ON-SITE ENGINEERING REPORT
OF THE SLURRY-PHASE
BIOLOGICAL REACTOR FOR
PILOT-SCALE TESTING ON
CONTAMINATED SOIL
by
IT Environmental Programs, Inc.
(formerly PEI Associates,'Inc.)
Cincinnati, Ohio 45246
Contract No. 68-C9-0036
Technical Project Officer
^ .
Richard P. Lauch
Water and Hazardous Waste Treatment Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45246
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
DISCLAIMER
This material has been funded wholly or in part by the United States Environ-
mental Protection Agency under Contract 68-C9-0036 to IT Environmental Programs,
Inc. It has been, subject to the Agency's review and it has been approved for publica-
tion as an EPA document. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
-------
FOREWORD
Today's rapidly developing and changing technologies and industrial products
and practices frequently carry with them the increased generation of materials that, if
improperly dealt with, can threaten both public health and the environment. The U.S.
Environmental Protection Agency (EPA) is charged by Congress with protecting the
Nation's land, air, and water resources. Under a mandate of national environmental
laws, the Agency strives to formulate and implement actions leading to a compatible
balance between human activities and the ability of natural systems to support and
nurture life. These laws direct the EPA to perform research to define our environmen-
tal problems, measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory (RREL) is responsible for planning,
implementing, and managing research, development, and demonstration programs to
provide an authoritative, defensible engineering basis in support of the policies,
programs, and regulations of the EPA with respect to drinking water, wastewater,
pesticides, toxic substances, solid and hazardous wastes, and Superfund-related
activities. This publication is one of the products of that research and provides a vital
communication link between the researcher and the user community.
This report describes the results of a pilot-scale test of slurry-phase bioremedia-
tion technology for treatment of creosote-contaminated soil. The data,will be used to
develop best demonstrated available technology (BOAT) standards for contaminated
soil in support of the land disposal restrictions under the 1984 Resource Conservation
and Recovery Act (RCRA) Hazardous and Solid Waste Amendments (HSWA).
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
in
-------
ABSTRACT
The EPA's Office of Solid Waste and Emergency Response (OSWER) is current-
ly developing land disposal restrictions (LDRs) for contaminated soil and debris
(CS&D). The Office of Research and Development, through its Risk Reduction Engi-
neering Laboratory (RREL), is providing support to OSWER by supplying technical
data on the performance of selected types of technologies for CS&D treatment.
Based on the technical data supplied by RREL and other data obtained from inde-
pendent sources, OSWER will prepare a regulatory package that establishes BOAT
standards for the level of CS&D treatment required prior to land disposal.
IT Environmental Programs (ITEP), is providing the U.S. Environmental
Protection Agency's (EPA's) Risk Reduction Engineering Laboratory (RREL) with tech-
nical data on the bioslurry treatment technology. The technology uses a slurry-phase
bioreactor in which the soil is mixed with water to form a slurry. Microorganisms and
nutrients are added to the slurry to enhance the biodegradation process, which con-
verts; organic wastes into relatively harmless byproducts of microbial metabolism and
inorganic salts.
A pilot-scale test of the slurry-phase bioremediation technology was performed
by ECOVA Corporation (ECOVA) at the U.S. EPA Test and Evaluation (T&E) facility
from May 8 through July 10, 1991 (12 weeks). The slurry-phase bioreactors were
tested on a creosote-contaminated soil from the Burlington Northern Superfund Site in
Brainerd, Minnesota. The results of the bench-scale study (performed by ECOVA
prior to the pilot-scale study) were used to optimize a pilot-scale bioreactor system
containing 64 liters of 30 percent slurry (soikwater, w/v). The pilot-scale phase utilized
an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders (9.3 x
107 per gram of soil), an inorganic nitrogen supplement in the form of NH4-N, and a
media broth containing potassium, phosphate, magnesium, calcium, and iron to
achieve an overall reduction. During the study, levels of soil-bound and liquid-phase
PAHs, total petroleum hydrocarbons (TPHs), nutrients, pH, dissolved oxygen,
temperature, toxicity, and microbial activity were monitored. The total percent
reduction of soil-bound PAHs achieved over 9 weeks of testing ranged from >44.2 to
>97.1 percent. The total percent reduction of PAHs achieved over 12 weeks ranged
from >74.2 to >90.6 percent. This report presents detailed information concerning
the operation, sampling and analysis, and results achieved with the pilot-scale slurry-
phase bioremediation system.
This report was submitted in fulfillment of Contract No. 68rC9-0036 by IT Envi-
ronmental Programs, Inc., under the sponsorship of the U.S. Environmental Protection
Agency. This report covers a period from 1 October 1989 to 31 March 1992, and
work was completed as of 31 March 1992.
IV
-------
CONTENTS
Page
Disclaimer jj
Foreword iii
Abstract iv
Figures viii
Tables x
List of Acronyms xv
Acknowledgment xvii
1. Introduction 1-1
2. Contaminated Soil Under Evaluation 2-1
3. Treatment System Under Evaluation 3-1
3.1 Description of treatment system 3-1
3.2 Bench-scale testing of Bioslurry reactor 3-4
3.3 Pilot-scale testing of Bioslurry reactors 3-5
4. Sampling and Analysis Activities 4-1
4.1 Sampling methods 4-1
4.2 Analytical procedures 4-21
4.3 Deviations from the Sampling and Analysis Plan 4-26
4.4 Safety 4-26
5. Design and Operating Data Collected 5-1
5.1 Material characterization 5-1
5.2 Operating data collected during treatment test 5-5
5.3 Evaluation of pilot-scale operations 5-27
-------
CONTENTS (continued)
Page
6. Analytical Results 6-1
6.1 Premilling and postmilling soil samples 6-9
6.2 Results of pretreatment and posttreatment soil samples 6-9
6.3 Pretreatment and posttreatment liquid samples 6-15
6.4 Bioreactor monitoring samples 6-20
6.5 Air samples 6-33
7. Quality Assurance/Quality Control Measures 7-1
7.1 Pretreatment and posttreatment samples 7-1
7.2 Air samples 7-27
7.3 Bioreactor monitoring samples 7-30
8. . Correspondence 8-1
Appendices
(The Appendices are contained in a separate volume and can be obtained,
for a limited time, from the Technical Project Monitor).
A. Sections of the Bioslurry Sampling and Analysis Plan Pertinent
to the Pilot-Scale Study A-1
B. Outline for Writing On-Site Engineering Report B-1
C. Characterization Data for Burlington Northern Soil C-1
D. Bench-Scale Process Optimization for Slurry-Phase Bioremediation
of PAHs D-1
E. Project Health and Safety Plan: Bioslurry Treatment Testing at
the T&E Facility E-1
F. Raw Data: Post Milling Total Solids F-1
G. Raw Data: Daily Monitoring of the Reactors G-1
H. Graphic Representation of Monitoring Data on Each Reactor H-1
I. Raw Data: Particle Size and Total Volatile Solids 1-1
J. Graphic Representation of Percent Total Solids Data for Pilot-
Scale Reactors j-1
K. Raw Data: Percent Dry Weight Removed From Each Port on Each
Reactor From Weeks T0 Through T10 K-1
L. Descriptions of Morphologically Distinct Total Heterotroph Colony Types L-1
M. Graphic Representation of PMS and PMSS Data for Phenanthrene and
Pyrene M-1
vi
-------
CONTENTS (continued)
Page
N. Analytical Data Provided by the ITAS Laboratory N-1
O. Corrective Action Recommendation Forms Issued for Systems and
Laboratory Audits O-1
VII
-------
FIGURES
Number page
2-1 Burlington Northern Superfund Site, Brainerd, Minnesota 2-2
2-2 Waste Pile Sampling Locations 2-5
2-3 Grain-Size Distribution for Burlington Northern Soil 2-6
3-1 EIMCO Biolift™ Reactor 3.3
3-2 Containment Area Layout 3-7
3-3 Screening, Mixing, and Milling Flow Diagram 3-8
4-1 Pilot-Scale Bioslurry Treatment Sampling Locations 4-5
5-1 Particle Sizing 5-8
5-2 Pilot-Scale Data on Total Volatile Solids on Various Particle-
Size Fractions 5.10
5-3 Percent Total Weight and Percent TVS in Each Sieve Fractions
at Week T8 5-12
5-4 Total Solids Data for All Pilot-Scale Reactors 5-14
5-5 Total Heterotrophs 5-20
5-6 Total Heterotrophs, Phenanthrene Degraders, and Pyrene
Degraders 5-22
5-7 Relative Effective Concentration Shows Decreasing Toxicity
and Increasing Benignity 5-26
VIII
-------
FIGURES (continued)
Number Page
6-1 Total PAH Soil Residue Levels 6-25
6-2 Two- and Three-Ring PAH Soil Residue Levels 6-26
6-3 Four- and Six-Ring PAH Soil Residual Levels 6-27
6-4 Two- and Three-Ring Individual Mean PAH Levels 6-29
6-5 Four- to Six-Ring Individual Mean PAH Levels 6-30
6-6 Standard Deviation of the Mean Concentration for 2- and
3-Ring PAH at Each Sample Interval During Slurry-
Phase Treatment 6-31
6-7 Standard Deviation of the Mean for 4- to 6-Ring PAHs at
Each Sampling Interval 6-32
6-8 THC Emission Data During the First 5 Days of Operation 6-37
IX
-------
TABLES
Number page
1-1 Key Personnel Involved in the Pilot-Scale Bioslurry Test 1-4
2-1 Sampling Depths for Burlington Northern Characterization Samples 2-4
2-2 Concentrations of Semivolatile Organics in Burlington Northern
Characterization Samples 2-7
2-3 Key Personnel Involved in the Excavation of Treatment
Soil From the Burlington Northern Superfund Site 2-9
2-4 Key Personnel Involved in the Repackaging of Drums for
the CS&D Treatment Studies 2-9
3-1 Inoculum and Surfactant Amendments 3-13
4-1 Reactor Monitoring Schedule 4-2
4-2 Sampling Frequency and Analyses for Bioslurry Pilot Demonstration 4-3
4-3 CS&D List by Constituent Type 4-6
4-4 Critical Contaminants of Interest for the Burlington Northern
Superfund Site 4-18
4-5 Sample Containers, Preservatives, and Maximum Holding Times 4-22
4-6 Soil Sample Preparation and Analytical Methods 4-24
5-1 Chemical Analyses 5-2
5-2 Enumeration of Bacteria Capable of Utilizing PAH as Sole Carbon
Source 5.4
-------
TABLES (continued)
Number page
5-3 Salicylate-Utilizing Bacteria With PAH Cooxidation Capability 5-4
5-4 Particle Size Fractions 5.7
5-5 Percent Total Solids Data 5.13
5-6 Fraction of Total Sample Removed From the Bottom Reactor
Port 5_15
5-7 Inorganic Nutrient Levels 5-17
5-8 Beginning and Ending Nutrient Levels 5-18
5-9 Total Heterotrophs 5_-|g
5-10 Summary of Total Heterotrophs and Specific PAH Degraders 5-21
5-11 PMS Data for Phenanthrene Degraders 5-24
5-12 PMS Data for Pyrene Degraders 5-24
5-13 PMSS Data for Phenanthrene Degraders 5-25
5-14 PMSS Data for Pyrene Degraders 5-25
5-15 Relative Effective Concentration of Microtox Analysis 5-27
5-16 Chronology of Mechanical Problems 5-29
6-1 Sample Tracking Information 6-2
6-2 ,CS&D Constituents Detected in the Characterization Analysis
of Premilling and Postmilling Samples 6-10
6-3 Concentrations of Critical Semivolatile Organic Contaminants
in Premilling and Postmilling Samples 6-11
6-4 Concentrations of Critical Semivolatile Organic Contaminants
in Pretreatment Soil Samples (Week T0) 6-12
XI
-------
TABLES (continued)
Number Page
6-5 Concentrations of Critical Semivolatile Organic Contaminants
in Posttreatment Soil Samples (Week Tg) 6-13
6-6 Concentrations of Critical Semivolatile Organic Contaminants
in Posttreatment Soil Samples (Week T12) 6-14
6-7 Percent Reduction of Critical Semivolatile Organic Contaminants
in Soil by Treatment with Bioslurry Reactors 6-16
6-8 Concentrations of Critical Semivolatile Organic Contaminants
in Pretreatment Liquid Samples (Week T0) 6-17
6-9 Concentrations of Critical Semivolatile Organic Contaminants
in Posttreatment Liquid Samples (Week T9) 6-18
6-10 Concentrations of Critical Semivolatile Organic Contaminants
in Posttreatment Liquid Samples (Week T12) 6-19
6-11 Concentrations of TPH in Soil 6-21
6-12 Total, 2- and 3-Ring, and 4- and 6- Ring PAH Levels 6-22
6-13 Total, 2-"and 3-Ring, and 4- and 6- Ring PAH Degradation Rates 6-23
6-14 Specific PAH Concentrations (Means and Std. Dev.) 6-28
6-15 Concentrations of TPH in Soil 6-34
6-16 THC Results-Exhaust Line 6-35
6-17 Semivolatile Organic Sample ID and Location 6-39
6-18 Hazardous Substance List of Semivolatiie Organics and
Their Detection Limits 6-40
6-19 Results of Semivolatile Organic Emissions Data 6-41
6-20 Volatile Organic Sample ID and Sampling Locations 6-42
XII
-------
TABLES (continued)
Number Page
6-21 Volatile Organics List and Approximate Detection Limits 6-44
6-22 Volatile Organic Emissions Data 6-45
7-1 Results From the Instrument Detection Limit (IDL) Study for
Semivolatile Organics on the Extrel 400 7-3
7-2 Method Detection Limits (MDLs) for Critical Semivolatile
Organic Contaminants by Method 3550/8270 (Treated Soil) 7-6
7-3 Method Detection Limits (MDLs) for Critical Semivolatile
Organic Contaminants by Method 3520/8270 (Treated
Liquid) 7-7
7-4 Practical Quantitation Limits (PQLs) for Critical Semivolatile
Organic Contaminants by Method 3550/8270 for Soil Matrix
and 3520/8270 for Liquid Matrix 7-8
7-5 Matrix Spike Data for Critical Semivolatile Contaminants,
Untreated Matrix 7-10
7-6 Matrix Spike Data for Critical Semivolatile Contaminants,
Treated Soil (Week T9) 7-11
7-7 Matrix Spike Data for Critical Semivolatile Contaminants,
Treated Soil (Week T12) 7-12
7-8 Matrix Spike Data for Critical Semivolatile Contaminants,
Treated Liquid (Week Tg) . 7-13
7-9 Matrix Spike Data for Critical Semivolatiie Contaminants,
treated Liquid (Week T12) 7-14
7-10 Precision Data for Critical Semivolatile Organic Contaminants
(Soil, Week T0, Week T9, and Week T12) 7-17
7-11 Precision Data for Critical Semivolatile Organic Contaminants
(Liquid, Week T0, Week T9, and Week T12) 7-18
XIII
-------
ACKNOWLEDGMENT
This report was prepared for the U.S. Environmental Protection Agency, Office
of Research and Development, Risk Reduction Engineering Laboratory, Cincinnati,
Ohio, by IT Environmental Programs (ITEP) under Contract No. 68-C9-0036. Mr.
Richard P. Lauch was the EPA Technical Project Monitor. The principal authors of this
report were Mr. Majid Dosani of ITEP and Dr. Alan Jones of ECOVA Corporation.
Other personnel contributing to the project were Ms. Judy Hessling (ITEP), Mr.
Michael Smith (ITEP), Mr. Ernie Grossman (U.S. EPA), Dr. William Mahaffey (ECOVA),
Ms. Madonna Brinkman (ECOVA), and Mr. Christopher Krauskopf (ECOVA).
XVII
-------
ACRONYMS (continued)
RPD Relative percent difference
RREL Risk Reduction Engineering Laboratory
SAP Sampling and Analysis Plan
SOP Standard Operating Procedure
TCL Target Compound List
TCLP Toxicity characteristic leaching procedure
T&E Test and evaluation (facility)
THC Total hydrocarbons
TKL Total Kjeldahl nitrogen
TOG Total organic carbon
TOX Total organic halogens
TPH Total petroleum hydrocarbons
TRPH Total recoverable petroleum hydrocarbons (by infrared spectroscopy)
TS Total solids
TSS Total suspended solids
TVS • Total volatile solids
TVSS Total volatile suspended solids
WCAP Waste Characteristic Approval Plan
XVI
-------
TABLES (continued)
Number Page
7-12 Blank Data From Analysis of Bioslurry Samples 7-20
7-13 Surrogate Recoveries in Semivolatile Organic Samples 7-21
7-14 Surrogate Recoveries in Volatile Organic Samples 7-23
7-15 Standard Reference Solution Results From Analysis for Metals
and Inorganics 7-25
7-16 Example Method 25A THC Calibration Data 7-29
7-17 Semivolatile Surrogate Recoveries on Sample and Field Blank
Tubes 7-29
7-18 Acceptable Surrogate Recovery Limits 7-30
7-19 Volatile Canister Blank Results 7-31
7-20 Example Surrogate Volatile Organic Recoveries 7-32
7-21 Sample Group Numbers Assigned by ECOVA Labs 7-32
7-22 Method Used to Monitor Reactors During Pilot-Scale Phase 7-33
7-23 Current Limits of Detection (LOD) of Individual PAHs at
the ECOVA Laboratories 7.35
8-1 Critical Activities and Correspondence 8-1
XIV
-------
LIST OF ACRONYMS
BOAT Best demonstrated available technology
BN Burlington Northern
BNA Base neutral and acids
CERCLA Comprehensive Environmental Response, Compensation and Liability
Act
CPU Colony-forming unit
CLP Contract Laboratory Program
CS&D Contaminated soil and debris
CMC Critical micelle concentration
CSTR Continuously stirred tank reactor
EPA Environmental Protection Agency
GC-MS Gas chromatography - mass spectrometry
GPC Gel permeation chromatography
HSWA Hazardous and Solid Waste Amendments
IDL Instrument detection limit
IT IT Corporation
ITAS IT Analytical Services
ITEP IT Environmental Programs
LDR Land disposal restrictions
LOD Limits of detection
LTTD Low-temperature thermal desorption
MDL Method detection limit
MS/MSD Matrix spike/matrix spike duplicate
O&G Oil and grease
OER Onsite Engineering Report
ORD Office of Research and Development
OSW Office of Solid Waste
OSWER Office of Solid Waste and Emergency Response
PAH Polynuciear aromatic hydrocarbon
PCA Plate count agar
PCB Polychlorinated biphenyl
PMS PAH mineral salts (plates)
PMSS PMS (plates) with 0.05% salicylate
POL Practical quantitation limit
QA/QC Quality assurance/quality control
RCRA Resource Conservation and Recovery Act
ROD Record of Decision
xv
-------
SECTION 1
INTRODUCTION
The 1984 Hazardous and Solid Waste Amendments (HSWA) to the Resource
Conservation and Recovery Act (RCRA) prohibit the continued land disposal of un-
treated hazardous wastes beyond specified dates. The statute requires the U.S.
Environmental Protection Agency (EPA) to set "levels or methods of treatment, if any,
which substantially diminish the toxicity of the waste or substantially reduce the likeli-
hood of migration of hazardous constituents from the waste so that short-term and
long-term threats to human health and the environment are minimized." The legislation
sets forth a series of deadlines beyond which further disposal of untreated wastes is
prohibited. Land disposal restrictions (LDRs) have been set for solvents and dioxins;
the California List; and first-, second-, and third-third hazardous wastes. These LDRs
establish concentration- or technology-based treatment standards that must be met
prior to land disposal of RCRA-regulated hazardous wastes. These treatment
standards are also applicable to soil and debris contaminated with these wastes at
uncontrolled hazardous waste sites under the Comprehensive Environmental
Response, Compensation and Liability Act: (CERCLA or Superfund) and at RCRA
corrective-action and closure sites.
Contaminated soil and debris (CS&D) pose a special problem because of their
complexity, and high degree of variability. Therefore, the EPA has determined the need
for a detailed evaluation of treatment technologies for CS&D to develop separate LDR
standards applicable to their disposal. These standards are being developed through
the evaluation of best demonstrated available technologies (BDATs). Once these
LDRs are promulgated, only CS&D wastes that meet the LDR standards will be per-
mitted to be disposed of in land disposal units unless a treatability variance is issued.
1-1
-------
The EPA's Office of Solid Waste and Emergency Response (OSWER) is cur-
rently developing LDRs for CS&D. The Office of Research and Development (ORD),
through its Risk Reduction Engineering Laboratory (RREL) in Cincinnati, Ohio, is sup- •
porting OSWER by providing technical data on the performance of various technolo-
gies used to treat CS&D. Based on the technical-data provided by RREL, along with
other data obtained from independent sources, OSWER will prepare a regulatory pack-
age that establishes BOAT standards for the level of CS&D treatment required prior to
land disposal.
In support of the CS&D program, RREL is developing data on biological treat-
ment of contaminated soil. Biodegradation involves the biooxidation of organic com-
pounds by microorganisms. The ultimate goal of biodegradation is to convert organic
wastes into biomass and relatively harmless byproducts of microbial metabolism such
as carbon dioxide (COg), methane (CH4), and inorganic salts. Several biodegradation
technologies are available for the remediation of soils and sludges contaminated with
organic compounds. These technologies include composting, in situ biodegradation,
solid-phase treatment, and slurry-phase treatment. In slurry-phase bioremediation
(bioslurry), contaminated soil is excavated and treated in a bioreactor in which the soil
is mixed with water to form a slurry. If necessary, nutrients, microorganisms, or
surfactants are added to the slurry to enhance the biodegradation process.
IT Environmental Programs (ITEP), in conjunction with RREL, evaluated the per-
formance of pilot-scale bioslurry treatment on creosote-contaminated soil from the
Burlington Northern (BN) Superfund site in Brainerd; Minnesota. ECOVA Corporation,
performed the testing on the contaminated soil at the U.S. EPA Test and Evaluation
(T&E) facility in Cincinnati, Ohio. ~:Routine monitoring and analysis were performed by-;.
ECOVA either on .site or at theinlaboratory-in Redmond, Washington. All critical mea-.
surements were performed by IT Analytical Services (ITAS) in Cincinnati, Ohio.
This onsite engineering report (OER) describes the operation, sampling and
analysis, and results achieved during the pilot-scale bioslurry treatment conducted on
the contaminated soil at the T&E facility. The sampling procedures followed during the
treatment study are outlined in the Sampling and Analysis Plan (SAP), which is
-------
included as Appendix A. Any deviations from the original SAP are noted in this OER.
The information presented in this OER will assist the CS&D group in evaluating the
bioslurry treatment technology.
The.OER was prepared in accordance with the guidelines established by the
Office of Solid Waste (OSW) in their "Quality Assurance Project Plan for Characteriza-
tion Sampling and Treatment Tests Conducted for the Contaminated Soil and Debris
(CS&D) Program" (Appendix B). Sections 2 and 3 of this report describe the con-
taminated soil and the treatment technology under evaluation, respectively. Section 4
addresses the sampling and analysis activities, and Section 5 addresses treatment
technology design and operating data collection. Section 6 presents data on all analy-
ses performed on the treatment test samples. Section 7 discusses the quality assur-
ance/quality control (QA/QC) measures associated with the analytical data. Any cor-
respondence critical to the performance or evaluation of the treatment test is
presented in Section 8.
The pilot-scale bioslurry test was performed from May 8 through July 10, 1991,
at the T&E facility. Representatives of the U.S. EPA, ITEP, ECOVA, and
S-Cubed (technical systems auditor) were present to observe the treatment technology
.in operation. Key personnel in attendance during the test or involved with the sam-
pling or analytical activities are listed in Table 1-1.
