United States
        Environmental Protection
        Agency
Great Lakes
National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
EPA 905-R94-007
May 1994
$EPA  Assessment and
        Remediation
        Of Contaminated Sediments
        (ARCS) Program


        BENCH SCALE EVALUATION OF
        ZIMPRO'S WET AIR OXIDATION
        PROCESS ON CONTAMINATED
        SEDIMENTS FROM THE GRAND
        CALUMET RIVER
                           United States Areas of Concern

                           ARCS Priority Areas of Concern

-------
                    Bench-Scale Evaluation of
              Zimpro's Wet Air Oxidation Process on
       Contaminated Sediments from the Grand Calumet River
                           Prepared by

                          Vic Engleman
             Science Applications International Corporation
                         San Diego, CA
                              for the
Assessment and Remediation of Contaminated Sediments (ARCS) Program
                U.S. Environmental Protection Agency
                 Great Lakes National Program Office
                          Chicago, Illinois

-------
                                       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.
                                                   U.S. Environmental Protection Agency
                                                   Region 5, Library  (PL-12J)
                                                   77 West Jackson  Boulevarjd, 12th Floor
                                                   Chicago,  IL  60604-3590

-------
                                  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 (USACE) 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 USACE
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). Vic Engleman of SAIC was the principal author 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 Zimpro's Wet Air
Oxidation Process on Contaminated Sediments from the Grand Calumet River," EPA 905-R94-007,
Great Lakes National Program Office, Chicago, IL.

-------
                                        ABSTRACT
       The Great Lakes National Program Office (GLNPO) leads efforts to carry out the provisions of
Section 118 of the Clean Water Act (CWA) and to fulfill U.S. obligations under the Great Lakes Water
Quality Agreement (GLWQA) with Canada. Under Section 118(c)(3) of the CWA, GLNPO was
responsible for undertaking a 5-year study and demonstration program for the remediation of contami-
nated sediments. GLNPO initiated an Assessment and Remediation of Contaminated Sediments
(ARCS) Program to carry out this responsibility. In order to develop a knowledge base from which
informed decisions may be made, demonstrations of sediment treatment technologies were conducted
as part of the ARCS Program.  Bench-scale studies of the Zimpro Wet Air Oxidation Process, the
subject of this report, took place at Zimpro Passavant Environmental Systems, Inc. (Zimpro) in
Rothschild, Wl on August 27 to 29,1991.  The primary objective for this effort was to determine the
feasibility and cost-effectiveness of the Zimpro wet air oxidation process for treating and removing
PAHs. The wet air oxidation process was not expected to treat PCBs, another known primary
contaminant group detected in  the sediments.


       The Zimpro Wet Air Oxidation Process was tested using a sediment obtained from the Grand
Calumet River.  The concentrations of the contaminants of concern in the sediment were 11.9 mg/kg
PCBs and 266 mg/kg PAHs. The PCB and PAH concentrations of  8.5 and <2.84 mg/kg, respectively,
were found in the treated solids.  This corresponds to PCB and PAH removals of 29 percent and >98.9
percent, respectively. Metals analyses were performed on the treated solids and untreated sediments.
The feed sediments and treated solids were analyzed for percent moisture, oil and grease, total organic
carbon (TOC), total volatile solids, and  pH. Due to the sampling and analytical program for these tests,
it was not possible to calculate a mass balance as part of this study.
                                             in

-------
                                   TABLE OF CONTENTS
Section                                                                                 Page

Disclaimer  	        i
Acknowledgements	        ii
Abstract	       Hi
List of Figures	        v
List of Tables	       vi

1.0    Executive Summary	        1

2.0    Introduction	        3

       2.1  Background	        4
       2.2 Sediment Descriptions  	        4
       2.3 Sediment Characterization  	        7
       2.4 Technology Description	        7

3.0    Treatability Study Approach	        9

       3.1  Test Objectives and Rationale	        9
       3.2 Experimental Design and Procedures  	       10
       3.3 Sampling and Analysis	       13

4.0    Results and Discussion	       15

       4.1  Summary of Phase I Results	       15
       4.2 Summary of Phase II  Results  	       15
       4.3 Summary of Vendor Cost Calculations	       21
       4.4 Quality Assurance/Quality Control 	       23

Appendix A -  Zimpro Reports for Phase I and Phase II 	       25
Appendix B -  Experimental Design  	       60
Appendix C - Quality Assurance Project Plan for GLNPO  	       75
Appendix D - Analytical Data  From Battelle  	      120
Appendix E -  Analysis of Quality Assurance/Quality Control  	      136
                                             IV

-------
                                    LIST OF FIGURES





Number



 1      ARCS Priority Areas of Concern	       5



 2      Grand Calumet River Sample Location	       6



 3      Wet Oxidation Flow Diagram for the Zimpro Wet Air Oxidation Process  	       8



 4      Conditions of Phase I Tests	      11



 5      Percent Destruction of PAH in Solids as a Function of Operating Conditions	      15

-------
                                     LIST OF TABLES


Number

 1      Summary of Total PAHs  	       1

 2      Summary of Total PCBs  	       1

 3      Characterization of Feed Sediments and Treated Solids  	       2

 4      Battelle Analysis - Characterization of Feed Sediments  	       7

 5      Wet Oxidation Feed  	      12

 6      SAIC's Analysis Schedule for Phase II Wet Air Oxidation of
       Grand Calumet River Sediments   	      14

 7      Zimpro Analyses	      15

 8      Feed and Treated Solids PAH Concentrations	      17

 9      Total PCBs	      17

10     Metal Concentrations in the Feed and Treated Solids  	      18

11      Reduction Percentages for Other Parameters	      19

12     PAH Concentrations in the Filtrate	      20

13     PCB Concentrations in the Filtrate	      20

14     Wet Oxidation Feed and Output   	      21

15     Time Required to Process Harbor Sediments as a Function of Unit Size	   21

16     System Design Parameters Selected by Zimpro  	   22

17     Capital Costs and Estimated Utility Requirements	   23

18     Annual Operating and Maintenance Costs for Treating Dredged Sediments  	   24
                                            VI

-------
1.0    EXECUTIVE SUMMARY
       The Wet Air Oxidation Process was tested using sediments obtained from the Grand Calumet
River. The contaminants of concern in the sediments for these tests were polynuclear aromatic
hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Samples of the feed material and the
treated solids produced using the Wet Air Oxidation Process were analyzed by Battelle Marine
Sciences Laboratory for residual PAH and PCB contamination. The data from these analyses are
presented in Tables 1 and 2.

                        Table 1. Summary of Total PAHs (mg/kg, dry)


     Sample                     Feed     •        Treated Solids         Destruction
     Total PAHs                   266                 >2.84               >98.9
       As these data demonstrate, the PAH destruction efficiency for the Grand Calumet River
sediment is about 99 percent.  The data demonstrate the technical feasibility of the Zimpro Wet Air
Oxidation Process for treating and removing PAHs.

       Feed material and treated solids were also analyzed for residual PCB concentrations.  Table 2
outlines the analytical results obtained by Battelle.

                        Table 2.  Summary of Total PCBs (mg/kg, dry)


      Sample                      Feed            Treated Solids          Destruction
      Total PCBs                  11.9                 8.5                   29
       The destruction efficiency for PCBs was only 29 percent, but the wet air oxidation process was
not expected to treat PCBs.

       Metal analyses were performed on the treated solids and untreated sediments (see Section
4.2.1.3).  The Battelle analyses demonstrate that the treatment process, as expected, had little effect on
metals removal from the sediments.

-------
       The feed and treated solids were analyzed for percent moisture, oil and grease, TOO, total
volatile solids, and pH (see Table 3). The percent moisture decreased.  Ninety percent of the oil and
grease was removed.  TOC and treated volatile solids were reduced more than 50 percent. The pH
dropped to 6.5.
                Table 3. Characterization of Feed Sediments and Treated Solids
                         (mg/kg, dry basis, unless otherwise specified)

Total PCBs
Total PAHs
Moisture, % (as received)
Oil & Grease
TOC, % weight
Total Volatile Solid, %
pH, S.U. (as received)
Feed Sediments
11.9
266
55.0
9890
19.3
15.0
7.67
Treated Solids
8.5
<2.84
43.3
951
9.3
7.3
6.51
       Because of the nature in which the organic material is oxidized, the TOC analysis shown in
Table 11  was used to calculate the mass balance of the solids.  The summation of the percent recovery
results indicates that 90 percent of the material charged to the reactor was recovered after treatment.
After correcting for the amount of sample oxidized during treatment and the amount known to be lost in
Run Number 4, about 94 percent of the original sample was accounted for. Since all the species
containing carbon and hydrogen in the sediment were not known and the organics were being oxidized
to carbon dioxide and water, it was not possible to conduct a  more detailed mass balance.

       Small vials of the residuals from the treatability test were retained and given to the EPA
Technical Project Manager for the GLNPO for "show" purposes.  All quantities of the test products
(solids and filtrate) from the treatability test were sent to the analytical laboratory, Battelle, for analysis.
Due to the small quantities generated from the tests, none were retained and shipped to EPA for
possible further treatability studies.

       Zimpro has estimated the capital costs of units to treat 10,000, 40,000, and 100,000 yd3 of
sediment at rates of 10 (60 TPD), 20 (120 TPD), and 40 gpm (240 TPD).  These estimates are
approximately $4,500,000 for the  10 gpm unit; $5,600,000 for the 20 gpm unit; and $7,300,000 for the

-------
40 gpm unit. The sediment would be treated at a rate of 60 to 240 tons per day using 10 to 40 gpm
units operated on a 24 hour per day, 5 days per week, 50 weeks per year basis.  The cost of treating
the sediment is estimated to be $329, $203, and $133/yd3 for the 10, 20, and 40 gpm units respective-
ly. This estimate by Zimpro includes capital and operating costs but does not account for the costs
associated with site excavation, civil work, applicable taxes, pre-screening needs, and overall site
management and disposition of the residuals.

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 is responsi-
ble for undertaking a 5-year study and demonstration program for the remediation of contaminated
sediments.  Five areas were specified for priority consideration in locating and conducting demonstra-
tion 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 wre also utilized.  The Engineering/Technology (ET) Work Group was charged with
overseeing the development and application of the bench- and pilot-scale tests.

       Science Applications International Corporation (SAIC)  was  contracted to provide technical
support to the ET Work Group. As part of this effort, SAIC was  charged with conducting  bench-scale
treatability studies on designated sediments to evaluate the removal of specific organic contaminants.
The bench-scale studies of the Zimpro Wet Air Oxidation Process,  the subject of this report, took place
at Zimpro Passavant Environmental Systems, Inc. (Zimpro) in Rothschild, Wisconsin on August 27 to
29, 1991.  The primary objective for this effort was to determine the feasibility and cost-effectiveness of
the Zimpro wet air oxidation process for treating and removing PAHs. The wet air oxidation process
was not expected to treat PCBs, another known primary contaminant group detected in the sediments.

-------
2.1    Background
       SAIC and its subcontractors have conducted seven bench-scale tests for the ARCS Program on
four different sediments using four treatment technologies: Wet Air Oxidation (Zimpro Passavant),
B.E.S.T.™ Solvent Extraction Process (RCC), Thermal Desorption Technology (ReTeC), and Anaerobic
Thermal Process Technology (SoilTech).  This report summarizes the approach used and results
obtained during treatability testing of the Zimpro Wet Air Oxidation Process.  The sediments tested
using this technology were obtained from the Grand Calumet River.

       The primary objective of this portion of the study was to determine the feasibility and cost-
effectiveness  of the Zimpro Wet Air Oxidation Process for treating and removing PAHs from the Grand
Calumet River sediment.  Based upon previous tests performed by Zimpro, the bench scale tests were
designed to provide data that closely simulate full-scale performance. 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
in the Great Lakes and their tributaries. These sediments were obtained from the Grand Calumet
River.  They are representative of locations around the Great Lakes where future field demonstration
projects may  be conducted.  The primary contaminants in the Grand Calumet River sediments for the
purpose of this study are PCBs and PAHs.

2.2.1   Site Names and Locations for Each Sediment
       GLNPO collected sediments for study from the following areas around the Great Lakes:
Saginaw River, Michigan; Sheboygan River, Wisconsin; Grand  Calumet River/Indiana Harbor Canal,
Indiana; Ashtabula River, Ohio; and Buffalo River, New York. SAIC was  contracted to treat four of the
sediments (from the Grand Calumet River, Buffalo River, Ashtabula River, and Saginaw River) using
four different technologies. Samples from the Grand Calumet River were treated using the Zimpro Wet
Air Oxidation  Process.  A map is provided in Figure 1 which shows the ARCS Priority Areas of
Concern. Specifics of the sample location for the Grand Calumet River are shown in Figure 2.

-------
C71
                                                   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
      H
  0  M 100  IBO MO
     KlOMCTtm
US ENVnONMENTAl PROTECTION MENCV
GREAT LAKES NATDNAl PROORAU Off «
                             Rgure 1. ARCS Priority Areas of Concern

-------
en
                                                      Sediment sample point
                                               GRAND CALUMET RIVER
                                                                                M    IJ   t»
                                                                                 t  • ••-<	ImlUt
                                    Figure 2. Grand Calumet River Sample Location

-------
2.2.2   Sediment Acquisition and Homogenization
       Prior to conducting the bench-scale treatability study using the wet air oxidation technology, the
GLNPO samples were homogenized and stored under refrigeration by the U.S. EPA Environmental
Research Laboratory in Duluth, MM.

       Approximately  1 gallon of the homogenized sediments were sent to SAIC by the Duluth
laboratory.  These sediment samples were then transferred by SAIC to Zimpro.  Zimpro used these
samples in Phase I to perform a  series of standard tests commonly performed to determine if the waste
sample was compatible with their process and to determine optimum testing conditions and procedures
for the Phase II treatability study. The sediments used during the treatability studies also originated
from this stock and were forwarded to Zimpro by SAIC.

2.3    Sediment Characterization
       SAIC was responsible for the physical and chemical characterization of the raw sediment
samples used during the tests. Under SAIC direction, the sediments and their residuals were analyzed
by Battelle Marine Sciences Laboratory in Sequim, WA.  Table 4 provides characterization data
pertaining to the sediments.  The results from the raw sediment samples analyzed by Battelle are
shown in Table 4.

               TABLE 4.  Battelle Analysis - Characterization  of Feed Sediments
                              (mg/kg, dry basis, unless specified)

                                                       Grand Calumet River
             Total PCBs                                         13.1
             Total PAHs                                         266
             Moisture, %  (as received)                            55.0
             Oil & Grease                                       9890
             TOG, % weight                                     19.3
             Total Volatile Solid, %                               15.0
             pH, S.U. (as received)                               7.67

2.4    Technology Description
       Wet air oxidation is  a process in which organic or inorganic substances are oxidized in the
presence of water at elevated temperatures and pressures.  The usual temperature range varies from

-------
approximately 350 to 600°F (175 to 320°C).  System pressures of 300 to well over 3000 psig are
required.  The reactor pressure is determined by the vapor pressure of the water and the amount of
excess oxidant used in the reactor. Compressed air or pure oxygen is the source of oxygen that
serves as the oxidizing agent in the wet air oxidation process. As the oxidation temperature is
increased, a larger portion of the organic compounds is oxidized. A basic flow diagram for the Zimpro
Wet Air Oxidation Process is shown in Figure 3.
      Q
      HIGH
   PRESSURE
     PUMP
            AIR COMPRESSOR
                                                                                            OXIDIZED
                                                                                            LIQUOR
               Figure 3.  Flow Diagram for the Zimpro Wet Air Oxidation Process.
                    (Source: Zimpro Passavant Environmental Systems, Inc.)
        In processing an aqueous waste, the waste stream containing the oxidizable material is first
 pumped to the system using a positive displacement, high pressure pump. The pressurized discharge
 from the high-pressure pump is combined with the air stream from the air compressor, forming a two-
 phase stream.
                                              8

-------
       Next the air/waste stream passes through the feed/effluent heat exchanger, recovering heat
from the hot, oxidized effluent.  The heated mixture is then routed through an auxiliary heat exchanger,
if needed. A vertical bubble-column is commonly used as the reactor to provide the required hydraulic
detention time to effect the desired reaction. The reactor contents are mixed by the action of the gas
phase rising through the liquid. As the gas phase rises and mixes with the liquid, oxygen is dissolved
into the liquid. The reactor is sized to  allow the oxidation reactions to proceed to the desired level.  The
desired reaction may range from  a mild oxidation, which requires a few minutes, to total waste
destruction, which requires an hour or more of detention time.

       The oxidized liquid, oxidation  product gases,  and spent air leave the reactor and are routed
through the shell side of the feed/effluent heat exchanger. A cooler can achieve additional  cooling, if
necessary. The cooled reactor effluent is throttled through a pressure control valve into the process
separator where the reactor effluent is separated into a gaseous stream and a liquid stream. The
gaseous stream from the process separator is routed through an off-gas cooler.  The liquid stream is
pumped beyond the treatment system's boundary limits.  Further treatment of these oxidized liquids by
a biological system may be required prior to discharge into the final receiving system (POTW, river,
lake).

3.0    TREATABILITY STUDY  APPROACH
3.1    Test Objectives and Rationale
       SAIC has been contracted by the ARCS Program to test four technologies in removing organic
contaminants (PCBs and PAHs) from sediments typical of locations around the Great Lakes.  This
treatability study has been done to determine the feasibility and cost-effectiveness of the Zimpro Wet
Air Oxidation Process for destroying PCBs and PAHs in Grand Calumet River sediments.  In order to
accomplish this, this bench-scale test had the following objectives:
       •       To record observations and data to predict full-scale performance of the Zimpro Wet Air
               Oxidation Process
       •       To take samples during the treatability tests and  conduct analyses sufficient to evaluate
               the solids and filtrate  with respect to  compounds of interest
       •       To calculate the  destruction efficiency of target compounds
       •       To obtain treated solids (330 g dry basis) and filtrate for independent analysis.

       Based upon previous tests performed by Zimpro, it is their experience that the data obtained
from the bench test simulate full-scale operation. Ultimately, this data may be used to estimate both

-------
the feasibility and treatment costs associated with a full-scale application of the technology.  The ability
to evaluate process feasibility from these tests was also reported in the Zimpro reports on the Phase I
and Phase II tests (see Appendix A).

       A two-phase approach was used during this study.  During Phase I, SAIC sent a sample of the
untreated sediment to Zimpro. The sample underwent a series of initial tests in order to determine the
optimum conditions to be used during the actual treatability tests (Phase II). During Phase II, untreated
sediment from the Grand Calumet River was sent to Zimpro. Samples of raw (untreated)  sediments
and the various end products generated during the treatability tests (Phase II) were obtained and
analyzed by SAIC. The data generated by SAIC were primarily  used to determine treatment efficien-
cies. Vendor-generated data are reported and commented on when available.

       This study is only one part of a much larger program and is not intended to evaluate the
treatment of the sediments completely.  In order to ensure that the data obtained from this study can be
objectively compared with data generated from the other studies performed in support of the ARCS
Program, Battelle was subcontracted to perform all analyses for  the different treatability studies
performed by SAIC (seven treatability studies utilizing four technologies on four  sediments).   Assuming
that the appropriate volumes of sediment and residuals were available, the same set of analyses
described in Table 6 were applied during the characterization of each raw sediment and the end
products from the different treatability tests.  In addition, representatives from SAIC observed all Phase
II treatability tests.

3.2     Experimental Design and  Procedures
3.2.1    Phase I
        Phase I was designed to allow Zimpro to explore  a range of variables in order to set test
parameters which would optimize the performance of the  wet air oxidation technology for the bench-
scale tests  (Phase II). In order to accomplish this, a one-gallon  sample of the Grand Calumet River
sediment was sent to Zimpro by SAIC prior to  bench-scale testing.

       A factorial-design wet oxidation test with three levels of each variable was performed on the
sediment to give an indication of the importance of the two experimental variables: residence time and
oxidation temperature.  Tests were  run at the conditions shown in Figure 4.
                                              10

-------
320
300
280
X

X

X

X

X
                                          30     60     90
                                         OXIDATION TIME (min)

                             Figure 4.  Conditions of Phase i Tests.

       At 280°C typical test pressures were 2100 to 2200 psig; at 300°C typical test pressures were 2400
to 2500 psig; at 320°C typical test pressures were 2800 to 3000 psig.  The Phase I wet air oxidation tests
were performed in stainless steel laboratory autoclaves, each having a capacity of 0.75 L.  The as-received
waste sample was diluted with 3 parts distilled water to 1 part sediment (by volume) to reduce the total
solids concentration and viscosity of the waste.  The  solids and water were slurried and  put into the
autoclaves with sufficient compressed air to result in an excess of oxygen following oxidation. The charged
autoclaves were then placed in a heater/shaker mechanism, heated to the desired temperature, and held
for the specified reaction time.  Immediately  following  oxidation, the autoclaves were cooled to room
temperature and depressurized.

       Materials screening tests were also performed on the prepared sediment slurry. The tests were
performed at 280°C for 100 hours. The following materials were tested, and all were found to have no
localized corrosion and a general corrosion rate of < 1.0 MPY: 316-L stainless,  Alloy 20cb-3, Alloy 625,
Hastelloy C-276, and Titanium Grade 2. The results of these materials tests indicate that 316-L stainless
steel would perform acceptably and be the most economical material of construction for a full-scale wet air
oxidation system.  A longer-term materials of construction test is  recommended once the final wet air
oxidation design conditions are determined.

3.2.2   Phase II
       The experimental design for Phase II of the treatability program is presented in Appendix B and
is summarized in this section.

       The Phase II wet air oxidation tests were performed in titanium-stirred laboratory autoclaves, each
having a capacity of 3.78 L.  The autoclaves were equipped with a magnetic stirring device to help the
                                               11

-------
oxygen diffuse into the liquid and keep the solids in suspension.  The stirrer remained on throughout the
oxidation.

       The as-received feed samples were removed from their jars and placed in a stainless-steel mixing
bowl. A continuous mixer was used to stir the samples to obtain homogeneity. A glass beaker was used
to remove aliquots and samples from the bowl, with the stirrer still in operation. The feed material was
divided into seven portions for testing and two samples for the analysis of the raw feed. Separate stirred
autoclave oxidations were performed using six of the seven samples.  The samples were diluted, using
HPLC  grade  water, to produce an  autoclave feed sample with a suspended solids concentration of
approximately 10 percent.  Ten percent suspended solids was  used to simulate  the 10 to 20 percent
concentrations that would be used in a commercial unit to allow the sediment to be pumped at pressure.
This does not mean that all the additional water needs to be supplied as feed water; some can be recycled
from the filtrate after treatment.  Based on the Phase I test, a reactor temperature of 280°C and a hydraulic
detention time of 90  minutes was selected for the Phase II  tests.  These conditions were selected to
provide a balance between PAH destruction and process economics. Table 5 presents information on the
feed samples charged to the stirred autoclave and the volume discharged.

                                 Table 5.  Wet Oxidation Feed
Run Number
1
2
3
4
5
6
Sample Number
US02
US04
US01
US03
US05
US06
Sample
Sediment
253
250
225
225
128
126
Charged
Water
597
601
626
625
627
625
       The autoclaves were charged with the sediment slurry and sufficient compressed air to result in
excess oxygen remaining following oxidation.  The charged autoclaves were then heated to the desired
oxidation temperature by electrical heating bands and held at that temperature for the specified reaction
time.  Immediately following the oxidation, the autoclaves were cooled to room temperature by internal
water cooling coils and then depressurized.

                                              12

-------
3.3    Sampling and Analysis
       The Quality Assurance Project Plan is provided in Appendix C.
3.3.1   Sampling
       At the beginning of the Phase II Treatability test, SAIC personnel observing Phase II packed and
shipped a sample  of the untreated Grand Calumet River sediment to SAIC's subcontract laboratory,
Battelle, in accordance with written detailed instructions supplied to the SAIC on-site representative.  The
material was thoroughly mixed to achieve homogeneity of the solids and liquids in order to obtain a sample
representative of the material  treated in the Zimpro Wet Air Oxidation Process.  There was no feed
preparation other than mixing prior to sampling or testing.

       After  each  of the six wet oxidation tests was complete,  samples of the final filtrate and solid
residuals were collected by SAIC for EPA and Zimpro. Samples from the six tests were composited to a
single sample for analysis.  The filtrate and solids were composited separately. As specified in the Quality
Assurance Project Plan (QAPP) a minimum of 300 g dry basis of solid material was required in order for
Battelle to be  able to complete the necessary analyses of that material. The net weight of sample collected
for Battelle was 394 g.  Zimpro was provided with approximately 30 g of sample and two show vials with
a small amount of solid material were collected for GLNPO.

3.3.2   Analysis
       The analyses specified in Table 6 were conducted by SAIC's subcontracted laboratory, Battelle,
on the sediments and the process by-products from Phase II.  Zimpro conducted analyses for COD, BOD,
total solids and ash, and pH.  Battelle's data was used for the results  presented in this report. Zimpro's
data, where possible, is discussed to facilitate interpretation  of the results of the treatability test.

3.3.2.1 Battelle Analyses
       Following the Phase II treatability test, Battelle conducted analyses on the raw sediment  and the
end products. The number of analyses conducted on these sediments and their residuals are listed in
Table 6.  Descriptions of the analytical methods employed can be found in the QA Section of this report.

