059191
3429703
5446732
50000
1035096
1136012
100916
202% '
963952
1009533
1131802
8%.
Acenaphlhylene
19097
20221
21624
23632
50000
6704
48182
41478
83%
6302
6673
7136
6%
Acenaphlhene
222203
230161
252976
321773
50000
77587
125749
48162
96%
73327
75953
83482
7%
Fluorene
339709
335848
370903
443841
50000
115111
167187
52076
104%
112104
110830
122398
6%
Phenanthrene
731688
768215
841633
878555
50000
257569
329560
71991
144% '
241457
253511
277739
7%
Anthracene
107361
113512
121824
124786
50000
37697
87079
49382
99%
35429
37459
40202
6%
U - Below detection limits
I - Mean ot replicated sample
' - Value oulsidu of inlomJl QC Minus (40 120%)
-------
SAIC GLNPO (CF »361)
PAH IN OIL
RETEC
REVISED
3/6/02
MSLCode
361-38. Rep 1
361-38. Rep 2
361-38. Rep 3
361-39
Sponsor 10
A OH RE, Rep 1
A OR RE. Rep 2
A OH HE. Rep 3
AOH RE3
Sample
Density
(a/ml)
O.B762
00762
0.9762
08985
Fluocan-
Ihena
13676
14358
15563
16406
Pyrene
79347
84016
90336
102881
Beruo(a)-
anthracene
20217
21377
23051
23944
Chrysene
46395
48052
51956
50444
Benzo(b)-
fluoianthene
8827
8658
9431
7090
Benzo (k)- Benzo(a)-
auoramhene pyrene
934 U 12047
1005 U 11877
1621 U 13334
2280 13137
Indeno
(U.S.c.d)
pyrene
1344
1501
1672
1798
Dibenzo
(a.h) anthra-
cene
1937
2060
U 2511
U 2000
Benzo(g.h.i)-
perylene
6292
6855
7574
7685
Method Blank
2710 U
2833 U
2702 U
2696 U
2054 U
1900U 2349 U
1960U
2039 U
1254 U
Hlqh Molecular Weight PAHs (ug/kgorf)
MSL Code
Sponsor 10
(%)
Fluoran-
Ihene
Pyrene
Beruo(a)
anthracene
Chrysene
Benzo(b)-
Auoranftene
Benzo (k)-
lluoranlhene
Benzo(a)-
pyrene
Indeno Dibenzo
(t.2,3.c.d) (a.h)anthra-
pyiene cene
B«nzo(Q.h.t)-
perylene
361-38. Rep 1 A OH RE. Rep 1
361-36. Rep 2 A OR HE, Rep 2
361-38. Hep 3 A OH RE. Rap 3
361-39 A-OR-HE3
MATRIX SPIKE RESULTS
Amount Spiked
361-38 •
361-38 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-38. Rep 1 A OH HE. Rep 1
361-38. Rep 2 A OR HE, Rep 2
361-38. Rep 3 A OH RE. Hep 3
BSD*
U - Below detection limits
* - Mean ol replicated sample.
' - Value outside ot Internal QC limits (40 120%)
3397
3397
3397
4861
41442
43509
47161
37286
240445
254594
273745
233820
61264
64779
69852
5441B
140591
145612
157442
114645
26748
26236
28579
16114
2830
3045
4912
5162
36506
35991
40406
29857
4073
4548
6067
4086
5870
6242
7609
4545
19067
20773
22952
17460
3397
3397
3397
4861
41442
43509
47161
37286
50000
14532
67624
53092
106%
13676
14358
15563
7%
240445
254594
273745
233820
50000
84566
130367
54801
110%
79347
84016
90336
7%
50000
14532
67624
53092
106%
50000
84566
130367
54801
110%
50000
21548
71401
49853
100%
50000
48801
99769
50968
102%
50000
8972
50897
41925
84%
60000
1187 U
45777
45777
92%
50000
12419
58869
46470
93%
60000
1423
47887
46664
93%
50000
2169
51116
48947
98%
SOOOO
6907
40012
33105
66%
8827 934U 12047
8658 1005 11877
9431 1621 U 13334
5% 32% 8%
1344 1937 6292
1501 2060 6855
1672 U 2511 7574
11% 14% 9K
-------
OJ
SAIC GLNPO (CF #361)
PAH IN OIL
MSLCode Sponsor ID
361-38. Rep t A-OR-RE, Rep 1
361-38, Rep 2 A OR RE. Hop 2
361-38, Rep 3 A OR RE. Rep 3
361-39 A-OR RE3
Method Blank
OIL CONCENTRATIONS ON % OIL BASIS
MSLCode Sponsor ID
361-38, Rep 1 A-OR-RE, Rep 1
361-38. Rep 2 A OR RE, Rep 2
361-38, Rep 3 A-OR-RE. Rep 3
361-39 AORRE3
MATRIX SPIKE RESULTS
Amount Spiked
361-38 »
361-38 t Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-38. Rep 1 A-OR-RE. Rep 1
361 38. Rep 2 A OR RE, Rep 2
361 38, Rep 3 A OR RE, Rep 3
RSO%
RETEC
1
D8 Naph-
thalene
72%
61%
72%
71%
23% '
1
08 Naph-
thalene
72%
61%
72%
71%
NA
69%
75%
NA
NA
72%
61%
72%
9%
Surrogate Recovery %
D10 Acenaph
thalene
81%
68%
80%
109%
26% '
Surrogate Recovery %
01 0 Acenaph-
thalene
81%
68%
80%
109%
NA
85%
86%
NA
NA
81%
68%
80%
9%
REVISED
3/6/92
1
012 Perylene
94%
80%
89%
90%
72%
1
012 Perylene
94%
80%
89%
90%
NA
88%
92%
NA
NA
94%
80%
89%
8%
* - Mean ol replicated sample
- Value outside ol inlurnal QC limits (40-120%)
NA - Not applicable
-------
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