1-3
-------
TABLE 1-1. KEY PERSONNEL INVOLVED IN THE
PILOT-SCALE BIOSLURRY TEST
Treatment Test Facility:
Test Facility Coordinator:
Date of Treatment Test:
EPA Personnel:
Contract Personnel:
OER Preparation:
Laboratory Manager:
U.S. EPA Test and Evaluation Facility
1600 Gest Street
Cincinnati, Ohio 45204
Mr. Frank Evans, Director
U.S. EPA T&E Facility
1600 Gest Street
Cincinnati, Ohio 45204
(513) 684-2621
May 8 through July 31, 1991
Richard P. Lauch
Technical Project Monitor
Judy Hessling, ITEP, CS&D Project Manager
Majid Dosarii, ITEP, Bioslurry Work Assignment
Manager
Michael Smith, ITEP, Soil Sampling Coordinator
Dr. Alan Jones, ECOVA, Project Manager
Dr. William Mahaffey, ECOVA, Technical Principal
Madonna Brinkmann, ECOVA, Project Scientist
Christopher Krauskopf, ECOVA, Project Scientist
Burt Blackburn, S-Cubed, Technical Systems Auditor
Greg Swanson, S-Cubed,' Technical Systems Auditor
Majid Dosani, ITEP
Alan Jones, ECOVA
Richard Gurley
IT Analytical Services
11499 Chester Road
Cincinnati, Ohio 45246
1-4
-------
SECTION 2
CONTAMINATED SOIL UNDER EVALUATION
The BN Super-fund Site is located on the border between Baxter and Brainerd,
Minnesota. State Highway 371 is approximately 800 to 1000 feet north of the site, and
the Mississippi River flows about 3000 feet east of the plant. Residential areas are
located within 1000 feet to the northeast and southeast of the site. Burlington North-
ern has owned and operated the railroad tie treatment plant on this site since 1907.
The plant uses creosote mixtures to preserve railroad ties. During the 1950s, BN
began blending creosote with No. 5 fuel oil in a 1:1 ratio. At some undetermined time,
this mixture was changed to creosote and coal tar, which are currently being used at
the plant in the ratio of 7:3.
Historically, wastewater generated from the wood-treating process was sent to
shallow, unlined surface impoundments for disposal. The first impoundment, which
covered an area, of approximately 60,000 ft2, eventually became filled with sludge; and
in the 1930s, it was buried under clean fill. A second impoundment was used until
October 1982, when a wastewater pretreatment plant was completed. The discharge
of wastewater to the disposal ponds generated a sludge that contaminated both the '
soil and groundwater beneath both ponds. As a result, the site was included on the
proposed National-Priorities List issued by the U.S. EPA in December 1982. Figure
2-1 is a map of the BN Superfund Site.
All wastewater and creosote have been removed from the second impound-
ment. The wastewater was transported to BN's Northtown, Minnesota, wastewater
treatment plant for pretreatment and subsequent discharge to the sanitary sewer.
Creosote was pumped from the pond for reuse or recycling at the BN plant. The
2-1
-------
i
m
o
0)
•»->
(O
I
(0
Si
X O)
e *
JE o c
(0 Z ®
^ O)
m c <
Q.
(O
0)
r
o
I
O)
3
m
I
&
u_
C3) o
^ !S
II
0) O
"o E
•o Sz
® «.
Is
o
2-2.
-------
removal of wastewater and creosote left behind a heavy sludge layer approximately
6 inches to 1 foot thick in localized areas of the impoundment.
The Record of Decision (ROD) for the BN Superfund Site was signed by the Re-
gional Administrator on June 4, 1986. The recommended alternative for treatment of
the contaminated sludges and soils was onsite land treatment. Land treatment is a
managed technology that involves the controlled application of a waste on a soil sur-
face and the incorporation of the waste into the upper soil zone. Aerobic microorga-
nisms in the top layer of the soil then break down and transform the organic contami-
nants into harmless byproducts and aid in the immobilization of other organic and
inorganic contaminants. The annual waste application rate is expected to be less than
6 inches/year. At this rate, the last waste application should be in the fifth year after
the system startup, which occurred in 1986.
The ROD specifies that only visibly contaminated soils and sludges will be exca-
vated from the site for onsite treatment. Visibly contaminated soil was characterized
as being heavily stained, dark brown to black in color, visibly oily, and usually having a
pronounced creosote odor. The second impoundment from which wastewater and
creosote were removed contained an estimated 6000 yd3 of contaminated soil and
1000 yd3 of contaminated sludge. The first impoundment, which was closed in the
1930s, contained an additional 2500 yd3 of contaminated soil. Together, the two im- .
poundments contained an estimated 9500 yd3 of contaminated material.
Initial sampling showed the primary constituents of concern to be polynuclear
aromatic hydrocarbons (PAHs), heterocyclic compounds, and phenols. Concentra-
tions of these contaminants ranged from 34,388 mg/kg total PAHs and heterocyclics
t1
and 16 mg/kg total phenols in the old impoundment to 134,044 mg/kg total PAHs and
heterocyclics and 130 mg/kg total phenols in the second impoundment. Groundwater
monitoring results indicated that the groundwater contamination is restricted to a rela-
tively small area downgradient from the site. All contaminated soils have been exca-
vated from the lagoon areas and are currently stored in a waste pile on site, which is
just east of the existing lagoon area. Each spring a new layer of waste from the
2-3
-------
covered waste stockpile is placed on the adjacent landfarm designed for biological
degradation of organic contaminants.
On November 7, 1989, ITEP sent a sampling team to the BN site to character-
ize the stockpiled soil and to find the hot spot for PAHs. Six soil samples were taken
from the waste pile at the locations shown in Figure 2-2. The sampling depths for
these locations are listed in Table 2-1. The soil under investigation is a fine, sandy
soil, of which 75 percent has a grain size between 0.1 and 0.4 mm in diameter. Figure
2-3 presents a graphical display of grain-size distribution. The soil has a, relatively low
moisture content (10 percent) and a heat value below 500 Btu/lb.. A review of the
analytical data indicated that Sampling Point 4 contains the highest levels of PAHs
detected. Table 2-2 summarizes the concentrations of PAHs and other semivolatile
organics detected in the soil. Appendix C contains complete characterization data for
Burlington Northern soil.
TABLE 2-1. SAMPLING DEPTHS FOR
BURLINGTON NORTHERN
CHARACTERIZATION SAMPLES
Sampl
0
ing point
1
2
3
4
5
6
Depth of sample,
in.
6-24
0-19
21-48
25-48
12-40
0-24
On November 20, 1989, ITEP returned to the site to excavate soil for the CS&D
treatment studies. Although Sampling Point 4 showed the highest levels of PAHs,
Sampling Point 5 was chosen for the excavation site. The Site Coordinator, James
Brown, believed that Sampling Point 5 posed the least threat with regard to liner
damage by the backhoe and offered more area for maneuverability of the backhoe.
2-4
-------
Tracks
Access Road
Temporary Waste
Stockpile
Excavation
Area
(10ftx15tt)
A
N
Figure 2-2. Waste pile sampling locations.
2-5
-------
1
u_
.
-o'
d
CO
>
2
O
±±
CO
m
in
o
2
o
o
CD
c
LU
i
CB
o
O
r
^
/
~» r
X*"
-» e
i***'
~» r
.
•*"**
-> <•
-
•
-> f
^
-> f
***
-* e.
-* e
-•
•5 C
1
t
3 e
VJ
C>
..
rss
^~ O
0 «
^^ E
m £
0
Aq
2-6
-------
TABLE 2-2. CONCENTRATIONS OF SEMIVOLATILE ORGANICS IN BURLINGTON
NORTHERN CHARACTERIZATION SAMPLES
(mg/kg)
Sampl itig
Analyte
Semi volatile organics
Naphthalene
2-Methyl naphthalene
Acenaphthylene
Acenaphthene
Dibenzofuran
Fl uorene
Phenanthrene
Anthracene
Fl uoranthene
Pyrene
Benzo ( a) anthracene
Chrysene
Benzo(b)fl uoranthene
Benzo(a)pyrene
Indleno(l,2,3-cd)pyrene
Dibenzo(a,h) anthracene
Benzo (g , h , i ) peryl ene
Phenol
2-Methyl phenol
4-Methyl phenol
2 , 4-Dimethyl phenol
Total semi volatile
constituents
1
110-
56
11 Ja
120
91
150
420
880
350
"410
130
340
150
82
41 .
19 J
32 J
ND
ND
ND
ND
3392
2
170
81
14 J
130
90
120
360
120
350
330
91
120
120
70
35 J
18 J
34 J
ND
ND
ND
ND
2253
3
860
260
16 J
370
250
360
1000
340
570
370
110
120
77
41
16 J
7 J
12 J
ND
ND
ND
ND
4779
point
4
5200
1200
18 J
1900
1100
1500
4000
560
1800
1400
350
350
120
84
28 J
ND
10 J
28 J
24 J
58
39 J
19769
5
1200
310
41
320
270
380
1000
540
580
370
150
160
120
7 J
NDb
6 J
22 J
ND
3 J
ND
6 J
•5485
6
2300
590
70
600
480
630
1800
840
1000
760
330
350
300
150
64
16 J ,
38 J
4 J
8 J
10 J
18 J
10358
Estimated value for constituent detected below the established
detection limit of 40 mg/kg.
ND = Compound not detected above established detection limit of 40 mg/kg.
2-7
-------
A 10-by-15-ft cut was made in the liner to the north side of Sampling Point 5,
and the liner was pulled back to the west. The north side of the cut was excavated to
a width of about 5 ft, and the upper 2 ft was pulled back. Soil was then removed to a
depth of 2 to 6 ft and placed in 55-gallon drums. Seven drums were filled by the
backhoe, and three drums were filled by hand from the excess backhoed material.
The drums were then sealed with lids, labeled, covered, and stored on site. Table 2-3
lists the key personnel present at the site during the excavation of the contaminated
soil into the drums.
The drummed soil from the original excavation was stored at the BN site for one
year. On October 15, 1990, ITEP returned to the site to repackage two drums and
collect four pails of contaminated soil for the CS&D treatment studies. The drums
were repackaged to ensure that samples used for the treatment tests were thoroughly
homogenized.
The sampling crew emptied the entire contents of two drums of soil and half of
a third drum onto a plastic liner. Over the course of the year, most of the heavy
sludge from the site had settled to the bottom of the drums. Shovels were used to
mix (homogenize) the soil manually. When the soil was thoroughly homogenized
(based on the evenness in soil color throughout the pile), the crew began to fill two
drums and four pails of soil. Leftover soil in the pile was placed back in the third
drum, which was then returned to the covered waste stockpile at the BN site. One
drum was shipped to the T&E facility for pilot-scale bioslurry tests, and three pails
were shipped to ECOVA for bench-scale bioslurry tests. The other drum and pail
9
were shipped to IT-Knoxville for low-temperature thermal desorption (LTTD) treatment
tests. Key personnel Involved with repackaging^and shipment of the drums are listed,
in Table 2-4.
2-8
-------
TABLE 2-3. KEY PERSONNEL INVOLVED IN THE EXCAVATION OF
TREATMENT SOIL FROM THE BURLINGTON NORTHERN SUPERFUND SITE
Excavation Site Facility: Burlington Northern Superfund Site
West City Limits
Brainerd, Minnesota 56401
Excavation Location: Temporary Waste Stockpile
Sampling Point 5 (as shown in Figure 2-2)
Site Remediation Coordinator: James Brown
Remediation Technologies, Inc.
602 Ninth Avenue
Brainerd, Minnesota 56401
(218) 829-9756
Date of Excavation: November 20, 1989
Contract Personnel: Philip Utrecht, ITEP, Sampling Team Leader
Steve Giti-Pour, ITEP, Sampling Team Member
Wade Johnson, Dust Coating, Inc., Backhoe
Operator
TABLE 2-4. KEY PERSONNEL INVOLVED IN THE
REPACKAGING OF DRUMS FOR THE CS&D TREATMENT STUDIES
Excavation Site Facility: Burlington Northern Superfund Site
West City Limits
Brainerd, Minnesota 56401
Repackaging Location: Concrete pad adjacent to site's work shed
Site Remediation Coordinator: James Brown
Remediation Technologies, Inc.
602 Ninth Avenue
Brainerd, Minnesota 56401
(218) 829-9756
Date of Repackaging: October 15, 1990
Contract Personnel: Philip Utrecht, ITEP, Sampling Team Leader
Michael Smith, ITEP, Sampling Team Member
Transport Company: Hyman Freightways, Baxter, Minnesota
2-9
-------
-------
SECTION 3
TREATMENT SYSTEM UNDER EVALUATION
3.1 Description of Treatment System
Since 1986, landfarming has been conducted on contaminated soil and sludges
at the Burlington Northern site. Although this work has resulted in significant reduc-
tions in 2- and 3-ring PAHs, the degradation of 4-ring and larger PAHs and benzene-
extractable hydrocarbons has been less successful.
Biodegradation rates of 4-ring and larger PAHs could be improved appreciably
through the use of slurry-phase biological treatment.- In this process, the soil is sus-
pended to obtain a pumpabie slurry, which is fed to a large-capacity, continuously
stirred tank reactor (CSTR). The reactor is then supplemented with oxygen, nutrients,
and when necessary, a specific inoculum of microorganisms to enhance the biodegra-
dation process. This treatment method has several advantages because the engineer-
ing and biotechnology required to provide an optimal environment for biodegradation
of the organic contaminants can be controlled with a high degree of confidence. Bio-
logical reactions can be accelerated in a slurry system because of the increased con-
tact efficiency that can be achieved between contaminants and microorganisms by
successfully maintaining higher bacterial populations (108/mL). A slurry-phase
process can also be operated as a continuous-flow system, which reduces the impact
of toxic waste levels by instantaneously diluting the feed stream as .it enters the reac-
tor. In addition, toxic end products of microbial metabolism, which may repress bacte-
rial activity, do not accumulate to inhibitory levels.
ECOVA, in conjunction with ITEP, conducted pilot-scale process studies at the
U.S. EPA T&E facility in Cincinnati, Ohio, using a slurry-phase biotreatment design to
3-1
-------
evaluate bioremediation of PAHs in creosote-contaminated soil. The treatment pro-
gram was initially designed to evaluate six replicate batch slurry-phase reactors; how-
ever, mechanical difficulties encountered during startup caused this number to be re-
duced to five.
The EIMCO Biolift™ Reactor (60-liter) was selected for this study. These reac-
tors are made of stainless steel and equipped with agitation, aeration, and temperature
controls. Agitation is provided by three mechanical methods. First, a rake mechanism
moves the settled material from the bottom of the reactor to the second agitation
mechanism, an airlift circulation system that circulates the material to the top of the
reactor. The third agitation mechanism is a low-sheer impeller located approximately
in the middle of the central shaft of the reactor. Aeration is supplied by a set of air
diffusers that are attached to the rake arm at the bottom of the reactor. Temperature
is controlled by a heat tape system with a digital readout.
The EIMCO Biolift™ Reactor can be sampled in two ways. An opening at the
front top of the reactor allows access at the top surface of the liquid. This permits
visual inspection of the mechanical actions within the reactor as well as data collection
with hand-'held instruments that can be inserted into the slurry from the top. Samples
are collected from the three sampling ports located along the side of the reactor at
three vertical penetrations through the reactor wall. Samples collected from each of
4
•the.three ports represent three distinct zones of the slurry. The bottom sampling ports
provide sample material from within the rake mixing zone, where the heaviest particles
are likely to be present. The middle sampling port provides sample material from with-
in the most well-mixed zone of optimal, grain size. Finally, the top sampling port pro-
»
vides sample material from the finest mixing distribution. These three ports are crucial
in the evaluation of the mechanical efficiency of the reactor as well as collection of
samples of the contaminated material. An EIMCO Biolift™ Reactor Diagram is
presented in Figure 3-1.
3-2
-------
QlrFUSER A(R SUPPLY
ROTARY VALVE
RAKE DRIVE SHAFT
SUPPORT SEARINGS
IMPELLER DRIVE SHAFT
SUPPORT BEARINGS
AIRLFT DISCHARGE (2)
a
AIRLIFTS (2)
SAMPLE AND
DRAM VALVES
RAKE DRIVE
GHARMOTOR
IMPELLER DRIVE
GEARMOTOR fcN
(1JD A6RATX3N DIFFUSES
(PARTIALITY SHOWNI
RAKE BLADES (S)
AIRLIFT A
-------
3.2 Bench-Scale Flask Study
In January 1991, ECOVA conducted bench-scale process development studies
using 250 ml_ Erlenmeyer flasks to evaluate bioremediation of PAHs in creosote-con-
taminated soil collected from the Burlington Northern site. The objective of the bench-
scale studies was to develop the data necessary to determine the optimum process
conditions for the pilot-scale treatment, which will use a 60-liter EIMCO Biolift™ reac-
tor.
Physical, chemical, and microbial characterization of site soils was performed.
The information generated was used to evaluate the soil characteristics and to assist
in the development of an appropriate treatability study design. Physical characteriza-
tion was performed to determine the particle size distribution of the soil by using stan-
dard sieve analysis and to estimate terminal settling velocities of soil particles. This
information was used to determine appropriate slurry concentrations and to estimate
energy requirements for the slurry-phase bioreactor. Chemical and microbial charac-
terizations were performed to determine the levels of target contaminants, to determine
required inorganic nutrients that may limit microbial growth, and to ensure that specific
microbial degrader populations were present.
At the end of the bench-scale flask study, a physical characterization of the site
soils was performed for the scale-up exercise from the bench-scale flask study to the
single 64-liter EIMCO Biolift™ reactor. The results of this study indicated that there
was a substantial amount of heavy, coarse-grained particulates comprising this soil.
The volume percentage of soil fines less than 100 mesh in size was only 9 percent of
the total soil volume, with 72.4 percent greater than 100 mesh in size. These data
suggested that there would be significant difficulties encountered in generating a man-
ageable slurry from this soil. Hence, it was clear that an additional step would be
necessary to prepare the soil for use in the biosiurry reactor. The soil was subjected
to a milling process to pulverize the coarse-grained material and creosote inclusions to
yield a final material that was enriched in the -200-mesh particle fraction. This proce-
dure was quite useful for generating a material amenable to the formation of a man-
ageable slurry.
3-4
-------
For the purpose of the BOAT program effort, U.S. EPA program managers from
the Office of Solid Waste, in conjunction with representatives from, the U.S. EPA RREL
in Cincinnati and various support contractors, reviewed the above options and decided
to endorse the soil milling option as a pretreatment step prior to pilot-scale processing.
While this type of pretreatment step would not be efficient for a full-scale processing
option, it provides the information necessary to evaluate bioslurry treatment under
some of the most difficult technical and materials handling conditions.
Based on the scale-up exercise using the single 64-liter reactor, it was deter-
mined that to maintain efficient mechanical operation of the bioreactors during the
pilot-scale testing, a 30 percent solids slurry with an airflow of 50 standard cubic feet
per hour (scfh) to the diffusers and airlift mechanisms should be used.
Based on the bench-scale results and observations, it was also concluded that
the pilot-scale slurries should be amended with inorganic nutrients and a concentrated
inoculum of indigenous microorganisms selected for their ability to metabolize or co-
oxidize PAHs to ensure an optimal rate of bioprocessing. Supplementation with a sur-
factant such as Tween 80 would be necessary if degradation rates appeared lower
than expected on the basis of the bench-scale studies. To ensure a sufficiently active
surfactant-enabled desorption, the surfactant concentration should always remain far
above the critical micelle concentration (CMC). However, lacking.a specific assay to
evaluate surfactant concentration, it was generally concluded that it would be best to
use the surfactant only after the BOAT data requirements had been satisfied.
A report describing the results of the benchrscale* development of the slurry-
phase process is included in Appendix D.
3.3 Pilot-Scale Testing of Bioslurry Reactors
The pilot-scale slurry-phase testing program started on May 8, 1991, at the U.S.
EPA T&E facility. The six reactors selected for this study were the reactors (60-liter
EIMCO Biolift™ reactor) were identical to the one used in the scale-up exercise at
ECOVA following the completion of the b,ench-scale flask study. Representatives of
U.S. EPA, IT Corporation, and ECOVA Corporation were involved in conducting the
3-5
-------
pilot-scale testing. All pilot-scale study activities described in this document were gov-
erned by the U.S. EPA-approved Health and Safety Plan (Appendix E).
The operational volume of the EIMCO Biolift™ Reactor is 64 liters. Because of.
the large volumes of slurry to be removed at the initial T0 time point, however, it was
concluded that the reactors should initially be loaded to a volume of 66 liters. This
volume was immediately decreased after the collection of the first sample set, which
allowed for the maximum loading of the batch slurry reactor. Nutrient and inoculum
calculations were based on a 66-liter initial reactor volume at 30 percent slurry.
3.3.1 Soil Screening
9
A temporary enclosure was constructed at the T&E facility to house the soil
screening and' milling activities. (Figure 3-2 shows the layout of the containment area.)
Soil was shoveled from a 55-gallon drum in which it had been transported from the
site, and then passed through a Vz-\n. screen to remove any debris and oversized ma-
terial. The soil was worked through the screen by hand and with a trowel.
The screened soil was shoveled from the collection area below the screen onto
a plastic-wrapped board to form the stockpile. The rejected material was diverted into
a 5-gallon pail. Most of the rejected material consisted of wood fragments, pieces of
brick, and coarse gravel (>!£-in.). In general, the soil was brown to black, fine- to
medium-grained sand with some minor gravel content, and it was somewhat resilient
and greasy. The color and texture of the soil suggested it was highly contaminated.
The screened material formed a pile approximately 3 feet high and 4 feet in
diameter. The pile was spread out on the board, leveled off, and mixed by quartering.
This splitting process took place twice. (Figure 3-3 shows the splitting sequence.)
Several samples were taken of the material during these activities, and the rejected
material was returned to the original 55-gallon drum.
3.3.2 Soil Milling
After the soil was screened, a 5-gallon bucket was half-filled with soil and water
and mixed into a slurry. The original plan was to pump the slurry into a ball mill by
3-6
-------
o
0)
__
0> E
> c
o> .-
c
o
(ft
o
CL
CD
cn
0
J>s
_o;
Q.
O
O
o
o
E
o
CM
to
LL ;_
c
o
o
c
E
o
c
o
u
CM
-------
2
D)
CO
I
5=
O)
•a
c
co
en
c
"x
"E
en
"c
CD
£
o
CO
CO
CO
§
OJ
3-8
-------
using a 2-gpm Randolph peristaltic pump. When this method failed because the grav-
el in the slurry repeatedly plugged the pump, it was decided to pour the slurry into the
mill through a flexible funnel. A number of buckets were used for continuously mixing
the slurry and feeding it into the ball mill. Fourteen buckets were used to collect the
slurry at the mill outlet. The slurry was caught in the buckets at 1-minute intervals until
all of the soil had been processed. Samples were collected at the outlet of the mill as '
the slurry was being milled for postmilling analysis for PAHs.
The slurry was milled a second time, "after which a wet-sieve analysis was per-
formed to determine if the particles would pass through a No. 10 sieve. The slurry
was collected in two sets of six buckets each, marked 1 through 6 and 1a through 6a,
respectively. Abundant siliceous gravel still remained in the slurry, and it was clear
that a third milling was necessary before the material could be added to the reactors.
Another round of sampling was performed during the second milling.
During the third milling, the slurry was added at a slower rate to allow for a
longer retention time and better pulverization of the gravel. Also, the slurry was contin-
uously screened with a "No. 8 sieve at the outlet of the mill. After passing through the
sieve, the effluent appearedjo be well-mixed and was sampled again. Another sieve
analysis showed that the third milling, combined with screening, produced a slurry with
a grain size distribution suitable for charging to the reactors.
The next step in the process was to allow the slurry to settle, to decant the
liquid, and to take samples for percent solids analysis. After one hour, the slurry had
not settled enough to produce an obvious liquid-sediment interface. At this point, the
buckets were se'aled and left overnight. The following day, the liquid was decanted
from all 12 buckets into a 55-gallon drum by use of the Randolph pump. This consist-
ed of approximately 10 gallons of water, which was then mixed and sampled for per-
cent solids. Samples weighing approximately 30 grams were also collected from each
, of the buckets and analyzed for percent solids.