3.3.2.2 Zimpro Analyses
       Zimpro analyzed the treated solids  and filtrate for  COD, BOD, total  ash and solids, and pH.
Table 7 shows the analyses performed by Zimpro. Details on the analytical methods used by Zimpro are
presented in Appendix A.
                                              13

-------
       Table 6. SAIC's Analysis Schedule For the Phase II Wet Air Oxidation of Grand Calumet River Sediments
Parameters
Total Solids
(Moisture)
Volatile Solids
O&G
Metals
PCBs
PAHs
TOC
Total Cyanide
Total Phosphorus
PH
BOD
Total Suspended
Solids
Conductivity
QC Sample
and
Method Blank
(1)
YES
(1)
YES
(1)
YES
(0)
YES
(0)
YES
(0)
YRS
(0)
YES
(0)
YES
(«)
YES
(0)
_ YES
NA
NA
NA
Untreated
Sediment
(1)
G
(1)
G
0)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G



MS



(1)
G
(1)
G
(1)
G
NA
NA
NA




Tripli-
cate
(2)
G
(2)
G
(2)
G
(2)
G
(2)
G
(2)
1 G
NA
NA
NA
NA



Treated
Solids
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G
(1)
G



MS



(1)
G
(1)
G
0)
G
NA
NA
NA




MSD




(1)
G
(1)
G
NA






Tripli-
cate
(2)
G
(2)
G
(2)
G
(2)


-
NA
NA
NA



Water

NA*
NA
NA
(1)
G
(1)
G
NA
NA
NA
NA
NA
NA
NA
MS



NA
(1)
G
(1)
G
NA
NA
NA




MSD



: .........
(1)
G
(1)
G







Tripli-
cate

NA
NA
NA
;:xx .-. • •••:
.'• " • ;.;•: :

NA
NA
NA
NA
NA
NA
NA
Oil




NA
NA







MS




NA
NA

••' 	 ;••





Tripli-
cate




NA
NA







* Not Analyzed
(1) = Number of Analyses
G = Grand Calumet River
MS = Matrix Spike
MSD = Matrix Spike Duplicate

-------
                                  Table 7. Zimpro Analyses
Matrix Sample
Treated Solids
Filtrate
COD
yes
yes
BOD5
no
yes
Total
Solids
yes
yes
Total
Ash
yes
yes
PH
no
yes
4.0    RESULTS AND DISCUSSION
4.1    Summary of Phase I Results
       The principal objectives for the Phase I study were to ascertain the degree of destruction of PAHs
and COD found in the sediment sludge. In addition, a preliminary materials of construction evaluation was
conducted. Oxidations were performed in laboratory  autoclaves at temperatures of 280, 300, and 320°C.
The residence time for the oxidations ranged from 30 to 90 minutes.  The conditions tested are illustrated
in Figure 5, which indicates the destruction efficiency for PAHs. The Phase I study concluded that the PAH
destruction was in the range of 94 to 99 percent and the COD  destruction was in the range of 45 to 70
percent. The condition selected by Zimpro as optimum was a reactor temperature of 280°C and a hydraulic
detention time of 90 minutes.
320
300
280
96.2%

97.3%

94.2%

98.8%

95.7%
                                        30      60     90
                                      OXIDATION TIME (min)

     Figure 5.  Percent Destruction of PAH in Solids as a Function of Operating Conditions.
4.2    Summary of Phase II Results
       The concentrations of PAHs, PCBs, metals, total solids, volatile solids, and oil and grease present
in the untreated sediments and treated solids were measured in this study.  The following sections briefly
address the analytical results obtained for contaminant concentrations present in the raw sediments and
                                             15

-------
the process residuals (i.e., treated solids and filtrate). The analytical data  received from Battelle can be
found in Appendix D.

       Individual PAH compounds, PCB Aroclors, and metals were quantitated during sample analyses.
In order to determine overall destruction 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 less than the sum
of the detected components plus the sum of the detection limits of the undetected components.

4.2.1   Sediments/Treated Solids
4.2.1.1 PAHs
       Feed material and treated  solids  were analyzed for PAHs.   As shown in Table 8, total PAH
concentrations of less than 2.84 mg/kg were found in the solids produced by treating the Grand Calumet
River sediments. These values correspond to a destruction efficiency of greater than 98.9 percent.  Some
of the organics in the untreated sediment were destroyed during  treatment, thereby reducing the volume
of the sediments.  Based on results for TOC (shown in Table 11), it appears that about 10 percent by
weight of the sediment was destroyed by wet oxidation. Since the mass balance (Section 4.2.3) indicates
that over 90  percent of the material charged to the reactor was recovered, the calculation  for PAH
destruction was based on the PAH concentrations in the solids before and after treatment.

4.2.1.2 PCBs
       Samples of the feed material and the treated solids produced using the Zimpro Wet Air Oxidation
Process were analyzed for PCB contamination. The data from these analyses are presented in Table 9.

       A PCB concentration of 8.5 mg/kg was found in the treated  solids generated from  the  Grand
Calumet River sediment. This corresponds to a PCB  destruction efficiency of 29 percent.  However, the
Wet Air Oxidation Process was not expected to treat PCBs since previous tests have shown that PCBs are
too refractory for effective treatment by wet oxidation  under these test conditions.
                                              16

-------
      Table 8. Feed and Treated Solids PAH Concentrations
                         (mg/kg, dry basis)
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
1 Average of three analyses
2 Single analysis
Feed1
4.2
3.1
4.4
4.9
15.9
6.4
33.3
33.0
21.4
29.4
25.0
16.3
27.6
19.5
7.1
14.4
265.9

Grand Calumet
Treated2
0.03
<0.15
<0.02
<0.02
0.17
0.04
0.11
0.18
0.24
0.84
0.29
<0.004
0.27
0.12
0.17
0.19
<2.84

River
% Destruction
99.3
>95.2
>99.5
>99.6
98.9
99.4
99.7
99.5
98.9
97.1
98.8
>99.9
99.0
99.4
97.6
98.7
>98.9

Table 9. Total PCBs
(mg/kg, dry)
Sample Feed2
Total PCBs1 11.9


Treated Solids3
8.5
%
Destruction
29
1 Identified as Aroclors 1248 and 1254
2 Average of three analyses
3 Single analysis
                                 17

-------
4.2.1.3  Total Metals
       The data in Table 10 highlight the results for the metal contaminants present in the untreated feed
and the treated solids.  As demonstrated by the fact the metals concentrations are higher in the treated
solid than in the untreated sediment, the Wet Air Oxidation Process does not effectively remove metals.
The increase is probably related to the 10 percent volume reduction for the subject sediment achieved from
the destruction of the organics by the Wet Air Oxidation Process.

                TABLE 10. Metal Concentrations in the Feed and Treated Solids
                                         (mg/kg, dry)
Contaminant
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
Feed
27.6
283
7.7
1075
254
173,000
746
1910
1.40
115
5.4
4.8
3030
Treated Solids
29.1
368
13.0
1437
350
227,000
1095
2677
2.26
138
6.7
6.9
4290
4.2.1.4  Other Analyses
       The feed sediments and treated solids were analyzed for percent moisture, oil and grease, TOC,
total volatile solids, and pH as shown in Table 11.  The oil and grease was reduced by 90 percent. The
TOC was initially 19.3 percent by weight and was reduced to 9.3 percent by weight, including a 10 percent
weight loss caused by destruction of the organics.  The pH was reduced from about 7.5 to 6.5 in the
treated solids.
                                              18

-------
                    Table 11.  Reduction Percentages for Other Parameters
                              (mg/kg, dry basis, unless specified)
Contaminant
Total PAHs
Total PCBs
Moisture, %
(as received)
Oil & Grease
TOC, % weight
Total Volatile Solids, %
pH, S.U. (as received)
Feed
266
11.9
55.0
9890
19.3
15.0
7.67
Percent
Treated Solids Reduction or Destruction
<2.84
8.5
43.3
951
9.3
7.3
6.51
>98.9
29

90
52
51

4.2.2   Filtrate
       The concentrations of PAHs and PCBs in the filtrate from the wet oxidation reactor can be found
in Tables 12 and 13.  Individual PAH concentrations were mainly below the detection limits. The results
indicate that the wet oxidation process destroys the PAHs and some of the PCBs, but does not extract
large amounts into the water.

4.2.3   Mass Balance Calculations
       Wet air oxidation is a process in which organic material is oxidized in the presence of water.
Hydrocarbons are oxidized to water and carbon dioxide, while chlorine reacts to form HCI. Because of the
interaction between the organic material and water, the sum of the solids and the water is used for the
mass balance. Table 11 indicates that the TOC in the solids (Dry Basis) is reduced from 19.3 percent to
9.3 percent. This amounts to an 11 percent weight loss for the dry sediment, which is equivalent to a 5
percent weight loss for the wet sediment.  This weight loss from reaction amounts to about 1.5 percent of
the total weight of sediment and water charged to the reactor.  An additional 100 to 150 g of sample were
lost in a transfer procedure in Run Number 4.  This represents 2 to 3 percent of the total mass of the six
test runs. The summation of the percent recovery results shown in Table 14 indicates that 90 percent of
the material charged to the reactor was recovered after treatment.  Correcting for the  amount of sample
oxidized during treatment, and the amount known to be lost in Run Number 4, about 94 percent of the
original sample was accounted for.  Since all the species containing carbon and hydrogen in the sediment
were not known and the organics were being oxidized to carbon dioxide and water, it is not possible to
conduct a more detailed mass balance.

                                              19

-------
 Table 12. PAH Concentrations in the Filtrate (ug/L)

  Contaminant                          Filtrate
  Naphthalene                           0.96
  Acenaphthylene                       <0.15
  Acenaphthene                        <0.22
  Fluorene                             <0.19
  Phenanthrene                         1.04
  Anthracene                           <0.14
  Fluoranthene                          0.16
  Pyrene                                0.14
  Benzo(a) anthracene                   <0.10
  Chrysene                             <0.10
  Benzo(b)fluoranthene                  <0.07
  Benzo(k)fluoranthene                  <0.06
  Benzo(a)pyrene                       <0.08
  lndeno(1,2,3-cd)pyrene                <0.07
  Dibenzo(a,h)anthracene                <0.09
  Benzo(g,h,i)perylene                   <0.07
  Total PAHs                           <3.64
  Table 13.  PCB Concentrations in the Filtrate (ug/L)

Contaminant                         Filtrate
Aroclor 1242                          <0.2
Aroclor 1248                          <0.2
Aroclor 1254                          <0.1
Aroclor 1260                          <0.1
                         20

-------
                       Table 14. Wet Oxidation Feed and Output (grams)
Run Number
1
2
3
43
5
6
Sample
Number1
US02
US04
US01
US03
US05
US06
Sample Charged
Sediment Water
253
250
225
225
128
126
597
601
626
625
627
625
Sample Removed
Solids
88
84
108
66
51
43
Filtrate
682
685
703
545
615
657
Percent
Recovered2
91
90
95
84
88
93
1    Note that Table 1 in Appendix A, Phase II is based on Sample Number instead of Run Number.
2   Before accounting for weight loss by oxidation. Average of all six percentages is 90 percent.
3   Pump tubing leaked causing small loss of sample (100-150 ml). Sample was considered valid since the loss was small and
    sample appeared representative.

4.3    Summary of Vendor Cost Calculations
       Zimpro and SAIC mutually developed three scenarios for the full-scale wet air oxidation of the
Grand Calumet River sediments.  The three scenarios involve the treatment of 10,000,40,000, and 100,000
yd3 of all sediments;  all at 40 percent solids. The Wet Air  Oxidation Process designed can handle
sediments at a solids concentration of 10 percent; therefore a 3 to 1 dilution, using water from the harbor
that is being dredged, would be required.   Wet air oxidation units of 10, 20 and 40 gallons per minute
capacity  would handle these volumes of sediment as shown in Table 15. The design parameters for the
proposed systems are presented in Table 16.

        Table 15.  Time Required to Process Harbor Sediments as a Function of Unit Size

WAO Capacity, gpm
10
20
40

10,000yd3
2.25
1.12
0.56
Time to Process Sediments, Yrs^
40,0000 yd3
6.75
3.38
1.69

100,000yd3
22.50
11.25
5.62
                                               21

-------
                   Table 16. System Design Parameters Selected by Zimpro
Design Flow Rate (U.S. gpm) 10.0
20.0
40.0
Operating Schedule
Normal Operating Mode
Reactor Hydraulic Detention Time (minutes)
COD Reduction (%)
Mechanical Design Temperature (°F)
Mechanical Design Pressure (psig)
Operating Temperature (°F)
Operating Pressure (psig)
Material of Construction for Waste Wetted Surfaces
System 1
System 2
System 3
24 hours/day
5 days/week
50 weeks/year
Autothermal
90
83
570
2,000
536
1,500
31 6L
       Detailed information on the equipment and the capital cost basis may be found in Appendix A. The
estimated supply and installation cost for each of the systems is given in Table 17. Costs do not include
provisions for the following items:
       •   Any applicable state, local, or federal taxes, permits, bonds, fees, or duties
       •   Design or supply of foundations, civil work, sumps, concrete lining, or sewers
       •   Design, supply, or installation of equalization tanks
       •   Design, supply, or installation of the post-treatment system
       •   Equipment storage necessitated due to action of the purchaser
       •   Any operational spare parts other than spare rotating equipment specified by Zimpro
       •   Any piping or wiring beyond the proposed system boundary limits.

Table 17 also includes the estimated utility  requirements.
                                              22

-------
                  Table 17. Capital Cost and Estimated Utility Requirements
 Capital Cost ($)
System 1       System 2      System 3
4,500,000      5,600,000      7,300,000
 Natural Gas @1000 BTU/scf - startup only
 (scfm)
 Cooling Water @ 65°F
 (U.S. gpm)
 Operating Power
 (kWh/hr)
   135
   130
                  10
275
265
               36
550
530
Table 18 provides information on the operating costs for the wet air oxidation units.

4.4    Quality Assurance/Quality Control
       The conclusions and limitations of data obtained during the evaluation of Zimpro's wet air oxidation
process are summarized in the following paragraphs.

       Upon review of all  sample data and associated QC results,  data generated  for the Zimpro
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.

       Refer to Appendix E for the analyses related to Quality Assurance/Quality Control.
                                              23

-------
      Table 18.  Annual Operating and Maintenance Costs for Treating Dredged Sediments

Energy
Natural Gas @ $5.00/MBTU
8 hr/day, 5 day/wk, 50 wk/yr
Power @ $0.05/kwh
Water and Chemicals
Cooling Water @$0.50/1000 gal
Labor
Operation @ $20.00/hr
24 hr/day, 5 day/wk, 50 wk/yr
Maintenance @ $20.00/hr
24 hr/day, 5 day/wk, 50 wk/yr
Supervision @ $30.00/hr
8 hr/day, 5 day/wk, 50 wk/yr
Maintenance
Materials @ 2% of Capital
Waste Disposal
Supernatant and Filtrate
@ 3750 mg/l BOD
POTW Sewer Chg $0.15/lb BOD
Annual Capital Cost1
Amortized over 1 0 yr @ 10%
Taxes
@ 4% of Capital Cost
Overhead Charges
@ 60% of Labor and Maintenance
Total Annual O&M Costs
Sediment Processed (ydVyr)
Volume Processed (gal/yr)
Cost ($/gal)
Cost ($/yd3)
System 1

360

39,000

24,300

120,000

24,000

60,000


90,000

17,000


732,354

180,000

176,400

$1,463,414
4,444
3,600,000
0.406
329.30
System 2

1200

79,500

49,500

120,000

24,000

60,000


112,000

34,000


911,374

224,000

189,600

$1,805,174
8,889
7,200,000
0.251
203.10
System 3

4320

159,000

99,000

120,000

24,000

60,000


146,000

68,000


1,188,041

292,000

210,000

$2,370,361
17,778
14,400,000
0.163
133.33
1    It is assumed that the system will be used for other purposes after completion of remediation. Therefore a 10-year lifetime is
    assumed for uniformity.
                                                 24

-------
              APPENDIX  A
   BENCH-SCALE SHAKING AUTOCLAVE RESULTS  TOR




      WET AIR OXIDATION SYSTEM TREATMENT




      OF INDIAN HARBOR SEDIMENT SLUDGE




SCIENCE APPLICATIONS  INTERNATICNAL CORPORATION




                   PHASE  I




      SAIC SUBCONTRACT NO. 16-920034-51
             SEPTEMBER 18,  1991
                 25

-------
  i.o annoDucnoN
  Laboratory wet air oxidation  tests vere performed on sediment  sludge
  from the Indiana harbor.  The  test vork vas performed for Science
  Applications International Corporation (SAIC) under contracted vith
  the U.S. EPA.   The principal objectives for this Phase I study vere
  to ascertain the degree of destruction of poly-aromatic hydrocarbons
  (PAHs)  and  chemical oxygen demand (COO) found in the  sediment sludge.

  Oxidations  vere  performed in laboratory autoclaves at  temperatures
  of  280,  300, and  320°C.   The residence time for  the oxidations  ranged
  from 30  to  90 minutes.   Data from this report will provide  the  basis
  for evaluation of vet  air oxidation  for treatment of the sediment
  sludge.

 2.0 VET AIR OXIDATION  PERFORMANCE
 The initial sediment sample contained  approximately 48 percent  total
 solids and contained approximately 140 g/1 of COD.  The sample vas
 not size classified and did contain some particles over 1/16  inch.
 The "as  received" sample had to be diluted to reduce  the total solids
 concentration and viscosity of the solution.  A dilution of 3 parts
 distilled vater  to 1 par: sediment (by volume)  vas mixed.   The
 analysis  of  this  autoclave feed sample is presented in  Table 1.
 The  autoclave feed mixture contained  33.7 g/1 of  COD.   The  total
 solids of the feed vas  measured at 119.2 g/1.  The total  PAHs
 concentration vas  measured at  2761.6  ug/1.

 A 2  factorial vet air  oxidation :est  vas  performed on  the sediment
 sludge.   The  factorial  tes: vill give  an indication of  the importance
 of  :he :vo experimental  variaoles:  residence  tiae. and oxidation
                                 ^
 temperature.  A diagram  of  r.le  2"  factorial  rest can be seen  in
 Figure 1.  The reductions  of COD  (YCOD)  and of total PAHs C*pAHs>
obtained by the  vet air oxidation  testing vere fitted to a first
order .•nodel:

                    Y__.,   » o  - b.X,  -  b,Z.
       and           COD     °    ' l    2 "

                           ' bo * blXl  * b2X2
                              26

-------
        vhere:
                        X. - Temperature - 300"C
                                 20 °C
                            X, . Time - 60"C
                             4  30 minutes
                               b  »   17
                                0    "FT
        •-•here N » 5 experimental points
                           b.  » 0.5(Y_ - YT)
                            A.         n    w
        vhere !„ is the average of the results at  the high
        temperature and Y,  is  the- average of the lov temperature
        results.
        Likevise:
                           b.  - 0.5(Y_ - Y.)
                            «.         n    L
       vnere  Y.,  is  the  average  of  the results at the high
       time and  Y,  is  the  average  of  the lov time results.

Certain assumptions  must  be  made  to determine the values for the
first order models since suspended solid concentration in the
oxidized effluents vere r.ot  aeasur:'!.   First ve assume that the ash
content of the influent ana  oxidized  effluent are equal and that the
effluent ash  content is divided betveen  suspended ash and soluble
ash, vnich vas measured.   Therefore the  suspended ash content is
given by the  equation:

     Suspended Ash (SAS) « Total Asn(119.2  g/1)  - Solunle Ash   (1)
in addition:
           Total Solids (TS) «  SAS - Volatile  Solids (VS)       (2)
vnere:
                   	_--  -  VS--  COD/1.3                        (3)
                                            27

-------
  Where the COD is given as a fraction (mg/g) of the total solids
  (f*TS).  By combining and rearrangement of (2) and (3)  the  total
  solids is obtained as follovs:

                           TS « SAS/(l-f/1.3)

  Assuming  the  density of the suspended  solids  is  1.2  then the volume
  of  filtrate obtained for  each  oxidized  effluent  can  be calculated
  using  the  relationship:

                Volume of filtrate - 1.0 liters - TS/1.2

 Using the above relationships: the concentration of suspended  solids,
 the COD and total PAHs concentrations in the effluents,  and  the
 volumes of filtrate  for each oxidation condition can be  determined.
 These calculated values are reported in Tables 1 and 2 under  the
 calculated values heading.

 COD REDUCTION
 The first  order coefficients far  the COD reduction (see Table 1)
 are determined as  follovs:

                              bo . 59.23

                        b.  = 0.5(69.3 - 55.15)

                         b. =  3.5(61.3 -62.65)
                         ^

The  first order -noaei for  :CD reauction  is  then given as:
The first order aooei  for  :.k.e COD reauction shovs a strong  dependency
on the temperature  (X.) ana a negative dependency on  time (X,).
                     j.                                       4.
These results are slightly iisieading, in most cases COD destruction
should increase vith respect to time.  One possible explanation  for
                             28

-------
   the  results  is analytical error of the COD values.  The measured COD
   of  the  autoclave feed vas 33.7  g/1 and the oxygen uptake for the
   280'C oxidation at  30 minutes vas  calculated at 33.8 g/1.   By adding
   33.8 g/1  to  the remaining COD in  the  oxidized effluent at  the same
   condition  (14.8 g/1)  one  vould  estimate  the feed COD at 48.6 g/1 and
   not  the measured value  of 33.7  g/1.   The  oxidation process  could
   have partially destroyed  some organic  compound that  did not
   completely respond  to  the feed  COD  test,  thus yielding additional  COD
   in the oxidized  effluents.

  The reductions  in COD obtained  by vet air oxidation  ranged from  56.1
  percent  at 280eC  for 30 minutes  to 69.4 percent  at 320'C for  90
  minutes.  The COD remaining after vet air oxidation  appears  to be
  very biodegradable as indicated  by the BOD^/COD  ratios.  The  BOD./COD
  ratios  in  the filtered effluents vere greater  than 0.5.  The
  remaining  COD is most likely partially oxidized  organic compounds in
  the  fora of lov molecular  veight organic acids.

  PAHs  REDUCTION
  The  first  order model for  PAHs reduction  can also be calculated in
  the same manner and  is given as:

                      Y,,,,  « 96.-  - 0.5X. * 0.25X,
                       ?Afl              I        t.

 The firs: order moael  for  :r.e PAHs  destruction indicates only a
 slight dependency on  both  temperature  (X,) and time (X.,).  Excellent
                                         ^              ^
 reduction of  the total  PAfls  vas  ootained by  vet air oxidation.  For
 the conditions  tested,  recuction of  the total  PAfls  concentration
 ranged from 94.2  to  98.S percent.  The PAHs  data  is somevhat
 misleading in  that the 200°C oxidation has a slightly  lover
 reduction then  at  the  2SO°C. 20 minutes sample.   Analytical error in
 the PAHs  analysis  of  the filtered affluent appears  to  be  the source
 of the discrepancy.  A limitation of sediment  sample  prevented a
 repeat of this vet air oxidation  run.

 Using the data obtained frsm :ne  shaking autoclave study, parameters
 for the demonstration  tes::r.g in  a stirred autoclave (Phase II) vere
 set.   It  vas recommenced :nat additional testing vould be performed
-at, ?fln«r_ f«r— QQ .qjjiir^^—  "H ^ rprppmanda t i nn jg based On PAHs
                                   29

-------
  destruction vhich  shoved  only  slight  improvement  by  increasing the
  temperature to 320°C.

  3.0 MATERIALS OP CONSTRUCTION  EVALUATION
  Materials screening tests vere performed on  the diluted sediment
  sludge.   The test vas performed at 280°C for 100 hours.  The
  objective of the screening test vas to identify types of alloys
  vhich could be considered candidate materials of construction for a
  full scale vet air oxidation system.

  The  alloys selected for  the  screening vere 316-U  Alloy 20,  625,  C-
  276,  and  titanium  grade  2.    A  list of the alloy's nominal  chemical
  compositions can be found  in  Table 3.   These  materials  vere  selected
  for  their  knovn corrosion  resistance  in the vet  air oxidation
  environment.

 The results indicate that all the  alloys tested vould be acceptable
 materials.  The general corrosion  rates vere  less  than  1.0 mpy
 (0.001 inches per year).   The results  form  the testing are presented
 in Table  i.  None of the alloys shoved signs of pitting or
 transgranular stress corrosion cracking (TGSCC).    The lov chloride
 levels and near neutral pH of the sediment sludge make it non-
 aggressive to these alloys at the elevated temperature.   The results
 of  this materials  test  indicate  that 316-L vould  perform acceptably
 and  be :ne most economical material of construction for  a full scale
 ve:  air oxidation  system.   A  longer term materials  of  construction
 test  is recommended once  the  final  vet  air  oxidation design
 conditions  have been deter-ir.ed.

 4.0 EXPERIMENTAL PROCEDURES
 4.1 Vet Air Oxidation Tesr:.-.g
 All vet air oxidation  rests vere perforaed  in  laboratory stainless
 steel autoclaves each ha_vir.g a capacity of  720 sis.  Autoclaves  vere
 charged vith the vaste and sufficient compressed air to  result  in
 excess  residual oxygen following oxidation.  The charged  autoclaves
vere then  placed in  a heater/shaker  mechanism, heated  to  the  desired
oxidation  temperature ano held for  the  specified reaction time.
                             30

-------
  Immediately  following  oxidation,  the autoclaves were cooled to room
  temperature  and depressurized.
 All analyses included as a part of  the  oxidation testing vere
 performed by the Zimpro/Passavant analytical laboratory,  Enviroscan,
 according to Standard Methods1 or EPA Methods for the  Chemical
 Analysis of Water and Uasre:

 4.2 Materials of Construction Testing
 Materials screening testing vas performed in  a 500 ml  capacity
 titanium shaking autoclave similar to that used  in the vet air
 oxidation testing.   The coupons that vere utilized in  testing vere
 velded u-bends  fabricated from commercial sheet  stock of various
 alloys.   The u-bend coupons vere  not annealed after velding and
 bending.   Therefore,  the test  coupons vere in a  plastically strained
 and residually  stressed  metallurgical state.   The placement of the
 coupons  in the  autoclave vas  facilitated through use of a threaded
 rod and  nuts.   Teflon  vasners  vere  placed betveen the coupons and
 retaining nuts  to produce a crevice  area for  monitoring of crevice
 corrosion.

 Prior  to  and  after  testing, the alloy coupons vere cleaned in iOZ
 nitric acid,  veighed and neasured to  determine a.  general  corrosion
 rate.  Visual and microscopic  examinations vere  performed  after
 testing  to identify the  presence of any  localized corrosion.

 5.0 ZIMFRO* VET AIR OXIDATION STSTEMS
Thermal oxidation is a videly accepted approach  to vaste  treatment.3
Vet air oxidation (VAO) is a process  that comoines the  effectiveness
of  thermal oxidation vith fuel economy vhen handling aaueous  streams
and slurries.4  Vith the exception of a  fev polysubstituted
halogenated organic compounds  (kepone. PCS), '.'AO  can destroy most
organic compounds.
            ZIMPRO is a registered trademark of Ziapro Passavant
            Environmental Systems,.Inc.
                                     31

-------
  The vet air oxidation process is based on the discovery that many
  chemicals vill oxidize (bum) in the aqueous phase at relatively lov
  temperatures.   The reaction mechanisms involve a family of related
  oxidation and  hydrolysis reactions.   The enhanced solubility of
  oxygen  in aqueous  solution  at elevated temperature and pressure
  provides  a strong  driving force  for  oxidation.   The source of oxygen
  for  the process  is usually  compressed air.   High pressure  pure oxygen
  may  also  be used.