For the final mixing, 12 designated (reactor) buckets were labeled A1 through
F1 and A2 through F2. After mixing the contents of Bucket 1a with a shovel and trow-
el, approximately 1 liter of the material was placed into each of the 12 reactor buckets.
3-9
-------
This was repeatecfuntil all of the material from Bucket 1 a was distributed into all 12
reactor buckets. The same procedure was repeated for the remaining 11 buckets (1
through 6 and 2a through 6a). The contents of the 12 reactor buckets were thorough-
ly mixed, weighed, and sampled for percent moisture.
Water decanted from the slurry (after the third milling) and placed in the
55-gallon drum was mixed, divided evenly into six buckets, and weighed. This water
was used for the initial charging of the reactors.
At this point, the work in the containment area was complete. Calculations
were made to determine the weight (volume) of water and slurry needed to charge the
reactors to 66 liters at 30 percent solids.
The entire process of screening, milling, and mixing took 1 Vz days and
approximately 35 man-hours to complete. Milling the slurry three times was time-con-
suming and inefficient. Using a screen or series of screens with smaller openings and
a mill that could pulverize the gravel might eliminate multiple passes through the mill.
For either a pilot-scale or full-scale project, however, this is not likely to be cost-effec-
tive. Milling the slurry also results in considerable spillage during the charging of the
slurry into thd- mill. Having to process the slurry three times added to this unavoidable
problem. The general conclusion was that the soil processed at the EPA facility was
quite different from the material tested at the ECOVA Technology Development Center,
which only had to be milled twice and did not plug the Randolph pump.
3.3.3 Reactor Charging
As a result of the screening, mixing, and milling process, twelve 5-gallon buck-
ets of milled slurry were generated. The buckets were labeled 1 through 6 to corre-
spond to the reactor designations. More slurry was generated than could be accom-
modated by six buckets alone; therefore, an additional set of six buckets was used to
collect the remainder of the slurry from the milling process. The bucket designations
then became 1a through 6a for the first set and 1b through 6b for the second set
(Figure 3-3). Because 12 buckets of slurry were collected during the milling process,
ECOVA's lead technical person expressed concern over the potential inhomogeneities
3-10
-------
that might exist among the buckets and the need for each reactor to be charged with
material that was statistically similar with respect to contaminant loading and percent
solids. Toward this end, ECOVA, in consultation with IT. Corporation and S-Cubed,
proposed and executed the following Standard Operating Procedure (SOP) for
charging the slurry bioreactors:
1) . The 12 buckets of slurry were subjected to a 14- to 16-hour settling peri-
od under quiescent conditions. After the specified settling interval, the
aqueous supernate solutions were pumped to a single 55-gallon drum for
interim storage and mixing.
2) Six clean feed buckets were labeled with the designations A through F
(one for each of the slurry bioreactors) and weighed to determine the
mass of each empty bucket.
3) Settled soil from each bucket was stirred with a hand-held grain-feed
scoop to mix and homogenize. An aliquot was removed from each of
the 12 buckets with the hand-held scoop and weighed into feed bucket A
until a total 32 kg (70.11 Ib) wet weight of soil had been dispensed. This
process was repeated for each of the remaining buckets (B, C, D, E, and
F). Soil mass was calculated on the basis of the following assumptions:
Soil density = 1.3 kg/L
Specific gravity of slurry = 1.074 (30% slurry)
Moisture of feed soil = 24.83 ± 0.31%
Total slurry volume = 66 liters
Total slurry mass = 70.88 kg
Dry soil mass required = 21.27kg
Water mass required = 49.61 kg
4) Samples from each of Buckets A through F were collected and analyzed
for dry weight to determine the total dry mass of soil added to each reac-
tor. (See Appendix F for raw data table.)
5) After the water content of the wet makeup soil was factored (6.30 kg or
13.85 Ib water), it was determined that a total of 97.35 Ib of additional
makeup water was required to achieve the specified slurry composition.
Included in this makeup water volume was the supernate water collected
after the initial settling step described under Item 1. This represented
14 Ib of the 97.35 Ib required for each reactor.
6) Each of the EIMCO airlift reactors was charged with 76 Ib of water. The
remaining 21.35 Ib of makeup water was reserved for preparation of the
required inorganic nutrient supplements.
3-11
-------
7) The airlift, impellers, and rake controllers for the bioreactors were en-
gaged with the rake speed set at 4 rpm, the impeller speed set at 7 rpm,
and the airlift set at approximately 50 scfm. Diffusers were run at a flow
rate of 30 scfm.
8) The contents of each of the soil feed buckets (A through F) were dis-
pensed into the respectively designated bioreactors by using a funnel
and a hand-held scoop. After most of the soil had been dispensed, the
bucket was rinsed with the remaining volume of nutrient-amended make-
up water and the contents were added to the reactor. This procedure
was repeated for each of the remaining reactors until all reactors were
charged to specification.
3.3.4 Inoculation
A concentrated inoculum was prepared at the ECOVA Research and Develop-
ment Facility in Redmond, Washington. The inoculum consisted of three bacterial
isolates (Pseudomonas stutzeri, Pseudomonas fluorescens, and Pseudomonas stutzeri
strain FLN-1) obtained from the Burlington Northern site soil samples shipped to
ECOVA for bench-scale testing. A total of 60 liters of culture was prepared and con-
centrated to a final volume of 4.0 liters. The total number of bacteria in the concen-
trate was 1.2 x 1013. During bench-scale testing, a desired inoculum level was deter-
mined to be approximately 1.0 x 10s bacteria per gram dry weight of soil. Therefore,
each reactor would require supplementation with a targeted number of 2.13 x 1012
bacteria.
«
After each of the slurry bioreactors had been charged with slurry, the inoculum
(cold slurry concentrate) was added at a volume of 666 ml_ per reactor. Based on the
titer of bacteria in the available inoculum, this translated to an actual inoculum titer of
1.98 x 1012 per reactor, or 9.3 x 107 per gram of soil. At the time of inoculation, the
inoculum was 48 hours past its recommended holding time for optimal viability.
3.3.5 Nutrient Amendment
The results of the inorganic analyses performed on the soil samples during the
bench-scale study (see Appendix D) suggest that the soil was depleted in available
phosphorous measured as o-phosphate. The ratio of total organic carbon (TOC) to
3-12
-------
total Kjeldahl nitrogen (TKN) was approximately 40:1, which suggests that a supply of
nitrogen would be available for microbial activity. The amount of free nitrogen as mea-
sured by ammonia nitrogen, however, was quite low (TOC:N = 950:1); this suggests
that ammonia supplementation would be necessary to enhance optimal microbial ac-
tivity. Elemental analysis for calcium, magnesium, potassium, and sodium was per-
formed to obtain data that could* be used to estimate potential effects on the hardness
of the aqueous phase of the slurry and, therefore, the impact on surfactant behavior.
Based on the levels of these elements, no appreciable effect on water hardness was
expected. Therefore, foaming of ionic surfactants could present some materials han-
dling problems.
The postmilled material was analyzed for total volatile solids prior to loading the
reactors to ensure a carbon level close to that previously reported. These samples
indicated a carbon concentration of 38,888 ppm (see Appendix F). Because this value
was higher than that previously reported, it was used for all nutrient calculations.
Nutrient amendments added to the reactor included ammonia and phosphate,
along with trace amendments of magnesium, calcium, iron, and ammonium molyb-
date. Concentration calculations were based on a 66-liter volume of 30 percent soil
slurry. Nutrients were added to the reactors by dissolving them in a subsample of
preweighed reactor water.
3.3.6 Reinoculation of Bioreactors
After the 9 weeks of treatment testing, Bioreactors 2, 4, 5, and 6 were reinocu-
lated with 125 ml_ of inoculum. In addition to the inoculum, 5.93 ml_ of Tween 80 sur-
factant was added into .Reactors 5 and 6. No inoculum or surfactant was added into
Reactor 1. Inoculum and surfactant amendments are presented in Table 3-1.
TABLE 3-1. INOCULUM AND SURFACTANT AMENDMENTS
Reactor No.
1
2
4
5
6
Amendment
None
Inoculum
Inoculum
Inoculum/Tween 80
Inoculum/Tween 80
Amount, ml
125
125
125/5.93
125/5.93
3-13
-------
-------
SECTION 4
SAMPLING AND ANALYSIS ACTIVITIES
Sampling of the bioslurry reactors during the pilot-scale testing was conducted
in accordance with the "Sampling and Analysis Plan (SAP) for the Treatment Testing of
Slurry-Phase Biological Reactor on Contaminated Soils" (see Appendix A). In addition
to the sampling from the bioreactors, air sampling was also incorporated into the
sampling and analysis effort to characterize the vapors coming off the bioslurry reac-
tors.
Sampling and analysis activities performed during the pilo't-scale test are pre-
sented in Subsections 4.1 and 4.2, respectively, and deviations from the SAP-are pre-
sented in Subsection 4.3. Subsection 4.4 contains information about safety considera-
tions observed during the sampling activities.
4.1 Sampling Methods
*
Composite samples were collected from each reactor for pre- and posttreat-
ment analysis and throughout the study to monitor system operation. Composite
sampling ensured that analyses were performed with a representative sample of the
entire slurry column. Some analyses (e.g., particle size distribution, plate counts) were
performed on samples collected from individual sampling ports to determine potential
differences among the three slurry zones.
All parameters in this study were monitored in accordance with the sampling
schedule presented in Table 4-1. Week T0 corresponds to May 8, 1991, and Week T12
corresponds to July 31, 1991. The values in Table 4-1 refer to the volumes of slurry, .
soil, or water taken for each analysis at each point in time. Table 4-2 presents the
sampling constituents and sampling frequency during the run for each of the five
«
4-1
-------
UJ
_J
Q .
UJ
I
O
C/3
O
•z.
fT"
••••
^^
t
—
o
-"*^
(T •
g
O
^^
UJ
oc
•^
UJ
_J
DQ
^f
1-
..
p
"o ~~
CO <"
CD £
rr ^
Q. fil
£-
*f
E <°
CO
CO
_^
CD
CD
5
CM
^
O
T-
cn
co
co
10
"sj-
co
CM
T~
O
co
'co
"5
t=
ooooooooooorr rr nr <
O CO O O -st" i— T— T— CM CO O Q O G Z
O 1— T- 1—
CM
oo o o o rr rr fr <
•st- o •*- 1o -;• — §-« £§)
° 5 P ^"C £ S J- frt & CD
.| 3 -_,§-§• 2 IE, | 3 | §
— olJ-d^2~a)g>x--sl— "S ^ OT
IllliillSlilU
o o o o
i- o in co
in i- CM i-
CM CM
0000
T- o in co
in T- CM i-
o o o o
T- o in co
IO ^~ CM ^
O 0 0 0
T- o in CD
IT) i- CM T-
CM CM
O
0
0000
T- o in co
m i- CM t-
o
o o o o
i- O IT) CO
in i- CM i-
o o o o
o o r^ co
CO T- >r-
o o o o
co o in i-
m T- CM CM
o o o
CO f~- CD
^~
o o o o
CO CD IT} in
CD T- CM CM
CM CM
Zj '—
—.^•1=.
. . P CD -C
^7" o- o> .-^
•§-"cD J '"
t
-"_:««
l>lcl
|- t UJ UJ
•t O O> CO O
co ,_; en in co
" CO ^~ *~ CO
CM
•* O O) CO O5
co co en in ^r
^ — co'
CM
•^ o en co r —
co co a> in co
'r" — co
CM
•* o en co in
CD co en in co
^*~ ^^ *
co
CM
•^J- O O O *vf
CO CO O
cri
CM
-* O O O -tf
CO CO O
cri
CM
Tj- O CD CO ^d"
co co en in o
'r~ r~ cri
CM
•si- O O O CM
CD CO CM
O5
ca
'd- o en co CM
co co en in CM
^~ ^~ cri
CM
•<* O CO O i-
CD CO N- CD "*
cri
CM
•sf O CO CO CO
CO CO T- CO •*}•
^ — cri
CM
•sf O *-: <35 CO
CD CO in CO CD
O)
CM
•sT O CO CO CO
CD co en CM h-
CM CM cfj
CM
Dl
|s|
^i.'— o $» co
| ^ £ ll
O m ^ . >?
5f&!&
'o co ^ o -3
I- CO CO CO CO
ts
CD
E
B
1o
cz
c: '
^
ca
CD
V
I
73
CO
01
"co -^
ZJ -O
-0 .8
® ~ci
=> Q.
CD -g
2 z
II II
g£
CO J3
4-2
-------
Q
CO
rr
o
<
UJ "Z.
CC
LU
-Jt-
OE
COs.
28
CQ
g§
CM
t
"tf
UJ
_1
CD
CO
^
m
CM
-
o
en
co
^
CD
in
-
CO
CM
-
o
co
CO
CO
c
CM
CM
=
O
CO
5
2
I CS&D constituents
in
T—
in
in
in
ro
,O
+ZZ
O
s
1 Semivolatile organ
I contaminant list)
o
Tf
m
in
in
in
in
m
in
in
CO
t
X
CL
O
CM
in
in
in
in
'5
CO
t
X
Q.
O
(M
in
•
in
in
in
t—
-------
reactors. These analyses include the critical constituents, the design and operating
parameters, and volatile organics from air emissions.
Figure 4-1 shows the points at which samples were collected during the pilot-
scale test. The purpose for collecting each sample, the sampling location, the method
and frequency of sampling, and the constituents to be analyzed are presented for
each sampling point in Subsections 4.1.1 through 4.1.5, respectively. Details regard-
ing sample containers and sample preparation techniques are presented in Subsec-
tion 4.1.6.
4.1.1 Sampling Point 1 - Premilling Sample
Purpose
A premilling sample was collected to characterize the contaminated soil.
Description of Sampling Point
A grab sample was scooped from the homogenized pile of soil at the end of the
screening process.
Sample Collection Method
A grab sample of soil was collected from the pile of homogenized screened
material in eleven 8-oz wide-mouth glass jars.
Frequency of Sampling
One soil sample was collected from the homogenized soil prior to milling.
Constituents Analyzed
The premilling sample was analyzed for the complete CS&D list' presented in
Table 4-3.
4.7.2 Sampling Point 2 - Postmilling Sample
Purpose
, •
A postrriilling sample was collected to characterize the milled soil and to deter-
mine the effect of milling on the contaminants.
4-4
-------
Sampling
Point 1
Sampling
Point 2
Untreated
Soil
Sampling
Points
Screened Milled Exhaust
Untreated Untreated Gases
Soil Soil i
Screening
t..
Milling
|
f
Bioslurry
Reactor
Untreated Untreated
Soil Liquid
Sampling
Point3
Treated Treated
Soil Liquid
Residuals ^Residuals
Sampling
Point 4
Figure 4-1. Pilot-scale bioslurry treatment sampling locations.
4-5
-------
TABLE 4-3. CS&D LIST BY CONSTITUENT TYPE
Constituent
Volatile organics
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Benzene
Bromodi chl oromethane
Bromomethane
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Ch'loro-l,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Dibromomethane
cis~l,4-Dichloro-2-butene
trans- 1,4-Di chl oro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Oiehloroethane
1,1-Dichloroethylene
CAS No.a
67-64-1
75-05-8
107-02-8 '
107-13-1
71-43-2
75-27-4
74-83-9
56-23-5
75-15-0
108-90-7
12-6-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
96-12-8
106-93-4
74-95-3
1476-11-5
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
BOAT
Reference
No. .
222
1
2
3
4
. 5
6
7
8
9
10
11
12
13
14
15
17
18
19
234
20
21
22
23
24
(continued) 4-6
-------
TABLE 4-3 (continued)
Constituent
Volatile organics (continued)
trans- 1 -2-Di chl oroethene
1,2-Dichloropropane
trans- 1,3-Di chl oropropene
cis-l,3-Dichloropropene
1,4-Dioxane
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethyl ene oxide
2-Hexanone
lodomethane
Methyl ethyl ketone
4-Methyl -2-pentanone
Methyl methacrylate
Methacryl oni tri 1 e
Methyl ene chloride
Styrene ~
•1,1,1 , 2-Tetrachl oroethane
1,1,2, 2-Tetrachl oroethane
Tetrachl oroethene
Toluene •
Tribromomethane
1,1, 1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Tri chl oroethene
CAS No.a
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
141-78-6
100-41-4
107-12-0
6.0-29-7
97-63-2
75-21-8
591-78-6
74-88-4
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
100-42-5
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
BOAT
Reference
No.a
25
26
27
28
29
225
226
30
227
31
214
-
32
34
-
35
37
38
-
40
41
42
43
44
45
46
47
(continued)
4-7
-------
TABLE 4-3 (continued)
Constituent
Volatile organ ics (continued)
Tri chl oromonof 1 uoromethane
1 , 2 , 3-Tr i chl oropropane
1,1, 2-Tri chl oro- 1 , 2 ,.2-tri f 1 uoroethane
Vinyl acetate
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Senrivol ati 1 e organi cs
Acenaphthylene
Acenaphthene
Acetophenone ^
2-Acetyl ami nof 1 uorene
Aery 1 amide
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benzo (a) anthracene
Benzal chloride
»
Benzenethiol
Benzo(a)pyrene
Benzo ( b) f 1 uoranthene
Benzo(g,h,i)perylene
Benzo ( k) f 1 uoranthene
Benzoic acid
p-Benzoquinone
Benzyl alcohol
CAS No.a
75-69-4
96-18-4
76-13-1
108-05-4
75-01-4
97-47-6
108-38-3
106r44-5
208-96-8
83-32-9
96-86-2
53-96-3
79-06-1
92-67-1 •
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3 '
108-98-5
50-32-8
205-99-2
191-24-2
207-08-9
65-85-0
106-51-4
* 100-51-6
BOAT
Reference
No.
48
49
231
-
50
215
216
217
51
52
53
54
233
55
56
57
58
59
218
60
62
63
64
65
-
- 66
1 _
(continued) 4-8
-------
TABLE 4-3 (continued)
Constituent
Semi volatile organics (continued)
Bis(2-ch1oroethoxy)methane
Bi s (2-chl oroethyl )ether
Bi s (2-chl oroi sopropyl ) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
ButyT benzy] phthalate
2-sec-Butyl -4,6-dinitrophenol
p-Ch'loroaniline
Chi orobenzi late
p-Chloro-m-cresol
2-Chl oronaphthal ene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
2-Methyl phenol
4-Methyl phenol
Cyclohexanone
Dibenzo( a, h) anthracene
£
Dibenzofuran
m-Dichlorobenzene
o-Dichlorobenzene •
p-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
CAS No.a
111-91-1
111-44-4
39638-32-9
117-81-7.
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
• 7005-72-3
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
132-64-9 .
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
. BOAT
Reference
No.a
67
68
69
70
• 71
72
73
74
75
76
77
78
-
80
81
82
232
83
_
86
87
88
89
90
91
92
(continued) 4-9
-------
TABLE 4-3 (continued)
Constituent
Semi volatile organlcs (continued)
3,3'-Dimethoxybenzidine
p-Di methyl ami noazobenzene
3, 3' -Dimethyl benzidine
2, 4-Dimethyl phenol
Dimethyl phthalate
Di-n-butyl phthalate
1,4-Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2;6-Dinitrotoluene
Di-n--octyl phthalate
Di -n--propyl ni trosami ne
Diphenylamine
Di phenyl ni trosami ne
1 , 2-Di phenyl hydrazi ne
Fluoranthene
Fl uorene
Hexachl orobenzene
Hexachlorobutadiene '
Hexachl orocycl opentadi ene
Hexachl oroethane
Hexachl orophene
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isophorone
Isosafrole
CAS No.a
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
121r14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
78-59-1
120-58-1
BOAT
Reference '
No.
93
94
95
96
97
98
99
100
101
102
,- 103
104
105
106
219
107
108
109
110
111
112
113
114
115
116
•
117
(continued) '4-10
-------
TABLE 4-3 (continued)
Constituent
Semi volatile organics (continued)
Methapyrilene „ '
3-Methyl chol anthrene
4, 4 ' -Methyl enebi s (2-chl oroani 1 i ne)
Methyl methanesulfonate
2-Methyl naphthalene
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
m-Nitroaniline
o-Nitroaniline
p-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Ni trosodi -n-butyl ami ne
N-Ni trosodi ethyl ami ne
N-Ni trosodimethyl ami ne
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorphol ine
N-Ni trosopi peri di ne
N-Ni trosopyrroli dine
5-Nitro-o-toluidine
Pentachl orobenzene
Pentachloroethane
Pentachl oroni trobenzene
. Pentachl orophenol
CAS No.a
91-80-5
56-49-5
101-14-4
66-27-3
91-57-6
91-20-3
130-15-4
134-32-7
91-59-8
99-09-2
88-74-4
100-01-6
98-95-3
88-75-5
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-55-8
608-93-5
76-01-7
82-68-8
87-86-5
•BOAT
Reference
No.
118
119
120
36
-
121
122
123
124
-
- .
125
126
•
127
128
129
130
131
132
133
134
135
136
137 -
138
139
(continued) 4-11
-------
TABLE 4-3 (continued)
Constituent
Semi volatile orqanics (continued)
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
Pronamide
Pyrene
Pyridine
Resoircinol
Saf rol e
1 , 2 , 4 , 5-Tetrachl orobenzene
2,3,4, 6-Tetrachl orophenol
1 , 2, 4-Trichl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Trichl orophenol
Metals (Total and TCLP)
Al umi num
Antimony
Arsenic
Barium
Beryl 1 i urn
Calcium
Cadmium
Chromium (total)
Chromium (hexavalent)
Cobalt
Copper
Iron
BOAT
Reference
CAS No. No.
62-44-2
85-01-8
108-95-2
85-44-9
23950-58-5
129-00-0
110-86-1
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-70-1
7440-43-9
7440-47-3
•
7440-48-4
7440-50-8
7439-89-6
140
141
142
220
144
145
39
146
147
'148
149
150
151
152
'. .
154
155
156
157
-
158
159
221
-
160
_
(continued) 4-12
-------
TABLE .4-3 (continued)
Constituent
Metal s (continued)
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium .
Silver
Sodium
Thallium
•Vanadium
Zinc
Inoraanics other than metals
Cyanide
Fluoride
Sulfide
: Orqanochlorine pesticides'
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma- BHC
Chlordane
p,p'-DDD
o,p'-DDD
p,p'-DDE
o,p'-DDE
CAS No.a
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-0
7440-09-7
7782-49-2
7440-22-4
7440-23-5
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
53-19-0
72-55-9
3424-82-6
BOAT
Reference
No.^
161
-
-
162
163
-
164
165
-
166
167
168
169
170
171
172
173 .
174
175
176
177
178
235
179
236
(continued) 4-13
-------
TABLE 4-3 (continued)
Constituent
Orqanochlorine pesticides (continued)
p,p'-DDT
o,p'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxvacetic acid herbicides
2,4-Dichlorophenoxyacetic acid (2,4-D)
Silvex (2,4,5-TP)
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
Orqanoohosohorus insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
CAS No.a
50-29-3
789-02-6
60-57-1
939-98-8
33213-6-5
1031-07-8
72-20-8
7421-93-4
53494-70-5
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
•
12674-11-2
11104-28-2
BOAT
Reference
No.
180
237
181
182
183
238
184
185
-
186
187
188
189
190
191
192
193
- 194 '
195
196
197
198
199
200
201
(continued)
4-14
-------
TABLE 4-3 (continued)
Constituent
PCBs (continued)
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Dioxins and furans
Hexachl orodi benzo-p-di oxi ns
Hexachl orodi benzof urans
Pent achl orodi benzo-p-di oxi ns
• Pent achl orodi benzof urans
Tetrachl orodi benzo-p-di oxi ns
Tetrachl orodi benzof urans
2,3,7, 8-Tetrachl orodi benzo-p-di oxi n
CAS No.a
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
-
-
-
.-
-
-
1746-01-6
BOAT
Reference
No.
202
203
204
205
206
207
208
209 .
210
211
.212
213
Reference numbers taken from Table 3.2 from "Quality Assurance Project
Plan for Characterization Sampling and Treatment Tests Conducted for
the Contaminated Soil and Debris (CS&D) Program" prepared by the U.S.
EPA Office of Solid Waste.
4-15
-------
Description of Sampling Point
Samples were collected at the outlet of the mill as the soil was being milled.
Sample Collection Method
A composite sample was obtained by taking a grab sample from each bucket
used to collect the effluent from the outlet of the mill. A portion of the composite
sample was placed into eleven 8-oz wide-mouth glass jars.
Frequency of Sampling
One composite postmilling soil sample was collected.
Constituents Analyzed
The postmilling sample was analyzed for the complete CS&D list presented in
Table 4-3.
4.1.3 Sampling Point 3 - Prefreafrnenf Samples (Week TJ
Purpose
The pretreatment samples were collected to determine the levels of the critical
PAH constituents in the soil prior to bioslurry treatment. These samples served as the
baseline for evaluating the technology's performance.
Description of Sampling Points
Composite samples were collected from the three sampling ports located along
the side of the reactor at three different vertical locations (Figure 3-1). Samples from
these three ports represented the three potentially distinct zones of the slurry. The
bottom sampling port provided sample material from within the rake mixing zone,
where the heaviest particles were likely to be present. The middle sampling port pro-
vided sample material from within the most well-mixed zone. Finally, the top sampling
port provided a sample of the finest material.
4-16
-------
Sample Collection Method
A 10- to 20-gram-sample was taken from each port prior to reactor sampling.
Samples were then dried at 98 °C for 2 hours. The percent total solids was calculated
for each port. Based on the percent total solids and the soil specific gravity, the
specific gravity for the slurry at each port was obtained from Denver tables of specific
gravity.
The percent total solids and specific gravity for each port were entered into a
spreadsheet program that'calculates the percent solids of a composite sample when
different volumes are sampled from each port. The total sample volume desired was
entered, and port volumes were adjusted proportionately until a 30 percent total solids
was obtained for the composite sample.
At a given volume, the. spreadsheet program also calculated (for each port) the
percentage of the total sample being taken, the sample weight from that port, and the
weight of dry soil from each port.
Sample volumes from each port were marked on the sampling jars prior to
sampling. Samples were collected from each 'port-the bottom port was sampled first,
followed by the middle and top ports. After collection of the sample, the container was
shaken to allow for homogenization of the sample. The contents of the container were
centrifuged to separate the liquid and sludge layers. The liquid was decanted into 1-
liter amber glass bottles and the sludge was collected into 8-oz. glass jars.
Frequency of Sampling
One pretreatment sample from each of the five, reactors was collected immedi-
ately after the reactors were initially charged (T0).
Constituents Analyzed
All five pretreatment samples (one from each reactor) were analyzed for the
critical contaminants listed in Table 4-4.
4-17
-------
TABLE 4-4. CRITICAL CONTAMINANTS OF INTEREST
FOR THE BURLINGTON NORTHERN SUPERFUND SITE
Semivolatlies Organics - Total Analysis
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)f1uoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Chrysene
Dibenzofuran
Fluoranthene
Fluorene
2-Methylnaphtha!ene
Naphthalene
Phenanthrene
, Pyrene
4-18
-------
4.1.4 Sampling Point 4 - Posttreatment Samples (Weeks T9 and T12)
Purpose -
The posttreatment samples were collected 9 and 12 weeks after the start of
testing to determine the levels of the critical PAH constituents remaining in the soil
after treatment. These samples were used to evaluate the technology's performance.
Description of Sampling Point
Composite samples were collected from the three sampling ports located along
the side of the reactor, as discussed in Subsection 4.1.3.
Sample Collection Method
The procedure used to collect the posttreatment samples was similar to that
discussed in Subsection 4.1.3.
Frequency of Sampling
One posttreatment sample from each of the five reactors was collected at
Week Tg and Week T12,
Constituents Analyzed
All five posttreatment samples from Weeks T9 and T12 were analyzed for the
critical contaminants listed in Table 4-4.
x
4.1.5 Sampling Point 5 - Off-Gas Samples
Purpose
Air sampling was conducted to characterize the off-gases emitted from the bio-
- reactors during the operations and to determine organic constituent loss through vola-
tilization. These samples were collected for information only and were not used to
evaluate the technology's performance.
Description of Sampling Point
All five reactors were vented through stainless steel piping into a manifold sys-
tem before carbon filtration and eventual exhausting to the outside air. The air
4-19
-------
monitoring was conducted at a point prior to the collective manifold to obtain emis-
sions from two individual reactors.
Sample Collection Method
Two sampling trains were constructed to collect samples for volatile and semi-
volatile organics. Volatile organics were collected in a SUMMA passivated canister,
and semivolatiles were collected in XAD-2 resin tubes. The XAD-2 resin tubes and
canisters were installed in the venting systems for the tested reactors.
Frequency of Sampling
Four consecutive sets of samples were collected from each of the two tested
reactors during the first week of operation. Two sets of samples were collected during
Weeks 2 through 5, and one set of samples was collected during Weeks 6, 7, and 9.
Constituents Analyzed
The XAD-2 resin tubes were analyzed for semivolatile organic compounds, and
the SUMMA passivated canisters were analyzed for volatile organic compounds from
the Target Compound List (TCL).
4.1.6 Sample Containers and Sample Preservation
For analyses requiring discrete zone samples, slurry samples were collected in
individual sample containers in the manner described previously (Subsections 4.1.3
and 4.1.4). The remaining samples were collected as composite samples .in clean
4-oz, 8-oz, or 1-liter amber glass bottles with Teflon-lined screw capsv Samples sub-
mitted to ITAS-Cincinnati laboratory for TPH and semivolatile analyses were preserved
with hydrochloric acid to inhibit biological activity. In addition, samples were centri-
fuged into discrete solid and liquid phases prior to analyses.
All samples were packed in coolers with ice to 4°C and were either shipped to
ECOVA laboratory by an overnight carrier or transported to ITAS-Cincinnati laboratory,
depending on the analyses to be performed. Proper shipping papers, chain-of-
custody forms, and request-for-analysis forms also accompanied the samples. Table
4-20
-------
4-5 summarizes sample containers, preservation methods, and maximum holding
times for the various parameter classes, as well as specific analytes for some samples.
4.2 Analytical Procedures
Table 4-6 lists the analytical parameters and the appropriate preparation and
analytical methods. A brief description of the methods used to analyze the
soil and liquid matrices for the critical parameters is presented in Subsections 4.2,1
and 4.2.2, respectively.
4.2.1 Semivolatile Organics Analysis (Soil Matrix)
The contaminants of most critical concern for this pilot-scale study were the
PAHs. Soil samples were prepared in accordance with Method 3550 in SW-846. This
method uses ultrasonic sound waves to penetrate and disrupt the soil matrix to allow
more efficient extraction of the target analytes. Because of the heavy loading of PAHs
expected in the untreated soil, the samples were prepared as medium-level soils. A
1-g soil sample was mixed with anhydrous sodium sulfate and solvent-extracted by
ultrasonic pulse's three times. The solvent layer was collected by vacuum filtration,
concentrated down to a 1-mL aliquot, and stored at 4°C until ready for analysis. Prior
to extraction, 1 ml_ of surrogate standard, solution was spiked into the sample to check
the extraction efficiency.
The sample was spiked with 20 juL of internal standard solution ^before analysis
to enable the quantitation of the target compounds identified in the sample. The
sample was then analyzed in accordance with Method 8270 in SW-846. This is a
direct-injection method for semivolatile compound analysis by use of a capillary
*
column and a full-scan mass spectrometer. The mass spectrometer allows qualitative
identification as well as quantitative analysis of the target analytes detected in the sam-
ples.
4.2.2 Semivolatile Organics Analysis (Liquid Matrix)
The liquid sample for semivolatile organics analysis was extracted by continu-
ous liquid-liquid extraction as outlined in Method 3520 in SW-846. An aliquot of liquid
4-21
-------
03
OD
LJJ
1
h-
o
•
CD
73
0
VI
CO
CO
TO
.0
JZ
1 Widemoul
^^
To
Volatile organics (tot
CO
>•»
CD
73
O
^~
_c
"5
f>
CD
N
"co
c
CD
c"
g
I
"x
CD
t
.O
CO
73
73
O
0
VI
CO
CO
CO
O)
JZ
1 Widemoul
<-*
CO
o
tn
Semivolatile organic;
CO
'5
"n
cz
TO
JD
co
r—
CZ
o
CD
C
o
'o
2
><
03
*
O
"*"
c/
C
CD
o
VI
CO
V.
TO
O
JZ
1 Widemoul
-
=
o
03
CZ
f^
03
O
CO
5
53
2
CO
5
fl
CZ
co
o
**""
CO
CT
73
CO
OJ
C
c
c
CT
><
CD
t
,0
CO
>,
CD
73
«
O
o
tt
VI
CO
CO
re
a
JZ
Widemoul
Total mercury
CO
>*
CD
73
0
•*
VI
CO
co
TO
0
JZ
1 Widemoul
CD
73
5
O
CO
>•
CD
73
cc
o
VI
CO
CO
re
a
JZ
1 Widemoul
Fluoride
CO
CT
O
o
VI
CO
CO
CD
a
JZ
Widemoul
03
73
"zi
CO
CO
T
O
C
f
^
cr
"n
c
CO
c
c
CT
"£
CD
,_
O
CO
CT
73
o
VI
CO
co
TO
O
JZ
1 Widemout
CD
iZ.
CO
03
73
O
Organochlorine pesti
CO
CD
73
O
C
••g
^
03
75
c
CD
cf
g
CO
"x
CD
u.
O
CO
73.
O
o
VI .
CO
CO
CD
D)
JZ
Widemout
CO
CD
73
0
-Q
03
JZ
Phenoxyacetic acid 1
(total)
CO
n
73
O
_cz
-•g
>
03
N
"CT
c
CO
CZ
.c
c
CT
"x
CD
t
o
CO
>,
CO
73
3
VI
CO
CO
TO
a
JZ
1 Widemout
CO
03
73
O
03
CO
C
Organophosphorus i
CO
rt
73
O
CZ
•|
>
03
N
J>
CT
CT
c
.g
CT
X
03
j_
0
CO
CT
O
o
VI
CO
CO
CD
a
JZ
Widemout
CO
CQ
O
a.
{j
*>
CT
C
CO
,
V)
CT
73
T^
Q_
c
H
o
CO
CD
73
o
VI
CO
CO
TO
o
JZ
Widemout
ST
«J
J
CO
g
ro
a
0
_CD
3
o
>
,0
CO
CD
73
O
^
CZ
.g
CD
"x
03
o
CO
CD '
73
r--
_i
O
h- .
0
CO CO
>> CO
o
o
VI
CO
CO
CD
en
_c
Widemout
a.
_j
^
Semivolatile organics
.0
CO
CD
73
O
^
CZ
.g
CO
"x
03
£
CO
CD
73
1^
a."
O
f-
\_
,0
co *£
•.
—
c
CZ
co
o
**~
CO
CT
Q,
CN
c
"e
n
x
CD
i_
,0
CO
CT
73
00
C\
O
o
VI
CO
CO
TO
o
_£;;
Widemout
TCLP mercury
CO
CT
73
cc
CM
O
o
VI
CO
CO
re
O
JZ
Widemout
Sulfate -
CO
>,
CT
CO
c\
f 1
0
VI
CO
CO
TO
0
j-;
Widemout
Chloride
CO
>,
CT
03
CM
r ••
0
Si
CO
CO
TO
D
JZ
Widemout
o
<
^
CD
"Z.
CO
CO
CO
o>
JZ
Widemout
r~
Grain size distributor
CO
CD
73
CO
OJ
73
O
o
VI
CO
CO
CD
OJ
J-
Widemout
03
CO
CD
0)
a
CD
<5
CO
>,
CT
CO
V—
f *
O
VI
CO
CO
TO
C
JZ
Widemout
x
CO
CO
73
CO
CM
73
O
O
Si
CO
CO
CD
O)
J—
Widemout
x
CO
o
oo
"*
O
0
VI
CO
co
TO
0
JZ
Widemout
Surfactants
CO
CT
73
CO
C\
o
VI
CO
CO
TO
D
,.
Widemout
-
Phosphorus
o
o
VI
CO
CO
CO
o
_
Widemout
Ammonia
o
VI
CO
CO
TO
O
JZ
o
E
03
73
Nutrients
a.
tv;
*3-
X
a
CO
CT
CO
OJ
O
0
VI
CO
co
CO
0
Widemouti
CO
CO
03
E
g
co
E
o
4-22
-------
Z3
CI
"c
O
in
ill
_i
CQ
£
o
Q)
£
I*"*
r^
a
c
"o
E
I
"x
CO
*—
JO
CO
03
>
CO
£
03
CO
£
Q.
03
CO
C
O
O
i_
03
^3
E
5
CO
Q_
Q3
E
Measure
CO
03
o
co
CO
03
n
ioreactor Slu
CQ
CO
"co
>\
CO
CO
o
**""
CO
>•»
CO
•a
o
^j-
cf
_o
•Q
re
x
03
i-
£
co
CO
T3
••"
CM
V
-X
^* ^
VI *"
O
X
CO
CO
co
O)
JZ
"23
o
03
f
8
CO
05
l_
0
Semivolatile
CO
CO
TQ
co
CM
CM
V
O"Q
^J- O
VI ~
o
X
CO
CO
JO
CD
JZ
"23
o
03
p
5
OL
CO
CO
T3
CO
CM
O
o
VI
CO
CO
CO
a
j=
^3
O
03
T3
5
Phosphorus
o
o
VI
CO
CO
CO
a
jc
^
o
03
T3
^
Ammonia
0
o
VI
to
CO
CO
a
jc
a
o
03
^
Nutrients
CO
CO
"0
tv-
O
o
VI
CO
CO
to
a
JZ
3
O
CD
•a
5
TSS/TVSS
CO
CO
T3
CM
0
o
VI
CO
CO
to
CT
JZ
^3
O
03
T3
5
CO
CD
•o
to
o:
03
-D
X
<
D_
1
Q.
2
2
03
03
"to
5
CO
03
QL
CO
CO
2
"ri
ioreactor Liqi
CQ
CO
"co
>-,
"CO
c
CO
«.
o
**^
CO
CO
XJ
o
^
c.
.5
o
CO
^— .
X
03
J5
CO
to
T3
^
CM
V
O CL
o
vi IT
0
X
t_
JO
E CO
^ CO
O3 CJ
t
T—
CO
to
g3
0
Semivolatile
CO
CO
*u
co
CM
CM
V
O" a
•^j- O
VI —
o
X
CO
CO
JO
D)
JC
"^
o
03
2
5
0_
c:
o
^5
LJJ
•o
JS
_
CD"
^3*
CO
>
7r*
UJ
CO
TO
0
*n
5
"to
o
£
CD
O
to
o
ir"
Q_
CO
13
C
co
5
0
CO
^r
"to
CO
''"
CD
E
"o
CD"
CD
a>
2
CO
1
^*
T3
C§
.£
to
i5
"to
>
UJ
J3
"*~
O
CD
s
S
Z)
to
.§«
1
— v."« '5
CD <0
0 g g .
4-23
-------
TABLE 4-6. SOIL SAMPLE PREPARATION AND ANALYTICAL METHODS
Parameter class
b
Preparation method Analytical method3
'Volatile organics
Semivolatiles, Solids
Liquid
Metals (total)
Antimony
; Arsenic
Barium
Beryl1i urn
Cadmium
Chromium (T)
Chromium (VI)
Copper
Lead
Mercury
Nickel
: Selenium
Silver
Thallium
Vanadium
Zinc
Aluminum
Calcium
Cobalt
Iron
Magnesium
Manganese
Potassium
Sodium
cl
(T)
Metals (TCLP)
Arsenic
Barium.
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
PAHs
Inorganics (other
| Cyanide(T)
; Fluoride
Sulfide
than metals)
Organochlorine pesticides
3550
3520
3050
3050
3050
3050
3050
3050
7196
3050
3050
7471
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3010
3010
3010
3010
3010
7470
3010
3010
See Appendix G of
SAP.
901Z-
13B6
Water extraction
3550
8240
8270
8270
6010
7060
6010
6010
6010
6010
7196
6010
6010
7471
6010
7740
6010
7841
6010
6010
6010
6010
6010
6010
6010
6010
6010
6010
7060
6010
6010
6010
6010
7470
7740
6010
8310
9012,
340.21
9030
8080
(continued)
4-24
-------
TABLE 4-6 (continued)
Parameter class
Preparation method3 Analytical method3
Phenoxyacetic acid herbicides
Organophosphorus insecticides
WCAPs and other soil/technology
parameters
. PH
Water content
Grain size distribution
Oil and grease
Sulfate
Chloride
TOC
TOX
Phosphorus content
Surfactants
Total petroleum hydrocarbons
Total suspended solids
Inorganic materials
Ammonia
Total heterotrophs and PAH
degraders
Microtox
Volatile air emissions
Semivolatile air emissions
8150
3550
NA
NA
NA
NA
Water extraction
Water extraction
Slurry with water
9020
NA
NA
NA .
SM 209n
NA
NA
NA
NA
TO-141
See Appendix I of
SAP
B150
8140
9045
ASTM 02216
ASTM D421-.859
413.1T
9038
9252
9060
9020
365.2f
425.ll
418.1T
SM 209n
300.0
Indophenol Blue
(Appendix G of SAP)
Method SM 907n
See Appendix G of
SAP
TO-14
8270
U.S. EPA - Test Methods for Evaluating Solid Waste. 1986. Volume IB.
Laboratory Manual Physical/Chemical Methods. SW-846, Third Edition.
Office of Solid Waste, Washington, D.C.
Alcohols listed in the volatile parameter class will be prepared/analyzed
by Methods 5040/8015 and the option of direct aqueous injection in Method
5040 will be used.
NA = Not applicable.
40 CFR Part 268.50, Subpart E, Appendix I, March 29, 1990.
40 CFR Part 60, Appendix A, Method 13B, September 14, 1987.
Methods for the Chemical Analysis of Water and Wastes (U.S. EPA 1983).
American Society for Testing and Materials.
Standard Methods for the Examination of Water and Wastewater (SM 1985).
Determination of volatile organic compounds (VOCs) in ambient air.
4-25
-------
sample was placed in an extraction vessel, and the pH of the sample was adjusted to
pH 2 for extraction of acid-type compounds. One milliliter of surrogate spiking solution
was added, and the sample was extracted for 18 hours with a continuous flow of
methylene chloride. The pH of the sample was then adjusted to pH 11 for extraction
of base-neutral compounds. The sample was extracted for another 18 hours with a
continuous flow of fresh methylene chloride. The solvent layers from both extracts
were combined in a concentrator tube, and the sample was blown down to a 1-mL
volume and stored at 4°C until ready for analysis.
The sample was spiked with 20 nl. of internal standard solution before analysis
to enable the quantitation of the target compounds identified in the sample. The
sample was then analyzed in accordance with Method 8270 in SW-846. This is a
direct-injection method for semivolatile compound analysis by use of a capillary
column and a full-scan mass spectrometer. The mass spectrometer allows for a
qualitative identification as well as quantitative analysis of the target analytes detected
in the samples.
4.3 Deviations From the Sampling and Analysis Plan
During the course of the study, several deviations from the SAP were made.
Because of the laboratory's difficulty in analyzing samples for TPH by ECOVA's
methodology, it was decided that EPA Method 418.1 would be used for TPH analysis.
The concentrations of contaminants increased during Weeks 4 through 6 of the study;
therefore, a decision was made to reinoculate the bioreactors. As a result, samples
were not collected during Week 8 of the study as scheduled. In addition, the final
sampling event was changed to Week 9 instead of Week 10. The reactors were rein-
oculated after the Week 9 sampling event. Additional sampling was performed during
Weeks; 10, 11, and 12 to monitor the effectiveness of the reinoculation.
4.4 Safety
Activities involved with the bioslurry treatment testing were in accordance with
all health and safety guidelines described in the Project Health and Safety Plan
(Appendix E).
4-26
-------
All personnel involved with the handling of the waste followed the directions of
the T&E Health and Safety Officer; no deviations from this plan took place without the
approval of the T&E Health and Safety Officer.
4-27
-------
-------
SECTION 5
v
DESIGN AND OPERATING DATA COLLECTED
Prior to the startup of the pilot-scale study at the T&E facility, ECOVA performed
a material characterization that involved the physical, chemical, and microbial charac-
terization of site soils. This information was necessary to develop an appropriate
design for pilot study. During the pilot-scale bioslurry testing, ECOVA collected and
analyzed a series of operating data (particle size, total heterotrophs, nutrient levels,
etc.) to monitor and evaluate the performance of bioreactor operations.
5.1 Material Characterization
The information on material characterization generated during the bench-scale
testing was also utilized for the pilot-scale testing. Physical characterization was per-
formed by using a standard sieve analysis to determine the particle size distribution of
the soil. This information was used to determine appropriate slurry concentrations and
to estimate nutrient requirements for the slurries. Chemical and microbial characteriza-
tions were performed to determine the levels of target contaminants, to determine the
inorganic nutrients required to enhance microbial growth, and to ensure that specific
microbial degrader populations were present.
5.1.1 Physical Characterization
The particle size distribution of the soil was determined by wet sieve analysis in
accordance with ASTM D 2217. Premilling and postmilling samples were collected for
particle size analysis and the results indicated that the milling process was beneficial in
reducing particle size. A detailed explanation of particle size analysis is given in
Subsection 5.2.2.
5-1
-------
5.1.2 Chemical Characterization
Baseline chemical analyses were performed on composited soil samples to
determine contaminant levels. Analysis for semivolatile contaminant levels was per-
formed in accordance with U.S. EPA Method 8270 (SW 846) and ECOVA's Method
SOP SSC-4. In addition, soil was analyzed for oil and grease, TPH, TOG, and inorgan-
ic nutrient ions (NO3, NH4, PO4, and SO4). The inorganic nutrient data were used to
determine whether, based on TOC levels, the ratio of nitrogen (N), phosphorus (P),
and sulfur (S) was sufficient to support optimal microbial activity. Soil pH-was mea-
sured at ECOVA's laboratories by shaking 10 g of soil in 10 mL of distilled water for
5 minutes and then analyzing it with a pH meter and probe. A soil toxicity test was
also performed by Microtox procedures. Table 5-1 presents a summary of the base-
*
line analyses performed.
: TABLE 5-1. CHEMICAL ANALYSES
Compound Method
Semivolatiles (BNAs) EPA 8270
ECOVA SSC-4
Oil and grease (O&G) EPA 413.1
Inorganic nutrients (N03, P04, S04, NH4) EPA 300.0
NH3 . EPA 350.2
T°C EPA 9060
TPH . EPA 418.1
Composited soil sample " Microtox
5.1.3 Microbial Characterization
A baseline microbiological evaluation was performed to determine the microbial
populations in the soil. Standard agar plate enumeration methods were used to deter-
mine total heterotrophic bacteria as well as specific PAH degraders. Total hetero-
„ *
trophic bacterial enumerations wer§ accomplished on a plate count agar (PCA) after
the serial dilution plating of samples in accordance with Standard Method 907. Plates
5-2
-------
were incubated at 27 °C and evaluated daily for growth. Results indicated the exis-
tence of a substantial population of heterotrophic bacteria consisting of 6.3 x 107
colony-forming units per gram of soil.
The PAH-degrading organisms were identified and enumerated by serial dilution
plating onto PAH mineral salts (PMS) plates and PMS plates with 0.05 percent salicy-
late (PMSS) [500 ppm]. Controls for bacterial enumeration included uninoculated
plates of the three media (PCA, PMS and PMSS plates). Quality control of the PMS
plates included plates inoculated but not sprayed with substrate. The PMS plates with
salicylate were incubated at 27° C in a humidity-controlled incubator. The PAH mineral
salts plates were sprayed with the appropriate substrate solution and incubated at
room temperature.
Substrate solutions were composed of 1 percent solutions of phenanthrene, py-
rene, fluoranthene, and fluorene dissolved in an appropriate solution. These solutions
were sprayed lightly over the surface of the PMS plates, which resulted in a thin film of
PAH coating on the agar surface. Crystals of naphthalene were added to the lid of
PMS plates and incubated separately because of the higher volatility of naphthalene.