  ZIHPRO's  Vet air oxidation  treatment  technology  has  been applied  to
  vaste liquors, slurries,  and  aqueous  streams  for  over  forty years.*
 The Vet Air Oxidation  process  is simple, exceptionally adaptable  to
 variations in feed  characteristics, and  is applicable  to a vide
 variety of oxidizable  materials.

 In most current applications, ve- air oxidation is used to treat
 hazardous  vastevaters vhicn  are prohibited from land disposal by new
 USEPA restrictions.4  Vet air oxidation has been specified as Best
 Demonstrated Available Technology (BOAT) by USZPA for some hazardous
 vaste classes  restricted by  the Resource Conservation and Recovery
 Act  (RCRA).

 A basic  flov diagram for :r.e ZI.MPP.O Vet Air Oxidation system is shovn
 in Figure  2.   According to :he flov scheme,  a stream containing
 oxidisaoie material is pu=?ed :o  the  system using a positive
 displacement,  high  pressure  pump.   In the vet air oxidation process
 eievatea pressures  are recuired :o  keep vater in  the liquid state.

 The  feea stream  is  prenea:aa by heat  excnange vith hot  oxidizea
 effluent.   Air  or oxygen is  introduced at the nign pressure pump
 discnarge  or injected  direc:iy into  :he vet  air oxidation reactor.
 The reac:or provides liquia  retention  time,  during vhich oxidation
 reactions  occur.  Liquid vater "catalyzes"  oxidation  so  that
 reactions  proceed at relatively lover  temperatures than vould  be
 required if  the sane materials vere oxidized  in open  flame
 comoustion.  The retention tiae varies from  a fev  minutes to several
hours depending on  ;he  type  of vastevater and  the  treatment
objectives.  The heat  of  oxidation  raises the  reactor temperature  to
                           32

-------
 che  desired  operating level.   Vater  moderates  oxidation rates,
 providing  a  medium  for heat  transfer and  removing excess heat by
 evaporation.
Oxidation  takes  place  at  temperatures of  175  to  320eC  (347  to  608°F)
and at  pressures  of  2,069  :o 20,690 kPa (300  to  3,000  psig).
Injection  of steam into  the reactor or external  heating  may  be used
to maintain  the  operating  temperature for systems not  generating
enough  heat  from  the oxidation process.

Effluent from  the oxidation reactor is cooled by heat  exchange vith
the feed before  the pressure is reduced through  a control valve.
The liquid and non-condensanie gases are disengaged in a separator
drum and released separately.   The aqueous stream is discharged or is
treated further.

Vet oxidation is  intrinsically energy conservative.   The heat  that is
reieasea in the oxidation process can be harnessed to produce  steam
or hot vater.  Vet oxidation consumes far less fuel than other  forms
of :her-al oxidation.
                                          33

-------
                                                                   TABLK 1
                                                    MKT AIB  011 OAT 10* or IBDIABA BABBOB SLUDGE
                                                Ton SCIKBCI  APfLICATIOMS IBTKBHATIOBAL COlrOBATIOB


AIFTOCI.AVK
tKKU
ANALKTICAI. Nil 54601
OXIDATIONS TEMP. C
TIME AT TtMPCNATIIHE, KIN.




'
1
i

1 i
I
t '
'i ;

* »
COD
T BOD
t BOD/COD
HI
SOI.. CHLORIDE

lill Al. -,IM 1 Ir,
TOTAL A:.II
OIL^/ullEA^E

CALCULATED VALUES
HEIOKE MI.TMATIUN
SUSPENDED SOLIDS
SUSPENDED ASM
9/1 ii.J
9/1 < 2 0
KATIU < 0.06
1 21
ta.j/ 1 120

• 1 1 1 1 •> i
.) 1 IHO 4
• •I/I 1 I


Ol EMLIILIIT
9/>
9/1
riLYIB riUTKB riLTIB PILTIB IMLTEB
ril.THATK CAII ril.THATK CAII riLTBATI CAII riLTBATK CAII riLTBATE CAB*
545-»4 54599 54595 54600 54597 54602 54591 5459*
2«0 210 210 210 100 100 120 120
10 10 90 90 60 60 10 10
5.«» SO. 6 «9/9 6.05 95.9 .9/9 5.5 120.1 .9/9 S.ll 57.2 »9/9
16 - 15 - 2.9 - l.l
0.60 - 0 SI - 0.51 - 0.60
4 95 - 4.91 - 5.01 - 5.17
-

4 •>'• il ft » ~J I'l 54 4 I 41 52 4 \ 5.11 54 1 i
261 9
-------
                                                                                   TAO1JI 2
                                                                  WET AIB OIIDATIOB Or IBDIABA BA8BO1 SLIIUCt
                                                              rOB SCIKBCC APPLIOTIOBS 1BTUBATIOBAJ. COIFOUITIOB

                                                                                 KPA HKTUOO  (10
I     I
I     i
 GJ
 O»
ANALYTICAL HO.

OXIDATIONS TEMP. C

TINE AT  TEMPERATURE,  HIM

ACCNAPIIENE
ACENAPIITIKtENC
AKTHRACENE
"eNZO
-------
                                TABLE  3
                      MATERIALS OP CONSTRUCTION
                                POR THE
                      WET AIR OXIDATION PROCESS
                                       NOMINAL
  ALLOT                           CHEMICAL COMPOSITION
                               Cr      Mi      Mo       C      Cu
316-L STAINLESS
20 cfa-3
625
HAS7ZLLOY C-276
TITANIUM - 2
bai
bai
3
;
18
20
22
16
CCMMEr.CIALLY
13
34
bai
bai
PURE TI
2
2


.25
.5
9
16
TANIUH
0.
0.
0.
0.
0.
03
03
05
02
01

3.5
-
-

                               36

-------
                                TABLE A
                           MATERIAL TESTING
                          280 "C for  100 hours
                       GENERAL RATE                   COMMENTS
                           MPT
316-L                     <1.0                 NO LOCALIZED  CORK.
20cb-3                    <1.0                 NO LOCALIZED  CORK.
6:-                       <1.3                 NO LOCALIZED  CORK.
c-:76                     <1.0                 NO LOCALIZED  CORK.
                                              NO LOCALIZED  CORR.
                                         37

-------
                               Figure 1

                         2  Factorial Testing
         320°C  -
Oxidation
Temperature
         300'C
i
        :ao»c  —
                                       e.  Minutes
                                  38

-------
                                          t'igurtt 2


                                   WET  AIR OXIDATION

                                GENERAL FLOW DIAGRAM
CJ
CD
OXIPIZABLE   f^
          WASTE
                    FEED
                    PUMP
                          D
                                     PROCESS
                                     HEAT
                                     .EXCHANGER
                                     REACTOR
                    AIR COMPRESSOR
                                                        APCV

                                                        j-JU_fc.
                                                              WASTEWATER

-------
 REFERENCES

 1.      Standard Methods  for  the Examination  of Vater  and  Vastevacer
        16th Ed., AFHA, AtfVA. VPCF, 1985.

 2.      Methods for Chemical Analysis of Water and Vastes, U.S. EPA
        EPA-600/4-79-020, Marcn, 1979.

 3-      Flynn,  B.L.,  "Vet Air Oxidation of Waste Streams," Chemical
        Engineering Progress.  April,  1979,  pp. 66-69

 <«•      Copa, V.M.,  e_t.  al.,  "Simultaneous  Sludge  Disposal and Carbon
        Regeneration,"  presented at the AIChE  National  Meeting, New
        York, 1987

5-      Force,  J.M. ed.,  "Vet  Air Oxidation  -  A Rediscovered
        Technology," REACTOR.  No. 65,  May 1989, p.4

6.     Dietrich, M.J., e_t. al.. "Vet  Air Oxidation of  Hazardous
       Organics in Vastevater," Environmental Proeress.  Vol.A, No. 3,
       August,  1985, p. 171
                   40

-------
    BENCH SCALE STIRRED AUTOCLAVE
   WET AIR ODODATICN DEMONSTRATION
  CM INDIANA HARBOR SEDIMENT SLUDCS
                FOR
SCIENCE APPLICAnON INTERNATIONAL CORP.
              PHASE II
  SAIC SUBCONTRACT NO. 16-920034-51
        Se^srr^er 27, 1991
         2IMPRO
         PASSAV^MMT
   ENVIRONMENTAL SYSTEMS. INC.
   An AfflUBc of tne Blacx Oawion Co.
   301 XV. Military ftaM.-RotnurtkL \M 544W
                       41

-------
                            TABLE OF CONTENTS





    I.   INTRODUCTION	1


   II.   WET AIR OXIDATION PERFORMANCE	1


  III.   EXPERIMENTAL PROCEDURES .  '	3


   IV.   PROCESS DESCRIPTION 	  3


   V.   DESIGN BASIS	6


  VI.   SCOPE OF OFFERING	7


 VII.   ESTIMATED UTILITIES	15


VIII.  PRICING	15
       REFERENCES.
IZIMPRO
PASSAVA/SJT
                                42

-------
            £N"i..tujXn-'X'j,CN

            Zimpro  Passavant  Environmental Systems,  Inc.  (ZIMPHO)  perfonned
            laboratory  wet air oxidation  tests on dredged  sediments from the
            Indiana   harbor.    The  test  work   was   perfonned  for  Science.
           Applications  International  Corporation (SAIC) under  contract with
            the  U.S.  EPA.   The  principal objectives  for this Phase II  study
           were  to  produce  a  volume  of  oxidized  samples  at  the  optimal
           operating conditions.  The operating  conditions  were determined by
           a  series  of shaking  autoclave  tests  perfonned  under the  Phase  I
           study.   The Phase  I  study  concluded that  the  optimal  condition
           was a reactor  temperature of 280eC and a hydraulic  detention time
           of  90 minutes.   The  oxidized  effluent  from Phase  II  shall  be
           analyzed  by others.    The   results from  the testing are  to  be
           presented to the  EPA  for  evaluation of  the wet  air  oxidation
           technology for treatment of the sediment sludge.

           This  report  includes  the procedures   used  and analytical  results
           obtained  from the  Phase  II wet   air oxidation  testing  of  the
           sediment sludce.
          WET ATR OXJUJftTICN PERFORMANCE

          The "as  received"  feed samples  were well  mixed and  divided out
          into eight  (8)  portions.    Separate stirred  autoclave oxidations
          were performed  using  six  (6)  of  the  eight  (8)  samples.    The
          samples  were diluted using  HPLC  grade water.  The  dilutions were
          made to produce an autoclave  feed sample with a  suspended solids
          concentration  of approximately ten  percent  (10%).  A  list of the
          feed samples  charged  to  the stirred  autoclave  and  the  volumes
          discr.arced is  reoorted  in  Table 1.
               TABLE 1:  VI'IWMHJ AUTOCLAVE  GBODATICN INFOHMATTCN

          SAMPLE CHARGED      SAMPLE REMOVED           OFF GAS ANALYSES,

Sample    Sedi.-r.ent  Water    Solids  Filtrate     CO.    0.    N.     CO
>Juir.cer     Gra.T.s    Grams    Grams    Grans          '
  1         225      625       56       545       13.1  3.7   32.0   nd   173
  2         253      597       88       682       14.3  2.1   32.1   0.5   229
  3         225      625      107       703       13.3  2.0   82.6   nd   150
  4         250      601       84       685       13.4  2.8   82.3   r.d   19"
  5         125      650       51       615       11.1  5.4   78.6   r.d   I'O
  6         123      650       43       657        9.2  8.4   79.2   nd   190
      *
        Pump tuning leaked causing seme less of sample
     nd  =  net detected
r    ZIMPRO
    PASSAVAJVT
                                               43

-------
        Following the  oxidation,  effluent samples  were  decanted from  the
        stirred autoclave  using a  peristaltic pump with  silicon  tubing.
        The samples  were  then vacuum filtered  using  Whatman  fl   filter
        paper.   The mass of both filtrate and filter cake was individually
        measured.   The  filter  cake samples were  placed  in  a glass bottle
        and the filtrate was  pumped into  a  Tedlar bag.   Blending  of all
        the  filtrate   samples,   and  cake  samples,  was   performed  on
        completion  of  the" stirred  autoclave  testing.    Sampling  of the
        blended  filter  cake and blended  filtrate  samoles was performed by
        SAIC.

       Analyses were  performed on  the oxidized  filter  cake  and  filtrate
       by  Enviroscan Corporation.   The tabulation of the obtained data  is
       located  in  Table 2.   Comparing the results from Phase I  to Phase
       II, the  testing  indicates  that the filtrates had equivalent CODs.
       The remaining  6,136 mg/1  of COD in the  filtered  effluent  would
       have to be reduced further.   The remaining COD appears to be  very
       biodegradable.     The  filtrate  had  a  BOD5/COD  ratio  of   0.55,
       indicating  that  biological  treatment  may be   acceptable   as  a
       polishing step.   The  filter cake  sample "had  a  higher  COD  when
       compared to  the Phase I results (187 mg/g  verses  96 rag/g).   Little
       more can be  said about  the samples due to  the limited scope  of the
       analyses.  A more complete  analytical  evaluation  of  the effluents
       will be  performed by SAIC once they have obtained the results  from
       their outside laboratcrv.
               TABLE 2:  ANALYTICAL RESULTS  FPCK PHASE II

                                                filtrate        Cake
  Analytical No.                    •             56,517      56,518

  Oxidation Temperature, 5C                        280        280

  COD                                        6,135 mg/1        187 mg/g
  BOD;                                        3,372 .7.9/1        	

  pH                                               sm2        	

  Total Solids                                4,563 mg/1       56.8%
  Total Asn                                  2.£44 mg/1       90.2%
ZIMPRO
                               44

-------
  III.  KXf taOMEUTRL PRDCCTURES

       All wet  air oxidation tests  were performed  in  laboratory  titanium
       stirred  autoclaves  eacn  having  a capacity of  3,780 mis.    The
       autoclaves  are  equipped  with  a  magnetic  stirring  device which
       helps diffusion  of oxygen  into  the lio^iid and keeps the solids in
       solution.   The  stirring mechanism is  on continuously throughout
       the oxidation.   The autoclaves were  charged with  the  waste  and
       sufficient  compressed air  to  result  in excess  residual oxygen
       following oxidation.   The  charged autoclaves were then heated  to
       the desired oxidation temperature by electric heating  bands  and
       held  for the specified  reaction  time.    Immediately  following
       oxidation,  the  autoclaves  were  cooled  to  room  temperature   by
       internal water cooling roils  and then depressurized.

       All analyses  included  as  part  of   the  oxidation testing  were
       performed by  the ZIMFRO  analytical laboratory, Enviroscan Corp.,
       according to  Standard ;ietnods:   or EPA  Methods  for the  Chemical
       Analysis of  Water and Waste' .
  IV.   PROCESS DESCRIPTION

       Wet  air  oxidation  is an aqueous  phase  oxidation  of organic  and
       inorganic compounds  by  dissolved molecular  oxygen  at  elevated
       temperatures  and pressures.   The  oxygen is typically supplied  to
       the  system as  compressed air;  however, pure  gaseous  oxygen  has
       also been used  in specific applications.  Depending  on the  overall
       desired treatment  level,  the  oxidation reactions  will  occur  at
       moderate  temperatures (400 - 600T)  and at pressures ranging  from
       300  to  over  3000  pounds  per  square  inch.    As  the  oxidation
       temperature   is  increased,   a  larger  portion  of  the   organic
       compounds  will  be  oxidized -/mien will correspond  to a higher
       overall  chemical oxygen  demand  (CCD)  reduction.    The  wet  air
       oxidation process will  oxidize simple organic compounds to carbon
      dioxide  and  water  wnile  seme  complex  compounds   are  partially
      oxidized  to  simpler  rcqpcur.ds,  such  as  acetate, which are  more
       readily biodegradable.

      Figure  1  presents the rasic wet  air  oxidation system process flow
      scr.eme.  The proposed flew scr.eme recommends the utilization of an
      equalization tanx to provide  snort term storage during maintenance
      snutdcwns and  to damper,  cut  ±ne effects  of  periodic changes  in
      waste   characteristics.    The   waste  is  transferred   from  the
      equalization tanx to  a -igr. oressure  diapnragm  pump  oy  means  of a
      centrifugal  low pressure pumc.  The pressurized discnarge from tr.e
      nign  pressure   pump   13   "mrir.ed with tne  air  stream  from  tr.e
      process air  ccmcressor t.-.erecv  fermine a two—pnase stream.
Z1MPRO
                                           45

-------
        I       <
                                       I        I
                                  t t.KD/
                                  milKH
                                   IIKAT
                      I!  II
                                          AIIXIUARY
                                       HEAT EXiTIIANtiCH
TANK
       •'    IIM:II rut .'.MIII
             mo PUMP
111* I'tlV.V.IHIt
  n.i:n  ruur
                                                                         (k)
                                                                                               OIT CHS
                                                                 l(t.ACT()K
                                                          runs
                                              HEAT HUNSFU SYMltl
                                                                                                                       01IDI1CD irrLUCHT TO
                                                                                                                       rOST TltATBtHT SISTKN
                                                                                                                            |BY OTHERS)
                                                                                                            oxiora.T>
                                                                                                           WASTE four
                        I-KOCCSS AIH
                        COUVRESSUR
                                                                                      rKELIHIHMI>
                                                                               MET Mil UXlDKTIUtl SYSTEM
                                                                                               DIAGRAH
                                                                                                                               > ZIWIPRO
                                                                                                                               •PASSAW
                                                                                                                                            ricuie

-------
            The two-phase air/waste  stream passes through the tube—side of the
            feed/effluent  heat  exchanger.    The  feed/effluent  is  used  to
            transfer  the sensible heat  from  the oxidized effluent  to  the un-
            reacted waste and air mixture.  The  heated  mixture  is  then routed
            through an  auxiliary heat  exchanger.   The auxiliary heat exchanger
            is   used,   when  necessary,   to   supplement  the  thermal   energy
            transferred to the air/waste  mixture.   The supplemental  thermal
            energy is  supplied by a thermal  fluid heat transfer system which
            may be either  fuel-fired  or  electrically  heated.    The  thermal
            fluid heat  transfer  system is used  to initially bring  the  system
            up  to operating temperature.

            The  heated  air/waste mixture  is  then  introduced in  the process
            reactor vessel.   The  reactor  vessel  is  a  vertically-oriented
            column type pressure  vessel.   The reactor  contents are mixed by
            the action of the gas phase rising through the liquid.   As the gas
           phase rises  and mixes with  the  liquid, oxygen  is  dissolved into
           the liquid.    The  dissolved oxygen is  then available to  take part
           in  the  oxidation  reactions.    The  reactor  is  sized  to  provide
           sufficient  hydraulic  detention   time  to  allow  the   oxidation
           reactions  to proceed  to  the desired level.

           The  oxidized liquid,  oxidation product  gases, and spent  air leave
           the  process  reactor and are  routed througn  the  shell side  of the
           previously mentioned  feed/effluent heat exchanger.  A substantial
           cooling of  the  reactor effluent  is achieved in  the  feed/effluent
           heat excnanger;  additional  cooling is accomplished by the process
           cooler.  In  the  process cooler, additional  sensible heat  energy is
           transferred  from the  reactor effluent to  a  cooling water stream.
           It  should  be  mentioned  that the  system is  still at  an elevated
           pressure at  this point.

           The  cooled  reactor  effluent  is   throttled   through  a  pressure
           control valve,  thereby depressurizing the  flow,  into  the process
           separator.     The reactor  effluent  is  separated  into  a gaseous
           stream and a liquid stream oy tne process separator.

          The  gaseous  stream from the  prccess  separator is  routed through
          the  process  off-gas  cooler.  The  off-gas  cooler  is  a  vertically
          oriented packed  column.   The process  gases enter  the base  of the
          column and flow  counter-current to a  flow of service water.   The
          service water cools the process gases  causing some Higher boiling
          point constituents  to  condense  cut and exit the off-gas  cooler
          witn  the service water;  trie  lisuids  leavinc the off-gas  cooler
          are discnarged into the prccess  senarator.
    ZIMPRO
itPASSAVAJVT
                                                47

-------
     At this  point in the  flew scheme,  the  process  separator  liquids
     are  pumped   beyond   the  treatment  system's  boundary   limits;
     typically another treatment  process receives  these  liquids.  The
     receiving process varies depending on the chemical characteristics
     of the oxidized  liquids  (ODD,  BOD,  pH, suspended  solids, etc.).
     Typically,  liquids with a high suspended solids are sent through a
     clarifier to  settle  out participate matter.   It should  be noted
     that  the  oxidized liquid may  still  contain a  relatively  high
     concentration  of  biological nutrients,   further treatment of these
     oxidized  liquids  by a biological  system may be required  prior  to
     discnarge to the  final  receiving system (lake,  river,  POTW).


V.  DESIGN BASIS

    ZIMFEO and  SAIC mutually  developed three scenarios  for the  full
    scale  wet air oxidation of  the dredged sediments.  These scenarios
    were based on  the laboratory findings  that  the wet air oxidation
    process   could   adequately  handle  sediments  at   a   solids
    concentration  of  approximately  ten percent  (10%).    The  dredged
    sediment  is  produced  at a solids   concentration  of  approximately
    forty  (40)  percent. Therefore,  the sediment would require a three
    (3)  to one (1)  dilution using water from  the harbor  that is being
    dredged.    The  three  scenarios  involve  the  treatment of  total
    dredgings  of  10,000; 40,000; and  100,000 yd1  [all  at  forty percent
    (40%)  total solids).   It  was  determined that  wet air  oxidation
    units  of  ten  (10), twenty  (20), and forty (40)  gallons  per minute
    [at  ten  percent (10%)  total solids) capacity would be  adequately
    sized  to  process   these  volumes  of  dredgings as  shown  in  the
    following taole.

                                  TTXE  TC PF.CCZSS DREDGING, YES
     WAG Cacacitv, =cn      10.300 vd1      40.000 vd5    100,000 vd'
           10                  2.25           6.75           22.50
           20                  1.12           3.38           11.25
           40                  0.35           1.59            5.52
   Eacr.  of the  three  '3!  prcposed wee air  oxidation  systems covered
   under  these scenarios  vas aesisr.ed based en SIMFEO's experience in
   the  construction of sirr-iiar  systems.   Each proposed  system snail
   be  constructed  to  the  standards  of  ZIT*.F?.0 and  all  appiiracls
   national cedes.
  characteristics as lister;  ir.  Tacie  3.
                          48

-------
                      TABLE 3:  WASTE CHARACTERISTICS

            Average COD,  (g/1):                             40.0
            Total Suspended Solids,  [wt  %J:                  10.0
            pH:                                                 7
            Chlorides,[ppmj:                                   12
        The  design parameters  for  the proposed systems  are presented in
        Table  4.
                    TABLE 4:  SYSTEM DESIGN PARAMETERS

     Design Flowrate,  [U.S.  G?M):                       10.0    SYSTEM 1
                                                       20.0    SYSTEM 2
                                                       40.0    SYSTEM 3

     Operating Schedule:                                    24 hours/day
                                                            5 days/week
                                                          50 weeks/year

     Normal Operating .M.ode:                                  Autothennal

     Reactor Hydraulic Detention Ti.-e, ;minutes 1:                      90

    COD Reduction, [%]:                                              83

    Mechanical Design Temperature,  \°~}:                             570

    Mecnanical Design Pressure,  [psigj:                            2,000

    Operating Temperature,  {°T}:                                     536
    Operating Pressure, [psigj:                                    1,500

    Material  of Construction
    for Waste Wetted  Surfaces:                                      316L
       SCCPE OF OFFERING
              proposes  tc  crevice  ail  engineering,  design,  equipment
       supply and  start-up services necessary to complete and install tne
       wet  air oxidation  systeir. tc tr.e extent described herein.
 ZIMPRO
rBASSAVAJVT
                                           49

-------
        The proposed major  equioment pieces and/or system components to be
        furnished  and  installed" by ZIMPRO  for each  system and  included in
        the proposed price, as  stated hereafter,  are listed  in  Table 5.
                            5:   MAJOR EQUIFMEUT LIST
                                       Quantity
Alloy Material of
   Construction
 - If Annlicable
1.
<- .
3.
4 .
5.
6.
^

8.
a _
10.
11 .
1 7
12 .
14.
T^Z _
15.
17.
18.
Lew Pressure Feed Pumr>
High Pressure Feed Pumn
Process Air Compressor"
Feed/Zf fluent Heat Exchanger
Auxiliary Heat Exchanoer
Thermal Heat Transfer System
Thermal Fluid
Recirculation Pump
Process Reactor
Process Cooler
Pressure Control Valve/Pot
Process Separator
Off— gas Cooler
Separator Bottoms Pumc
Instrument Air Ccmcresscr
Interconnecting Pice
Valves
Motor Control Center
Instrumentation
2 (1 standby)
1
1
1
1
1

2 ( 1 standby )
1
1
2
I
i_
2 (1 standby i
^
1 lot
1 lot
1
1 lot
316L SS Wetted
316L SS Wetted

316L SS
316L SS Tube/CS



316L SS Clad CS
316L SS Tube/CS

316L SS
316L SS
316L SS

As Required
As Required

As Required
Parts
Parts


Shell




Shell









      The majority of the  ecuirment  listed above shall be ore—piped and
      wired  3n equipment  sxids  to  facilitate  field erection  and/or
      installation of the  system by  3IMPF.O.   Other equipment  shall  be
      provided as  individual  items.    Skids  and  individual  equipment
      items,   as   provided,   are  designed   to  be  erected  on  concrete
      fcur.cations  provided ov  the  FURCHASr?..   Table  6 is a  listing  of
      the equipment skids -vnicn  are  anticipated to be  provided  for  the
      orcpcsed svstem.
r ZIMPRO
PASSAVA/VT
                                 50

-------
                      6:






1. Air Compressor Skid
2. Equipment Skid
3. High Pressure Pump
4. Thermal Fluid Heat
System Skid






1. Air Compressor Skid
2. Equipment Skid
3. Hisn Pressure Pump
4. Thermal Fluid Heat
System Skid
SYSTEM 1-10




Otv
1
1
Skid 1
Transfer
1
SYSTEM 2-20




Otv
1
1
Skid 1
Transfer
1
GPM
Approximate
Dimension
each
(L x W)
in feet
17 x 10
10 x 11
14 x 8
7x8
GPM
Approximate
Dimension
each
(L x W)
in feet
23 x 10
15 X 10
14 x 8

7x8


Approximate
Weight
each
Ibs.
21,500
30,000
25,000
7,000


Approximate
'weight
each
Ibs.
36,000
35,000
25,000

7 , 000
I
SYSTEM 3 - 40 GrM
Approximate




1. Air Compressor Skid
2. Equipment Skid
3. Hicn Pressure Pump
4. Thermal Fluid Heat
Svsrem Skid



Otv
1
1
Skid 1
Transfer
i
Dimension
eacn
(L x W)
in feet
23 x 10
16 x 12
14 x 10

X 3
Acoroximate
"weight
eacn
Ibs.
i
37,000
40,000
2~,000

7 , 000
ZIMPRO
                            51

-------
        Individual  equicment  items and/or  system  components such  as  the
        reactor,  feed/effluent  heat exchanger, auxiliary  heat  exchanger,
        process  cooler,  field valves, and  field instrumentation will  be
        fabricated  and  shipped  to  the  project site  for  installation,
        erection  and/or   independent mounting  by  ZIMFRO  on  separate
        concrete  foundations  to  be provided  by  the  PURCHASER.   Table  5
        lists  major  individual  equipment  items being offered  for the
        proposed wet  air oxidation systems which will  require independent
        mounting  and/or  installation.    Figures  2-A,  2-B,   and  2-C are
        preliminary plot plans showing the suggested equipment  layout and
        building size.   ZIMPRO will also  supply all pipe retired to make
        interconnections between  skids and free-standing equipment.
                    TABLE 5:   FREE-STANDING EQUIPMENT
SYSTEM 1-10


Qtv
Process Heactcr 1
Feed/Effluent Heat Excr.ar.cer 1
Process Ccoler 1
Auxiliary Heat Excr.anger 1
svs— '. : - 20



:tv.
GPM
Approximate
Dimension
each
(L x W)
in feet
3 (diam. )
3.5 x 2.0
2.5 x 2.0
1.5 x 2.0
GPM
Approximate
Dimension
each
(L x W)
in feet

Approximate
Weight
each
Ibs.
27,000
7,500
4,100
1,000

Approximate
Weight
eacn
Ibs.
Process Eeactor
Feed/Effluent Heat
Process Cooler
Auxiliary Heat txc

Excr.ar.csr

r.anser
1 4 'diam. !
1 3.3 x 2.3
1 4.3 x 2.3
1 2.3 x 2.3
53,300
21,100
10,300
7,130
ZIMPRO
                                      52

-------
           i      r
tn
CO
                                                      t       '
                                                                                  I       i.
©
                                                     SCAt£: I/B- - I*
                                                                          I    *
       	1 ^


                                                                                          WCT kin oximricM SISTOI
                                                                                                    run
                                                                                                10 crri S»STDI

                                                                                                —"1	ir
III.
Ha.
1
1
1
4
5
i
1
1
ti|ut|«ent
MW SKID
eouimcNT SIID
ntfXXSS MR COMJUESSOII SKID
niEraiM. nino HEAT TDAxsrai
SYSTDI
REACTOR VESSEL
nxD/frniiENr IKAT txaiMca
MniLlMt ICAT txauucai
rrocrsj anux
                                                ~r
                                                                            mSSAV^Ni
n
fiaiyr. 7-*

      i~

-------
qtldlNIZGS,
                                                    Mii'-;»'j ui'» u;
                                                   I 1IHJ AUVMIWI 11 1,1
                 U7IOCD SSXJOUJ
                 O.VJII
             1V3U iro/ruji/cuaj
      KUSNMU xvju auru Tvutaia
      aiis vossm-iuao mw
                      a i us juu
                                                               »  I   I

-------
en
01
                                                                                                   uocxai

                                                                                                     IAVKTCRT
                                                                     rn    TO
                                                                                                                   I .
                                                                                                                    EOUlFHDfT (KID
                                                                                                                    raooss AIR omrussot s*to
                                                                                                                    •nmwM. runo BEAT Twucrai EYSTDI
                                                                                                                     ms/trrunxt BTAT
                                                                                                                     MniUAmr HEAT naiwcn
                                                               SCAltl !/•" -
                                                                                    WET MK n«in*TICN STSTtn

                                                                                    PPEI inniMit nor lAtaurr
                                                                                         
-------
SYSTEM





Process Reactor
Feed/Effluent Heat Exc.-.anger
Process Cooler
Auxiliary Heat Exchanger

3-40




Qtv.
1
2
1
1
1
GPM
Approximate
Dimension
each
(L x W)
in feet
4.5 (diara. )
5.0 x 2.5
6 x 2.5
4.0 x 2.5
5.0 x 2.5


Approximate
Weight
each
Ibs.
104,000
27,000
24,000
24,000
26,000
 Please   note   that  tr.e   dimensions   and  weights
 approximations only and are suo^ect to change.
given   are
 Instrumentation  and  valves  associated  with  the  skid   mounted
 equipment  will  be installed and pre-piped on the appropriate  skids
 to tr.e  extent practical.   Skid  mounted instruments and start-stop
 stations shall  be pre—ared to skid mounted terminal strips/boxes.
 ZIMPP.O  shall supply a  control panel  for  each proposed  wet air
 oxidation  system  and cerfcrm  all  wiring  necessary to  provide a
 complete   system.    The  control  panel  shall   be  mounted on  an
 equipment  skid.

 ZIJ1PP.O has included  tr.e  cost of  a  building in each of the proposed
 systems.   Costs not included with the  building  are:   foundations,
 pili.-.gs. site preparation,  site  dewaterir.g,  or  equipment pads.

 The PURCHASER shall  re required  to supply utility  connections  at a
 poi.-.t not  greater tr.ar. a one  '!)  foot distance from the  building
•-•ail.   Utilities  -.-  ce  supplied by  the  PURCHASES shall  include I
 480 Volt,  3 Phase  electrical service;  120  volt,  1 Phase  electrical
service; ccr.diticr.ee reeling  water   at 55sr,- service  -vater;  and
natural  gas.   Table  ?  _s  a  listing jf .^ajor system comnonents and
the required  utilitv services.
                          56

-------
                    TABLE 6: REQUIBED UTILITY SERVICES

        	Item	       Reouired Utility Services

        1.  Air Compressor Skid          480  Volt 3* Electrical,  65eF
                                        (max.)  Cooling  Water

        2.  Equipment Skid               480  Volt 3* Electrical.  120 Volt
                                        1* Electrical,  65°F (max)  Cooling
                                        Water,  Service  Water

        3.  High Pressure Pump Skid      480  Volt  3*  Electrical,   65°F
                                        (max) Cooling Water

        4.  Thermal Fluid Heat
           Transfer System Skid         480  Volt 3$  Electrical,  Natural
                                        Gas

        5.  Process Cooler               S5°F (max) Coolino  Water
 VII.  ESTIMATED UTILITIES
       ;::^??.0 estimates that the proposed wet  air oxidation systems will
       require the  utility duties  presented  in Table 7.  Please note that
       these  are  estimates cr.iy and  are  sucnect to change.
                   TABLE 7:  ESTIMATED UTILITY DUTIES
                                   i SYSTEM  1  I  SYSTEM 2 I  SYSTEM 3
      | Natural Gas - Start-uc Cr.iv  I           |           |
      |  '=i:00 3TU/SCF,  !scf-"i:      I     3          10     I      36
      |Cc=li.-.= Water                j           |           |
      iar  fr;r,  [U.S. gem):         ]   135     j    275     |     550

      iCpersting Power, [kWh Hr ::      130     j    255     j     530
      T.K.e  ouagetary  price  i~-  t.-.e   supply  ar.d   installation  cf  the
      proposed wet air oxiostior. systems as defined anove is:

      SYSTZr: 1 - 10 G?.M.:     "our  .'".illion  five  Hundred  Thousand  and
                             :c :c: ^o._ars ,54.500,0001.
 ZIMPRO
rPASSAVANT
                                             57

-------
 SYSTOI 2-20 GFM:     Five  Million   Six  Hundred  Thousand  and
                        00/3.00 Dollars ($5.600,000) T
   STEM 3-40 GPM:      Seven Million  Three  Hundred Thousand  and
                        00/100 Dollars  ( 7 , 300 .
 These prices  do not include provisions for the following items:

 1.   Any  applicable  state,   local,   or  federal   taxes,   permits,
     bends,  fees or  duties.

 2.   Design  or supply of  foundations,  civil work, sumps,  concrete
     lining, or  sewers.

 3.   Design, supply, or installation of  equalization tanks.

 4.   Design, supply, or installation of  the post-treatment system.

 5.   Equipment  storage   necessitated  due  to  action   of  the
     PURCHASER.

5.  Any operational spare  parts other than  the spare  rotating
    equipment  previously listed.

7.  Any piping   or  wiring  beyond the  proposed  system  boundary
    Units.
                       58

-------
 REFERENCES
        1.   Standard Methods  for the Examination of Water and Wastewater,
            16th Ed., APHA, AWHA,  WFCF,  1985.


        2.   Methods  for  Chemical Analysis  of  Water and Wastes,  U.S.  EPA,
            EPA-600/4-79-020,  March,  1979.
iZIMPRO
rPASSAVAJVT
                                            59

-------
                       APPENDIX B
       EXPERIMENTAL DESIGN - ZIMPRO PASSAVANTS
       WET AIR OXIDATION TREATMENT TECHNOLOGY

                          FOR

GLNPO - ASSESSMENT AND REMEDIATION OF CONTAMINATED
    SEDIMENT TECHNOLOGY DEMONSTRATION SUPPORT
                        May 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-C8-0061, Work Assignment No. 2-18
             SAIC Project No.  1-832-03-207-40
                          60

-------
                                 TABLE OF CONTENTS



SECTION

       List of Tables and Figures	        iii

1.0     TECHNOLOGY DESCRIPTION	        1

2.0     TEST PLAN 	        3

       2.1    Purpose	        3
       2.2    Approach	        3
       2.3    Phase I  	        4
       2.4    Phase II	        7

3.0     RESIDUAL MANAGEMENT	       11

4.0     FINAL REPORT  	       12



       APPENDIX A - ENVIROSCAN  Environmental and Analytical Services Brochure

       APPENDIX B - Phase I Letter Report on Process Variables
                                         61

-------
                                           TABLES
 NUMBER

 2-1     Zimpro Passavant's Analysis Schedule for the Phase I
        Wet Air Oxidation of Indiana Harbor Sediment	
 2-2     Zimpro Passavant's Analysis Schedule for the Phase II
        Wet Air Oxidation of Indiana Harbor Sediment	
 2-3     SAIC's Analysis Schedule for the Phase II
        Wet Air Oxidation of Indiana Harbor Sediment
                                          FIGURES
NUMBER

1-1     Wet Oxidation Flow Diagram
2-1     22 Factorial Experimental Design for
       Wet Air Oxidation of Indiana Harbor Sediment
                                            62

-------
                                           SECTION 1
 1.0    TECHNOLOGY DESCRIPTION
        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 3000 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.

        The basic flow diagram for  a conventional  wet air oxidation process is shown  in  Figure 1-1.  In
 processing an aqueous waste, the wastestream containing the oxidizable material is first pumped into the
 system using  a positive displacement,  high pressure pump.   Next,  the waste  is preheated in  a heat
 exchanger with the hot oxidized effluent. The compressed air  or oxygen is injected into the wastestream
 either at the discharge of the high pressure pump or at the inlet to the reactor.  A vertical bubble column
 is commonly used as the reactor which provides the required hydraulic detention time to effect the desired
 reaction. The desired reaction may range from a mild oxidation,  which requires a few minutes, to total waste
 destruction, which requires an hour or more detention time. Exothermic heat of oxidation is released to the
 wastestream during oxidation.  This heat release  usually raises the temperature  of the wastestream  to the
 desired level in the reactor. The hot, oxidized effluent exits the reactor and is cooled in the process heat
 exchangers. The cooled effluent then exits the system through a pressure control valve. The oxidized liquid
 and non-condensible offgases are separated in a separator tank and discharged through separate lines.

        The  products of wet air oxidations vary with the degree  of oxidation that  is accomplished. For low
 degrees of oxidation, oxidizable organic matter is converted to  low molecular weight organic  compounds
 such as acetic acid. For high degrees of oxidation, oxidizable organic matter is chiefly converted to carbon
dioxide and  water.  Organic or inorganic sulfur  is converted to sulfate.   Organic nitrogen is converted
primarily to ammonia.  The halogens in halogenated organics are converted to inorganic halides.

       The  commercial  applications of wet air oxidation are chiefly in the disposal of aqueous wastes.
However, some applications  employ wet air oxidation for recovery of chemicals and energy production,
simultaneously with waste disposal.
                                              63

-------
Q
           «,
   HIGH
PRESSURE
  PUMP
        AIR COMPRESSOR
                                                  HOT WATER
REACTOR
                                                              H^lq-
               Figure 1-1. Wei Oxidation Flow Diagram (Source:  Zimpro Passavant)
                     rVENT
                     "
                  SEPARATOR
                                                                                 I	»» OXIDIZED
                                                                                      LIQUOR

-------
                                            SECTION 2
 2.0     TEST PLAN
 2.1     Purpose
         The primary objective of these tests is to determine the feasibility and cost effectiveness of Zimpro
 Passavant's Wet Air Oxidation process for treating and removing polyaromatic hydrocarbons (PAH's) from
 sediments. The Great Lakes National Program Office (GLNPO) has obtained and homogenized sediments
 collected for the Indiana Harbor near Gary,  Indiana.  The wet air oxidation process is not expected to treat
 polychlorinated biphenols (PCBs), another known primary contaminant group detected in the sediments.

        The bench scale treatability tests of the treatability study are designed to  provide data that closely
 simulates full scale performance.  The data generated by the tests allows Zimpro Passavant and EPA to
 evaluate feasibility of the process and to estimate treatment costs for full scale performance.

        The Bench Scale Treatability Test objectives are:
                •      To  record observations  and data to predict full-scale  performance of Zimpro
                      Passavant's wet  air oxidation process.
                •      Take samples during the oxidation tests and conduct analysis sufficient to allow for
                      calculation of mass balances for oil, water, solids  and other compounds of interest.
                •      To calculate the oxidation efficiency of target  compounds, specifically determining
                      the level of destruction of organic contaminants, principally PAHs. PCBs, the other
                      primary organic contaminant group in the sediments are not expected to be treated
                      by the wet air oxidation technology.
                •      To supply GLNPO with treated solids (300 grams  dry basis), and filtrate (water), for
                      independent analysis.
2.2     Approach
        In order to accomplish the test objectives a two phased approach will be used.  Phase I  is a
preliminary phase conducted by Zimpro Passavant to determine the optimum conditions to be used during
Phase II. Phase II is the treatability test at optimum conditions and GLNPO, through its contractor Science
Applications International Corporation (SAIC), will obtain samples of the untreated sediments and treated
residuals for analysis by an  independent laboratory.  All analyses for  this  treatability study program
(consisting of seven treatability studies utilizing four technologies on four sediments) will be conducted by
the same laboratory. This arrangement will eliminate intertaboratory variation from the  comparison of the
performance of these technologies. In addition representatives of both GLNPO and SAIC are scheduled to
observe the  conduct of Phase II of each treatability study.

                                               65

-------
 2.3     Phase I
 2.3.7   Procedures
        In Phase I, Zimpro Passavant will analyze the Indiana Harbor sediment for the parameters shown
 below in Table 2-1.  This Phase I analyses will be conducted by Zimpro Passavant since this initial phase
 serves as an optimization step for their wet air oxidation process.
                 Table 2-1. Zimpro Passavant's Analysis Schedule for the Phase I
                          Wet Air Oxidation of Indiana Harbor Sediment
Oxidized

Analysis
COD
BOD
Total Solids and Ash
Suspended Solids and Ash
PH
Oil/Grease
PAHs
Chloride
Feed
Slurry
1
1
1
1
1
1
1
1

Filtrate
5
5
5
-
5
5
5
0

Solids
5
-
5
-
-
5
5
0
Total No.
of Samples
11
6
11
1
6
11
11
1
        Zimpro Passavant will conduct the Phase I wet air oxidation treatability study in a shaking autoclave
at temperatures ranging from 280° C to 320° C using reactor residence times of 30 to 90 minutes.  The
batch shaking autoclaves are fabricated from various corrosion resistant alloys, including 316 stainless steel,
nickel, Inconel 600 and 625, Hastelloy C-276, and titanium. The shaking autoclaves have total volumes of
0.5 liters and 0.75 liters.

        Each wet air oxidation  test will be conducted by placing approximately one hundred (100) ml of
slurried sediment  in the shaking autoclave. The autoclave will be closed and pressurized with air so that
an amount of oxygen equivalent to 125 percent of Chemical Oxygen Demand (COD)  is charged to the
autoclave.  The autoclave will then be placed  in a heater  shaker mechanism and heated to the desired
reactor temperature. The autoclave will be held at temperature for the desired reaction residence time, after
which, ft will  be cooled to room temperature.   The non-condensible gas will  be analyzed for  oxygen,
nitrogen, carbon dioxide, carbon monoxide, total hydrocarbons, and methane. After completing the offgas

                                               66

-------
 analysis, the autoclave will be de-pressurized and opened. The oxidized effluents from each oxidation
 condition will be composited. The composite samples will be filtered using a laboratory vacuum filter funnel
 and collection flask.  The feed sediment slurry, oxidized filtrates, and solids will be analyzed by Zimpro
 Passavant according to the analysis schedule presented in Table 1-1, Section 1.3.

        The feed sediment slurry will be prepared by diluting the sediment that is provided to approximately
 ten (10) percent solids, using distilled water.

 2.3.2   7esf Conditions,  Process Variables and Schedule
        Zimpro Passavant will require approximately 500 grams of sediment solids (dry weight basis) to
 complete Phase I, which is equivalent to approximately 1300 grams of wet Indiana Harbor sediment (the
 Indiana Harbor sediment has a reported moisture content of approximately 39%).

        The Phase I test plan consists of a 22 factorial experimental design which will determine the effect
 of temperature and time at temperature on the destruction of organic contaminants in the sediment. The
 test plan will consist of the following autoclave oxidation conditions:
               Temperature °C                      Time at Temperature. Minutes

                  280                                            30
                  280                                            90
                  300                                            60
                  320                                            30
                  320                                            90
        A temperature-time diagram of the experimental plan is shown in Figure 2-1.  It is estimated by
Zimpro Passavant that five oxidations will be conducted at each condition to obtain sufficient samples which
will be used for analysis purposes.

        The Phase I work, including sample analysis, can be completed in approximately six (6) weeks after
receipt of the sediment solids.  The Phase I  work can  be initiated within two  (2)  weeks after receipt of
contract and notification to proceed.
                                               67

-------
   Figure 2-1. 2* Factorial Experimental Design for Wet Air Oxidation of Indiana Harbor Sediment
          O
         LU
         CC
         D
         r-
         <
         CC
         HI
         CL
         2
         LU
         r-
                320
300
280  -
               260
                    0           30           60           90          120

                         TIME  AT  TEMPERATURE,  MIN.
The process variables for Phase I test plan include the following:

                    Temperature (280° - 320° C)

              •     Time at Temperature (0.5 hours - 1 .5 hours)
Note:  Percent solids for feed (2 to 20 percent or maximum pumpable slurry concentration) was not
       included as a test variable because the destruction of organic contaminants is not concentration
       dependent. Also, pressure  (300 to 3000 psig) is not included as  a test variable because the
       destruction of organic contaminants is not dependent on the system pressure, provided excess
       oxygen is present.
2.3.3   Report

       At the completion of Phase I, a letter report specifying the wet air oxidation conditions required for

Phase II testing will be prepared and sent to SAIC. These would include, but would not necessarily be

limited to reaction temperature(s) and reactor residence time(s), and will reflect those conditions (process

variables) that produced the maximum destruction of target compounds, as determined in Phase I.
                                           68

-------
2.4     Phase II
2.4.1   Procedures
        Zimpro Passavant will conduct Phase II of the wet  air oxidation  treatability study  in stirred
autoclaves.  The stirred autoclaves are fabricated from 316 stainless steel and titanium.  The one-gallon
capacity of the stirred autoclave will facilitate the production of larger quantities of oxidized effluents. Zimpro
Passavant proposes to conduct the stirred autoclave test using the wet air oxidation conditions that produce
the maximum destruction of the polynuclear aromatic hydrocarbons, as determined in Phase I.

        In Phase II, the stirred autoclave will be charged  with approximately two (2) liters of slurried
sediment  (10 percent suspended solids).  The stirred autoclave would be charged with sufficient air to
provide an amount of oxygen equivalent to 125 percent of  the COD.  The stirred  autoclave will then be
heated to the desired temperature and kept at temperature for the desired length of time.  After completion
of the reaction time, the stirred autoclave will be cooled and the non-condensible gas will be analyzed for
oxygen, nitrogen, carbon dioxide, carbon monoxide, total hydrocarbons, and methane.  After completion
of the gas analysis, the stirred autoclave will be de-pressurized. The oxidized effluent will be withdrawn and
saved for analysis by SAIC and Zimpro Passavant.  It is anticipated that two (2) stirred autoclave oxidations
will be conducted  using the chosen wet air oxidation conditions.  The combined oxidation effluent will
produce approximately four (4) liters of filtrate and 400 grams of solids.  Zimpro  Passavant will require
approximately 250 ml  of filtrate and 10 grams of solids for analytical purposes.

2.4.2    Tesf Conditions and Process Variables
        Zimpro Passavant will require approximately 500 grams of sediment solids (dry weight  basis) to
complete Phase II as described herein.

        The Phase II work can be completed in three (3) weeks, approximately four (4) working days for
preparation of equipment and one (1) working day for conducting the stirred autoclave tests. The remaining
two (2) weeks will be required to complete the sample analyses, develop cost information, and report all of
the wet air oxidation test results to SAIC.

        The process variables for the Phase II test plan include oxygen content (equivalent to 125% of the
COD),  the percent solids used, the presssure of the stirred autoclaues, a specified temperature, and a
desired length of time.  The latter two variables will be determined from the Phase I test.

2.4.3    Sediment Sample Characterization and Analyses
        There will be two separate analytical matrices conducted on the Indiana Harbor sediment during
Phase II, one by Zimpro Passavant and one by SAIC's subcontract laboratory, Battelle.  Zimpro Passavant
will conduct analyses on the treated sediment according to the analytical matrix shown in Table 2-2.
                                               69

-------
                 Table 2-2.  Zimpro Passavant Analysis Schedule for the Phase II
                          Wet Air Oxidation of Indiana Harbor Sediment
Oxidized

Analysis
COD
BOD
Total Solids and Ash
Suspended Solids and Ash
pH
Feed
Slurry
1
1
1
1
1

Filtrate
1
1
1
-
1

Solids
1
-
1
-
"
Total No.
of Samples
3
2
3
1
2
        At the beginning of the Phase II treatability test, SAIC personnel observing Phase II will pack and
ship untreated  Indiana Harbor sediment  per written detailed instructions supplied to the SAIC  on-site
representative.  This sample will be obtained from a separate unopened container of the sediments sent for
Phase II. The analyses to be conducted on these sediments through SAIC's subcontract laboratory are
listed in Table 2-3.

        Following the Phase II treatability test, SAIC's subcontract laboratory will conduct analysis on the
untreated sediments and end products. The number of analyses conducted on the anticipated residuals are
also outlined in Table 2-3.

2.4.4    Quality Assurance  (QA)
        Zimpro Passavant will conduct their portion of this study according to the quality assurance/quality
control  procedures of their subsidiary laboratory, ENVIROSCAN, Inc. (Wisconsin Department of Natural
Resources Certification  No. 737 053 130).  ENVIROSCAN's QA program  includes the following internal
controls.
                     Sample protocols
                     Sample handling procedures
                     Chain of Custody
                     Sample receipt, preservation, and storage
                     Analytical procedures
                     Reporting results
                     Laboratory quality control programs
                     On-going employee training
                                              70

-------
                    Table 2-3. SAIC's Analysis Schedule lor the Phase II Wet Air Oxidation of Indiana Harbor Sediment
               QC. Simple ( )
                   »nd
               * fulho./ Blank
• Not Analyzed
(1)  - Number of Analyses
1   • Indiana Harbor Sediment
MS '-Matrix Spike *
MSD - Matrix Spike Duplicate

-------
       SAIC has developed and GLNPO has approved a QA project plan for this project. This QA project
plan is available as a separate document. Additional information on Zimpro Passavant's analytical laboratory
(ENVIROSCAN) is included in the ENVIROSCAN brochure (Appendix A).
                                           72

-------
                                          SECTION 3
3.0     RESIDUAL MANAGEMENT
        The anticipated residuals from the wet air oxidation treatability studies are of very small quantity
(estimated  at approximately 400 grams  of dry solids and 4 liters of filtrate).  A portion  of the Zimpro
Passavant complex is a permitted hazardous/toxic waste storage, treatment, and disposal facility (WI/EPA
Registration No., WID044393114). The pilot plant facilities, where the treatability tests will be conducted, are
within the same complex, thus Zimpro Passavant has in-house residual management capabilities.
                                              73

-------
                                           SECTION 4


4.0    FINAL REPORT

       Upon completion of the bench scale treatability program, Zimpro Passavant will prepare a Final

Report.  The Final Report will contain the following:


       •       Zimpro Passavant's wet air oxidation process description, test procedures, operating
               parameters, sampling locations and frequencies

       •       Test results discussion with analytical data

       •       Mass balance calculations, if applicable

       •       Projected full scale system configuration and operating parameters that would be used to
               treat site waste materials

       •       Treatment cost estimates in dollars per unit volume of soil for the Indiana Harbor type soil,
               based on the lowest cleanup level which can reasonable be achieved

       •       The following data will be presented in tabular form:

                     Initial contaminant concentrations; along with the moisture contents and pH values
                     and other relevant data

                     Final analytical results for all  streams generated from the extracts of each sample

                     Percentages of individual contaminants extracted for each sample, as well  as a
                     calculation  of total PAHs oxidized

                     Oxidation efficiency for each  contaminant


       •       Log books and chromatograms if generated.
                                              74

-------
                   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-C8-0061, Work Assignment No. 2-18
          SAJC Project No. 1-832-03-207-50
                        75

-------
                                                            GLNPO - QAPJP
                                                            Section No.:    Q
                                                            Revision No.:   2
                                                            Date:
                                                            Paiic:
               Feb. 15. U>91
               1 of 2
                                 TABLE OF CONTENTS
 SECTION
           REVISION    DATE
 1 1)    INTRODUCTION	

 2.0    PROJECT DESCRIPTION  	

 3.0    QUALITY ASSURANCE OBJECTIVES  . . .

 4.0    SAMPLE TRANSFER AND PREPARATION
             PROCEDURES 	

 5 0    ANALYTICAL PROCEDURES AND
             CALIBRATION   	

 0.0    DATA REDUCTION. VALIDATION AND
             REPORTING  	

 7.0    INTERNAL QUALITY CONTROL CHECKS

 8.0    PERFORMANCE SYSTEMS AUDITS  	

 9.0    CALCULATION OF DATA QUALITY
             IMPLICATORS  	

 10 ii    CORRECTIVE ACTION  .   . .       	