Plates were checked daily for growth. After 1 or 2 days, a significant amount of
growth was apparent on PMSS plates, and they were sprayed with substrate. Plates
were examined hourly during the first day and daily thereafter.
Baseline microbiological characterizations for total platable heterotrophic popu-
lations indicated that these soils contained a robust population of bacteria [on the
order of 6.3 x 107 colony-forming units (CPU) per gram of soil]. The more than~20
distinct colonial morphologies that plated out on the PCA reflect the bacterial
population diversity. Under the conditions of this assay, several of these were slow-
growing isolates (i.e., requiring more than 1 but no more than 3 weeks for colonies to'
appear). Tables 5-2 and 5-3 summarize the results of substrate-specific enumerations
performed on these soils for certain PAH substrates. The data suggest that
approximately 10 percent of the total heterotrophic population (platable isolates) is
capable of utilizing various PAHs as sole sources of carbon for growth. This subset of
the population totals approximately 106 CFU/gram of soil (Table 5-2).
5-3
-------
TABLE 5-2. ENUMERATION OF BACTERIA CAPABLE OF
UTILIZING PAH AS SOLE CARBON SOURCE
Substrate
Naphthalene
Fluorene
CFU/gram of soil
1 x 106
3 x 106
Colonies
Yellowinc
Reaction
turned dark brown.
j around colonies.
-
Zones of
Phenanthrene
Fluoranthene
Pyrene
clearing present.
2.5 x 106 Some yellowing around colonies.
clearing present.
- 1 x 106 Various shades of browning.
3.0 x 106 • Various shades of browning.
Zones of
TABLE 5-3. SALICYLATE-UTILIZING BACTERIA
WITH PAH COOXIDATION CAPABILITY
Compound CFU/gram
Reaction
Naphthalene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
1.1 x 106 Yellowing around colonies.
1.1 x 106 Dark yellow clearing zones
1.8 x 10s Dark yellow clearing zones,
9.0 x 105
9.6 x 105
No reaction.
No reaction.
Another subset of the total bacterial population enumerated consisted of those
isolates capable of growth with salicylate as the sole carbon source while also retain-
ing the capability of cooxidizing various PAH compounds.
The salicylate-utilizing population also averaged approximately 106 CPU per
gram of soil (Table 5-3). this population appeared to lack the capacity to cooxidize
PAHs greater than 3 rings in size. This was evident by the lack of reaction when fluo-
ranthene and pyrene were used as the screening substrates.
5-4
-------
5.2 Operating Data Collected During Treatment Test
The pilot-scale reactor startup was completed on May 8, 19911 At this time,
reactors were capped and samples taken for the initial Week T0. It should be noted
here that only five of the originally scheduled six bioreactors were brought on line.
5.2.1 Evaluation of Biological Conditions Within the fleactor
Evaluation of the environmental conditions created within the reactor was con-
fined to the daily monitoring of water level, pH, dissolved oxygen, temperature, and
foaming. Appendix G presents the raw data gathered. Figures H-1 through H-5 in
Appendix H present data gathered on each reactor.
Water measurements were taken by measuring the distance from the top of the
slurry surface to the top opening in the reactor. Fresh demineralized water was added
to the reactor to maintain a level of 14 inches from the top of the reactor. During the
first week, water loss in each reactor was 0.5 to 1 liter per day. Early in the pilot-scale
operations, the water loss was found to have a major impact on reactor performance.
Part of the material blockage problems in the airlift arms could be attributed to falling
slurry levels. If the slurry level dropped too far below the airlift arms, it became difficult
for the airlifts to push the slurry above the water column.
A hand-held OMEGA pH/Conductivity Meter (Model PHH-60/80) was used to
monitor pH and temperature. The pH meter was calibrated daily with pH 7.0 and pH
10 standard solutions. Reactor pH was determined by taking a 100- to-200 ml_ sam-
ple from the top port of the reactor and monitoring its pH for 5 minutes. Adjustments
to pH were made with NaOH or phosphoric acid. Daily monitoring of the pH in the
reactors revealed that it fluctuated drastically during the initial stages of PAH degrada-
tion, particularly during the first two weeks of this study.
-Dissolved oxygen (D.O.) readings were taken by using a hand-held YST Dis-
solved Oxygen Meter. Data indicate that the air delivery system on the EIMCO reac-
tors efficiently maintained the D.O. above the baseline 2-ppm concentration needed for
optimal aerobic bioactivity.
5-5
-------
Temperature readings were taken by using a hand-held YST Dissolved Oxygen
Meter with a temperature probe. Readings from the temperature control panels locat-
ed on the reactors were also taken, but were not tabulated because of the associated
instrument error. The Chromalox 3910 Temperature controllers on the EIMCO Biolift™
Reactors were not calibrated correctly for temperature before startup of the system.
Tine slurry temperature was also affected by the heat produced by the air compres-
sors.
Foaming within the reactor was monitored by rating the foam level within the
reactor on a scale of 0 to 4. If no foam was present, a rating of zero was given, and
foam filling the reactor was rated as 4. Foaming was monitored to evaluate air deliv-
ery, mechanical problems, and biosurfactant production. Foaming affected the reac-
tors by interfering with the air manifold systems.: This problem was alleviated by the
addition of food-grade antifoam.
5.2.2 Particle Size
A major factor of concern from the initiation of the pilot-scale phase was the
particle size of the slurried soil. It was important that at least 30 percent of the soil be
smaller than the 100-mesh fine fraction to produce the necessary viscosity for main-
taining a manageable slurry suspension.. Bioavailability of the soil-bound PAH residues
as a function of the path length from particle surface to innermost recesses was cru-
cial for'maintaining a timely^and efficient biodegradation rate. The soil was therefore
wet-milled by passing it through a ball mill three times before using it to charge the
reactors. Particle-sizing samples were taken before and after milling and at Week T8.
These samples were analyzed in accordance with ASTM D422-62. The resulting com-
minution of the soil particles is shown in Table 5-4 and Figure 5-1.
As a percentage of the total solids, soil directly from the site (premilled) has a
relatively high concentration of large-size particles (> 50 mesh). After milling
(postmilling), the fraction of this soil particle size is negligible. The fraction of soil
captured on the 100-mesh sieve represented an appreciably greater portion of the
total soil (42% vs. 26%). The milling process did increase the proportion of soil
5-6
-------
CO
O
p"*"*
O
cc
1 1
UL.
UJ
rsj
CO
UJ
__]
O
DC*
Q_
•^t
10
UJ
CD
*"
c
'CD
>
s
°
"o
CD
CD
0.
03
CD
CD
^^
OO
CT
C
1
CO
0_
a
I
CD
a!
E
E
co
r—
0
c
6
>
CD
CO
cor~.cocor-~cDCD CD-*
OCMCOOOT— r^OCOOTlf)
ooomcotnoo SOOCM
T- CO I" ^ I" 1-
on^SSSSoS?
OOOCDCX3T-r-~CDCJCD
CMOOCOO-r-O-<3-O CM1*
o^ CM CM r^ CD CD r^ * co •»—
T- 1- CM T-
-------
CO
So
CC2
ON
CQCO
LLILU
go-
OL
p
o
in
p
o
P
0
CD
O
DC
LU
III
O =i
CO
CO
LU
CO
o
-------
retained on the 325-mesh. This increase in fines was important in establishing suffi-
cient slurry viscosity to maintain reactor operation. An appreciable breakdown of the
larger sand particles to much finer sand particles occurred during this milling. This
downward shift in particle size distribution after milling was the intent of the milling
process.
Examination of the particle size data (Figure 5-1, Table 5-4) for Week T8 soil
reveals a further phenomenon that must have occurred within the reactors themselves.
The percentage of the soil with particle size < 140-mesh at Week T8 is appreciably
greater than that for the pre- orpostmilled soil. This indicates a further comminution
of the soil particles to a greater fraction of silt particles within the reactors over time.
Comminution increases the viscosity of the slurry (as the number of particles increas-
es), decreases the path length that the PAHs within the soil particles must diffuse to
the surface (which decreases the mass transfer limitations), creates greater surface
area to which bacteria can attach and adsorb PAHs for metabolism, and probably
increases the extraction efficiency of soil-bound PAHs.
5.2.3 Total Volatile Solids (TVS)
The data for total volatile solids (which, theoretically, are indicative of organic
matter1 in the form of bacteria, PAHs, other hydrocarbons, etc.) pertain to the particle-
sizing fractions determined at three of the sampling times (postmilling, premilling, and
Week T8); These data are presented in Tables 1-1 a, b, and c; l-2a, b, and c; and l-3a,
b, and c in Appendix I. Because the data were collected on individual sieve fractions,
interpretations should apply only to the performance of the EIMCO Airlift™ Reactors
and not to PAH degradative rates observed in the reactor slurries. The viscosity of the
slurry itself increased rapidly in the early part of the study as the fraction, of silt parti-
cles increased. Data on total volatile solids in various particle-size fractions are shown
in Figure 5-2. As shown in the figure the percent TVS within each fraction changes
substantially in the milling step, with the volatile fraction being shifted to the lower-sized
particles. The Week T8 sample also shows this trend.
5-9
-------
N
"CO
«
"JO
as
Q.
to
3
g
oj
>
c
o
t/)
33
"o
en
o
1.1
c
o
CO
_
CC
O
CO
cv
in
CD
5-10
-------
The total weight of each sieve fraction of soil and the fraction of total volatile
solids in each fraction were calculated at post-milled and Week T8. At post-milled,
although most of the soil was retained in the 70- and 100-mesh sizes, most of the total
volatile* solids were in the small volume of very large soil particles as well as the fine
sand and silt particles (<140-mesh size). At Week T8, the fraction of soil retained by
200- and 325-mesh sizes had increased and the 100-mesh size fraction had dramat-
ically declined (Figure 5-3). Also, the large fraction of TVS that had been in the >70-
mesh fraction of soil at post-milled had moved to the 140-mesh fraction by Week T8.
This phenomenon could reflect the bacterial degradation of the TVS in the >70-mesh
fraction of soil and the greater abundance of bacteria in the 140-mesh sieve. This
apparent translocation is further supporting evidence of the comminution of the soil
• within the reactors over the course of the study.
5.2.4 Total Solids
Total solids were measured at each of the three reactor ports (top, middle, and
bottom) at every time point through Week T10. These measurements determined the
proportion of slurry to be taken from each port to achieve a 30 percent slurry sample
each time from each reactor. This analysis was necessary because, with this
particular soil in a CSTR, the slurry in the reactor varied in solids content at different
levels. As indicated in the data presented in Table 5-5, fines tended to remain sus-
pended, whereas progressively heavier particles settled lower in the reactor. The sol-
ids content at each port averaged for all five reactors is shown in Rgure 5-4. The
graphic representations of Table 5-5 data are presented in Rgures J-1 through J-5 in
Appendix J.
Whenever the solids content at the bottom port dropped, more slurry was
removed from that port to compensate and to maintain a 30 percent slurry content in
the sample. Tables K-1 through K-8 in Appendix K present the raw data for the per-
• cent dry weight removed from each port on each reactor at each time point. So the
* same distribution of soil grain size would be maintained in each sample, the pro
5-11
-------
o
03
CD
CD
"CO
I
O
CO
c
O
0)
Q.
03
£
D)
"CD
~OJ
^«j
o
CD
S
CD
CL
CO
CD
zi
D)
5-12
-------
Q
CO
Q
_J
o
CO
LU
O
tr.
111
o.
LO
ub
LU
OQ
.
CD
»
in
o o o
000
T- co r^-
co co in
o en co
i- co
o o o
o o o
000
1"*^ QQ OQ
T- "3- CO
t- -r- I--
O O O
O O 0
co co co
CO •* O
o •<• co
•t- T- CD
o o o
o o o
CO CO OO
co co •'t
o co in
T- T- CD
o o o
o o o
in CD •*
•* •<* in
CM CM en
T- T- CO
o o o
o o o
•* co -t
co •* co
co inj---
O 0 0
o o o
T- co en
T- CO T-
in T- T-
E
Q.t3 0
o ^ r:
f- 2 o
m
in
000
o o o
co co ^f
co oo -3-
co co oo
in
o o o
o o o
CM CO CO
en in T-
Is- co co
CM
o o o
o o o
000
•* CM r~-
en en oo
CO
0 O 0
o o o
CD f- h-
CM •* •*
i- CO -i-
T- T- CO
o o o
o o o
co o co
•* CM h~
o co co
1- T- CO
000
o o o
in CM CM
t^ CO CM
CM i- r-~
T- T- co
O-O O
O O 0
in en co
CO CO CM
CM CO O
T- T- f-
000
o o o
in en o
en r~ eo
T- If- O)
1- T- CO
E
Q.T3 O
CD "* ^
I — «^ *c
m
eo
CM in •«*•
CM f~~ S-
co co ^^
in
CO CM O
in o co
en en ^^
CM CM CM
in T— co
o T- en
T- -I- CO
co Is- in
en ^ en
O*y^ ^^
V J l^»
T- T- CO
O 00 T-
cn in in
Of\t tf\
VM l&j
T— T- l V\l (AJ
T— T- CD
in co in
h- oq CM
co co en
T— T— eo
in h* f^-
co en CM
co cd o
E
Q.T3 O
CD «^^ fl
h~ ^ o
m
z
in
in CM •^f
o in m
CM r~- co
fY) »s^ (-ft
UJ 1^ WJ
CM o in
OO CO CO
co en T-
o co co
m tc\ f\\
vj VW '•Vl
T- CD in
CM
T— en oo
co en co
1 — T— CM
^»* fY\ N^.
OJ VAJ 1^
CD CM ^T
•f CM CO
CM en co
co in •*
CM CO CM
T- O O
CM CO 1 —
en o co
co CM en
ff\ |S^ f**
UU 1^ \Ji
CD O i-
T- in co
i^. tn o
in o CM
V— N*. ^~
^^ 1^ ^^
T- O T—
o en CD
in r- oo
CO CM CO
O^t* m
^^ VJ
CO tf Tj-
h- CM in
co en Is-
o co en
Tt CO 0
£
CXTD O
CD !^™ *~
J— ^ ^
m
Q
CO
5-13
-------
CO
Q
_I
O
CO
£
-------
portional volumes taken from each port had to be adjusted accordingly for each sam-
pling event. As an example of how the volumes from any given port changed over
time, Table 5-6 shows that fraction of total sample removed from the bottom reactor
port.
TABLE 5-6. FRACTION OF TOTAL
SAMPLE REMOVED FROM THE
BOTTOM REACTOR PORT
Week % Total sample volume
T0 21.7 ±7.1 '.
'T, 26.0 ± 1.6
T2 28.2 ±1.2
T3 • 30.9 ± 1.3
T4 30.9 ± 6.5
T6 30.2 ± 3.4
T9 41.8 ± 5.1
T10 30.4 ± 0.8
In Figure 5-4 (which shows the solids content at each port averaged for all five
reactors), at Week Tg a sharp dip in the apparent solids value occurred in the bottom
port. The technician was forced to ignore this reading and assume that the solids
content had not changed in the bottom port. Whereas it is possible that the solids
content at the bottom ports of all reactors did indeed drop at Week Tg (the airlift pres-
sure or the rake speed increased through all the reactors), the reactor monitoring
check-off sheets do not support this possibility. An analytical error is more likely to
have been the cause, inasmuch as the percent of bottom port slurry collected later at
Week T10 declined to normal levels.
5.2.5 Inorganic Nutrient Levels
The levels of orthophosphate, ammonia, and nitrate were monitored in accord-
ance with the sampling schedule in Table 4-1. The resulting data are presented in
5-15
-------
Table 5-7. Initially, the nutrient analyses were performed by a CLP laboratory (Pacific
Northwest Environmental Laboratory, Seattle, WA). By Week T6, however, this proto-
col proved to have far too long a turnaround time; therefore, ECOVA performed the
nutrient analyses for Weeks T6, T9, and T12 in-house.
Nutrient levels declined in all reactors over the entire course of the study ac-
cording the data presented in Table 5-8, which is a summary of Table 5-7 in which all
reactor values are averaged.
Ammonia nitrogen is typically the nitrogen source of choice for aerobic chemo-
heterotrophic bacteria; during active metabolism, the levels of available ammonia
should decline. Nitrate nitrogen is typically an oxidized end product of bacterial
metabolism, assuming the ammonia levels are adequate; however, nitrate nitrogen can
be a secondary source of nitrogen. As shown in Table 5-7, nitrate levels peaked at
Week Tg and then declined at Week T12, which indicates that between those two time
points ammonia nitrogen levels did indeed become limiting and the bacteria used the
available nitrate nitrogen. Ideally, when Reactors 2, 4, 5, and 6 were amended at
Week T10, the slurries should-have been supplemented with additional ammonia and
phosphorous. As indicated later in the data for total heterotrophic plate counts, how-
ever, a stable population of heterotrophic bacteria had been established by Week T3
and provided a stable, sufficient pool of nitrogen (total Kjeldahl nitrogen or TKN)
through nitrogen cycling for the duration of the study. -
5.2.6 Total Heterotrophs and Specific PAH Degraders
Levels of total heterotrophic bacteria were determined for the slurries of each
reactor in accordance with the sampling schedule in Table 4-1. Table 5-9 presents the
data in triplicate for each time point, including the means and standard deviations.
The graphic representation of these summarized data (means of triplicates) is shown
in Figure 5-5 on log-scale. Total heterotrophic bacteria counts initially rose from Week
T0 to Week Tv and then gradually declined over the first three weeks of the study from
5-16
-------
3-
1!
C/D
_J
LJU
UJ
—i
}—
2
UJ
CC
ID '
o
2*
^C
0
DC
0
1
10
UJ
CO
rf
1-
03
.2
2
"c
03
O
O
o
z"
CO
z,
CO
0
CO
CM
T~
03
03
CO
03
V-
03
03
CO
CD
\j»
mi*,
03
^J>
03
03
^
CM
03
I
CO
O
V*
O3
03
^
co ^ r»» ^ oo
CM CM -i- CM CM
i— i— Is- T- rf
CO CO CM CO CO
Tf CD -3- in T-
< r>Z)
o o o o o
i— ^— T— i— -r-
-§) n ^ 0 ^
o o o o o
T- CM •* in CD
o o o o o
t3 T3 T3 t3 c3
CO CO CO CO CO
03 03 03 03 03
CC CC CC CC CC
CO
o
1
03
0
c:
O
o
sr
0
Q_
0
CO
Q.
CO
O
Q.
t
O
t§
O
03 . r^ .
oS ^ o ^ o
oq 03 o T
co in T— co
r-~ gQ in CM CM
I^ .^ CD CO CM
T- "-1 T- T- CM
T— — ^ O3 O3 CJ3
oS co oJ oo
X. -3 -3 ^ ^
o o o o o
,_ T- T- T- T-
in CD h- -i- co
in Is- en ^ oo
CM •"*
E -d
>- 03
o ~
*fm \J
03 3
Q. 03
00 "°
113 0
CO ^
"m
^2 II
< ^
CO -Q
5-17
-------
1.21 x 109 (T,) to 1.08 x 108 (T3). Populations of heterotrophic bacteria remained sta-
ble from Week T6 through Week T10. At Week T12, three weeks after reinoculation of
Reactors 2, 4, 5, and 6, total heterotrophic counts had increased, whereas counts in -
unamended Reactor 1 continued to decline. The initial low values for total hetero-
trophs were a result of cell shock from the toxic, highly volatile fraction of phenols and
PAHs in the slurry, and perhaps some cell die-off during the period between the devel-
opmejnt of the inoculum and the charging of the reactors. Declines in total heterotroph
counts after Week T, can be simplistically attributed to the decline in levels of their
carbon energy sources.
TABLE 5-8. BEGINNING AND ENDING NUTRIENT LEVELS (mg/L)
Nutrient Week T0 Week T12
Ammonia 177.7 ± 7.4 2.3 ± 0.4
Nitrate ' < 10 73.8 ± 4.8
Orthophosphate 27.0 ± 2.2 9.1 ± 1.6
During the pilot-scale phase of this project, the diverse bacterial types within the
slurries were characterized and the data were assembled by sampling time point and
by reactor (Appendix L). At Week T0, eight morphologically distinct bacteria types
were present, with considerable diversity in the proportions of types among different
reactors. By Week T2, the number of types had increased to 14, and again the
different reactor slurries displayed a striking diversity in colony morphology. Finally, by
Week T12, as many as 16 distinct morphological types'of bacteria colonies were.
evident in the slurries. This increase in microorganism diversity reflects an increase in
the variety of carbon sources for energy and a decline in the dominance of PAH
metabolizing and co-oxidizing microorganisms. These additional carbon sources are
both metabolic by- and end-products of the metabolism of PAHs in the slurry, as well
as organic matter from microorganisms.
Specific bacterial PAH degrader populations were also monitored in accordance
with the sampling schedule of Table 4-1. Table 5-10 and Figure 5-6 present a quick
5-18
-------
CM
cn
u_
O,
CO
X
a.
O
i
DC
•UJ
UJ
X
co
CD
CD
co
10
LU
CQ
CM
Is- Is- Is- Is- co
00000
+ + + + +
UJ LLJ LLJ UJ til
•«- CD f- O O
CO cn CO O CO
i- i- CM C\J CM
r-. r-, r- Is- CD
o o o o o
+ + + + +
LLJ LLJ LLJ LLJ 111
O O O O O
CO CO h- a- in
Is- Is- r-- Is- co
o o o o o
+ + + + +
111 LLJ 111 UJ lil
O O O O O
-a- co o 1s- o
•- CM T- T- r-.
1s- Is- Is- co
00 00
+ + + +
LU LU LU UJ
•tO CM O
CO CO CO t
CO CM CO h»
T- • CD
* = Q
0 CO .
§ 11
CD ^ CO
CL
I-. Is- 1s- Is- co
o o o o o
+ + + + +
LU LU LU LU LU
O O O O O
o cn ^r T- o
in •* in in co
Is- Is- r»- Is- Is-
o o o o o
+ + + + +
LU LLJ LU UJ LU
O 0 0 0 0
co co in co CD
'co T co in CM
Is- Is- Is- Is- co
o o o o o
+ + + + +
LU LU LU UJ UJ
00000
CT> i- i- •* O
•* •t Tfr t If)
co 1s-- co co Is-
o o o o o
+ + + + +
LU LU LU LU LU
Ol O i- CO O
CM O O O -SI-
CO co oo oo Is*
00000
+ + + + +
in in in in in
co co in in o
t o i*. o. CM
i- CM •«- i- CO
t^ co r*. Is- Is-
o o o o o
+ + + + +
LU LU LU LLJ LU
0 T- 0 0 0
CO CM O) i- i-
CM T- o) co m
co ob oo co r^
o o o o o
+ + + + +
LU LU LU LU LU
en •* co in o
M- CM in Is- in
CM T- -r- f- CD
O) CO O) G3 OO
o o o o o
+ + + + +
III III III III III
in o co CM o
CM CM •* CM CO
T- O"> T- T— CM
co co co co
o o o o
+ + + +
111 UJ LU LU
o o o o
CM co o in
co co in CM
CM CD
X cQ
2 co .
8 icl
CD ^ VJ
DC
Is* l>- !>• 0- Is-
0 0 0 0 O
+ + + + +
LU LU LU LU LLJ
o o o o o
1- CM CO CM CO
in oo oo Is- t-
rv> r- c~. h- co
o o o o o
+ + + + +
LLJ LLJ LLJ LU LLJ
o o o o o
en co in o> o
in 1s- r^ co en
'Is- r^ co co Is-
o o o o o
+ + + + +
111 III III 111 III
O O Is- O O
co o in o o
CD oo i- i- in
Is- co Is- r- co
o o o o o
H- + + + +
III III III III 111
co o en Is- o
en oo T— T— oo
r«. h- 1s- 1s- Is-
o o o o o
+ + + + +
LU LU LU LU LU
O O O O O
CO •* Is- CM CM
CO i- T- CM i-
iv. r-. IV. r-. r-,
o o o o o
+ + + + +
III Ml III III III
O O O O O
CD en CD Is- in
Is- CO OO CD CM
00 00 OO CO OO
o o o o o
+ .+ + + +
LU LU LU LU LU
O O O O O
M- oo in co CM
co in -a- - t- i- Is-
•**• co Is- in T-
•* CD
X = Q
° CO .