 11.0    QA/QC REPORTS TO MANAGEMENT . . .

APPENDIX A - TECHNOLOGY SUMMARIES	
12
1/9/91

2/15/91

2/15/91


1/9/91


2/15/91


1/9/91
                       1 '9/91

                       1 "»/91

                       I/1', '91
                                           76

-------
                     QUALITY ASSURANCE PROJECT PLAN APPROVALS
 QA Projeer  Plan Title:    GLNPO   Assessment  and  Remediation of Contaminated
                          Sediment Technolooy Demonstration Suooort
 Prepared  by:    Science Applications  International  Corporation (SAIC)
      QA Project Category:
                             II
Revision Date:  January 9, 1990
 SAIC'3 Vcrx. Assignment Manager (print,
        C'yrie  J.  Diai
SAIC's QA Manager (print)
                                   /Dace
                                  v?/
            ure
        Steve  Y
       orr. Group Chair (print)
       signature
        Sf'an  Scnurnacre1"
Af.CS QA Officer (print)
       Signature
E?A.  IMSL-1V,  N'RD QA Officer  .print;
^?A .ecr.nicai  rroiect  Manager  (print.
      Signature
       ?ave Ccwoi'
                                                 '-&*
                                           77

-------
DISTRIBUTION LIST:
Gene Easterly

Brian Schumacher

Tony Kizlauskas

Thomas Wagner

Clyde Dial

Steve Garbaciak

Dennis Timberlake

Steve Yaksich

David Cowgill

Gary Baker

Vic Eneleman
U.S. EPA. EMSL (Las Vegas)

LOCKHEED (Las Vegas)

SAIC (Chicago)

SAJC (Cincinnati)

SAIC (Cincinnati)

U.S. COE (Chicago)

U.S. EPA, RREL (Cincinnati)

U.S. COE (Buffalo)

U.S. EPA, GLNPO (Chicago)

SAIC (Cincinnati)

SAJC (San Diego)
                                                      GLNPO - QAPjP
                                                      Section No.:   Q_
                                                      Revision No.:  2_
                                                      Date:
                                                      Page:
                                                Feb. 15. 1991
                                                2 of:
                                     78

-------
                                                         GLNPO - OAPjP
                                                         Section No.:    l_
                                                         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.
                                        79

-------
                                                        GLNPO - QAPjP
                                                        Section No.:   j_
                                                        Revision No.:   1
                                                        Date:        Jan. 9. 1991
                                                        Page:        2 of 2
      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.
                                      80

-------
                                                          GLNPO - QAPJP
                                                          Section No.:   2_
                                                          Revision No.:  2
                                                          Date:        Feb. 15. 1991
                                                          Page:        1 of 12
 2.0   PROJECT DESCRIPTION
 2.1   Background
       SAJC 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 Ashtabuia  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 Laboraton' in Duluth. The Duluth Laboratory is analyzing the sediments for total
 organic carbon/total inorganic carbon (TOC/TIC), particle 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 (Ashtabuia River)
       c.      Wet Air Oxidation (Zimpro Passavam) 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.
                                    81

-------
                                    TABLE 2-1 a. Preliminary Analytical Results on ARCS Sediments
00
to
Description
Saginaw 221
Saginaw TRP6
Ashlabula 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 Cd
33 0.9
81 4.7
55 3.0
320 9.4
85 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
TOO
1.4
1.2
2.6
21
2.0
O&G
O.I
0.3
1.7
5.8
0.5
(%)(*)
Moisture (b)
40.3
31.1
52.9
61.0
41.5
        (a) Concentration in ppm and dry weight basis unless otherwise indicated.

        (b) As received basis.
                                       TABLE 2-lb. Preliminary Particle Size Distribution (%)
Description
Buffalo River
Particle Size (a)
>50u 50-20 u 20-5 u 5-2 u 2-0.2 u 0.2-0.08 u < 0.08 u
19.8 12.1 29.0 11.8 24.3 2.4 0.6
Median
Diameter, u
9.3
                                                                                                                                     s, TJ
         (a) u micarons

-------
                                                           GLNPO - QAPjP
                                                           Section No.:   2_
                                                           Revision No.:  2
                                                           Date:         Feb. 15. 1991
                                                           Page:         3 of 12
 2.2    Testing Program for Chemical Characterization
       SAIC shall be primarily responsible for the physical and chemical characterization
 of both the sediment samples prior to testing and the residuals created during the tests.
 Analyses conducted by the vendors or subcontractors will not be depended on, but such data
 shall be reported whenever available.

       Two different sets of chemical analyses will be conducted during the performance of
 the treatability tests:  optimization test analyses and performance evaluation analysis.  The
 Phase I optimization test analyses will be conducted by the subcontractor or vendor during
 the series of initial technology tests.  The Phase 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 b\  the
                                        83

-------
                                                           GLNPO - QAPJP
                                                           Section No.:    2_
                                                           Revision No.:   2
                                                           Dale:         Feb. 15. 1991
                                                           Page:         4 of 12
 vendor  or  subcontractor shall be reported, as available.  For  the  tests  run at optimum
 conditions (Phase II), SAIC shall conduct the full suite of analyses, as detailed in Table 2-2,
 on the end products if sufficient quantities are produced by the technology.  Quotes solicited
 for each technology specified that a minimum 300 grams dry basis of treated solid had to
 be produced for 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.
                                          84

-------
                                                   GLNPO - QAPjP
                                                   Section No.:    2_
                                                   Revision No.:   2
                                                   Date:         Feb. 15. 1991
                                                   Page:         5 of 12

                              TABLE 2-2

    Parameters and Detection Limits for Analysis of ARCS Technologies
Parameter
TOC/TIC
Total Solids4
Volatile Solids4
Oil & Grease4
Total Cyanide
Total Phosphorus
Arsenic4
Barium4
Cadmium4
Chromium4
Copper4
Iron (total)4
Lead4
Manganese4
Mercury4
Nickel4'
Selenium4
Silver4
Zinc4
PCBs (total & Aroclors)4
PAHs (16)4-5
PH
BOD5
Total Suspended Solids4
Conductivity
Solid1
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



Water Qift-
1000

1000
1000
10
10
1
2
4
7
6
7
50
2
0.01
20
1
7
?
0.07 0.1
2 0.1
full range
1000^
1000
full range
NOTES:
Tlfli t o/*ti /~*n li t-rt i »c- r*~\ ^ r- *•% 1 1 /-4 r- n ^ A »-*»-n-i-i / r*^ rt 1 \s n /•)»•* * *tr^»rrli^ti\ ' 1 ~h & i^ T * e rr%^ TT^ A+«^lr rV^/^nt/-!
be obtainable by TCP 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.
                               85

-------
                                                          GLNPO - QAPjP
                                                          Section No.:    2.
                                                          Revision No.:   2.
                                                          Date:
                                                          Page:
                                       TABLE 2-3
                           Solid Sample Quantities for Analyses
Feb. 15. 1991
6 of 12

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
--
--

OC (g)
..
10
40
—
~
15
3
90(60)3
--
158(128)
—
--

Total (g)
15
15
60
10
5
20
4
90
20
269(239)
31(61)
300

OC Approach
None1
Triplicate/Control
Triplicate/Control
None2
None2
MS/Triplicate
MS/Triplicate
(3)
None"1



1  For sample set II that does not have such a limited quantity of solid. The QC described in
  footnote 3 will be implemented.

2  For sample set II. MS/triplicate QC will be implemented.

3  Quality control for untreated solids is Triplicate and spike and for treated solids matrix spike
  and matrix spike duplicate.

  For sample set 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.
                                        86

-------
                                               GLNPO - QAPJP
                                               Section No.:   2.
                                               Revision No.:  2_
                                               Date:
                                               Page:        7 of 12
                                                                      Feb. 15. 1991
                          TABLE 2-4
Sample Volumes Required and Priority Ranking for Water Analyses
Parameter
Priority
Analysis
Volume, ml
QC
Volume, ml
QC
Approach
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
7
5
6
7
7
4
7
2
2
_
2
2
2
3
7
4
2
T
1
1
7
7
5
7
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
—
d
2000
—
«
300
300
b
b
b
b
b
b
300
b
c
b
b
2.000
a
—
—
400
~~
None (e)
Triplicate/Control
Triplicate/Control
None (f)
None (f)
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/Triplicate
MS/MSD
MS/MSD
None (f)
None (f)
Triplicate/Control
None (f)
Note:

a) same aliquot as PCBs              e)
b) same aliquot as Barium            f)
c) same aliquot as Arsenic
d) same aliquot as Total Suspended Solids
                              see footnote 2, Table 2-3
                              see footnote 4, Table 2-3
                             87

-------
                                                           GLNPO - QAPJP
                                                           Section No.:   2_
                                                           Revision No.:  2
                                                           Date:         Feb. 15. 1991
                                                           Page:         8 of 12
 2.4    Purpose of Phase I Experimental Design
        The purpose of the Phase I technology experimental design is for each subcontractor
 to establish a range of variables best suited for feasibly implementing their technology on
 a full-scale basis (Phase 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 Treatabiiity 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.

                                         88

-------
                                                          GLNPO - QAPJP
                                                          Section No.:    2_
                                                          Revision No.:   2
                                                          Date:         Feb. 15. 1991
                                                          Page:         9 of 12
       All  data generated  by  the vendor  during Phase II 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.
                                          89

-------
                                                          GLNPO - QAPjP
                                                          Section No.:    2_
                                                          Revision No.:   2
                                                          Date:         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 part of a much larger program, and it is not necessarily  intended to
 evaluate the complete treatment of these sediments. Other aspects or treatment options are
 being evaluated by a number of agencies,  contractors, etc.

       Therefore, this study is based on the following assumptions:
       •     The percent removal  of the  PCBs and  PAHs from the  solid residual is the
             most important object of this study.
       •     The untreated sediments and solid residuals are the most important matrices.
       •     If water and oil residuals are generated by a technology, the existence of an
             appropriate treatment or disposal option for these  residuals is  assumed.
             PAHs and  PCBs will  be determined in these residuals  as a cross check of
             their fate in treating the solids.

      Based on the intents of this study, the critical measurements are PAHs, PCBs. metals.
total solids, volatile solids, and oil and grease in the untreated and treated solids.

2.6   Organization and Responsibilities
      A  project  organization and  authority  chart is  shown  in  Figure 2-1.    The
Environmental Monitoring Systems  Laboratory (EMSL) is cooperating with GLNPO and
SAIC on this evaluation.  Mr. Thomas Wagner is the SAIC Work Assignment Manager and
is responsible for  the technical and budgeting  aspects  of this work assignment.  Mr. Clyde
Dial is QA Manager and is responsible for QA oversight on this work assignment.
                                       90

-------
c   -^
                           z
                           <

                           s
                           z
C
e


u:
e


i

C
j;  <
                                              -
                                       U i
                                          "
                                   GLNPO - QAPJP

                                   Section No.:   2.

                                   Revision No.:  2.

                                   Date:

                                   Page:
                                                                         Feb. 15. 1991_

                                                                         11 of 12
                                       VI  rf   w

                                       =  S 5 H
                                       IU    « _


                                       &  S3 I
                                       >•  js   «
                                       VI  £ » *


                                       u  ^   LU

                                       o f * I
                                       ££   C
                                                                                  e
                                                                                  at


                                                                                 C
                                                                                  v

                                                                                  i
                                            = s.

                                            17
                                            -I
                                    91

-------
                                                           GLNPO - QAPjP
                                                           Section No.:   2_
                                                           Revision No.:  2
                                                           Date:         Feb. 15. 1991
                                                           Page:         12 of 12
2.7    Schedule
      The Phase I experimental designs are scheduled for mid to late February 1990, and
the Phase II Treatability Tests are scheduled for March and April 1991.
                                         92

-------
                                                          GLNPO - OAPJP
                                                          Section No.:    3_
                                                          Revision No.:   2
                                                          Date:         Feb. 15. 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.
                                         93

-------
                TABLE 3-1.  Qusility Assurance Objectives for Critical Measurements
                              (Sediments and Treated Solids)
Parameter
Total Solids
Volatile Solids
Oil & Grease
Arsenic
Barium
Cadmium
Chromium
Copper
Iron (total)
Lead ,
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
PCBs (total
& 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
0.1
0.2
0.4
0.7
0.6
0.7
5
0.2
O.I
2
0.2
0.7
0.2
0.02
0.2
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 1 and 2 of Table 2-2
(e) Detection limits based on extraction of 30 gram samples.
                                                                                                                              z z
                                                                                                                              o ° O

-------
                                                          GLNPO - QAPJP
                                                          Section No.:   4_
                                                          Revision No.:  1
                                                          Date:        Jan. 9. 1991
                                                          Page:        1 of 4
 4.0    SAMPLE TRANSFER AND PREPARATION PROCEDURES
       As described in Section 2, SAIC will receive a number of 5 gallon containers of
 previously homogenized sediments from the U. S. EPA in Duluth, Minnesota.  The number
 of containers of each sediment is dependent on the final determination by GLNPO of which
 sediments will be tested by the various technologies. Only if smaller portions of sediments
 are requested by the vendors will these containers be opened by SAIC.  If smaller portions
 are required, SAIC will resuspend the solids and water within an individual container by
 rolling, tumbling, and stirring of the contents.  The final  stirring will be in the  original
 containers using a metal stirrer as would be used to mix a 5 gallon container of paint.  The
 metal stirrer is appropriate because  metals are not  the primary constituents of concern in
 these treatability tests.

       The Chain of Custody Record  shown in Figure 4-1 will be completed for each cooler
shipped to the subcontractor or vendor that will conduct the optimization and performance
evaluation tests.  The samples obtained  from the  vendor  for analysis will be labeled as
shown in Figure 4-2.  The labels will  document the sample I.D., time and date of collection,
and the location from where the sample was taken.  The amount/type of preservative that
was added will also  be recorded.

       SAIC personnel will pack and ship the untreated sediment and the end product
samples (residuals) from the optimum conditions test for each technology.  The amount of
preservative will be recorded.   Samples will be  labeled (see Figure  4-2) and shipped by
overnight deliver}' 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.
                                        95

-------
                                                          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
Cool
Cool
Cool
4°
4°
4°
4°
C.
C
C.
C.
H:SO4

H2S04
NaOH
to pH

to pH
to pH
< 2

< 2
> 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, H:SO4 to pH <

HNO3 to pH < 2


Cool 4° C

Cool 4° C, store in dark


Cool 4° C



Cool 4° C
28 days

6 months except Hti
(Hg 28 days)

24 hours

Extract within 7 days
Analyze within 40 days

48 hours

Performed immediately

28 davs
                                        96

-------
' Science J»ppllc»l/on»
 /nlomallonal Corporation
 An Empfci
      Chain -of- Custody Record
Dale	     Page	 ol
                                                                                         Shipment No
Name
Address 	
Phone Numl
Projecl Nam
Job/PO No
ier 	
s 	

- —
....

Sampler (Signature) (Printed Name)
LrtKNaloiyNo













ftMrti



'









SmpkNo



/









DIM


-


-
"





-
fl»llnqulth»(J By
SlgnMin


-
C«K«nr
Rallnqulihod By
Sign*..
PiM*d*tem«
Cart**



I«T»

-





Dale
Tim*
Dale
lime



SKW7on«













Requeslcd Parameters





—

—






	












—

—









	





	



Racalvcd By
BlgMU.
l>IMMH«n«
C-^r,
RccdvtdBy
WgrMun
Pi*it«dN«m
Cutvwny


	



	












_._



—
Dale
Time
Dais
Time










-




—










-


-




—











	






—

	












	

—
















N
O
O
F
C
O
N
T
A
1
N
E
R
S




._







ToUl Numb«r« ol Conlilnwr
k»l
t F
2 C
1
3 F
n
In
4 F
•
1 h
a c
•
1C
ruclton*
11 mil lorm comptowly nopl lor ih«tad
•as (lab uMt only)
Afnptal* m foaHpolnl p*n Diiwon*Hn«
hfoiigh errors and initial
eqiwfl analyav* iwlng EPA method
imbenonly Corisirtl the protect OAPP lor
Mrucliona Comptale as shown
Wwenc* el IMd QC lamplei to the
ppHcable Blta or zone
kK4 d appHcabXi prmervallvai
Iroup ai aample oonlBln«(« and ftqttftiled
nalyses Irom one tampl'ng location
>oelh«r Do nol Itsl IndlvKjuully
I dboralorv Name
Address 	 	 	
Phone
Contact Name

OBSERVATIONS. COMMENTS.
SPECIAL INSTRUCTIONS













ShlfHiwnlktethwl-.
MIC locauon (clrcto)
Cmciiinab
KB W.u 70 S»«tf Suu 403 OH «52O3
tbt^l m 7000
IVasAngkin OC
irtOOoodri(lQ«CMv« UciMwt VA 22102
1703) 121 4300
OOuOQ*
MOOHiiMgarunilXw TK3H30
lei!>H029O3l
Paramus
On* s«*nj Ortv* Pwamua . HJ OJft&2
|20I)500«IOD
SanOopo
10240 Snn«mo Vktay HoMl &•!• 2O4 San Owgo CA 02121

-------
                                                 GLNPO - QAPjP
                                                 Section No.:    4_
                                                 Revision No.:   j_
                                                 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
                               98

-------
                                                          GLNPO - QAPjP
                                                          Section No.:    5_
                                                          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
parts  necessary for the  operation of the analytical  equipment in order to complete the
analysis in a timely  fashion.
                                         99

-------
                                                          GLNPO - QAPjP
                                                          Section No.:   .5	
                                                          Revision No.:  2	
                                                          Dale:         Feb. 15. 1991
                                                          Page:         2 of 3	
                                    TABLE 5-1

            Analytical Methods for Critical and Non-critical Measurements
                                             Methods-
Pammeter
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 8lOOb
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 8100h
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
                                         100

-------
                                                      GLNPO - QAPjP
                                                      Section No.:    5_
                                                      Revision No.:   2
                                                      Date:         Feb. 15. 1991
                                                      Page:         3 of 3	
                                 TABLE 5-2

                                List of PAHsa
          Acenaphthene                   Chrysene
          Acenaphthylene                 Dibenzo(a,h)anthracene
          Anthracene                     Fluoranthene
          Benzo(a)anthracene             Fluorene
          Benzo(a)pyrene                 Inden(l,2,3-cd)pyrene
          Benzo(b)fluoranthene            Naphthalene
          Benzo(k)fluoranthene            Phenanthrene
          Benzo(ghi)perylene              Pyrene
PAH analyses must determine these  16 compounds at a minimum.
                                     101

-------
                                                          GLNPO - OAPjP
                                                          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.

       Ail 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.
                                         102

-------
                                                        GLNPO - QAPJP
                                                        Section No.:    _7_	
                                                        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 <, 20% unless otherwise  stated
one per sample set
 ± 0.1 pH unit for pH
 ± 2 umhos/cm for conductivity
                                       103

-------
                                                          GLNPO - QAPJP
                                                          Section No.:    T_
                                                          Revision No.:   2
                                                          Date:         Feb. IS. 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 grains 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 will process treated soils at two  distinct points.  Therefore,
four treated  solids are produced from the two untreated sediments.
                                      104

-------
                                         lAHI.li 7-1.  Internal QC Checks for Measurements
o
en
Parameter
Solids
(Total &
Volatile
Oil & Grease
Metals
Metals
PCBs (b)
PAHs
Method (a)
160.3
160.4
f
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
                                                                                                                                  fli
                                                                                                                                   "
                                                                                                                                       O  :•  O
                                                                                                                                       :.    >
                                                                                                                                            T3
n
er

-------
                                    TA11LH 7-1. Internal QC Checks for Measurements (continued)
o
o>
Parameter
pli
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
o B r
*?•
«••

-------
                                                                  Section No.:
                                                                  Revision No.:
                                                                  Date:
                                                                  Page:
     15. 1991
5 of 7
^
 C
ts
 I
r-
                                          107

-------
                                                               TABLE 73.  Example
o
        trimeters
        oUl Solids
        Moisture)
        /olttile Solids
        rtettls
         Alls
        TOC
        ToUl Cyinide
        ToUl Photphorous
        PlL
        BOD
        ToUl Suspended
        Solids
        Conductivity
                          QC Sample
                             tnd
                          .fel/iod Blank
Yes
Yes
                             Yes
Yes
                             Yes
 Yes
 Yes
 Yes
 Yes
 Yes
          Untreated
          Sediment
                                                  MS
X
                                                   • >
                                                   l^i
     Tripli-
      cate
       X
Treated
Solids
MS

                          x
MSD
                                                      •t*r
                   X
                                                                                          c*te
Wtter
MS
MSD
'ripli-
ctle
                                                                                                      -o D 50
                                                                                                      w u o
                                                                                                                                 O B  r
                                                                                                                                 B 2
                                                                                                                                 2?;
                                                                                                                                 p :•  C

-------
             TABLE 7-4.  Analytical and QC Sample Matrix for GIJNPO Trcalabilily Studies (numbers of samples)
SAMPLE SET
SET I
Untreated S.
Treated S.
Water
Oil
SET IV
Untreated S.
Treated S.
Water
Oil
SET II
Untreated S.
Treated S.
Water
Oil
SETHI
Untreated S.
Treated S.
Water
TOTALS
Solids
Water
Oil
TOC/TIC
(•) QC(b)
3
3
2
4

1
1
1
1
16
1

-
I

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
SOLIDS
S QC

3


2
4


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

I

16
1


2


3
2


3
2
3

3
2

20
3

TOTAL
YANIDE
S QC

3


2
4


1
1

1
1

16
1


-


-


3
3
3

-

6
3

ror/tL
fHOS
S QC

3


2
4


1
1

1
1

16


-


-


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
3
2
4
2
2
1
1
1
1
1
16
7
6

2
1
3
3
2
I
3
3
2
2
3
3
2
2
20
6
9
PAH
S QC

3
3
3
2
4
2
2
1
1
I
16
7
6
3
2
1
3
3
2
I
3
3
2
2
3
3
2
2
20
6
9
pH
S QC
3
3
2
4
I
1
1
1
16
1
-
-
3
2
3
-
S
3
BOD
S QC
-
-
1
-
1
-
-
3
-
3
TSS
S QC
-
-
1
-
1
-
-
3
-
3
COND
S QC
-
-
1
-
•
-
-
3
-
3
                                                                                                                                                           r? o so % o
                                                                                                                                                          mis
                                                                                                                                                                     •"d
                                                                                                                                                                     o
                                                                                                                                                                   " o
                                                                                                                                                                :-     ^
(a) Number of original simples.
(b) Number of quality control samples. A "3" represent) two additional replicates (triplicate determination) ind • spike or control
  sample analysis resulting in an additional Ituee QC analyses. A "2' represents matrix spike/matrix spike duplicate analysis
  scheme resulting in an additional two QC  analyses. A * I * 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.
^J
o
   S

-------
                                                         GLNPO - QAPjP
                                                         Section No.:    8_
                                                         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 treatabilit\ studies.  Thus the ARCS QA officer can be present during
Phase II of anv or all of the treatabilirv studies.
                                       110

-------
                                                          GLNPO - QAPJP
                                                          Section No.:   9_
                                                          Revision No.:  1
                                                          Date:        Jan. 9. 199]
                                                          Page:        1 of 3
 9.0    CALCULATION OF DATA QUALITY INDICATORS

 9.1    Accuracy

       Accuracy for PAHs, PCB and metals will be determined as the percent recovery of
 matrix spike samples.  The percent recovery  is calculated according to the following
 equation:


             % R  =  100%  xC' ~£? _
 where
       9tR   =  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:
             9c R  =  1009c    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:
                                        111

-------
                                                   GLNPO - QAPjP
                                                   Section No.:   £_
                                                   Revision No.:  J_
                                                   Date:
                                                   Page:
                                       Jan. 9. 1991
                                       2 of 3
 When 2 values are available:
            RpD =     [Q -  C2] x 100%

                          [C,  + C,]/2
where
      RPD  = Relative percent difference
      Cj    = The larger of two observed values
      C,    = The smaller of the two observed values
When more than 2 values are available:
            S  =
  N
  I
i = 1
      N
i     r  x
N  i  = l
                                   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
                                    112

-------
                                                         GLNPO - QAPJP
                                                         Section No.:   9_
                                                         Revision No.:  1
                                                         Date:        Jan. 9. 1991
                                                         Page:        3 of 3	
where
       RSD  = relative standard deviation, expressed in percent
      .S   = 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
                          TDP
where
      VDP =  number of valid data points
      TDP =  total number of samples obtained.
                                        113

-------
                                                            GLNPO - QAPjP
                                                            Section No.:   10
                                                            Revision No.:   1
                                                            Date:         Jan. 9. 1991
                                                                         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/imerfield comparison studies

       All corrective action procedures consist of six elements:
       •     Recognition that a Quality Problem exists
       •     Identification of the cause of the problem
       •     Determination of the appropriate corrective action
       •     Implementation of the corrective action
       •     Verification of the corrective action
       •     Documentation of the corrective action

       For these treatabiliry studies after initial recognition of a data quality problem, the
data calculation will be checked first.  If an error is found, the data will be recalculated and
no further action will be taken.  If no  calculation error is found, further investigation will
be conducted.  Depending on the cause  and  the availability  of the appropriate samples.
reanalysis or flagging of the original data will  be utilized.
                                         114

-------
                                                         GLNPO - QAPJP
                                                         Section No.:    10
                                                         Revision No.:   1
                                                         Date:         Jan. 9. 1991
                                                         Page:         2 of 2
      All corrective action initiations, resolutions, etc. will be implemented immediately and
will be reported in Sections One and Two (Difficulties Encountered and Corrective Actions
Taken, respectively)  in the existing monthly progress reporting mechanisms established
between SAIC, EPA-RREL, GLNPO, AND THE ARCS QA officer and in the QA section
of the final report. The QA Manager will determine if a correction action has resolved the
QC problem.
                                        115

-------
                                                          GLNPO - QAPjP
                                                          Section No.:    11
                                                          Revision No.:   1
                                                          Date:         Jan. 9. 1991
                                                          Paue:         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.
                                         116

-------
                              GLNPO - QAPjP
                              Section No.:    Appendix A
                              Revision No.:   1	
                              Date:         Jan. 9. 1991
                              Page:         1 of 3
        APPENDIX A
TECHNOLOGY SUMMARIES
              117

-------
                                                            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
                                     118

-------
                                                           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.
                                         119

-------
ro
o
     SAIC-GLNPO (CF #361)

     CONVENTIONALS IN UNTREATED SEDIMENT
ZIMPRO
MSLCode Sponsor ID
MX
361 26/27, Rep 1 I-US-ZP. Rep 1
361-26/27. Rep 2 I-US-ZP. Rep 2
361-26/27. Rep 3 1 US ZP. Rep 3
Method Blank
STANDARD REFERENCE MATERIAL
MESS 1 SRM
In-house Concensus value tt
MATRIX SPIKE RESULTS
Amount Spiked
361-26/27
361-26/27 + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-26/27, Rep 1 1 US-ZP, Rep 1
361-26/27, Rep 2 I-US-ZP, Rep 2
361-26/27, Rep 3 1 US-ZP, Rep 3
RSD%
% Moisture
001%
54.97
55.12
NA
NA

NA


NA
NA
NA
NA
NA

54.97
NA
NA
NA
% Total
pH Volatile Solid
NA 0 00%
7.67
NA
NA
NA

NA


NA
NA
NA
NA
NA

7.67
NA
NA
NA
14.73
15.28
15.12
NA

NA


NA
NA
NA
NA
NA

14.73
15.28
15.12
2%
Oil & Grease
(mg/kg)
20.0
9811
10016
9851
20 U

NA


17944
9811
12005
2194
12% x

9811
10016
9851
1%
TOC
% weight
0.007
19.25
NA
NA
0.014

2.12
2.3

NA
NA
NA
NA
NA

19.25
NA
NA
NA
Total Cyanide Total Phosphorus
(mg/kg) (mg P/kg)
0.2 0002
223
24.9
NA
0.2 U

NA


343.0
22.3
357.5
335.2
98%

22.3
NA
NA
NA
2919
NA
NA
0.005

NA


4177
4743
9007
4264
102%

2919
NA
NA
NA
      NA = Not analyzed
      U  = Below detection limit
      H   =  Value based on past in-house anulysus ot MfcSS-1.  Not statistically dotormined
      x   =  Most likely analyst error and spiko not addud
      NOTE:  Convenlionals results roportod on dry woiyhl basis.
                                                                TJ
                                                                TJ
                                                                rn
                                                                o
                                                                x

-------
SAIC GLNPO (CF #361)

CONVENTIONALS IN TREATED SEDIMENT
                  ZIMPRO
MSLCode Sponsor ID
MTL
361 29. REP 1 I-TS-ZP
361 29, HEP 2 I-TS-ZP
361-29. REP 3 1-1 S ZP
Method Blank
STANDARD REFERENCE MATERIAL
MESS-1 SRM
In-house Concensus value #
MATRIX SPIKE RESULTS
Amount Spiked
361-26/27
361-26/27 + Spike
Amount Recovered
% Recovery
REPLICATE ANALYSES
361-29, Rep 1 I-TS-ZP. REP 1
361-29. Rep 2 I-TS ZP. REP 2
361-29, Rep 3 I-TS-ZP. REP 3
RSD%
% Moisture
001%
43 3
NA
NA
NA

NA


NA
NA
NA
NA
NA

433
NA
NA
NA
% Total
pit Volatile Solid
NA 0 00%
6.51
6.52
NA
NA

NA


NA
NA
NA
NA
NA

6 51
NA
NA
NA
7.78
7.19
7.05
NA

NA


NA
NA
NA
NA
NA

7.78
7.19
7.05
5%
Oil & Grease
(mg/kg)
20 0
1058
1093
702
20 U

NA


17944
9811
12005
2194
12% x

1058
1093
702
23%
TOC
% weight
0 007
9 28
NA
NA
0 014

2.12
23

NA
NA
NA
NA
NA

9.28
NA
NA
hC
Total Cyanide Total Phosphorus
(mg/kg) (mg P/kg)
02 0 002
145
NA
NA
02 U

NA


343.0
22 3
357.5
335.2
98%

14.5
NA
NA
N3
4743
NA
NA
0.005

NA


4177
4743
9007
4264
102%

4743
NA
NA
N3
 NA - Not analyzed
 U  « Below detection limit
 #  -  Value based on past In-house analyses ol MESS-1.
 X  =» Most likely analyst error and spike not added
 NOTE:   Conventionals results reported on dry weight basis.
Not statistically determined

-------
SAIC GLNPO (CF »361)

METALS IN UNTREATED SEDIMENT

(Conconlrations In  ug/g dry weight)
                                                                                           ZIMPHO
MSLCode Sponsor ID
MDL
36126/27, Rep 1 1 US ZP. Rep 1
361 26/27, Rep 2 1 US ZP. Hop 2
361 26/27. Hop 3 1 US ZP. Rop 3
Method Blank
STANDARD REFERENCE MATERIAL
-4646 SRM
yj
VB)U«
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 *
361 26/27 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-26/27. Rep 1 1 US ZP. Rop 1
361 26/27, Rep 2 1 US ZP, Rop 2
361 26/27. Rep 3 1 US ZP. Hop 3
RSO%
Ag
AA
0 007
4 78
4 90
4 81
0 20

0 11

NC

2
4 83
7 12
229
115%

4 78
4 90
4 81
1%
As
2 5
21 6
34 6
26 6
NA

1 1 26
11 6
±1 3

NS
NS
NS
NS
NS

21 6
34 6
26 6
24%
Ba
43
282
281
287
NA

387
NC
rC

NS
NS
NS
NS
NS

282
281
287
1%
Cd
AA
0 006
7 71
8 17
7 35
0 006

0 40
0 36
10 07

2
7 74
9 88
2 14
107%

7 71
8 17
7 35
5%
Cr
33
1082
1047
1096
NA

66
76
13

NS
NS
NS
NS
NS

1082
1047
1096
2%
Cu
5 5
267
250
244
NA

21 4
18
±3

NS
NS
NS
NS
NS

267
250
244
ET/o
%Fo
0 26
17 45
17 12
17 22
NA

3 38
3 35
10 1

NS
NS
NS
NS
NS

17 45
17 12
17 22
1%
Hg
CVAA
0 0003
1 385
1 369
1 439
0 00013

0 066
0 063
10 012

1 984
\ 398
3 257
1.859
94%

1 385
t 369
1 439
3%
Ml
Ml
56
1920
1910
1890
NA

345
375
±20

NS
NS
NS
NS
NS

1920
1910
1890
1%
Nl
at
7 5
1 19
1 13
1 12
NA

308
32
13

NS
NS
NS
NS
NS

119
1 13
112
3%
Pb
6 2
764
707
766
NA

27 5
28 2
±1 8

NS
NS
NS
NS
NS

764
707
766
4%
So
AA
0 22
5 38
5 54
5 41
0 22 U

0 74
NC
NC

2 70
5 44
8 44
3
111%

5 38
5 54
5 41
2%
Zn
Xf
7 8
3090
2930
3070
NA

122 4
138
16

NS
NS
NS
NS
NS

309C
293C
307(
3°X
 U   -  Below detection  limits
 NA  - Not analyzed
 NC  - Not cerlihed
 NS  - Not spiked
 '  - Moan ot triplicated sample
 x  - Sample was inadvertently not spikud
 NOTE   All metals results aro blank corrected

-------
SAIC GLNPO (CF »36t)

METALS IN TREATED SEDIMENT

(Concentrations  In ug/g dry weight)
                                                                                           ZIMPRO
MSL Code Sponsor ID
MX
361 29, Rep 1 I-TS-ZP. Rep 1
361 29. Rep 2 1 TS ZP. Hop 2
361 29, Rep 3 1 TS ZP. Hop 3
Method Blank
1646 SRM
cetllllBd
valua
MATRIX SPIKE RESULTS
Amount Spiked
361 29m
361 29 4 Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
361-29, Rep 1 I-TS-ZP. Rep 1
361 29. Rep 2 1 TS ZP, Hep 2
361 29, Rep 3 1 TS ZP. Rep 3
RSD%
Ag
AA
0007
697
6 72
704
002
0 12
NO
SC

2
691
563
-1 28
NA x

6 97
6 72
704
2%
As
»F
2 5
202
35 0
32 2
NA
12 1
11 6
±1 3

NS
NS
NS
NS
NS

20 2
35 0
32 2
27%
Ba
43
351
367
387
NA
393
NC
N3

NS
NS
NS
NS
NS

351
367
387
5%
Cd
AA
0006
13.47
12 69
12 80
0006 U
0 41
0 36
±0 07

2
130
153
23
115%

13 47
12 69
12 80
3%
Cr
MT
33
1471
1467
1372
NA
98
76
±3

NS
NS
NS
NS
NS

1471
1467
1372
4%
Cu
55
299
360
392
NA
21 4
18
13

NS
NS
NS
NS
NS

299
360
392
13%
%Fe
0 26
21 6
22 7
23 7
NA
3 39
3 35
±0 1

NS
NS
NS
NS
NS

21 6
22.7
23.7
5%
Hg
CVAA
0 0003
2 286
2 253
2 241
0 00013
0 065
0 063
±0 012

1 967
2 260
4 303
2 043
103%

2 286
2 253
2 241
1%
Ml
Mf
56
2570
2700
2760
NA
323
375
±20

NS
NS
NS
NS
NS

2570
2700
2760
4%
Nl
XHF
7 5
126
150
138
NA
36 1
32
±3

NS
NS
NS
NS
NS

126
ISO
138
9%
Pb
6 2
938
1080
1266
NA
26 8
28 2
11 8

NS
NS
NS
NS
NS

938
1080
1266
15%
Se
AA
0 22
701
6 41
6 59
0 22 U
0 87
NC
rC

2 73
6 67
9 47
28
103%

701
6 41
6.59
5%
Zn
7 8
3720
4260
4890
NA
131 4
138
16

NS
NS
NS
NS
NS

3720
4260
489C
14%
 U  - Below detection limits
 NA - Not analyzed
 NC  - Not certified.
 NS - Not spiked.
 *  - Mean ol triplicated sample.
 x  • Sample was inadvertently not spikod
 NOTE.   All metals  results  are blank corrected

-------
               SAIC GLNPO (CF »36()
                                                                                            ZIMPRO
to
               PAH IN UNTREATED SEDIMENT
               Low Molecular Welghl PAHs (nq/q dry welqhl)
MSL Coda
361-26/27, Rep 1
361 26/27. Rep 2
361 26/27. Rep 3
Method Blank 3
Sponsor ID
I-US-2P. Rep 1
I-US-ZP. Rop 2
I-US-ZP. Rep 3

Naphthalene Acenaphthytone Acenaphlhene
4479 0
4269 D
3749 0
921 CU
3011 0
2975 D
3347 D
987 OJ
4404 D
4214 D
4525 D
1389 (XI
Fluorene Phenanthrene Anthracene
4891 D
4592 D
5120 D
1163 DU
16498 D
14979 D
16191 D
681 OJ
6282 D
6056 D
6955 D
773 DU
STANDARD REFERENCE MATERIAL
SRMNIST1941
carlllled value
364
NC
54 U
NC
60 U
NC
63 U
NC
550
577
164 U
202
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 «
361-26/27 4 Spike
Amount Recovered
Percent Recovery

4237 D
4172 D
7960 D
3808
90%
4237 D
3111 D
8037 D
4926
116%
4237 D
4381 D
8814 D
4433
105%
4237 D
4868 D
9668 D
4800
1 1 3%
4237 D
15889 0
22250 D
6361
150% '
4237 D
6431 D
12387 D
5956
141%'
REPLICATE ANALYSES
361-26/27. Rep 1
361 26/27, Rep 2
361-26/27, Rep 3
1 US ZP. Rep 1
1 US ZP. Rep 2
I-US-ZP. Rep 3
RSD%
4479 D
4289 D
3749 D
9%
3011 D
2975 D
3347 D
7%
4404 D
4214 D
4525 D
4%
4891 D
4592 D
5120 D
9-/o
16498 0
14979 D
16191 D
95i
6282 D
6056 D
6955 D
7%
                D  - Samples diluted 110 and re-run
                U   -  Below detection limits
                t  - Mean ol triplicated samples
                NC - Not certified.
                •   - Value outside ol Internal QC limits (40 120%)

-------
ro
en
          SAICGINPO (CF *361)

          PAH IN UNTREATED SEDIMENT

          High Molecular Weighl PAHs (ng/g dry woighl)
ZIMPRO
MSL Code Sponsor ID
361 26/27. Rep 1 I-US-ZP.
361 26/27. Hop 2 1 US ZP.
361 26/27. Hep 3 1 US ZP.
Method Blank- 3
Rep t
Hop 2
Rop 3

Fluor an
thane
32492 D
31816 D
35549 0
446 UJ
Indono Dibonzo
Pyrene Benzo(a) Chrysene Benzo(b) Benzo (k)- Benzo(a)- (1.2.3.c.d) (a.h) Benzo(g.h.l)
anliuacone lluoranlhpne Biioranlhorw pyrene pyrene anthracene ooivlene
32303 D
31993 D
34572 D
465 DU
20662 0
21303 D
22074 D
439 DJ
28641 D
29430 D
29878 D
418 DU
24190 D
25225 D
25514 D
335 DU
15552 D
15889 D
17357 D
275 DU
26124 0
28986 D
27576 D
357 DU
18664 0
19499 D
20438 D
367 DU
6622 D
7985 0
6654 0
360 DU
13355 D
15571 D
14165 D
243 D
STANDARD REFERENCE MATERIAL
SHM NIST1941
c»rllll»d
MATRIX SPIKE RESULTS
Amount Spiked
361 26/27 II
361 26/27 t Spike
Amount Recovered
Percent Racovory
REPLICATE ANALYSES
value



361-26/27, Rep 1 1 US ZP. Rep 1
361 26/27. Rep 2 1 US ZP. Rop 2
361 26/27. Rep 3 1 US ZP, Rep 3
BSD*
1114
1220

4237 D
33286 D
43798 D
10512
248% '

32402 D
31816 D
35549 D
&•/.
1034
1080

4237 D
32956 D
41981 0
9025
2U% '

32303 D
31993 D
34572 D
4%
481
550

4237 D
21083 0
29133 D
8051
190% '

20862 D
21303 0
22074 D
3%
703
NC

4237 D
29136 D
36811 0
7676
181% '

28841 D
29430 D
29878 D
2%
766
780

4237 D
24976 D
33607 0
8631
204% '

24190 D
25225 0
25514 D
3%
603
444

4237 D
16266 D
22897 D
6631
157% '

15552 O
15889 D
17357 D
6%
500
670

4237 D
27562 D
35567 D
8005
189% '

26124 D
28986 D
27576 D
5%
498
569

4237 D
19534 D
27151 D
7617
180% *

18664 D
19499 D
20438 D
5%
141
tc

4237 D
10725 D
13977 D
3252
77% | ', .

6622 D
7985 0
6654 D
11%
421
516

4237 D
14364 D
18877 D
4513
107%

13355 D
15571 D
14165 D
8%
           D   - Samples diluted 1:10 and re run
           U   - Below detection limits
           *   - Mean ol triplicated samples.
           NC - Not certified.
           '   - Value outside ol Internal QC limits (40 120%)

-------
             SAIC GLNPO (CF »361)
                                        ZIMPRO
             PAH IN UNTREATED SEDIMENT

MSLCode
361-26/27,
361 26/27.
361 26/27.
Sponsoi ID
Rep
Rep
Hop
1
2
3
1 US ZP,
I-US-2P.
1 US ZP.
Rep
Rep
Rop
Surrogate Recovery %
D8 Naph-
thalene
1 31%
2 29%
3 21%
010
D'
D'
D-
Acenaph-
thalene
65%
61%
61%
D12 Perylene
D
D
D
112%
1 08%
110%
D
D
D
              Method  Blank 3

              STANDARD REFERENCE MATERIAL

              SRM NIST1941
                                                                    25% D'
                                                                    28% '
                                                                                     24% D'
                                                                                     47%
                                                                                                     90% D
                                                                                                     74%
to
              MATRIX SPIKE RESULTS

              Amount Spiked
              361 26/27   I
              361-26/27  + Spike
              Amount  Recovered
              Percent Recovery

              REPLICATE ANALYSES

              361 26/27, Rep  1
              361-26/27. Rop  2
              361 26/27, Rep  3
I US ZP. Hep  1
I US ZP. Rop  2
I US ZP. Hep  3
 RSD%
              D   - Samples diluted 1  10 and re-run
              »   > Mean ol triplicated samples
              NC - Not certified
                  - Value outside ol Internal QC limits (40 120%)
              NA - Not applicable
NA
27% D-
37% D '
NA
NA
NA
62% D
72% D
NA
NA
NA
110% D
112% D
NA
NA
31% D'
29% D'
21% D'
20%
65% D
61% D
61% D
 4%
112% D
108% 0
110% D
  2%

-------
              SAICGUNPO (CF »361)
                                                                                         ZIMPRO
to
              PAH IN TREATED SEDIMENT

              Low Molecular Weight PAHs (ng/q dry weigh!)
MSL Code Sponsor ID
361 29 R I-TS ZP
Method Blank R
STANDARD REFERENCE MATERIAL
SHMNIST1941
c»rtlll»d v«lu*
MATRIX SPIKE RESULTS
Amount Spiked
361 29 R
361 29 + Spike
Amount Rocoveied
Percent Recoveiy
Amounl Spiked
361 29 R
361 29 + Spike DUP
Amounl Recovered
Percent Recovery
Naphthalene Acenaphlhylene Aconaphlhene
30
1 1

364
NC

3049
30
1931
1902
62%
3623
30
1063
1034
29% '
145 U
11 U

54 U
rC

3049
145 U
2139
2139
70%
3623
145 U
1418
1418
39% *
22 U
16 U

60 U
NC

3049
22 U
2376
2376
78%
3623
22 U
1588
1588
44%
Fluotene Phenanlhrene
18 U
13 U

63U
NC

3049
18 U
2628
2628
86%
3623
IB U
2194
2194
61%
174
9

550
577

3049
174
3074
2899
95%
3623
174
3260
3086
85%
Anlhracone
39
9 U

164 U
202

3049
39
2322
2282
75%
3623
39
2295
2256
62%
               R   - Re extracted sample  results
               U   - Below detection limits
               NC  - Not collided
               *    . Value outside of Internal QC limits (40 120%)

-------
          SAICGLNPO(CF »361)

          PAH IN TREATED SEDIMENT

          High Molecular Welghl PAHs (nqfr dry weighl)
                                                                                          ZIMPRO

MSL Code Sponsor ID
361-29 R I-TS-2P
Method Blank R
Indeno
Fluoran- Pyrene Benzo(a)- Chrysene Beruo(b) Benzo(k)- Benzo(a)- (1.2,3.c.d) Diberuo(a.h)- Benzo(g.h,l)-
Ihune anthracene Huoranlhone lluoranlhene pyrene pyrene anthracene perylene
114 181 241 840 286 4U 273 116 168 189
9 9 SUS 6 5 5 5 4U 6
          STANDARD REFERENCE MATERIAL
          SHMNIST1941
ro
00
                          ccrtlllid vilu*
                                             1114
                                             1220
                                              1034
                                              1080
MATRIX SPIKE RESULTS

Amount Spiked
361 29  R
361 29 t Spike
Amount  Recovered
Percent Recovery

Amount Spiked
361 29  R
361 29 + Spike   DUP
Amount Recovered
Percent Recovery
           R   > Re-extracted sample results.
           U   - Below detection  limits
           NC - Not certilied.
           *   - Value outside ol Internal QC limits (40 120%)
481
550
                                                                                 703
766
780
498
569
                                                                                                                                            141
421
516
3049
1 14
3031
29)8
96%
3623
1 14
3436
3322
92%
3049
181
3060
2879
94%
3623
181
3459
3278
90%
3049
241
3265
3024
99%
3623
241
3541
3300
91%
3049
840
3283
2443
80%
3623
840
3499
2659
73%
3049
286
2785
2499
82%
3623
286
3220
2934
81%
3049
4 U
2351
2351
77%
3623
4 U
2853
2853
79%
3049
273
2205
1932
63%
3623
273
3092
2820
78%
3049
1 16
2755
2640
87%
3623
116
2931
2816
78%
3049
168
381 1
3643
119%
3623
168
3944
3776
104%
3049
189
2846
2658
87%
3623
189
2942
2753
76%

-------
             SAICGLNPO (CF »361)
                                                                            ZIMPRO
             PAH IN TREATED SEDIMENT

MSLCode
Sponsor ID
Surrogate Recovery %
D8 Naph- DtO Acenaph- D12 Perylene
thalene thalene
              361-29  R        I-TS ZP

              Method Blank H

              STANDARD REFERENCE MATERIAL
                                                      23% '

                                                      51%
34%"

62%
76%

72%
              SRM NIST1941
                                                                    28%
                                                                                     47%
                                                                                                     74%
10
MATRIX SPIKE RESULTS

Amount Spiked
361 29   R
361 29  + Spike
Amount  Recovered
Percenl  Recovery

Amount  Spiked
361 29    R
361 29 + Spike   DUP
Amount  Recovered
Percent  Recovery

R   - Re extracted sample results
*  - Values outside ol Internal QC  limits  (40-120%)
NA - Not applicable
                                                                     MA
                                                                    23% '
                                                                    30% '
                                                                     NA
                                                                     NA

                                                                     NA
                                                                    23% '
                                                                    25% '
                                                                     NA
                                                                     NA
 NA
34% '
66%
 NA
 NA

 NA
34% '
41%
 NA
 NA
 NA
76%
64%
 NA
 NA

 NA
76%
73%
 NA
 NA

-------
               SAICGLNPO (CF #361)



               PAH IN WATER
                                                                                           ZIMPRO
               Low Molecular Weight PAHs (ng/l)
CO
O
MSI Code Sponsor 10
361-30 I-WR-ZP
Method Blank 7
MATRIX SPIKE RESULTS
Amount Spiked
361-30
361 30* Spike
Amount Recovered
Percent Recovery
Amount Spiked
Blank 7
Blank 7 + Spike
Amount Recovered
Percent Recovery
Naphthalene Acenaphlhylene Acenaphlhene
956
266 U

25000
956
5987
5031
20% '
25000
266 U
8947
8947
36% '
152 U
275 U

2SOOO
152 U
8313
8313
33% '
25000
275 U
10024
10024
40%
218 U
395 U

25000
218 U
7027
7027
28% '
25000
395 U
10259
10259
41%
Fluorene Phenanlhrene Anthracene
192 U
348 U

25000
192 U
12931
12931
52%
25000
348 U
11685
11685
47%
1037
230 U

25000
1037
20485
19448
78%
25000
230 U
15262
15032
60%
142U
258 U

25000
142U
14663
14663
59%
25000
258 U
16941
16941
68%
                U   - Below detection limits

                   - Value outside ol internal QC limits (40 120%)

-------
SAIC GLNPO (CF *361)

PAH IN WATER

High Molecular Weigh! PAHs  (ng/l)
ZIMPRO
MSL Code Sponsor ID
361-30 1 WH ZP
Method Blank- 7
MATRIX SPIKE RESULTS
Amount Spiked
361 30 I-WR-ZP
361 -30 f Spike
Amount Rocovoied
Percent Recovery
Amount Spiked
Blank 7
Blank 7 + Spike
Amount Recovered
Pel cent Recovery
Fluoran-
Ihune
162
175 U

25000
162
23080
22910
92%
25000
175 U
22732
22732
91%
Pyrena Beruo(a)
anthracene
137
181 U

25000
137
22094
21957
88%
25000
181 U
22303
22303
89%
98 U
177 U

25000
98 U
23216
23216
93%
25000
177 U
27433
27433
110%
Chrysene Bonzofb) Benzo (k)-
fluoranlhone rluoranlhene
95 U
171 U

25000
95 U
22754
22754
91%
25000
171 U
24443
24443
98%
70 U
127 U

25000
70 U
22338
22338
89%
25000
127 U
24350
24350
97%
61 U
11 1 U

25000
61 U
20690
20690
83%
25000
111 U
22597
22597
90%
Indent)
Bonzo(a) (1.2.3.c.d) Diberao(a.h)- Beruo(g.h.i)
pyrene pyrene anthracene oeivlone
79 U
143 U

25000
79 U
15479
15479
62%
25000
143 U
23230
23230
93%
72 U
131 U

25000
72 U
20532
20532
82%
25000
131 U
23647
23647
95%
92 U
166 U

25000
92 U
26638
26638
107%
25000
166 U
30175
30175
121% '
70 U
142

25000
70 U
1S953
18953
76%
25000
142
22117
2197S
88%
 U   - Below detection limits
    - Value outside ol Internal QC limits (40-120%)

-------
              SAIC GLNPO (CF »361)

              PAH IN WATER
                                                                             ZIMPRO

MSLCode Sponsor 10
Surrogate Recovery %
D8 Naph-
thalene
361-30 1 WR-ZP 35%
Method Blank 7 16%
DID Aconaph-
thalene
47%
18% '
012 Perylene
58%
80%
CO
ro
MATRIX SPIKE RESULTS

Amount Spiked
361 30
361 30* Spike
Amount  Recovered
Percent Recovery

Amount Spiked
Blank 7
Blank-7 + Spike
Amount Recovered
Percent Recovery

'  - Value  outsldo ol Internal QC limits (40 120%)
NA . Not applicable
 NA
35% '
20% *
 NA
 NA

 NA
 16%  •
 22% '
 NA
 NA
 NA
47%
27% •
 NA
 NA

 NA
 18%  '
 27%'
 NA
 NA
 NA
58%
60%
 NA
 NA

 NA
80%
80%
 NA
 NA

-------
co
CO
        RE-PROCESSED  RESULTS (1/92)
        PCDi IN UNTREATED SEDIMENT
        Conconlrollons In  un/kn dry wolghl
     ZIMPRO
SAIC-GLNPO (CF II3G1)
2/12/92
                                   % Surrogate rtocovory

MSLCoda
361-26/27. Rep 1 D
361-26/27. Rep 2 D
361-26/27. Rep 3 D
Blank-6

Sponsor ID
I-US-ZP. Rop 1
I-US-ZP. (tap 2
I-US-ZP. Hop 3

Aroclor
1242
2000 U
2000 U
2000 U
200 U
Aroclor Aroclor Aroclor
1240 1254 1260
9470 D 1000 U 1000 U
9GOO D 1000 U 1000 U
1 1300 D 3106 D 1000 U
200 U 100 U 100 U
Tolrachloro- Oclachloro-
m-Xylone naphthalene
84.0% 91 6%
01 4% 73 0%
80.9% B9 4%
53.0% 02.1%
STANDARD REFERENCE MATERIAL
SRM 5 (US 2)
MATRIX 8PIKE RESULTS
Amount Splkod
361-26/27 *
361-26/27 + Spike
Amount Recovered
Percent Recovery
REPLICATE ANALYSES
381-26/27. Rep 1 D
381-26/27, Hop 2 D
361-26/27. Rop 3 D
certified value





I-US-ZP, Rop 1
l-US ZP, Rop 2
I-US-ZP. Hop 3
RSDV.
100 U
N3

MS
NS
NS
N3
NS

2000 U
2000 U
2000 U
0%
100 U G9 50 U
he 111 itf;

NS 4237 NS
hS 3106 D NS
NS 6019 NS
NS 3633 NS
NS 06% NS

67 6% 96 2%
N3 N3

NA NA
021% 04.7%
07.3% 91.5%
NA NA
NA NA

0470 D 1000 U 1000 U 04.0% 01.6%
0000 D 1000 U 1000 U 01.4% 73.0%
11300 D 3100 D 1000 U 00.0% 00.4%
10% 73% 0% 2% 12%
        D • Samples diluted 1:10 and ro-run.
        U • Below  detection limits.
        • - Value outside  ol Inlornal QC limits (40-120%).
        NC -  Not corllllod.
        II - Moon ol ropllcDlod  onmplo.
        NS - Not aplkod         NA -  Not applicable.