O CD T3
§ 255'
tr
Is- Is- r^ Is- Is-
o o o o o
+ + + + +
LU LU LU UJ LU
O O O O O
CO f- •* O CM
Is- Is- en co i-
Is- r- Is- Is- Is-
o o o o o
+ + + -f +
UJ UJ UJ UJ LU
O O O O O
co o in o co
CM CO CO T T-
r~, t^ 1s- Is- co
o o o o o
+ + + + +
LU LU LU LU LU
O O O O O
in Is- co o o
co -^ co ^ co
CO CO Is- Is- Is-
o o o o o
+ + + + +
til LU LU LU UJ
o o cn co co
CO T— CO T— ^*
co co oo oo Is-
o o o o o
+ + + + +
in in in in in
o o o o o
CO CO ^ O O
in in - T- T-
Is- CO Is- Is- CO
00000
+ + + + +
LLJ LU til UJ til
CM o o in o
O CO CM O -<*•
T- en t- T- T-
m CD
o g°.
1 li
oc
Is- Is- Is- Is- Is-
o o o o o
+ + + + +
LU LU LU LU LU
o o o o o
Is- T- T}- T- CM
co cn oo oo t-
r- r-- r-, r- K
o o o o o
+ + + + +
uj til til LU LU
0 O O O O
O CO Is- CM CO
co r- -a- CD i-
r-, Is- Is- Is- Is-
o o o o o
+ + + -f +
ill LLJ UJ UJ LU
o o o o o
Is- T- in co in
co •*• co ^ i-
Is- Is- co Is- Is-
o o o o o
+ + + + +
III HI III 111 III
o o o o o
en co o en en
in CM •*— CM CM
Is- co co CD co
00000
+ + + + +
LU til LU til LU
o o o o o
T- O O O O
t- Is- co cn CM
co h- co oo r**
o o o o o
+ + + + +
LU LU LU LU LU
co o i- cn o
CM Is- CM t •*
T- en CM t- co
Is- Is- CO Is- Is-
0 0 0 O 0
+ + + + +
III III III III 111
C3 O CO O O
CM Is- -r- cn •*
in co T- Is- co
CO CO 00 00 CO
o o o o o
+ + + + +
LU LU LU LU LU
O O O O O
co in T- -i- co
co oo cn co i-
r>-. r-, r-, t-, CD
o o o o o
+ + + + +
LU til lil LU til
CO T- Is- O O
CO •* T- CO CM
CD ' CD
X = Q
o co .
O CD T3
2 255
DC
5-19
-------
CO
ILlF
ftfc
eg
_
co<
ii.
__ o
--
-------
u_
O,
tyj
DC
UJ
Q
DC
O
UJ
Q
HI
CL
O
u_
O
UJ
Q_
CO
Q
C/D
X
a.
s
6
DC
UJ
u_
O
DC
to
UJ
^£
Oj ^— VU
•*^ .C O
co i= UJ
1 co - UJ
a. x
. Q.
CO '
CO CO
*IE i^
a. Q-
co
o
UJ
fx.
[•».
1-
f^.
o
LU
l*x»
CO
T—
JQ
^
^.
o
+
LU
h-
co
•<-
r-
o
>{-
UJ
fSfc,
in
CM
co
o
LU
in
m
T—
00
o
UJ
o
CM
•«-
,^.
O
UJ
O5
CM
f^
0
UJ
TT
•rr
CM
oc
>
CL
I
CO
^>
CL
f^.
O
LU
CO
0
CO
f^
o
LU
co
CO
in
^
o
+
LU
CO
in
in
t^
o
-j.
LU
co
•«}•
in
co
o
•{>
UJ
CM
CO
••-
oo
o
UJ
co
0
"TT-
00
o
LU
in
in
CM
OJ
o
UJ
f—
CM
T-
(^
0
LU
in
CM
CM
<
{J
a.
in m
o o
UJ LU
CM Tf
CO •*
T- T-
in rt
o o
LU UJ
CM 0
a. o_
1 f
CO CO
CO CO
J> ^j§
a. a.
(V.
o
LU
O
co
CM
(x.
O
LU
CO
oo
r-
o
+
UJ
CO
CM
cvi
(X.
o
-J-
UJ
in
CO
CO
co
o
-f-
LU
CM
O
•"-
CO
o
UJ
in
in
co
(v.
o
UJ
o
00
CM
oo
o
UJ
0
CM
<*•
CO
o
LU
O
CO
CO
LU
j:
a.
t
CO
*si
Q_
CO
0
UJ
px.
r*~
T-
[X.
O
LU
rv.
CO
T-
^
5
^^_
[X^
o
•f"
LU
rv.
CO
•*-
(x.
o
-}-
UJ
f**.
in
CM
CO
0
UJ
in
in
••-
00
o
LU
o
CM
••-
fx,
O
LU
O)
CM
fs.
O
UJ
^~
T—
CM
DC
^m
Q.
t
CO
aC
Q.
•
•
CO
«—
™
c
co
CO
B
.
c
o
Tn
CO
CO
E
3
a>
"co
•TT
2
o
2
as
Q>
(0
!•
cc
o
•^
II
•<
z
J3
5-21
-------
co
CO
crz
O LU
"CD
.C
Is
."o
CO
.U5
CD
3
O)
Z)
III
o
5-22
-------
summary of the total heterotrophic count data and the specific PAH degrader data.
As might be expected, the decline of these specific bacterial populations, which pri-
marily use PAHs for their carbon energy source, was more severe than that of the
heterotrophic population as a whole.
Aliquots of each reactor at each-time point were plated in triplicate at three
different dilutions on both PAH mineral salts supplemented with salicylate (PMSS) and
PAH mineral salts alone (PMS). Tables 5-11 and 5-12 present the PMS data for phe-
nanthrene and pyrene degraders respectively. The PMSS data-for phenanthrene and.
pyrene are summarized in Tables 5-13 and 5-14. All of the PAH degraders in PMSS
appeared to rebound at Week T, from very nearly -zero activity at Week T0. Initial inac-
tivity results from the travel of the bacteria at 4°C from Redmond to Cincinnati and,
probably, tfie toxicity of the slurries. Both phenanthrene and pyrene degraders done
on PMS peaked in colony-forming units (CPUs) at Week T3. Phenanthrene, more
easily metabolized than pyrene, again caused a more severe decline in CPUs that
specifically metabolize phenanthrene. There appeared to be a substantial reduction in
co-oxidizing bacteria (evidenced by decreased numbers of microorganisms on the
PMSS plates) over time. This implies a shift in population type and diversity, again
reflecting a growing change and diversity in the carbon sources for microorganic
metabolism. As the concentration of PAHs declined in the slurry, non-PAH degrading
microorganisms gained eminence and metabolic importance. The PMS and PMSS
data for phenanthene and pyrene degraders are also presented graphically on a log
scale in Figures M-1 through M-5 in Appendix M. •
5.2.7 Microtox
The Microtox analysis is designed to reveal toxic conditions that might inhibit or
suppress microbial activity. ECOVA used this analysis to monitor toxicity levels over
the course of the study. These data are presented in Table 5-15 and Figure 5-7. In
this analysis, gasoline, organics, and solvents give immediate toxic responses. Metals
give a somewhat slower toxic response. It is important to note that individual data
5-23
-------
ID
u_
O,
C/D
DC
UJ
Q
<
CC
o
UJ
Q
UJ
Z
LU
DC
X
z:
UJ
IE
Q_
DC
O
u_
o
OD
LU
CO
CD
CM
^^
O
T~
CD
^t
CO
CM
o
co co co co co
o o o o o
HI HI HI HI HI
CM CO CJ) CO O
co co T- in CM
t- CM i- T- CM
tO IN, IN, IN, in
O O O O O
HI HI HI HI HI
o cn o co o
o in co co o
in CM T- i- co
Z Z Z Z Z
r^- CD r**« ^^ r^
0 0 O O 0
HI HI HI HI HI
Tt O CO O CM
o co IN, o in
CM in CM T- T-
fN. CD IN. IN,
.0000
JQ + + + +
cn in o IN. cn
IN. <* T- CO T-
IN. IN, [N. fN. CO
O O O O O
111 111 in in 111
O CO IN. CO O
i- T- CM O CM.
^" ^ T- CM CO
IN, TT IN. CO CO
o o o o o
HI HI HI HI HI
O O i- O O
!*• O O> CO O
IN. -t- t- CO -r-
T- CM •*' in CD
O O O O O
^3 "Q 'S T3 ^3
co co cO co co
CC CC CC CC CC
co in
o o
+ +
HI HI
IN. CO
IN, IN.
T- "t
IN. IN,
0 0
+ +
HI HI
fN. Tf
CO O
z z
0 O
HI HI
IN. O
CO T-
•r- -r-
IN,
O
u5<
t*- Z
in
CM'
CO CO
o o
+ +
HI HI
in CM
UJ T-
V* T-
co co
o o
+ +
HI HI
0 CO
CM CO
*- "-
IN, IN.
0 O
+ +
HI HI
cn fN.
-3- in
CM t-
fN. fN.
o o
+ +
Hi HI
T- CM
i- C\
CM CO
3.
Q
§°
2 CO
.
CO
.£
to
CL
CO
S
CL
CO
C
8O
15
c.
CD
3 J£
CD CO
11
o> o
~° II
i^
Q. Z
CO XI
as
UL
5^,
CO
DC
LU
Q
*^
DC
O
LU
Q
LU
m
DC
>-
Q.
DC
0
LL
<;
1—
^t
Q
CO
^
^£
Q.
oj
"*""
If)
LU
CO
<
H-
CD
(jj
CM
v™
0
*—
Ci
CO
^
CO
CM
o
o o o o o
HI HI HI HI HI
0> in CD co in
CM T- co in i-
CM T- CM CM •*
[N» IN. IN-
o o o
HI ^ ^ HI HI
o z Z o o
r-. co Tt
CM' t' co"
FN. IN. p^. co IN.
o o o o o
HI HI HI HI HI
O O O O O
CM in cn o o
TT CM Tf CO CM
r-. Is-
O 0
UJ UJ<< ^
0 0 Z Z Z
co •*
IN! CD
co r**1 r*"** oo
0000
HI HI HI HI ^
o o o o Z
o cn co o
T^ TJ CD i^
CO CO
0 0
T- CM T- CM CO
T- CM •* in CD
0 O O O 0
rrt rrt rrt cS rB
CD
c Q
CO
CD T
2 co
CO
TO
C
CT3
"3.
CO
S
Q_
CO
? .
S
CD
1 co
c S
CD m
CD §
k. 4^
0) O
CD Z
I "
rff" *^
CL Z
CO JD
5-24
-------
u_
CO
DC
UJ
Q
<
a:
CD
LU
Q
UJ
z:
LLJ
CC
X
h-
UJ
X
Q_
OC
O
u_
Q
CO
CO
CO
LO
UJ
CD
CD
CO
CM
O
cn
CO
^
co
CM
,-
O
•<• "3- m •* m m in
o-o o o o o o
LJ LU LU LU LU LU LU
CO O O CD O CM O5
O O CO O CD CO O
co i- ••* in co T- CM
in in CD in in in in
o o o o o o o
LU LU UJ LU LU LU LU
in m CD o o in o
o co •* CM o co o
T- T- T- oo T- in co
in in in in in in in
o o o o o- o o
UJ LU LU LU LU LU LU
o in o o o cn co
CM co CM CM o r-~ in
•» r^ r*» r^ r*«
o o o o o o o
LU LU LU LU LU LU LLJ
o o o o o r^ CD
o o o CM -i- in o
T- T- i- CM i- CM •^~
co co in in co r^ oo
o o 0,0 o o o
LU LU LU LU LU LU LU
O O O O O CO O
r-~ co in o co in CM
CM in en •" CM in *-
f*» r*- oo oo t^- oo oc
p o o o o CD o
LU LU LU LU LU LU LL
O O f CO O t*^ OO
CM CM Is- O5 OJ T- iT-
CM 1^ T- CM i- i- T-
03 CO CO CO CO 00 h~
O O O O O O O
LU LU LU UJ LU LU LL
cn oo o m co o o>
oo •*— co f» co co co
•i- T- CM co CM CM cn
in in t^. in in co co
o o o o o o c
LU LU LU LU LU LU LL
o o T- o o in o
oo o o co cn -^ CM
t^ i^. T- t-. -sr CM rr
T- CM •* in co
2'2 222 c
co co co co co % —.
CD CD 03 CD CD *" J>
DC DC CC DC OC 2 CO
^
c/i
_C
"o.
0
£0
s, PMS/salk
ader enumeration
O)
CO
T3
X
DL
(0
<0^
U_
co
CC
UJ
Q
<
OC
o
LLJ
Q
LU
•z.
LLJ
CC.
a.
cc
2
Q
CO
CO
LO
LLJ
_1
m
CD
a
CM
O
cn
co
TJ-
co
CM
•^
0
Tf •*}• in •* m in in
o o o o o o o
LU LU LU LU LU LU LU
O O O O O *sf OO
in o -r— f*~ f~~ *f in
^•in^rr ^ *-T-
o o o o o o o
LU UJ LU LU LU LU LU
o o in o o o CM
o in co co Is- •* m
in in -r- Is* in Is*- co
in •* in in •**• in in
o o o o o o o
LU UJ LU LU LU LU LU
o r~- o o o in en
CM CO CO CM O CD CM
T- co CM co CM i- t-
m in in in in in in
o o o o o o o
UJ LU LU LU LU UJ LU
••» r»» •f co o Tf co
in o CM •* o CD •^~
co m i- -^ co co v-
m f» co 1s* in (•>- i*»
o o o o o o o
LU LU LU LU LU LU LU
o o o o o r-- T-
O CM O CM O in CO
i- CO CO i- T- CM i-
m in co in r^ co CD
o o o o o o o
UJ LU LU LU UJ LU LLJ
co o o o CD o> en
co o co o o oo co
CO i f- -r- CM •«S-
CD h» r>- co in r~~ r-~
o o o o o o o
LU LU LU LU LU LU LL
O O CO CM O CM CM
CM in CM o o in T-
in -t CM T- co co •*
oo oo co co oo co r^
o o o o o o o
4- + + + + + +
LU LU LU LU LU LU LU
in CD CM co co co co
co cn oo CD o co in
in in h- in in co co
o o o o o o c
LU LU LU LU LU LU LL
O O T- O'O CM CO
h- O O) CM T- T- CO
r*. t- T- CM •<*• •t co
i- CM •<* in co
o o o o o ,2
•5 t3 o o 13 EQ
co ca ca co co ™ T-I
CO CO CO CD CO <5 2
DC DC DC DC DC 2 CO
rn
1
a.
CD
CO
">f
0
s, PMS/sal
ader enumeration
0)
CO
•a
X
CL-
OT
5-25
-------
o
to
O
o
£
£
o
s
o o o o o o
-^ -°
-- O5
-- 03
-- 1^-
-- CD
i^
"5 uj
5
-- •*
-- CO
-- CNJ
O O5 CO
CO
«:
O
1
CD
DC
,
O)
"c
CD
m
05
"O
"x
o
-*— •
O)
c
'co
CO
2
o
-t~-t »—
OS 0)
4= -a
If
O °3
O 2
O O
> c
"5
a:
E
3
O)
u_
5-26
-------
points may express appreciable variation, and only trends in a succession of data
points should be considered for interpretation.
The general trend in toxicity revealed by these analyses is a decline over the 12
weeks. At Week T4, some toxicity was still present in all the reactor slurries; and by
Week T9, Reactors 5 and 6 still appeared to have some residual toxicity. By Week T10,
either marginal or no toxicity was associated with the slurries.
TABLE 5-15. RELATIVE EFFECTIVE CONCENTRATION OF
MICROTOX ANALYSIS3
Week
Reactor 1
Reactor 2
Reactor 4
Reactor 5
Reactor 6
0
9.69
8.57
8.72
6.51
7.38
4
39.3
48.9
37.6
37.8
52.5
9
94.4
N/Aa
74.4
57.8
47.9
10
100
82.6
68 •
70.4
N/Ab
3 Decreasing toxicity indicates increasing benignity.
N/A = not analyzed.
5.3 Evaluation of Pilot-Scale Operations
5.3.1 Problems Encountered During Startup
Immediate difficulties were encountered in the startup of Reactor 3. After the
reactor had been completely charged, the cap was tightened. An immediate back
pressure occurred within the reactor, slurry was forced up through its center shaft,
and a large amount of slurry was spilled on the area around the reactor. *The reactor
was immediately shut down and the cap loosened. Because of the time restraints in
loading the other reactors, the cause of the back pressure was not investigated. An
attempt was made to restart the reactor later, but this could not be done without
emptying the slurry. After consultation with IT Corporation and U.S. EPA officials, the
. decision was made to leave this reactor off line because of time constraints and a
concern that any analytical data gathered from this reactor would be compromised as
5-27
-------
a result of the loss of slurry material as well as the loss of the volatile constituents
during the drainage of the reactor.
Later discussions revealed possible reasons for the failure of Reactor 3. The air
outlet manifold may not have been large enough to vent the reactors efficiently, which
could create back pressure. A clog in this manifold also could have caused the back-
pressure buildup. A third possibility is that the air pressure coming into the reactor
could have been too great for the manifold system. It should be noted that Reactor 3
was somewhat different from the other reactors; i.e, it was an older reactor with four
side ports, and-it was of a slightly different design.
5.3.2 Mechanical Evaluation of Problems
Table 5-16 presents a listing of the problems encountered during the pilot-scale
operation of the EIMGO Biolift™ Reactors, most of which were encountered and
corrected within the first 2 weeks of operation. None of these mechanical" problems
had any significant impact on the test results. These problems generally fall into four
categories-electrical, air-compressor-related, air-manifold-related, and material block-
age of the airlifts.
For the most part, the electrical problems encountered during the operation of
the pilot-scale reactors were minimal. Twice during reactor operations, fuses were
blown on the controller box of the Dayton Gearmotors that rotate the rake and impeller
drives. The first fuse was blown on the rake arm control of Reactor 5 prior to startup.
A second fuse was blown on the impeller arm control of Reactor 1 on the second day
of pilot-scale operations.
Another concern was the backup power supply in the event of a power outage.
This power supply was assured by use of a backup generator, as specified in the orig-
inal design. A power outage was encountered once during startup, at which time the
emergency generator came on within 7 seconds and operated as expected.
Throughout the pilot-scale operations, this generator was maintained and tested
weekly to ensure its performance in an emergency.
5-28
-------
TABLE 5-16. CHRONOLOGY QF MECHANICAL PROBLEMS
Date
(1991) Mechanical observation
May 8 Reactor setup complete.
Reactor 3 experienced back-pressure buildup and clogged airlifts. The
decision was made to take it off line.
Back pressure on the air compressors caused the influent air to heat.
Overheating may be a problem within the reactors.
Back pressure was experienced in Reactor 4.
Air compressor on Reactor 4 was changed out.
May 9 Airlift arms stopped on Reactor 2.
Airlift arms plugged on Reactor 2.
May 10 Impeller fuse in Reactor 1 was replaced.
Air manifold on Reactor 1 clogged as a result of foaming. Slurry was sent
up the center shaft. Air monitoring system was disconnected by
uncapping reactors.
May 11 Substantial foaming was experienced in all reactors.
Air lines on Reactors 2, 5, and 6 tore because of overheating. Air lines
were later replaced on these reactors.
Airlifts on Reactor 2 plugged because of a soil blockage of the air lines
coming into the reactor.
May 12 Airlift pressure was increased on Reactors 2 and 6 to enhance output
from the airlifts.
May 13 Thermal overload on Reactor 1 was caused by the air.compressor.
Air manifold was changed to 3/4-in. polyvinyl chloride (PVC) to stop the
clogging problem caused by reactor foaming.
May 16 Bleed valves were placed on air lines to relieve back pressure on the air
compressors.
June 19 Air compressor 5 was changed out because of mechanical difficulties.
July 11 Reactors 2 and 4 were reinoculated with fresh inoculum. Reactors 5 and
6 were reinoculated and 340 ppm Tween 80 was added. Reactor 1 was
left as a control reactor.
5-29
-------
A third electrical problem was encountered on May 14 when the air compressor
on Reactor 1 caused a thermal overload on the circuit. Immediate response by IT
operations personnel, who changed the bad air compressor and reinitialized the cir-
cuit, prevented the failure of Reactor 1. The design of the entire system placed each
reactor on a different circuit, which allowed for the failure and startup of a single reac-
tor without affecting the others.
Air compressor problems centered largely around the fact that the air compres-
sors originally designed for the EIMCO Biolift™ Reactors were too small in case extra-
air was needed to remove blockages in the airlift lines. For this reason, larger air com-
pressors were installed in the bioreactor setup; these air compressors proved to be
too large for the reactor air demand. The resulting continual back pressure existed oh
the air compressors and caused constant overheating. Overheating in the air
compressors caused a continual flow of heated air to the reactor, which resulted in
overheating and tearing of the air delivery line to the reactors and increased the tem-
perature of the reactor slurry.
A May 13 discussion between IT Corporation and EPA officials resulted in an
investigation into alternative air delivery systems. As a result, the bleed air pressure.
valves were installed on the lines coming off the compressors. Pressure gauges were
installed in conjunction with these valves to ensure the pressure going to the reactor
was adequate for each reactor.
Other air compressor problems included the May 14 failure of one air compres-
sor on Reactor 1 and an occasional tear in the compressor diaphragm.
The third problem encountered in the pilot operation was back-pressure buildup
irr Reactors 1, 3, and 4. This buildup can be attributed primarily to a blockage in the
air manifold lines, which can occur in one of two ways. Soil foam from the reactor
may block the 1/4-in. air manifold, or moisture from the reactor may condense in the
central manifold or drain back down through the 1/4-in. manifold toward the reactor
and prevent the flow of air out of the reactor. The buildup of back pressure in the
reactor forces the slurry up through the center shaft of the reactor .and out the top.
5-30
-------
On May 13, a meeting was held with IT Corporation and EPA representatives to
find solutions to these problems. Subsequently, 3/4-in. polyvinyl chloride manifolds
were installed coming off the reactors to the central manifold system. This design cor-
rection prevented further problems with back-pressure buildup.
The final (and perhaps most difficult) problem encountered in the operation of
the reactor system was the mechanical blockage of the airlift arms by settled material.
This occurred once in Reactor 4 and multiple times in Reactor 2. Clearing the airlift
arms entailed manually removing the obstruction by partially draining the reactor slurry
material and opening the side port of the reactor to gain entrance to the airlift arms.
The removal of the obstruction involved pumping recirculated slurry material down
through the opening of the. airlift and forcing the settled material out. As the settled
material is loosened, the airflow coming up through the airlift arms further frees the
compacted material. Because the airlift arms must be turned off during this process, a
A
Randolph pump was used to recirculate material between the middle and lower ports
and thereby ensured that the majority of the slurry material would not settle and pre-
vent the rake from functioning.
Preventive measures for dealing with material blockage of the airlift arms includ-
ed increasing the speed of the airlift arms and the air pressure to them, as well as
maintaining a constant liquid level in the reactors.
5-31
-------
-------
SECTIONS .
ANALYTICAL RESULTS
This sectfon presents the results of the analyses of pre- and posttreatment soil
and liquid samples for CS&D List and critical contaminants (PAHs) to evaluate the
performance of the bioslurry treatment system. Also presented are results of the
analyses of air characterization samples collected during the pilot-scale study. All of
these samples were collected by ITEP, and the analyses were performed by ITAS-
Cincinnati. In addition to ITEP's sampling and analyses, ECOVA performed PAH
analyses to evaluate the design and operation of the system. All of these analyses
were performed by the ECOVA laboratory in Redmond, Washington.