-------
RE-PROCESSED RESULTS (1/92)
PCBs IN TREATED SEDIMENT
Concentrations In uq/kg dry weight
     ZIMPRO
SAIC-GLNPO (CF #361)
2/12/92
                                  % Surrogate Recovery
MSL Coda Sponsor ID
381-20 I-TS-ZP
BLANK-8
STANDARD REFERENCE MATERIAL
SRM-S (H3-2)
certified voluo
MATRIX SPIKE RESULTS
Amount Spiked
361-29
361-29 + Spike
Amount Recovered
Percent Recovery
Amount Splkod
361-29 DUP
361-29 + Spike DUP
Amount Recovered
Percent Recovery
Aroclor
1242
200 U
200 U

100 U
1C

NS
he
NS
NS
NS
NS
he
NS
NS
NS
Aroclor Aroclor Aroclor
12-18 1254 1200
4008 3555 100 U
200 U 100 U 100 U

100 U 00 50 U
N3 111 rC

NS 3876 NS
NS 3555 NS
NS 7630 NS
NS 4075 NS
NS 105% NS
NS 3049 NS
NS 3555 NS
NS 4052 NS
NS 1207 NS
NS 43% NS
Tolrachloro- Oclachloro-
m-Xylono naphlholono
87.1% 73.1%
53.9% 821%

87.6% 00.2%
N3 NO

NA NA
67.1% 73.1%
61 .6% 93.0%
NA NA
NA NA
NA NA
67.1% 73.1%
03.0% 57.7%
NA NA
NA NA
 U - Below detection limits.
 * - Value oulsldo of Internal QC limits (40-120%).
 NC - Nol corllllod.
 NS - Nol eplked.        NA - Not applicable.

-------
RE-PROCESSED RESULTS  (1/92)
PCBi IN WATER SAMPLES
Concentrations  In ug/L
     ZIMPRO
SAIC-GLNPO (CF #361)
2/12/92
                                  % Surrogate Recovery
MSLCode Sponsor ID
381-30 I-WR-ZP
Blank-7
MATRIX SPIKE RESULTS
Amount Spiked
361-30
381-30 + Spike
Amount Recovered
Percent Recovery
Aroclor
1242
0.2 U
0.2 U

NS
NS
NS
NS
NS
Aroclor Aroclor Aroclor
1240 1254 1260
0.2 U 0.1 U 0.1 U
0.2 U 0.1 U 0.1 U

NS 25 NS
NS 0.1 U NS
NS 21 NS
NS 21 NS
NS 0-1% NS
Telrachloro- Oclachloro-
m-Xylone nophlhalono
85.8% 900%
20 2% * 90 0%

NA NA
85.8% 90.0%
67.4% 77.8%
NA NA
NA NA
U » Betow detection limits.
* > Value outside  ol Internal QC limits (40-120%).
NC - Not certified.
NS - Nol spiked.        NA » Not applicable.

-------
                                         Appendix E
                          QUALITY ASSURANCE/QUALITY CONTROL
       In order to obtain data of known quality to be used in evaluating the different technologies for
the different sediments, a Quality Assurance Project Plan (QAPP) was prepared. The QAPP specified
the guidelines to be used to ensure that each measurement system was in control.  In order to show
the effectiveness of the different technologies, the following measurements were identified in the QAPP
as critical - PAHs, PCBs, metals, total solids, oil and grease and volatile solids in the untreated and
treated sediments. Other parameters analyzed in the sediments included  pH, TOO, total cyanide, and
total phosphorus.  If water and oil residuals were generated by a technology, then polynuclear aromatic
hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined as a check on their fate
resulting  from in treating the sediments.  Each of these measurements and the associated quality
control (QC) data will be discussed in this section. It should  be noted that the ZIMPRO technology
developers do not claim that the process will remove PCBs.  Therefore PCB analysis is not critical in
demonstrating the effectiveness of this technology.

       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.

       Attached to this appendix is an abridged version of the Data Verification report completed by
the ARCS Program QA Officer.  Copies of the entire Data Verification report are available from GLNPO.

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
                                             136

-------
target analyte(s) used to document the accuracy of a method in a given sample matrix. For matrix
spikes, recovery is calculated as follows:
              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 =   °m    x   100
              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):
                             RPD=
              where: C,  =   the larger of two observed values
                     C2  =   the smaller of two observed values
                                             137

-------
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 ZIMPRO treatability studies, no samples were lost due to field
or analytical problems.  Though all guidelines for QA objectives were not  met, all data generated was
deemed useable.

Representativeness
       Representativeness refers to the degree with which analytical results accurately and precisely
represent actual conditions present at locations chosen for sample collection.  Sediment samples were
collected prior to this demonstration and were reported to  be representative of the areas to be
remediated. Samples of untreated and treated sediment and residuals were taken by SAIC personnel
during Phase II of these tests. Samples were shipped under chain-of-custody to Battelle Marine
Sciences Laboratory in Sequim, Washington.  Therefore, the data is representative  of material actually
treated.

Comparability
       Comparability expresses the extent with which one data set can be  compared to another. As
will  be discussed in more detail in the section Modifications and Deviations  From the QAPP, the data
generated are comparable within this project and within other projects conducted for the ARCS
                                             138

-------
Program.  However, because specialized procedures were used in some instances, the data may not
be directly comparable to projects outside the ARCS Program.

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 ZIMPRO 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.  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 ZIMPRO demonstration are summarized in
Table QA-1. If more than one of the three surrogates fell outside the control limits used, corrective
action (reanalysis) was necessary. (This criteria was not applied by Battelle to method blanks.)
Surrogate recoveries were generally low for samples and method blanks, indicating a possible
analytical problem rather than matrix effects. An investigation indicated possible problems with the
evaporator used to concentrate the extracts. In summary, low surrogate recoveries indicate that PAH
target concentrations may be biased somewhat low. Since both the untreated and treated sediments
were affected similarly, relative removal percentages should be valid.

       It should also be noted that surrogate recoveries for both the initial analysis and the re-
extracted analysis for the treated solid (I-TS-ZP) did not meet acceptance criteria.

       As required by the QAPP, triplicate analyses of the Indiana Harbor untreated sediment  (I-US-
ZP) were performed to assess precision.  These  results are summarized in Table QA-2. A matrix spike
                                             139

-------
                        TABLE QA-1.  PAH SURROGATE RECOVERIES
d8-Naphthalene
Sample (%)
I-US-ZP
I-US-ZP
I-US-ZP
Method Blank
I-TS-ZP (Re-extract)
Method Blank
I-WR-ZP
Method Blank
31*
29*
21*
25*
23*
51
35*
16*
dIO-Acenaphthalene d12-Perylene
(%) (%)
65
61
61
24*
34*
62
47
18*
112
108
110
90
76
72
58
80
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
* Outside Control Limits

was performed on this same sample to assess accuracy.  These results are included in Table QA-2.
All RSDs fell within the control limits specified. Several matrix spike recoveries fell outside control limits
due to inappropriate spiking levels. For several compounds, the spiking level was between 10 and 30
percent of the sample concentration.  Recoveries for these compounds may not be indicative of actual
matrix interferences.

       As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MD) analysis was
performed for the treated Indiana Harbor sediment (I-TS-ZP). These results are presented in Table
QA-3. Recoveries were generally acceptable. RPDs for the lighter compounds were outside the
guidelines specified in the QAPP.  As minimal or none of these  compounds were present in the sample,
project results should not be affected.

       A matrix spike analysis was performed on the Indiana Harbor water residual (I-WR-ZP). These
results are summarized in Tables QA-4.

       One certified National Institute of Science and Technology (MIST) standard reference material
(SRM) was extracted and analyzed with the sediment samples.  The recoveries for this standard are
summarized in Table QA-5.

       Method blanks were extracted and analyzed with each set of samples extracted.  Minimal
quantities of several PAHs were found in all three PAH method  blanks; total concentrations are
                                            140

-------
TABLE QA-2. PAH REPLICATE AND SPIKE RESULTS FOR I-US-ZP
Compound
Naphthalene
Acoriaphthylene
Acenaphthene
Fluor ene
Phenanthrene
Anthracene
Fluoianthene
Pyrene
Boi i/o(a)anthracene
Chiysene
Bonzo(b)1luoranthene
Bi -n/o(k)f luoranthene
Beii7o(a)pyrene
lnd'3no(1 ,2,3,c,d)pyrene
Dibenzo(a,h)anthracene
Bon7O(g,h,i)perylene
* Outside Control Limits
(1) Spiking level ranged from
Replicate 1
dry ppb
4480
3010
4400
4890
16500
6280
32500
32300
20900
28800
24200
15600
26100
18700
6620
13400

1 0 to 30 percent
Replicate
dry ppb
4290
2980
4210
4590
15000
6060
31800
32000
21300
29400
25200
15900
29000
19500
7980
15600

of sample
2 Replicate 3
dry ppb
3750
3350
4520
5120
16200
6960
35500
34600
22100
29900
25500
17400
27600
20400
6650
14200

concentration.
Mean
4170
3110
4380
4870
15900
6430
33300
33000
21100
29100
25000
16300
27600
19500
7090
14400


RSD
(%)
9
7
4
5
5
7
6
4
3
2
3
6
5
5
11
8


Precision
Control
Limits (%)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20


Recovery
(%)
90
116
105
113
150*{1)
141*
248*(1)
213*(1)
190*(1)
181*(1)
204*(1)
157*(1)
189*(1)
180*(1)
163*
107


Accuracy
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120



-------
                 TABLE QA-3. PAH MS/MSD RESULTS FOR I-TS-ZP
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranathene
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
(%)
62
70
78
86
95
75
96
94
99
80
82
77
63
87
119
87
MSD
Recovery
(%)
29*
39*
44
61
85
62
92
90
91
73
81
79
78
78
104
76
RPD
73*
57*
56*
34*
11
19
4
4
8
9
1
3
21*
11
13
13
Accuracy
Control
Limits (%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
Precision
Control Limits
(%)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Outside Control Limits
                  TABLE QA-4.  PAH MS RESULTS FOR I-WR-ZP
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a) anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3,0,00 pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
MS Recovery (%)
20
33
28
52
78
59
92
88
93
91
89
83
62
82
107
76
Control Limits (%)
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
                                   142

-------
                              TABLE QA-5.  PAH SRM RESULTS
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluor anthene
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 (%)
NC
NC
NC
NC
95
NR
91
96
87
NC
98
136*
75*
88
NC
82
Control Limits (%)
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
NC = Not Certified
* = Outside Control Limits
NR = Not Recovered- certified value near detection limit.

unaffected.  No corrections were performed for method blanks as no consistent significant contamina-
tion 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. Two surrogates, tetrachloro-m-
xylene and  octachloronaphthalene, were added to all samples and blanks prior to extraction. The gas
chromatograph (GC) employed electron capture detection (ECD) and was calibrated at three levels for
each of four Aroclors (1242, 1248, 1254, 1260). The RSD of the response factors for each Aroclor was
required to  be <25 percent.  Calibrations were verified after every ten samples; criteria for percent
                                             143

-------
difference from the initial calibration was <25 percent.  An internal standard, dibromooctafluorobiphenyl,
was added prior to cleanup and was used to correct PCB concentrations for loss during cleanup and
extract matrix effects.

Quantification of Aroclors was performed on two columns (DB-5, primary and 608, confirmation) as a
confirmation  of their presence.

PCB QC Results and Discussion
       Surrogate recoveries for all PCB samples for the ZIMPRO demonstration are summarized in
Table QA-6.  If both recoveries fell outside the control  limits used, correction action (reanalysis) was
necessary.  All samples were acceptable with respect to the surrogate criteria used.
                        TABLE QA-6.  PCB SURROGATE RECOVERIES
Sample
I-US-ZP Rep.1
I-US-ZP Rep.2
I-US-ZP Rep.3
Method Blank
I-TS-ZP
Method Blank
I-WR-ZP
Method Blank
Tetrachloro-m-xylene
(%)
84
81
81
54
67
54
86
20
Octachloronaphthalene
(%)
92
73
89
82
73
82
90
90
Control Limits
(%)
40-120
40-120
40-120
40-120
40-120
40-120
40-120
40-120
« = Outside Control Limits
NC = Not Certified
NR = Not recovered - certified value near detection limit.
        As required by the QAPP, triplicate analyses of the Indiana Harbor untreated sediment (I-US-
 ZP) were performed to assess precision.  These results are summarized in Table QA-7. A matrix spike
 using Aroclor 1254 was performed on the same sample to assess accuracy; these results are included
 in Table QA-7. The RSD and recovery for individual Aroclors are both within control limits.  The RSD
 for total PCBs is 25 percent.
                                             144

-------
                                     TABLE QA-7. PCB REPLICATE AND SPIKE RESULTS FOR I-US-ZP
en
Replicate 1 ppb Replicate 2 ppb Replicate 3 ppb RSD
Aroclor dry . dry dry Mean (%)
1242 2000 U 2000 U 2000 U 2000 U NC
1248 9470 9680 11300 10200 10
1254 1000 U 1000 U 3190 NC NC
1260 1000 U 1000 U 1000 U 1000 U NC
U = Undetected
* = Outside Control Limits
NC Not Calculated
NS Not Spiked
TABLE QA-6. PCB MS/MSD RESULTS FOR
MS Recovery MSD Recovery
PCI! (%) (%) RPD
Aroclor 1254 105 43 84*
Precision Accuracy Control
Guideline Limits Recovery Limits (%)
(%) (%)
20 NS 40-120
20 NS 40-120
20 86 40-120
20 NS 40-120




I-TS-ZP
Accuracy Control Limits Precision Guideline Limits
(%) (%)
40-120 20
       U   Undetected




       *  Outside Control Limits




       NC  Not Calculated




       NS  Not Spiked

-------
       As required by the QAPP, a matrix spike and a matrix spike duplicate (MS/MSD) analysis was
performed for the treated Indiana Harbor sediment combustor solids (I-TS-ZP). These results are
presented in Table QA-8. Matrix spike recoveries were within guidelines but the RPO was not.  No
explanation was determined. As PCBs were not critical to meeting project objectives, no reanalyses
were performed.

       A matrix spike analysis was performed on the Indiana Harbor water residual (I-WR-ZP). These
results are summarized in Table QA-9.

       One standard reference material (SRM) certified by the National Research Council of Canada
(NRCC) for Aroclor 1254 was extracted  and analyzed with the sediment samples.  A recovery of 62%
was obtained.

       Method blanks were extracted and analyzed with each set of samples extracted. No PCBs were
found in any method blanks.

                        TABLE QA-9.  PCB MS RESULT FOR I-WR-ZP
                                         MS Recovery                    Control Limits
 PCB                                         (%)                            (%)
 Aroclor 1254                                   84                        Not Specified

METALS
Metals Procedure
       Sediments were prepared for metals analysis by freeze-drying, blending, and grinding.

       Sediments for Ag, Cd, Hg, and Se were digested using nitric and hydrofluoric acids. The
digestates were analyzed for Ag, Cd, and Se by graphite furnace atomic absorption (GFAA) by SW-846
Method 7000 series using Zeeman background correction.  The digestates were analyzed for mercury
by cold vapor AA (CVAA) using SW-846 Method 7470.

       Sediments for As, Ba, Cr, Cu, Fe,  Mn,  Ni, Pb, and Zn were analyzed by energy-diffusive X-Ray
fluorescence (XRF) following the method of Sanders (1987). The XRF analysis was performed on a
0.5 g aliquot of dried, ground sediment pressed into a pellet with  a diameter of 2 cm.
                                            146

-------
Metals QC Results and Discussion
       Triplicate analyses of the Indiana Harbor untreated sediment (I-US-ZP) and treated sediment
  (I-TS-2P) were performed to assess precision.  Matrix spikes were analyzed for the same samples to
assess accuracy.  Results are summarized in Tables QA-10 and QA-11.  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-10 and QA-11.  RSD results outside limits are due to concentrations near the
analytical detection limits. These exceptions have little, if any, impact on data quality and project
results.

       One NIST certified standard reference material (SRM) was digested and analyzed twice with
the sediment samples for XRF,  GFAA, and CVAA analyses. These results are presented in Table QA-
12.

       Method blanks were digested and analyzed for the metals analyzed by GFAA and CVAA.
(Method blanks are not applicable to XRF analysis).  If analyte was detected in the method blank, blank
correction was performed. Minimal amounts of some metals were detected; data quality is not affected.

OIL AND GREASE
Oil and Grease Procedures
       Sediment samples were extracted with freon  using Soxhlet extraction according to SW-846
Method 9071.  The extract was analyzed for oil and grease by infra-red (IR) as outlined in Method
418.1 (Methods for Chemical Analysis of Water and Wastes, 1983).

Oil and Grease QC Results and Discussion
       Both the untreated and treated Indiana Harbor sediment (I-US-ZP and I-TS-ZP) were analyzed
for oil and grease in triplicate. In addition, a matrix spike was performed for I-US-ZP.  Results are
presented in Table QA-13. As indicated, I-US-ZP was probably not spiked due to laboratory error. The
RSD for I-TS-ZP was outside control limits; removal efficiencies may be affected minimally.
                                             147

-------
                            TABLE QA-10.  METALS REPLICATE AND SPIKE RESULTS FOR I-US-ZP
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe{1)
Hg
Mn
Ni
Pb
So
Zn
Method
GFAA
XRF
XRF
GFAA
XRF
XRF
XRF
CVAA
XRF
XRF
XRF
GFAA
XRF
Replicate 1 .
ppm dry
4.78
21.6
282
7.71
1080
267
17.4
1.38
1920
119
764
5.38
3090
Replicate 2,
ppm dry
4.90
34.6
281
8.17
1050
250
17.1
1.37
1910
113
707
5.54
2930
Replicate 3,
ppm dry
4.81
26.6
287
7.35
1100
244
17.2
1.44
1890
112
766
5.41
3070
Mean
4.83
30.9
283
7.74
1080
254
17.3
1 40
1910
115
746
544
3030
RSD
1
24*
1
5
2
5
1
3
1
3
4
2
3
Precision
Control Limits
20
20
20
20
20
20
20
20
20
20
20
20
20
Recovery
115
NS
NS
107
NS
NS
NS
103
NS
NS
NS
111
NS
Accuracy
Control Limits
85-115


85-115



85-115



85-115

NS -    Not Spiked




*      Outside Control Limits




(1) -    Results in Percent for Fe

-------
                            TABLE QA-11.  METALS REPLICATE AND SPIKE RESULTS FOR I-TS-ZP
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
6.97
20.2
351
13.5
1470
299
21.6
2.29
2570
126
938
7.01
3720
Replicate 2,
ppm dry
6.72
35.0
367
12.7
1470
360
22.7
2.25
2700
150
1080
6.41
4260
Replicate 3,
ppm dry
7.04
32.2
387
12.8
1370
392
23.7
224
2760
138
1270
6.59
4890
Mean
691
29.1
368
13.0
1440
350
22.7
226
2680
138
1100
6.67
4290
RSD
2
27*
5
3
4
13
5
1
4
9
15
5
14
Precision
Control Limits
20
20
20
20
20
20
20
20
20
20
20
20
20
Recovery
NS
NS
NS
115
NS
NS
NS
103
NS
NS
NS
103
NS
Accuracy
Control Limits
85-115


85-115



85-115



85-115

NS =    Not Spiked




*       Outside Control Limits




(1)     Result in Percent for Fe

-------
                         TABLE QA-12.  METALS SRM RECOVERIES
Metal
Ag
As
Ba
Cd
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Se
Zn
SRM-1
(%)
NC
97.1
NC
111
86.8
119
101
105
92.0
96.2
97.5
NC
88.7
SRM-2
(%)
NC
104
NC
114
128*
119
101
103
86.1
113
95.0
NC
95.0
Control Limits
(%)
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
* = Outside control limits
NC = Not Certified
          TABLE QA-13. OIL AND GREASE REPLICATES AND SPIKE RESULTS FOR
                                     I-US-ZP AND I-TS-ZP
           Replicate 1,   Replicate 2,   Replicate 3,
Sample       ppm dry     ppm dry     ppm dry
                                               Mean
                                                                 Precision              Accuracy
                                                                 Control                Control
                                                         RSD      Limits    Recovery     Limits
I-US-ZP
I-TS-ZP
9810
1060
10000
1090
9850
702
9890
951
1
23*
20
20
12*(1) 80-120
NS 80-120
NS = Not Spiked

* = Outside Control Limits

(1) = Laboratory results indicated that the sample probably was not spiked


TOTAL VOLATILE SOUDS

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.


Total Volatile Solid QC Results and Discussion

       Both the Indiana Harbor  untreated and treated sediment (I-US-ZP and IT-TS-ZP) were analyzed

for TVS in triplicate.  Results are summarized in Table QA-14. Both RSDs fell within specified control

limits.
                                             150

-------
                 TABLE QA-14. TVS REPLICATES FOR I-US-ZP AND I-TS-ZP
Sample
I-US-ZP
I-TS-ZP
Replicate 1 ,
%dry
14.7
7.78
Replicate 2,
% dry
15.3
7.19
Replicate 3,
%dry
15.1
7.05
Mean
15.0
7.34
RSD
(%)
2
5
Control Limits
(%)
20
20
OTHER ANALYSES
       Sediment samples were analyzed for pH using SW-846 Method 9045. Sediment and water
were combined in a 1:1 ratio and mixed prior to pH determination.

Total Organic Carbon (TOG)
       Sediment samples were analyzed for TOC using SW-846 Method 9060.  One SRM was
analyzed with the sediments, yielding a recovery of 92.2 percent.

Total Cyanide
       Sediment samples were analyzed for cyanide by SW-846 Method 9010.  Approximately 5 g of
sediment was distilled;  the distillate was analyzed spectrophotometrically.  A matrix spike was analyzed
for I-US-ZP; a recovery of 98 percent was obtained.

Total Phosphorus
       Sediment samples were analyzed for phosphorus by EPA Method 365.2.  Approximately 1 g of
sediment was digested; the digestate was analyzed spectrophotometrically. A matrix spike was
analyzed for  I-TS-ZP; a recovery of 102 percent was obtained.

Total Phosphorus
       Sediment samples were analyzed for Phosphorus by EPA Method 365.2.  Approximately 1 g of
sediment was digested; the digestate was analyzed spectrophotometrically. A matrix spike was
analyzed for  I-TS-ZP; a recovery of 102 percent was obtained.

AUDIT FINDINGS
       An audit of the Battelle-Marine Sciences Laboratory was conducted on September 25 and 26,
1991 . Participants included EPA, GLNPO, and SAIC personnel. The path of a sample from  receipt to
reporting was observed specifically for samples from these bench-scale treat ability tests. Two concerns
                                           151

-------
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 demon-
strations for contaminated sediments. To date, all laboratory analyses performed in support of the
ARCS Program  have been done at the Battelle-Marine Sciences Laboratory (MSL) in Sequim,
Washington. Standard procedures used by Battelle-MSL often do not follow those procedures identified
in SW-846 and the QAPP. While these nonstandard procedures yield results of acceptable quality,
comparability with analyses performed outside the ARCS Program is not possible.
PAH Analysis
              Samples were co-extracted with 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 its recovery. Neither of these  internal standards are
              specified in Method 8270.
              SW-846 Method 8270 was modified to quantify the samples using Selective Ion
              Monitoring (SIM) Gas Chromatography/Mass Spectrometry (GC/MS). This modification
              results in improved detection limits.
              Three isotopically-labelled PAH compounds were used as surrogates rather than those
              recommended in Method 8270.  Recoveries of these compounds should better repre-
              sent the recoveries of target PAHs.