The pretreatment samples were collected at the start of testing (Week T0) to
determine the baseline concentration of the critical contaminants in the soil prior to
treatment. The posttreatment samples were collected 9 weeks (T9) arid 12 weeks (T12)
after the start of testing to determine the levels of the critical contaminants remaining in
the soil after treatment. The data obtained from Week T9 should be used for evaluat-
ing the technology's performance and for BOAT rulemaking. The data from Week T12,
# i
air sampling, and bioreactor monitoring (e.g., TPH) should be used only for infor-
mation purposes.
The methods for analyzing for critical parameters were described in Subsection
4.2; the other analytical methods used were listed in Table 4-6. Table 6-1 presents the
ITEP field sample coding, the ITAS-Cincinnati. laboratory sample coding, and the dates
samples were received, extracted, and analyzed in the laboratory.
-J. 6-1
-------
^COCOCOCOCOCOCOCDCOCOCPCOCOCOCOCOCOOOCOCO
u
01
0)
en
CO
>
S
01
a
0
r^
CM
oo
oo oooooo
cocoaooo
oocoooQO
cocococo
«o
QQ
PE
o
a
in co
o o
i i
r*. »^
co
in
r^ r^» . r«»
ZJT3 I3T3
o
0)
1 1 1 i
i t * .V
-o
O)
Q- a. i— a_ o- co QQ co co co co co ca ca co
o
o
6-2
-------
" T3
"re
re
01
re
a
T3
a)
-*-»
re
X
01
re
o
-o
01
? X X
3C Z 31
1— h- h-
CO CO CO
1 1 1
1 1 1
1— t— t—
-o
CD
3
O
U
6-3
-------
1
V— ^
1—1
1
(0
Ul
IS
r—
(V
-M
"O
OJ
2xtrac
0)
•t-»
TO
O
•o
a
0)
0
t-
0)
+-»
as
a
OiCOO|cnc«C^COCOCO^CO^^^
^^c^c^CCC^CCCC^l^^
J3 Jt ^ ^ ^ ^ ^ ^
^cococococococo
^oococococococo
oSooooooooocpcpoci)
?'?VVTVVili 'ri.rLrlri.
? ? ? §0 0000000000
ac az 3: a: nz 3: n:
a_ Q. O- o_ d. a_ d.
Coco^coco-Sco'coscoarco^cos
22^2221^2 -ssssss
1 1 1 1 t 1 1 1 t 1 1 1 1 1 1
^ ^*- to CO CO CO CO CO CO CO CO CO CO CO CO
^ t- |_ H- 1— t-t-l— 1— I— 1— t- 1— 1— H-
OJ
oo
•—I
CO
-^
CO
o3
oo
in
o
1
1
CO
I
CO
1
cn
1 —
OJ
«— 1
00
CO
^~
CO
•a-
03
CO
O
1
0
t
CD
t
C
(O
-H
£
CO
o
E
(0
D
O
0)
n
"c
-o
O)
=1
C
6-4
-------
+J»
c
o
u
••"S
I
o
, '
CO
a>
Cu
cu
c;
cn £
c: cn o
. — . — o
•r- »— O
E — c
•*J E <0
co cu o
0 (- (.
a. a. o
CO CO
«— 1 •— 4
*- 4 ^^
CO CO
«— 1 «— 4
cn co
CO CO
«— 4 *»4
cn co
4n in
O 0
CO CO
CD O
CO OO ,
in in
in in
CO CO
.-4 CVJ
0 O
1 t
in in
CD CD
1 1
in in
0 CD
i i
x: i<
-u
o
i —
j_
CO
•a
u
u
cn +J
c: cn cu
•»- c o
i 1 1
CO O) CU
O t- -C
«-H «— 1
cn en
^ — .
«— « «— i
CD CD
cn cn
^ ^
CD CD
cn en
m in
0 O
in m
«— i «— t
OO CO
CD O
m m
in in
CO CO
*-* CM
CD 0
1 1
r-. r-*
in in
o o
i i
m in
CD CD
1 1
•M
(^
U
QJ
C
CO
i-
o
cn a
c: cn co
— c o
EE *j~ C
co
o,
o
6-5
-------
9
+^
• c
o
rH
Ui
J
CQ
T3
Ol Ol .Ol C
c^ Si gg ^^ oS c
C>JCM ZLZ; ^t ^ CMCM C
in in to to m , m L
,_H *-H ^H*-H ^<^| ^H v-l »
oioi 0101 o> 01 oiai c
into tnio ioin into t
_Q JQ ry.
CMCM CMCM CM1^ CM*^ d
to m .— « «— i • -— * tn *
CMCM 00 °5 H^S *
0101 0101 ^S CD^
*-lCM »HCM .-HCM ^HCM
CDC3 CD CD OO OO
II II II II
into torn mm mm
OO CDCD CDCD OO
m to torn mm min
OCD OCD OCD OCD
II II 1 1 1 1
*^ *— 1 «— 1 ^H ^^ *—* ^H ^~*
XX XX XX XX
&
to
(_
o
r~
O) Ol O) D Ol
CO) C O> C O) CO C O)
^-c -^-c ^- c o t- c
eu, — ^- i — -r-aji — t- .c t— t-
-o-'-^l'-^-S-^:0-^:^:"
O -M E CI 4-* £ O •*-* E IO(-i— OS-OOU3I
o ex. a_ o| a_ ex. U- o_ a. i — ex. ex. col
H *-H «—•*—) *— 1 •— 1
Fl Ol Ol Ol Ol Ol
3 CD CD CD OJ Ol
Q CO *— * *— * CM CM
o in m to m in
.
-4 «-« *— 1 •— 1 •— 1 *— 1
n 01 01 01 01 01
D" CD CD CD CO Ol
O CO •— « «— < CM CM
T in in to mm
-| ^-( ^-| «— t ' T-* *— 1
7> Ol Ol Ol Ol Ol
o 10 mm to to
fB OO O CD O CD
O CO CO CO CO CO
3 O O CD CD O
71 Ol Ol Ol Ol Ol
r— 4 CM •— i CM *-H CM
O O O O O O
t 1 II II
n to mm m to
O CD CD CD CD CD
n tn mm to m
O CD CD CD O O
II II II
XX X X X X
c
o
t_
o
u
O> Ol C O>
CO) C O) (d C O)
o t- 'si o t- o o t-
a. a. co| o_ o_ j— a_ o_
-o
CD
3 .
O
O
6-6
-------
.
•
""
•*£
o
u
1
(O
Ul
_J
CO
«c
T3
s
c
5
O
0)
t_
0)
•*-*
TO
Q
to
CO
^
TO
«i
O
_•
C/l
1 —
O
2
o_
LU
,-H -H
CO O)
LO In
in to
• .— i •— <
CO CO
m tn
T-H T— t
in In
cn co
r-* r-*
LO in
CD 0
CM CM
O O
cn cn
»-H CM
CD CD
1 1
LO tO
O CD
LO LO
O CD
CO
c
CD
D
O
ID
1C
O
E cn
§ £ I?
o £H ,^
f— "E ^
03 -M 6 CO
O O S- CD
1- 0_ 0_ 3-
cn cn
cn cn
-LO in
<— 4 *— 1
CO CO
cn cn
In In
*— 1 »-H
CO CO
r^ r^
in in
_£J
T-H .
tn ^^
s ~
»-l CM
O CD
1 1
r-~ r«-
in in
o o
in in
0 0
O)
C 0)
••— !""
CO CD
O t-
0. OL
-O
0)
0) N
-U >>
(O i —
c
IQ (J)
° 2
<0
CO
CO
>,
"*
O
CO
£
0
CD
o_
LU
t—
cn cn
£ ^
^ ^r
^-i •— *
CO CO
CO CO
^ *"* ~~*
.
LO LO
CD CD
1 1
in in
0 0
f t *-t
— .
i
o
1 — "*"•
1
tn o
O I—
E
, t-
**- c cn o
4J i- C
£ ^2 ;z £
1 1 i '5
E co
4-» e c
CO CU 0)
O t- -C
a_ o_ a.
O) CO
CO CO
CO CO
CO CO
**> ^^
CM CM
LO LO
*-H ^H
O Ol
CO CO
.^^ ,^^^
LO LO
Ol Ol
*^ ^»^
LO LO
CD CD
tn tn
^H •«— t
CO CO
CD CD
CM CM
LO LO
CO CO
«— 1 CM
O CD
1 1
in in
O CD
I f
in LO
CD CD
f 1
.
Q_
C Ol O
— C t-
•— 1—
O I- CD
0_ Q_ 3E
( Ol CO Ol Ol
— t CD CD O
CM CM CO CM
LO LO LO LO
CO CO CO CO
o? i^ f^ r^
^H *— < *— 1 i— 1
in tn tn tn
*— 1 <— 1 *— 1 f— 1
Ol Ol Ol Ol
CO CO CO CO
^^ '**^ "*^» "^fc
< in in m m
*—t r~ 1 •— t •— <
CO CO CO CO
^•^ ^.^ »«,^ ".^^
LO LO LO LO
CD O
*— ) CO
i°^S 5
CD CD
CO CO
• ,_,
• CD
I
in
CD
1
LO
CD
«-H
cn
c
• ^
'i
p -M
CO
£ '
=3
C
, C
o
o
6-7
-------
u
2
01 f*"* P*"*
in in in to
01 OT o> <
CO CO CO CO
*-H «—1 «—I r-l
LO in in LO
QJ
-M
-------
6.1 Premilling and Postmilling Soil Samples
6.1.1 CS&DUst
The samples collected from premilling and postmilling processes were analyzed
for the CS&D List of volatile organics, semivolatile organics, pesticides, PCBs, dioxins,
furans, metals, and inorganics. Table 6-2 presents the CS&D constituents detected in
the characterization analysis of premilling and postmilling samples.
6.1.2 Critical Semivolatile Organic Contaminants
The premilling and postmilling samples were also analyzed for the critical semi-
volatile organic contaminants. Table 6-3 presents the concentrations of critical semi-
volatile organic contaminants. As shown in Table 6-3, concentrations of the individual
PAHs varied before and after milling; some concentrations actually increased after the
milling process. Analyses showed an overall 13.8 percent drop in PAHs after milling.
This drop is not as statistically significant as it would appear because of the con-
siderable variation in analytical results that occurred throughout testing.
Copies of the analytical data provided by the ITAS laboratory for the CS&D
constituents and critical contaminants in the premilling and postmilling samples are
included in Appendix N.
6.2 Results of Pretreatment and Posttreatment Soil Samples
Table 6-4 presents a summary of the results of analysis for critical semivolatile
organic contaminants in the pretreatment soil samples (Week T0) for the five reactors.
Tables 6-5 and 6-6 present the results for the posttreatment soil samples for the five
reactors for Weeks T9 and T12, respectively.
In addition to the analytical results, Tables 6-5 and 6-6 list the Method Detection
Limit (MDLs) for the contaminants in the soil matrix. The MDLs are based on laborato-
ry results from instrument detection limits for semivolatile compounds injected in the
GC/MS and the matrix spike/matrix spike duplicate results from the posttreatment soil
samples. Section 7 contains a complete discussion on determining MDLs. When
6-9
-------
C/D
C/D
NCO
CC UJ
UJ -J
I— a.
DC W
<_J
o
Or)
£D.
UJQ
Q2:
co<
wyj
ZS:
o°-
OU_
08
CO
O
CVJ
CD
CO
c
"E
to
O
Ol
c
E
CL
V.
1
Constitl
05
o
ra
CO
:
'oiaiiis uraanic noiai. i
Methylene chloride
CO
CO
CO
CD
co
•^
.
2-Butanone
•vj
ci
Benzene
m
CO
oj
as
c\
Toluene
:-
Ethvlbenzene
<°.
•r-
T3
0 § -2
CD "S
CD •*-' T?
f||
C CO "•
< UJ n
U II Q
03 -3 Z
to .a o
6-10
-------
O
CO
CD
c
£
a.
S
~o
N
C
CD
CO
c3
O
CO
CD
C
CD
I
co
CM
~o
CD
•o
c
o
V
o
CD
C
CD
1
_TO
.E
re"
I
CD
Q
••*
0>
CD
C
_O>
I
j£
•S
~o
N
CD
CO
CO
O5
CM
CO
CM
CO
CO
B
6-11
-------
C/D
^
<
in
O
•z.
O
O
CD
LLJ
CQ
CO
DC
fl
a
£
a:
| Contaminan
s
o
T^*
in
o
o
co
CO
o
o
co
| Naphthalene
CO
CM
o
t —
CM
CO
O
CO
0
CM
CM
1 2-Methylnaphthalene
co
en
Vj'
in
in
CO
en
CO
1 Acenaphthylene
in
en
o
CM
CO
CO
•<*
o
CO
0
CM
1 Acenaphthene
co
o
CO
CM
CO
O
o
1 —
0
en
| Dibenzofuran
o
o
oo
CO
in
o
in
V—
0
CO
CO
I Fluorene
o
o
CO
O
•^
00
o
in
o
co
0
co
co
| Phenanthrene
o
"fr
o
CM
in
CM
en
o
o
CO
0
| Anthracene
O
co
o
CO
CO
o
CO
o
CO
CO
0
in
| Fluoranthene
0
in
o
o
in
CO
CO
o
CM
o
co
CO
CD
c
1
Q_
"*
O
co
CM
O
CO
0
-sf
I Benzo(a)anthracene
s
o
CM
CM
in
co
0
CD
c
CD
-------
z:
C/D
o
o
O o
I"
S<
LUCO -55
CO _i
"
Em
02
^t
o <
^UJ
cocc
H
•z.
in
o
2:
O
O
LO
co
LLJ
CD
CO
_J
O
f?
ffi
S
E
1 Contaminan
•
CR
O
s
CD
C
2
J
"ci
*M
c
c
CQ
•>—
CM
O
•-.
CM
V
lv
^_
^*
cv
V
CD
CJ
J
CO
c\
"c
c
T3
C
in
o
CO
in
•<—
V
in
V
in
cr
in
CO
a
|
~c
a
CI
"c
c
e
C
o
en
o
CO
0
en
V
V
0
en
V
o
en
V
en
\t
CD
C
4
>•
a
c
*—
X
_c
"c
c
m
m
CM
: )
M
V
in
CO
J)
CO
V
CO
CO
o
V
^
T-
r--
V
CO
cc
V
"5
._;
e
c
c3
CD
CD
T3
0
CD
Q.
3
0
CD
X)
-a
2
CD
CD
T3
2 c
•-; Q.
-1 e
fe 8
t3 -s
3MDLs =' Method Dete
bj = Estimated value c
6-13
-------
8
O
z: ^_^
< CM
gn
0«
UJ 05
<0 E
QCO^
^2
U_ I—
0<
it
CCEL
LJJ
O
O
O
CD
CO
UJ
CO
«
V
£
a
g
s
,-
Contaminant
"
o
CO
f^
CO
T—
CD
CD
CM
CO
Naphthalene
T—
•"^
*-
Is*.
T-
V
5
s
•«-
t^
V
2-Methylnaphthalene
Q
ir
in
"*
o>
CO
in
»—
o>
in
V
^_
in
Acenaphthylene
*~
^
v
j^
w—
V
tf,
z
*-
t^
V
Acenaphthene
CO
r
c\
d
T-*
IT
CO
CM
3
CM
Oibenzofuran
CO
^^
'-
CO
T—
V
Si
CO
'v
CO
*—
V
Fluorene
in
CV
o
o
09
fh^
tA
CM
in
00
•r-
Phenanthrene
**
in
CO
o>
in
co1
T-
3
•*
CD
CO
Anthracene
CO
a
co
CO
i^
CM
CO
CO
en
**
Fluoranthene
00
CO
00
CO
CO
<&
CM
o
O)
o
CO
CD
I
(X
CD
in
in
in
in
u^
T—
CD
"*
O)
in
Benzo(a)anthracene
CM
o>
5
CO
~vL
CO
erf
T—
O
s
00
a>
Q>
TO
C
CO
CO
o
o
00
o*
CC
o
co
o
^
Benzo(b)fluoranthene
«;
co
S
o
CM
£»
cv
3
*_
CJ
I
B
D
a
CD
m
CD
•^
in
T—
7
cv
CO*
O)
"v
CD
e>
I
I
co
CM
D
B
CM
^
CD
^-
CD
,J
CM
^
CO
c
c
ra
D
M
C
O
JO
o
T—
N:
v
CO
CO
f^
r-
V
j:
v
—
Benzo(g,h,i)perylene
0
?
CO
Q
CD
rj-
V
CC
c
o
'v
E7>
0>
M
V
^.
in
CO
co
v
5
5
.ts
E
o
"m
•o
1
"5
CD
s-
_o
•o
£
CD
CD
•o
w 1
i|
j |-
18
MDLs - Method Detect
J - Estimated value of
(0 J3
6-14
-------
compounds were not detected, the results are reported as being less than the detec-
tion limit.
The concentrations of the PAH contaminants' in the pretreatment soil samples
ranged from 5.5 to 840 mg/kg. The concentrations of the PAHs in posttreatment
samples indicated a significant reduction of PAHs in the soil matrix. Results from the
posttreatment samples indicate the more complex PAHs, such as benzo(b)fluoran-
thene and benzo(a)pyrene were more recalcitrant to the biological activity than the less
complex PAHs, such as naphthalene and acenaphthene. Results from Week 12 indi-
cate that additional spiking during Week 9 did not assist in further degradation of the
complex PAHs. On the contrary, the level of contamfnation due to the presence of the
more complex PAHs was greater in Week 12 than in Week 9. The lower level of PAHs
contamination in Week 9 soil samples may have resulted due to inconsistent labora-
tory procedures. These nonhomogeneous soil samples may not have been thor-
oughly remixed'before the sample aliquot was obtained for extraction.
Table 6-7 presents the percentage reduction of PAHs in the soil matrix based
on the data in Tables 6-4 through 6-6. The total percent reduction of PAHs for Week
T9 samples for the five reactors ranged from >44.2 to >97.1 percent. The total per-
cent reduction of PAHs for Week T12 samples for the five reactors ranged from >74.2
to >90.6 percent.
Copies of the analytical data provided by the ITAS laboratory for the critical
contaminants in the pre- and posttreatment soil samples are included in Appendix N.
6.3 Pretreatment and Posttreatment Liquid Samples
Table 6-8 presents a summary of analytical results for critical semivolatile organ-
ic contaminants in the pretreatment liquid samples (Week T0) for the five reactors.
Tables 6-9 and 6-10 present the results for the posttreatment liquid samples for the
five reactors for Weeks T9 and T12, respectively. The MDLs for the contaminants in the
liquid matrix are also listed in Tables 6-9 and 6-10.
6-15
-------
CD
O
CO
z;
CO
<
z:
O
O
o
^
) Is-
> O5
4 O
3 cn
5 cn
3 CO
3 CV
1 05
A
t CD
f CD'
n cn
n co
O CO
n cn
A
3 in
O Cv
o •»—
A
«- oo
35 cn
35 cn
XI CO
XI O5
35 cn
^
—
.£P.
£ .
"OL '
Z CV
CO
o
CO
on
^
i!
CD
cn
A
cc
CD
co
00
03
in
"?
O
CD
cn
in
cn
CO
<
CM
CD
m
CM
cn
cn
CO
CO
cn
oo
7)
JC
CO
O5
cn
cn
00
O5
co
cn
cn
oo
co
O5
—
C
in o
co r--
cn 01
CD 1-
cn cr
O5 O"
A
T— if
cn a
O5 O
cn o
oo a
cn a
A
m c*
cn o
cn a
A
05 -:
co' o
cn c
O5 C
O5 C
o r
O5 C
OO <
35 '
in
cn
cn
L
CM
in
O5
cn
CO
O5
) CO
> CO
> cn
j TI-
3 00
5 O5
^
3 00
•> O5
t •*
d h-I
n cn
n oo
O CO
n cn
- l^
35 en
A
O CD
35 cn
35 O5
n in
xi oo
35 CJ5
-c
Q- <
co •«-
CM "•*
cn cn
O CO
00 00
cn cn
in f~-
35 O5
o r-^
r~- in
O5 O5
in co
35 05
05 05
in in
cn cn
0^
oo oo
cn cn
03 .Tj-
o oo
O5 CO
CM O)
O5 CO
cn cn
f-. CM
f- f-
05 05
_c
LL C
CO^
co -* in
CO CO OQ
cn cn cn
co in IT
cn cn
00 O 0
CO CO f-
05 05 T;
CO CM ^1
Tt- 00 T-
05 00 U
00 0 C
in •* c
cn cn c
in co c
•r O5 V
cn 03 -^
O O T
1^ CD T
0) cn c
T— CO C
^ CD C
O CM C
CO CD <
cn cn -
co •^r
in co
O5 O5
4_l
J5. (D
•—
CO O
CD
CO
CO
in
h~
oo
) O
- o
• o
i- in
5 in
3 CO
i •>*
3 CM
F5 •^f
3 CC
- CM
M *
O O5
3 O
D O
X3 O
* f-
_, ^.
r—
5
^
it*. ^—
"o ""
C C
z
in
CM
CD
in
35
~*L
O
O
in
n
•%.
<
•z.
00
cn
co
at
z
CD
CD
>•!
"O
cr
rv
c
c
^
\
Z
O
O
CD
O
co
O5
^
^
m
CD
in
o
ff
z
CO
"T
00
cr
oo
C
'z-
o
in
^
ff*
<
<£-
_
LO
C
^r
<
z
z
^c
^
—
c
CM
V.
^
in
o
O5
A
CM
so
oo
A
CO
x>
A
CD
o
cn
A
CD
co
A
00
CM
O)
CV1
^
A
^
35
A
in
CM
c
t
H
CD
J3
-------
o
o
CDH
tr*.
o *
V 05
5 E
OLD
u-2
oca.
O
•z..
O
O
CO
CD
LU
CD
g
Q?
S
s
'c
CO
1 Contamin
m
o
X)
CO
0
o
o
o
CO
•»—
0
<3
CO
CM
,_!
1 Naphthalene
CD
CM
0
CO
O
O
O
CM
CO
•<*•
0
O
V
CO
0
CD
75
x:
x:
c
n
">
X|
a
S
CM
10
o
0
-3
CD
CO
0
0
CO
CO
o
— )
CO
o
o
^
CD
O
0
CD
J
Xj
c
a
c
CD
C.
CM
CO
0
CM
CM
0
05
CM
CM
CM
O
CO
CM
0
0)
a
c
n
c
CD
C.
CM
0
CD
O
CM
CM
CO
O
00
0
1 Dibenzofuran
M
0
CO
o
00
CM
0
o
O5
o
1 Fluorene
^
o
in
CM
o
CM
r-
CM
o
CM
o
1 Phenanthrene
oo
o
o
o
o
in
0
o
00
CM
CO
in
o
o
in
in
o
o
1 Anthracene
r-
o
05
0
O
in
CO
CM
en
0
o
CO
o
o
1 Fluoranthene
<*
o
in
o
o
o>
CM
CO
CD
0
0
CD
in
o
o
CD
c:
a
I
~3
CO
CO
o
o
CM
O
0
T-
—)
O
o
Cv
o
o
CO
1 Benzo(a)anthracen
b
o
—i
o
o
co
,—
—3
0
0
—3
co
O
0
CD
a
V
x
b
0
-3
f-
O
O
0
^
1—
-3
CO
0
o
-3
CM
O
0
CD
C
1 Benzo(b)fluoranthe
-3
CM
T—
O
0
o
o
CM
O
o
0
V
0
o
v
CD
a
|
"c
c
a
m
s
o
V
o
o
V
in
CM
o
•«*•
o
o
V
0
d
w
CD
C
p
.•—
c
CO
c\
*•_••
a
£
Tfr
O
V
o
0
V
••*
o
o
0
o
V
0
0
V
CD
1
1 Dibenzo(a,h)anthra
0
O
V
o
0
CM
0
0
o
V
o
0
V
CD
CO
it
0)
c
.*•
X
j:
"c
I
^
0
CM
O
-3
0
CM
O
T-
O
"c
a
a.