                                            152

-------
PCB Analysis
               Samples were extracted using the modified extraction procedures as described for the
               PAH analysis. An internal standard, dibromooctafluorobiphenyl, was added prior to the
               HPLC clean-up to monitor losses. Final results were corrected for the recovery of this
               standard. A second internal standard, 1,2,3-trichlorobenzene (required by QAPP) was
               added prior to analysis; however, no corrections were made based on its recovery.

               Quantification of PCBs was not done on a total basis as required by SW-846 Method
               8080 but by quantifying four peaks for each Aroclor and averaging these results.
               Peaks were considered valid if the peak shape was good, if there was no tailing, and if
               there was little or no coelution with other peaks. A definite Aroclor pattern was
               necessary for quantification of PCBs.

               A three-point calibration for each peak was used instead of the five-point calibration
               required by Method 8080. This modification should have minimal effect  on data quality.

               The surrogate required by the QAPP, tetrachloro-m-xylene, was used. A second
               surrogate, octochloronaphthalene, was also added to monitor extraction  efficiency.
Metals Analysis
               Nine of the 13 metals analyzed for sediment samples were measured by energy-
               diffusive X-Ray fluorescence (XRF) - As, Ba, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. This
               procedure yields a total metals concentration instead of the recoverable metals
               determined by SW-846 methods.

               Sediments for Ag, Cd, Hg, and Se were subjected to an acid digestion using nitric and
               hydrofluoric acids. This digestion again yields total rather than recoverable metals.
Oil and Grease

        •       Oil and grease extracts for sediments were analyzed using infrared (IR) detection rather
               than the  gravimetric procedures specified in the QAPP.  This should have no effect on
               data quality.


QUALITY ASSURANCE  OBJECTIVES

        Many of the guideline QA objectives and internal QC checks criteria guidelines specified in the

QAPP (particularly for organic analyses) are not routinely achievable by standard or nonstandard

methods.  To avoid excessive reanalyses (both costly and time-consuming), some acceptance criteria

established 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 to 130 percent. For surrogates, Battelle actually used internal limits of 40 to 120,
               with one percent of the three surrogates out of limits being acceptable.  If more than

                                              153

-------
PCB Analysis
               one surrogate did not fall within 40 to 120 percent, reanalysis was required.  For matrix
               spikes, internal limits of 40 to 120 percent were also used; no reanalyses however,
               were performed based on exceedences of these limits.

               Limits for continuing calibration checks were specified as ±10 percent in the QAPP;
               limits of ±25 percent were used.
               Both surrogate and matrix spike objectives for PCBs were specified in the QAPP to be
               70 to 130 percent. For surrogates, Battelle actually used internal limits of 40 to 120
               percent. If both surrogates exceeded these limits, re-extraction was performed. For
               matrix spikes, internal limits of 40 to 120 percent were also used; no reanalyses,
               however, were performed if these limits were exceeded.
               Limits for continuing calibration checks were specified as ±10 percent in the QAPP;
               limits of ±25 percent were used.
Metals Analysis

       •      Samples analyzed by XRF cannot be spiked. Therefore, no measure of sample
              accuracy was obtained for those metals previously identified as being analyzed by XRF.
              An SRM was analyzed, providing a means to measure method accuracy for eight of the
              nine metals determined by XRF (all but Ba).


SAMPLE HOLDING TIMES

Water Samples

       The QAPP specified holding times for water samples only. All water extractions and analyses

for the critical parameters were performed within these holding times (from the time of sample receipt).


Sediment Samples

       Though holding times for organics in sediment 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

       Initial triplicate analyses of the Indiana Harbor untreated sediments yielded concentrations for
several compounds above the calibration range. Dilutions were analyzed approximately two months

past the 40 day extract holding  time. No significant differences were observed between the original

analysis and the diluted analysis; removal efficiencies should not be affected.
                                             154

-------
       The Indiana Harbor treated sediment was re-extracted over two months past the 14 day
extraction holding time due to unacceptable surrogate recoveries. (Surrogate recoveries for the re-
extracted sample also did not meet acceptance criteria.) The re-extracted values were approximately
60 percent of the initial values.  Because of the minimal amounts of PAHs present after treatment
relative to the amount in the feed, the accuracy of the results for the treated sediment is less critical. If
the concentration of total PAHs were actually two to five times higher than the reported value; removal
efficiencies would still be greater than 95 percent.

CONCLUSIONS AND LIMITATIONS OF DATA
       Upon review of all sample data and associated  QC results, the data generated for the ZIMPRO
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.

       As discussed previously, the analytical laboratory used several specialized methods when
analyzing samples from the ZIMPRO 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 ZIMPRO treatability study may not be comparable to data generated by standard
EPA methods, it is comparable to data generated within the ARCS Program.
        The abridged version of the Data Verification Report prepared by the ARCS Program
        QA Officer follows.
                                             155

-------
  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 KelJy Johnson Drive
                   Las Vegas, Nevada 89119
                         Version 1.0
                  Work Assignment Manager
                    Brian A. Schumacher
              Exposure Assessment Research Division
           Environmental Monitoring Systems Laboratory
                   Las Vegas, Nevada 89193
           Environmental Monitoring Systems Laboratory
               Office of Research and Development
              U. S. Environmental Protection Agency
                   Las Vegas, Nevada 89193

-------
                              ABSTRACT

       Data submitted  by the Science  Applications International  Corporation
(SAIC) of Cincinnati, Ohio, have been  verified  for compliance of the QA/QC
requirements of the  Assessment and Remediation  of Contaminated  Sediment
(ARCS) program.  This data set includes results from bench-scale technology
demonstration tests  on  wet contaminated  sediments  using  four treatment
technologies, namely, B.E.S.T.  (extraction process), RETEC (low temperature
stripping),  ZIMPRO (wet  air  oxidation),  and  Soil Tech  (low  temperature
stripping).  The primary contaminants in these sediments were polychlorinated
biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs).  In addition,
metal contents and conventionals (% moisture, pH, % total volatile solids, oil and
grease, total organic carbon  (TOC), total cyanide, and total phosphorus) in these
sediments were also considered for this project. The objective of the bench-scale
technology  demonstration  study  was  to  evaluate  four  different  treatment
techniques for removing different organic contaminants from  sediments.  Both
treated and untreated sediment samples were analyzed to  determine treatment
efficiencies.

       A total of seven sediment samples from four different areas of concerns
(Buffalo River,  Ashtabula River,  Indiana  Harbor,  and  Saginaw  River)  uere
analyzed under the bench-scale technology demonstration project.  The samples
from these areas of concern  (AOCs) were collected by the Great Lakes National
Program Office (GLNPO)  in Chicago, IL,  and sample homogenization  was
performed by the U.  S. EPA in  Duluth, MN.  SAIC was primarily responsible
for the characterization of  the sediment samples prior  to testing and for the
residues created during the test.  The solid fraction analyses were performed by
SAIC's analytical subcontractor Battelle-Marine Sciences Laboratory of Sequim,
Washington, and Analytical  Resources Incorporated of Seattle, Washington.

       The submitted data sets represent analyses of untreated sediments, as well
as solid, water, and  oil residues obtained  by using different treatments. The
verified data set is divided into several parameter groups by sampled media. The
data verifications are presented in parameter groups that include:  metals, PCBs,
conventionals, and PAHs.

       The  results  of the verified data  are presented as a combination of an
evaluation  (or rating) number and  any appropriate data flags  that may  be
applicable.  The templates used to assess each individual analyte are attached in
case the data user  needs  the verified data  of a  single parameter  instead of a
parameter group.

-------
                                   INTRODUCTION
        The bench-scale technology demonstration  project was  undertaken to evaluate  the
 efficiencies of four techniques used for the removal of specific contaminants from wet sediments
 collected from designated  Great Lakes areas of concern.  Four  different sediment treatment
 techniques, namely, B.E.S.T (Basic Extraction Sludge Technology), RETEC, ZIMPRO, and Soil
 Tech were considered for evaluation. B.E.S.T. is a solvent extraction process, RETEC and Soil
 Tech are low temperature stripping  techniques, and ZIMPRO is a wet air oxidation technique.
 Wet sediments were collected by the Great Lakes National Program Office (GLNPO) from four
 Great Lakes sites, namely, the Buffalo River in New York,  the Saginaw River/Bay (referred to
 as Saginaw River throughout the  following discussions)  in  Michigan, the Grand  Calumet
 River/Indiana Harbor (referred to as Indiana Harbor throughout the following discussions) in
 Indiana, and the Ashtabula River in  Ohio. The four techniques were used to treat the sediment
 samples from these four sites.  The sediment samples represent  the sediment that  would be
 obtained for on-site treatment.

        The B.E.S.T. process is a patented solvent extraction technology that uses the inverse
 miscibility of triethylamine as a solvent.  At 65° F, triethylamine is completely soLt'.e in water
 and above this temperature, triethylamine and v,a:er are parJa^y r.iscib'e.  Th:s rrcr-erty of
 inverse miscibility is used  since cold triethylamine can simultaneously solvate oil and water.
 RETEC and the Soil Tech (low temperature stripping) are  techniques to separate volatile and
 semivolatile contaminants from soils, sediments,  sludges and filter cakes. The low temperature
 stripping  (LTS)  technology heats contaminated  media  to temperatures between 100 -200° F,
 evaporating off water and volatile organic contaminants. The resultant gas may be burned in
 an afterburner and condensed to a reduced volume for disposal or can be captured by carbon
 absorption beds.  For these treatability studies, only the processes that capture the driven off
 contaminants were considered.  The ZIMPRO  (wet air oxidation) process accomplishes  an
 aqueous phase oxidation of organic and  inorganic compounds at elevated temperatures and
 pressures.  The temperature range for this process is between 350 to 600° F (175 to 320° C).
 System  pressure of 300 psi to well over 300 psi  may be required.  In this process, air or pure
 oxygen  is used as an oxidizing agent.

       Samples for the technology demonstration projects were obtained by GLNPO (Chicago,
 Illinois) and were analyzed by Battelle-Marine Sciences Laboratory (Battelle-MSL, Sequim, WA)
 and by  Analytical Resources  Incorporated  (Seattle,  WA).    To evaluate the bench-scale
 technologies, the sample analyses were divided  into four parts:  (1) raw untreated  sediment
 samples, (2) treated sediments, (3) water residues, and (4) oil residues.  The amount of residues
available  for the analyses  depended upon the corresponding  sediment samples and on  the
individual technology used to treat those sediment samples.

      The analyses of sediment and residue parameters for these projects were divided into four
different categories: (1)  metals, including  Ag. As. Ba. Cd. Cr. Cu. Fe. Hg,  Mr.. Ni.  ?b. Se.
and Zn; (2) polychlorinated biph.en\is (PCBs;: (5; p-:'.;~._:^ar a::~a::c r.vcrocarrr-.s  ?AHsr.

-------
and (4) conventional*, including percent moisture, pH, percent total volatile, oil and grease, total
organic carbon  (TOC),  total cyanide,  and  total phosphorus.   Analyses  of metals and
convenuonals were performed on treated and  untreated sediment samples only for B.E.S.T.,
ZIKfPRO, 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:
    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  denned as, three times the standard deviation for 15 replicate analyses of a  sample with
an ar.alv.e concentration within a factor of 10 above the expected or required limit of detection.
I";!. -.c _:L ~i~ rr.eter detect:" !:m:ts are presented in the approved quality assurance project plan
:';: 5  -.'.~ '.- f.'.e r. ::.e Gre^:  Lixes Nr.:cr.il  Program Office in Chicago, IL.

-------
                                                                                     3

       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 meia's and  70 to 130 percent of the spiJcr.g
value for organics (PCBs ard  PAHs).

       Surrogate spike anahses were onlv required for each  sample in organic analyses. The
acceptable  limits  for the surrogate recover)'  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 ±1056 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.

-------
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 calculation^ 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
ccrr.'rina::?." c:"  a number value and a flag list.

       T'e r.-T.encal value for the rating of a given parameter was assigned based upon  the
success:'.: completion of each required  QA/QC sample or measurement.  The QA/QC samples
were broken down into four different sample groups, namely, accuracy, precision, blanks, and
spike recoveries.   A fifth category was included  for  QA/QC  measurements to address  the
successful completion of instrument calibrations (both initial and ongoing) and the determination
of method detection limits.  If the  laboratory successfully met the acceptance criteria of 50
percent or more of the parameters in a given QA/QC sample group, then the laboratory received
the full value for that category. For example, if 50 percent or  more of the reagent blanks  for
the metals in sediment analyses had measured values below the method detection limit, then
three points were awarded  for that category, assuming reagent blanks were the only blank
samples analyzed by the laboratory. The individual point values for each QA/QC sample type
or measurement and the minimum acceptance levels for each category are presented in Appendix
B.  The final numerical rating presented for each parameter  category  is the summation of the
point values from each of the five categories.

       Along with each numerical rating, a list of appropriate flags has been attached to the final
rating  value (Appendix C). The flag indicates where discrepancies exist between the laboratory
data and the acceptance limits of the required QA program.  Different flags are presented for
each category of QA sample (accuracy, precision,  blanks, and  spike  recoveries) and for the
QA/QC measurements (instrument calibration and detection limit determination). The flags have
a lener 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 f ::5  .-:.:::e discrepancies in the  use of accuracy checking samples,  such  as reference
- _•;:._.:  ;- __r:::;s   A :".;: v.:-.h a subscnp: of 1 indicates that the laboratory failed to meet

-------
the acceptance criteria. Using the example of the A, flag, this flag would then indicate a failure
of the laboratory to meet the QA/QC requirements for the use of reference materials in their
appraisal of accuracy.  A flag with the subscript 0 indicates that no information was received
(or no standards were available  in the case of accuracy) from the analytical laboratory, and
therefore, no points could be allotted towards the final calculated rating value for that particular
category.   It should  be noted that the 0 flag does not necessarily indicate that the analytical
laboratory did not perform the QA/QC analyses, only that no information was received from the
laboratory.

       The subscript 9 flag indicates that the sample  category or QA/QC measurement  is not
applicable to that particular parameter or parameter group (Appendix C).  For example, an S,
flag indicates that a matrix spike  for that given parameter or analyte is not applicable, such as
was the case for percent moisture. Where subscript 9 flags occur, an adjustment to the passing
and maximum scores (to be discussed) for a parameter group was made and will be reported in
the appropriate tables.

       A complete presentation of the QA/QC rating factors (point values by sample type) and
the various data flags and their subscripts are presented  in Appendices B and C, respectively.
A more complete discussion of the  rating  scale can  be found in the report  submitted to the
RA'M workgroup by Schumacher  and ConkJing entitled.  "User's  Guide  to  the  Quality
Assurance/Qualitv 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
lechr.olog'.es st-Cied based cr. r.e current ARCS QA  progra.r..  The rarr.gs of these variable

-------
classes  are  presented to provide the data user with a means  for comparing the ARCS QA
program-based verified  results with other data sets, using the same or similar parameters, that
were generated prior to and after the initiation of the formal ARCS QA program.

       Table 2 provides the data user with the full compliance and acceptable scores presented
for each parameter group based upon the current ARCS QA program.  The full compliance score
represents the numerical rating value if all required QA/QC samples and measurements were
performed by the analytical laboratory and successfully met all the QA/QC requirements of the
ARCS QA program. An acceptable score is lower than the full  compliance score and accounts
for laboratory error that can be reasonably expected during an analysis of multiple samples.
Any final rating value less than the acceptable score indicates that problems were identified in
the data that could adversely effect the quality of the data.  The acceptable score was set at 60
percent of the  full  compliance  score.  To determine the percentage of QA/QC samples and
measurements successfully analyzed for a given parameter versus the number analyzed following
the complete ARCS QA protocols, divide the numerical rating received by the full compliance
score.  An acceptable data set, in this case, has a rating of 60 percent or greater.

       In some cases, all  the QA/QC requirements may not be  applicable (e.g., matrix spikes
for percent solids are not applicable). If this is the case,  a flag  with  the subscript 9 was used,
and the  full compliance and acceptable scores were adj-r.ed 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-B. C0 D0 S0, then the data user could
potent!illy  add 14 points to the score since the blank ar.i!>ses. spike information, detection limit,

-------
and calibration (initial and ongoing) information was not available for verification. The resulting
data would then have a rating of 20.
      TABLE 1.  Verified Data Ratings Based on the Current ARCS QA Program
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
D.t.3. 1 •
12-QDo
0-A, B, 0, D, Po S,
0-A, B, 0, D, PO S,
6-A,CoD»S,
15-A, Ct
12-C. Po S,
14-Ao P0
14-Ao P0
17-B: D0
17-Do S,
ZIMPRO
12-CoDo
3-A, B, Q D, S,
0-A, B, Q D, P0 S,
3-A, BO Q D, S,
6-A, B, C6 D, S,
12-C6P0S,
14-AoPo
14-.Ao P0
14- A, B; DD
11-B2D0S. S;
Soil Tech
12-CoDo
0-A,B,CoD,P0S,
0-A, B, Co D, P0 S,
6-A, C0 D, S,
6-A, B, C4 D, S0
12-C6P0S,
11-AoPoSo
14-A.Po
14- A, B, Dc
17-D0S:
RETEC
12-CoD0
3-A, B, Q D, S,
3-A, B, C, D, S,
6-A, Q D, S,
9-A, DO Ct So
9-C.D0P0S,
8-Ao D, P, So
11-A.DoSo
11-A, B:D0S5
20.D0
Treated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Total
phosphorus
PCBs
PAHs
12-CoD0
0-A, B, Co D, P0 S,
0-A,B,CoD,P0S,
6-A, Co D, S,
15-A, C6
12-C«P0S,
14-Ao P0
14-Aj Po
14-B, D0 P,
14-D9 P, S-
12-QDo
0-A, B, Q, D, P0 S,
3-A,B,CoD,S,
3-A, BO Q D, S,
6-A, Bj C6 D, S,
12-C. P0 S,
14-Ao PO
14-Ao PO
ll-A^DoP,
17-Do S:
12-QDo
3-A, B, Q D, S,
0-A, B, Q, D, Po S,
6-A,CoD,S,
9-A, B, Ce D,
12-C6P0S,
14-Ao P0
14-Ao P0
14-B:D0P,
14-Do P, S:
12-QDo
3-A,B,CoD,S,
3-A,B,C,D,S9
6-A,C,D,S,
6- A, C, DO P, So
12-C, D, S,
11-AoDoPo
14-Ao D0
14-A, Bj DO
20-D0

-------
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
•*
**
»•
««
*s

**
««
**
• *
*•
• *

• «
*•
*«
•*
• *
**

**
** ** : *•*
• *
**
**
14-Bj D0 P0
ll-A^DoP, S,
<•
**
**
14-B, D0 P0
17-DoS,
9 *
«*
**
5-A, B, DO P0 S,
S6
17-Do P0
Oil residue
PCBs
PAHs
11-A.BjDoS,
11-AoBjDoS,
•
•
17-B, Do
14-B, DO S,

20
**
3-A, B, Q D, S,
6-A,CoD, S,
6-A, Q, D, S,
6- A, Co D, S,
12-A, C6 D0
9-.\, C. D, S, i
14- ^ D0
14-A^Do
9-A, C. D, S,
5-AoBjDoPoS,
S6
Il-A.D.P.S,

il-^DoP.S,
17-B; DO
*   No oil residue was produced by this treatment
**  Analyses were not conducted for this treatment

-------
TABLE 2. Full Compliance and Acceptable Scores Based on the Current ARCS QA Program
Variable Class
Metals in Treated Sediment
Metals in Untreated Sediment
% Moisture
pH
%TVS
Oil and grease
TOC
Total cyanide
Tc:ai phosphorus
Conductivity
Suspended Solids
Total Solids
PAHs
PCBs
Full Compliance
20
20
8
8
9
17
17
20
20
14
9
9
23
23
Acceptable
12
12
5
5
6
11
11
12
12
9
6
6
14
14
       Table 3 presents the verified data ratings for each variable class in the four technologies
based on their full potential value.  All data qualifying flags with the subscripts 5, 6, 9, or 0
have been removed.  The appropriate point values for each of the 5, 6, or 0 flags (Appendices
B and C) were added  to the final rating scores  for each parameter or parameter group.  In
contrast, the removal of the subscript 9 flags resulted in an adjustment to the full compliance and
acceptable scores, and npj in an addition to the calculated point scores since these analyses were
not applicable to the methodologies used by the laboratory (Table 2).

-------
                                                                     10
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
Untreated
Sediments
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cvanide
Tool phosphorus
PCBs
PAHs
B«t«o< 1 •
20
8
8
6
17
17
20
20
20- B,
20-S:
ZIMPRO
20
8
8
6
8-B;D, S;
17
20
:o
17-A. B-
14-B, S, S.
• I •
Soil Tech
20
8
8
6
11-B-D,
17
20
:o
17-A.B,
20-S:
RETEC
20
8
8
6
17
17
17-P,
:o
17-A.B,
23
Treated
Sediments
Metals
% Moisture
PH
%TVS
Oil and grease
TOC
Total cyanide
Total phosphorus
PCBs
PAHs
20
8
8
6
17
17
20
20
H-B, P,
17-P, S:
20
8
8
6
8-B, D, S,
17
20
20
14-A,B: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,
23

-------
                                                                                      11
TABLE 3. Verified Data Ratings Based on the Full Potential of the Data set
(continued)
Water
residue
Metals
% Moisture
pH
%TVS
Oil and grease
TOC
Total cvanide
Total phosphorus
i O^u:tr.;r.
.1 Susper.deJ Solids
Total Solids
PCBs
PAHs
»*
*>
••
**
*•
•*
**
•*
*«
K C
C*
20-B,
17-P,S:
**
•*
**
•*
•*
**
»*
«*
**
«*
**
20-B,
20-S,
Oil residue
PCBs
PAHs
14-A, B, S,
17-B, S,
«
•
•*
••
••
**
•*
•*
*«
•*
• •
**
•<
M-A.BjS,
23

20-B,
17-8,5,

20
8
8
6
17
17
20
20
14
6
6
20-B,
14-A, P, 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 bv  the data user.

-------
                                                                                    12
Data Verification Results for Bench-scale Technoloev 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
bo'uh 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
•A here ongoing  calibration information was not available. Detection limits  were satisfactory' for
r'ru: (o:'. ar.d grease, TOC, total cyanide, and total phosphorus) of the  se\er.  ccr.'. er.ticr.al

-------
                                                                                     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, chryscne, 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
:rei:ed sediments, the precision information was satisfactory for fluorene, phenar.threr.e.  ar.d

-------
                                                                                    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,
ar.d 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
:il.bra::on information  was  not available, and for TOC  and oii ar.d  grease, where cr.gr.rg

-------
                                                                                      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 ongo;~g calibraticr. uas  sa::sfa:'.or>  for  all  PCB
analyses in both treated and untreated sediments as -Aell 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 QA??.  CaJibra:::- I:.T.::S 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, conventional s, 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 ;-; rr.aiont\ of the cases studied, the accuracy objective v,as satisfactory for the metal
               .   ,                              r   J                   *
analyses  in  treated  and  untreated  sediments. Of the  thirteen metals  analyzed,  accuracy
information \vas 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
rhespherji.  In the remaining four conventional analyses, accuracy was not applicable. In both
sec.-;."•.£. :":.: of the sever. con\er.'uonals CSTVS, TOC, toial 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 9&TVS.  The
 precision information  was satisfactory  for % moisture, 9&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 125-1.  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.ri)amhracene) analyses in both
 treated a^d untreated sediments.   The accuracy  ob;ecti\e *aj net satisfactory  for ber.zoilo

-------
                                                                                     18

fluoranthene in treated  or  untreated  sediments nor  for  benzo(g,h,i)perylene  in  untreated
sediment.   Accuracy information  was  satisfactory for the PAH analyses  in water  and oil
residues.  In treated and untreated sediments and water residues, PAH analyses satisfied ARCS
specified  QA/QC  requirements for blank analyses.   In all cases of oil residues,  the blank
analyses exceeded the MDL.   Calibration limits for PAH analyses met the ARCS QA/QC
specifications for both treated and untreated sediments as well as water and oil residue analyses.
Detection limit information was  not available  for PAH  analyses in treated and  untreated
sediments nor for water and  oil residues. In untreated sediment and oil residues, the precision
information was satisfactory for all PAH analyses, except for acenaphthene and acenaphthene
in untreated sediment, and naphthalene in  oil residues, where no precision information  was
available.   In treated sediments, the precision  information was satisfactory for  naphthalene,
acenaphthylene acenaphthene, fluorene,  phenanthrene, and  anthracene, and was unsatisfactory
for the remaining PAH analyses. In water residues, no precision information was available for
any of the PAH analyses. The  matrix spike information was satisfactory for twelve of sixteen
PAH analyses in treated sediment, and for thirteen of the sixteen analyses in untreated sediment
and ten of the sixteen analyses in water and all  analyses in oil residues.  Surrogate recoveries
were unsatisfactory for PAHs in either sediment and oil residue analyses but were satisfactory
in water residue.
  RT~"~T~ T~ f
  C i C.
       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),
ciJibrr.ic- :",:"::"2::rr: *s:e  no: ava'lable.  Detection  limits information for metal analyses in
::;.:  . ; ;.r; _~.-:.y;_ ;=: -e.r.s -ere r:: a\ arable 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  \vas not applicable.   In both treated  and  ur.treated sediments and in water residue
analyses.  rcTVS,  oil and grease, TOC,  total cyanide,  ar.d total phosphorus satisfied QA/QC
requirements for blanks. Also, the blank information was satisfactory for  total solids ar.d 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
conventional,  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
hformation uas available for six PAHs  (naphthalene, acer.aphth\ler.e acenaphthene, fluorene,
chrysene. dibenzo(a.h)anthracene) analyses in  treated and untreated  sediment.  The accuracy
objective was  not  satisfactory  for  benzo(lc)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(lc)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 ar.ilytes in  untreated  sediment, for thirteen of the analytes in oil
resid-es.  ir.d :c: three of the ar.alvtes 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
Analytical Replicate
   3


   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

-------
   APPENDK 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

C0 = no information available
C,  = initial calibration problem
C,  = on-going calibration problem
Cs  = no information on initial calibration
C6  = 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
P, = 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
S> = no information available on surrogate spike recovery
S, = spike rece-.ery rot applicable

-------