LU
o
^~
LU
CO
O
O
T-
LU
CD
h-
O
LU
}^
O
"c
a
c
£
t
CM
LLJ
0
r~
CM
in
o
s
o
3
o
LU
00
0
"c
c
CD
f
>
0
LU
co
1—
LU
T-
LU
CM
»"
1 1 1
,-
•»—
1 2,4-Dimethylpheno
CD
CO **
c E
CD c
£ .S
b S
II
- a>
m ?-
18.
ca
s*
"S "°
"o f\
"S ®
~° -o
C g-
M
E £
b 8
"o 75
S CD
3E o Estimated vali
''J a Estimated valu
6-17
-------
.
o
o
o
i
oc
O
bi-
Qll!
<0
UJ
o
•z.
o
o
O5
CD
LJJ
CO
en
_J
O
s
•0-
a
T—
^
CO
1 Contam
^3.
o
0
o
o
o
V
ro
0
d
r_
0
o
V
^_
rl-
C
V
^_
o
o
o
0
o
o
V
^
3
q
v
N.
o
o
o
V
f-
o
q
v
^
c
o
c
CD
C
a
a
^
c
"i
"c
N
C
CD
m
n
M
o
o
in
M
v
in
M
o
v
in
CM
0
o
V
..
c
V
in
ex
c
CD
C
c
jq
n
Y—
O
o
o
o
^.
d
o
o
d
CM
o
o
CD
CD
.C
C
c
2
1
c
CO
*tf-
M
O
O
—3
M
O
O
in
o
d
CM
0
o
r-
o
d
_o
"' J
CO
o
o
1 Benzo(a)pyrene
co
D
O
0
CO
o
o
V
M
O
d
CO
o
o
°
in
c
d
CO
o
o
°
CD
C
Q.
cr
CV
"o
c
c
n
r>
^>
o
0
in
r)
3
V
n
->
d
m
CO
o
o
o
v
in
CO
c
V
ir
cr
c
c
CD
r~
CD
C.
ro
^
c
c
^~*
n
•»
c
<
if
in
o
o
o
in
n
v
CO
M
q
d
in
in
0
o
v
in
in
c
c
v
in
IT
"3
CD
C
&
C
i
_c
c
m
*^f
o
o
o
v
vj
q
v
o
0
V
q
v
0
c
"c
c
<
0_
^-
o
o
o
V
vj
q
v
0
0
v
o
V
0
o
V
"c
c
.c
i
"c
CM
Tj"
O
0
0
V
v|
o
V
0
o
v
o
V
c
o
V
"c
c
c
j
J
*
^-
o
0
o
V
vj
o
V
o
o
y
o
d
V
o
c
^n
cz
0
_c
s.
0
S
b
•«;
CM
•|
C
O
0
CD
CD
T3
•o
' O
s
-------
3
*<§£
-£
.12
r^
0
Z
<
I
o
o
o
o
rr
LU
LUCO
OQ
O)
E
rr
o
I-
•z.
Ml
E
go..
LJJ
O
O
o
CD
til
_J
CO
CO
CO
1
O
rr
rr
f$~
u.
s
| Contaminan
a
i
CM
0
o
o
CM
O
o
o
V
<\l
0
o
0
V
CM
o
o
0
V
^>
CM
0
O
O
V
^}-
CM
O
0
O
V
1 Naphthalene
.
CD
2
CM
0
••)
^ —
0
0
o
o
0
°
0
o
0
V
0
0
o
V
0
o
(—1
V
0
o
<3
CD
CD
>,
a
CO
c
CD
O
a
«
en
CM
0
o
en
CM
0
o
V
r\i
o
o
V
m
0.1
o
0
V
O5
CM
o
(— >
V
en
CM
o
o
V
CD
CD
JC
*-•
x:
a
re
c
CD
O
O
II
t —
t —
o
o
^
o
°
^_
o
Q
•r—
o
o
V
o
<— >
V
••-
o
o
V
1 Dibenzofuran
o
t
ro
o
o
0
CO
0
o
o
V
ro
0
o
r>
V
m
0
o
o
V
CO
o
o
<-}
V
CO
o
o
*3
1 Fluorene
o
i
^j-
0
O
0
o
0
o
V
T-
o
0
o
V
,-
o
0
0
V
^ —
o
0
r>
V
T —
o
o
o
V
I Phenanthrene
a
a
rn
0
0
0
5>
o
0
o
V
en
o
0
0
V
f
0
o
CO
o
0
V
co
o
1-1
V
CO
T—
0
o
V
CD
c
£
jl
"c
N
C
CD
CQ
co
o
o
o
CO
o
o
o
V
co
o
o
0
V
CD
o
o
o
V
CO
Tfr
o
o
0
V
co
0
o
o
V
<1>
£
>,
Q.
f
CO
c\i
»•— -
o
c
CD
T3
C
m
O.I
o
o
o
CM
o
o
o
V
en
CM
o
o
0
V
en
CM
o
o
o
V
en
CM
o
o
o
V
en
CM
0
o
0
V
1 Dibenzo(a,h)anthracer
CO
T^-
0
o
CO
0
v
on
0
0
V
m
0
0
V
co
0
0
V
co
0
o
V
CD
c
CD
>,
CD
Q.
*— *
jf
.0
C
CD
m
•^j-
0
o
•st-
o
o
V
^3-
o
0
V
^}-
o
o
V
:*
o
o
V
,3.
o
°
"c
c
d
Q.
^J-
o
0
o
o
V
Tj-
o
0
V
•53-
o
o
V
o
0
V
^
o
°
"5
CD
o
>.
a
C\l
T^-
o
0
o
o
V
^J-
o
o
V
^J-
o
o
V
o
Q
V
^.
o
o
V
"o
a
c
>.
'S
4
^>
o
0
o
o
V
rj-
o
o
V
^J-
o
o
V
o
o
V
^.
o
o
V
1 2,4-Dimethylphenol
~
c
o
^
CD
CD
o
CD
a.
CO
5
o
_Q
-o
t3
CD
CD
•o
~!
e o
-3 p"
§ R
t5 —
£
"m CD
Q =
•g >
l-s
a> •-•
2 g
II •£=
jiS
O II
2 -,
<*} ft
6-19
-------
The concentrations of the PAH contaminants in the pretreatment samples
ranged from 0.006 to 18 mg/L The concentrations for the majority of PAHs in the
posttreatment samples were below the established MDLs for the instrument. After 9
weeks of treatment, only the more recalcitrant complex PAHs remained in the liquid
matrix. These contaminants ranged in concentration from 0.013 to 0.14 mg/L.
Results; from Week 12 indicated a further reduction in contamination of the treatment
matrix as the levels of complex PAHs in the soil were diminished and the MDLs for the
contaminants from Week 12 were lower than MDLs for the contaminants from Week 9.
The lower MDLs from Week 12 may have been due to less interferences and less
contamination as a result of a cleaner matrix as discussed in Subsection 6.2.
Copies of the analytical data provided by the ITAS Laboratory for the critical
contaminants in the pre- and posttreatment liquid samples are included in Appendix N.
6.4 Bioreactor Monitoring Samples
6.4.1 Polycyclic Aromatic Hydrocarbons (PAH)
Table 6-11 summarizes the results of the baseline (Week T0) characterization of
the soil used in the pilot-scale phase of this study. These samples were analyzed by
ECOVA by HPLC Method which was developed by ECOVA. Naphthalene, acenaph-
thene, and fluoranthene appear to be the constituents present at the highest levels
(range of 2170
± 250 ppm), followed by fluorene and benzo(a)anthracene (range of 960 ± 8 ppm).
Total PAH levels in these soils are 10,970 ppm. The 2- and 3-ring PAHs constitute
5890 ppm of the total, and the 4+ ring PAHs account for 5080 ppm.
Total PAHs were degraded 93.4 ± 3.2 percent over all five operating reactors'
during the 12-week study (Tables 6-12 and 6-13). After only 2 weeks of slurry-phase
treatment, 89.3 ± 3.9 percent of the total PAHs were degraded. Degradation rates
(mg/kg/wk) for 2- and 3-ring PAHs were appreciably higher at two weeks (95.9
± 1.8%) than they were for 4+ ring PAHs (89.3 ± 3.9%). The more rapid degradation
of the lower-molecular-weight PAHs reflects the preference of the bacterial populations
:for these PAHs over the higher-molecular-weight PAHs. The final levels at Week T12
6-20
-------
TABLE 6-11. BASELINE SOIL PAH
CONCENTRATIONS (Week
PAH
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo (b)f luoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
DiBenzo(a,h)anthracene
lndeno(1 ,2,3-cd)pyrene
Mean (5),b
ppm
2143.3
17.4
1937.1
967.8
518.9
307.0
2428.7
161.1
957.2
468.1
389.4
279.6
260.2
119.9
17.2
Std. Dev.,
ppm
710
7.6
1016.8
288.4
12.1
34.7
732.6
51.2 ;
284.8
129.6
112.7
83.1
75.4
94.1
4.8
a Data generated by ECOVA Corporation using HPLC.
i_
Average of the five reactors.
6-21
-------
CO
UJ
CO
<
X
Q-
o
CO,
CO
LU
UJ
X
Q_
O
2
CC
CD
Q
CD
z
tr
CO
Q
Cvl
§
_a
CO
e
2
CO
"o
a.
_CD
CO
O
CO
m
CO
CD
UJ
en
«-r
CL
a
c
tr
CO
•n
(0
CM
CM Cn f^ CM CM
•* CM 05 t^ CO
co in -3- en CM
r^ en o -ifr co
T- CM CM
in co T- CM rf
O CO ••* -r- •*
O CM T— O CM
o a> m oo -
CD CD CM If) ^
CO O> LO O> CD
CD c\i i-^ |-^ co
in h» O *— CD
CO CO
O) |-^ C5 ^ i-
o co o o h-
CO CD ^ m CO
CD T— CM CO CO
CO CO CO CM
•»—
•^r •* co in co
•^f co en
en Tt T- CM
•* co T- •* in
CM o oo in T-
m in -^ co N-
•* co co ^c en
en co CD i— i—
o CM co en co
r^ in o -^- en
-«• in in •* •<*
CM ** |^ -^- CM
co en in co TJ-
co co en en ^
CO CO •* -
CM CO CO i- CO
m o en en in
•^t- co o in co
••* •* ^ in o
co co co co
CM CM CM CO CO
co CM o ^r t^
•* -<3- "* 'SJ- l~~
O O) CO CO 00
i- CO f"* CO
T- i- •"•; en co
co" -^ JT: r^ en
t^ v> 52 en in
CM r^- °° co CM
CM CO JI CM CO
CO CO t^- •* T-
co m T- en -- r- r>. •* ^
^ in in co r^
t- CM en i^ t-~
•^- in r^ co CM
CM T- T- T-
•^- co co CM ^~
CO CM CO CM CO
CM CO i- -^- O
co co in -^ eo
•>3- in •* co i-
CO CO CM CO
in o) co co CM
in CM en c\i CM
in o CM T- co
CO r— O CO i—
•<*• in ™ co CM
en co <". -a- en
in •* r: i- i^
i- CM £? CO 0
o t-^ t o CM
CO TJ- ^ CO •*
g 8 5 {2 «
§SS®5
RSg?:?
•^ CM ^ in co
o o o o o
CO CO CO CO (0
IT LT LT IT IT
6-22
-------
DC
UJ
LU
cv
ODC
HO
UJ
CD <
LLJ0-
_J
CD
0
g
3
c
ct
c
£
•c
.0
E
2
ct
c
CD
S
op
c
-_*•?
51
Q
m
CD
0)
C\
0
"
CO
\
c
"J
T:
c
H
Q
0s
a
a
DC
cr
.9
a
a
I
I
D.
ra
c
DC
T3
cc
CM
T- in co CD in
CM Tf Tfr CO C\
co" co' cd co tv
Cn G) Cn Cn Cn
CO O |v N. O
CM O N. CO If
CD C\i T^ |v O
00 G) G) G) C
i- CM i- •* CM
N. co •«* in c\
oo co' in T-' en
O> O) Cn Cn G)
CD T- in - G) G) G> G)
oo rl- CM co en
CM in o i- p
en CD' in oo en
O) O) O> CT) €75
T- oo CD co in
^" en f*» ^
T- i- co fv CM
en o> en r-- oo
G) G) G) G) G)
r~ en c- CM o
co co i- in •*
CM f- IV. m CD
O> G) O5 G) O5
co in -^- CM en
m CM CD co iv.
00 •<»• CD i- CO
co co in co co
•«- CM ^ in CD
D O O O O
3 ^3 ^3 ^3 T>
C CO CO CO CO
CD CD CD CD CD
CC CC CC CC CC
c
_c
c
fj
c
c
3?
a
DC
c:
'^
•^
ra
a
^
OL
D:
CC
CO
T3
c
CO
4
CD i- CM 'd- |v.
•«-; *^f CO CO C
CD c\i ^- CM o
co en O) co CT)
i- CO CM ^- O
T— T— (V. If) If
in' T-' CM CD a
co en o> co co
in o tv TJ a>
CD CO CO CD O
co' o c\i cd i-
co en en co en
co co o in en
CM CO ir- CD U
co' •<-' co' co if
en en en co en
in co oo in co
•^ ••-; CM en ir
oo' o cvi ^ co'
CO CO (V. CO O)
O CD CM CO in
co in CM iv co
O tv O O CO
in tv en CD co
IV. CD O> CD in
co in tv co co
tv. i- CO CO CO
co en en co co
*- CO CO CO O
^ ^ CM co cn
o co tv o in
v CO CO OO OO
•»3- o T- in o
in *- •<- CD co
in ^ o co lv
CO CO iv. CM '*
T- CM •«*• in CD
5 o o o o
3 T5 ^5 T3 ^5
0 CO CO CO CO
CD CD CD CD CD
DC CC CC CC CC
c:
'a
n
c
a
Q
3?
a
n
CC
c:
.C
n
S
a
—
X
QL
c
co in en CD •«—
cq in co T- e\
CM in CD co' rf
en en G) co G>
CD O it O5 t
tv CD CM CO CO
in -r-' CM en ^
CO CT) G) CO CT)
CO CO O CO CO
CO_ |v- O) CM i—
CO •sf CO O) CO
en en o) co o>
CO O G) G) CO
i- -r- CO O «
CD in in T^ CD
G) G) G) CD G)
i- in co co i-
co co iv -^- cn
•<*' CO CO* CM CD
G) CO CO CO G)
CM CO CM CO O
rt" i- O •«* CO
en iv. -^ CD T-
CD CO CD TV O)
O) CO i— in CD
oo •* to CD en
co in cd o i-
G> G) en en en
CD o co co in
co tv CM in en
CM 0 CM CO i-
CO G> G) CO G)
CD in in CM •*
co •*— r^ tv co
i— O O CO T-
CO CD -i^- in tv
i- CM •* in co
3 Q O O O
B CO CO CO CO
CD CD CD CD CD
CC CC DC CC CC
6-23
-------
were 653.5 ± 178.9 ppm for total PAHs, 152.1 ± 81.9 ppm for 2- and 3-ring PAHs,
and 501.4 ± 103.5 ppm for 4+ ring PAHs.
As shown in Figures 6-1, 6-2, and 6-3, the degradation rates of the different
PAHs varied appreciably during the course of the study to reflect changes in the reac-
tor environments. Clearly, a very large amount of the total PAH residue was degraded
after only 2 weeks; however, the apparent level of soil-bound PAH residues began to
rise slightly for all PAHs through Week T6, to decrease through Week Tg, to rise again
through Week T1V and finally, to decrease through Week T12. It is important to note
that these data necessarily reflect not only the nominal concentrations of soil-bound
PAHs, but also the extraction efficiency of the analytical method. Apparent increases
in the levels of soil-bound PAHs probably reflect an increased PAH extraction efficiency
rather than the unlikely production of soil-bound PAHs during the study. The phenom-
enon of increasing PAH residue levels shown in these figures has been seen else-
where (personal communication from Dr. Ron Lewis, U.S. EPA Cincinnati, 7/29/91)
and clearly reflects a widespread, intractable, methodological problem. The variations
in concentrations of sotl-bound individual PAHs mirror the results for classes of PAHs,
as shown in Table 6-14 and Figures 6-4 through 6-7.
Immediately after sampling at Week T9, Reactors 2 and 4 were reinoculated with
fresh bacterial populations, and Reactors 5 and 6 were both reinoculated and
amencJed with the surfactant Tween 80. Reactor 1 was hot amended in any way. At
Week T1V levels of total PAHs in unamended Reactor 1 and reinoculated Reactors 2
»
and 4 increased dramatically; whereas total levels in reinoculated and surfactant-
amended Reactors 5 and 6 essentially did not change (Table 6-13, Figures 6-1, 6-2,
and 6-3). By Week T12, the total levels in Reactors 1, 2, and 4 had again declined, but
total levels in Reactors 5 and 6 increased. '. '
Anomalies in the PAH degradation rates occurred in Reactor 4 for 4+ ring
PAHs at Weeks T, and T6 (Figure 6-3). At both points in time, the total PAH level was
appreciably higher than for all other reactor levels. Among the individual PAHs, levels
6-24
-------
-- CO
JW
CD
a.
o
£2.
w
<:
a.
LU
05
3
P
"to
O
W
£
CO
--CM
CO
I
D3
L.
§
a.
a.
6-25
-------
-------
~
CO
El
o
tQCO,
08
o
(0
O)
X
'en
T5
o
u_
CO
to
13
g>
U.
(U
tr
31
a. Q.
6-27
-------
UJ
Q
to
inmcococMcocoo>
•^J- o '- Tl-CMCM-«-OCQCOCOCM
•*T-CV|i-o^'lv-'— coco-«— ocM
T- cncsjioco^
CM •>— CM
CD
CD CD CD 5
C CD CD CO >
1 fill*
.
5-g.-g.gs8f
co
,
co
oomcncoojcncoco-r-cococnot^in
CM T- CM
•i- CO
CM
i-CMT-CM'-
CMCMCOCni^-T-OOOCO-'-OCO-^'*
CO
T- T- CM 1- •
CM co co "^ co o co en T— co
o-r-inOT-cq^f-^cMcococacococq
ci-^-cscooicM-^uicsodioco'cD'irio
£-1-1-1-10 CM-*a>COI^-lOCM
CM
oc\jcoi--T-;O>cncocMcqcpT-o>cqoi
CM CMr-r-.COCMt-CM'T-COTfi-OOCO
CM 10 •^-inr---*cocMCM
r-- o CM
CM i- i- '
a> a> •
8 ££ ^5
® S c c « -s =5
£ O>
-------
cc
o
_
o>
to
1
ta
7.2
15
CO,
_r/5
<
CL
CD
Z
cc
1
c
CO
CD
E
"cc
=5
T3
C
05
CO
I
CD
D5
Q.
Q.
6-29
-------
2
to
75
to
p
ir
£
•*
J/J
Q
I
CO
a>
E
"5
0)
X
"w
o
up
CD
O)
6-30
-------
52
1
co
in
"co
tn
•TO
I
03
LLI
2
Z
O
1-
CC
CD
HI
Q
<
Q.
CD
Z
CC
co
08
CM
U_
O
LU
O
O
cc
co
LU
LU
LU rf
LU j£
^ X
X n
l~ ^
X Z
Q. LU
< O
z <
1
1
•t
LU LU
LU LU LU
x cc z
i_ m T LU
X Z H- 0
Q. LU Z <
< CC < CC
^
L
C
<
-
Q § s
g i g
1
•f-
D ?
c ;
L <
( <
C
^
3
CO
- CM
CM
Q.
Q.
I
D)
cz
•sz
CO
i CD
-i
o to
o.
t8«
•> Q.
T3 CO
CD
CD
I
O)
LT
6-31
-------
S
%
IB
03
S
"3
OT,
-2
I
•S
Q
Q
<
a:
o
UJ
a
<
D.
eg
a:
CO
u.
C)
2:
q
a
a:
2:
£
CO
CJ
QL
Q.
CD
OS
CO
D)
CD
c'rt
03 £»
o'o.
c E
O CO
•4= CO
—
05
•o
CD
CD
3
D5
u_
6-32
-------
of acenaphthene were clearly higher than those of other 2- and 3-ring PAHs at Weeks
T4 and Tn (Figure 6-2). This anomaly may be related to widely varying levels of
acenaphthene among the five reactors (see standard deviation data for acenaphthene
in Figure 6-6 or Table 6-14). A final anomaly was the surge in both the mean levels
and standard deviations for the 4+ ring PAHs at Week Tv This was not exhibited by
the 2- and 3-ring PAHs for that time point, and the standard deviations were appre-
ciably higher than those for all other time points for all PAH types (Rgure 6-7).
These anomalies are indicative of several problems and events. Clearly, further
comminution of the soil particles accounted for a portion of the rise in soil-bound PAH
residues by reducing the resistance to mass transfer. This, in turn, allowed a higher
extraction efficiency in the analytical method and therefore higher apparent concentra-
tions. Although acenaphthene is an identifiable compound in an analytical method, it
is difficult to quantitate accurately. It has the lowest molar extinction coefficient of all
the PAHs in ECOVA's analytical method and is therefore the PAH most subject to er-
rors in quantitation. After Week T2, PAH residue levels were low enough that a small
error in the area assessed for acenaphthene could have an enormous effecfon the
total levels of PAH residues. =»
6.4.2 Total Petroleum Hydrocarbons (TPH)
ITEP monitored TPH by gas chromatographic analysis over the course of the
study. The data for soil-bound TPH are presented in Table 6-15. These data indicate
that, as with the PAH data, variations occurred in TPH levels in the slurry. As with the
PAHs, the greatest decline in TPH occurred in the first 2 weeks of the study. A rise in
the levels of TPH occurred at Week T6, however, which is 2 weeks after Total PAHs
rose in the slurries. This delay could reflect the actual production of TPH compounds
as metabolic products of the biodegradation of the PAHs. It could also reflect a sim-
ple rise in extraction efficiency due to soil particle comminution.
6.5 Air Samples
The air sampling program measured semivolatile, volatile, and total organics
during the first 9 weeks of treatment. Total organics as methane was determined
6-33
-------
according to procedures in U.S. EPA Method 25A.a This sampling was conducted
continuously at the main exhaust line for the first 5 days of operation. Sampling for
volatiles (by Modified Method TO14)b and semivolatiles (for Modified Method TO13)1
was conducted periodically during the first 9 weeks of operation.
TABLE 6-15. CONCENTRATIONS OF TPH IN SOIL (mg/kg)
Reactor
1
2
4
5
6
0
35000
17500
13000
16000
19500
" 2 .
7200
2600
2700
3600
2400
4
1800
1800
1600
2300
2400
Week
6
3100
2300
2100
2900
3600
9
1800
3200
1800
1700
2200
11 •
1900
1700
1700
3700
4900
12
1700'
1800
1900
2700
2700
6.5.1 Total Hydrocarbons (THC)
Table 6-16 presents the THC emission results of the exhaust-line sampling.
These exhaust line data encompass data from all five operating reactors. The back-
ground/ambient air shows THC concentrations averaging 3 ppm on a dry basis. THC
emissions gradually increase during charging of the reactors, with peak concentrations
averaging 390 ppm from 1751 to 1800 on May 8, 1991. Table 6-16 presents concen-
trations, emission rates, and flow rates used to calculate emissions.. All data are re-
ported as methane because it was the calibration gas used during sampling.
Figure 6-8 is a graph of the THC data during the 5 days of continuous monitor
operation. The THC data compare well with the other organic data, showing extreme-
ly high emissions the first 2 days of process operation, followed by a steady decline
and eventually baseline recordings by the fifth day of operation.
a 40 CFR 60, Appendix A.
b Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Compounds in Ambient Air. EPA-600/4-84-041. April 1984.
6-34
-------
o oo
= 1=1?
Ol O) O>
01
4J
o
<- 0.0 00
"5 ^.-^ coto
..
raiocoioraoionsra
ZOSZOT32SSC
.-«-HCMcococo*Tin4-*-M4->-M-4-» _Q
5 O O O OO'OO O O ••-
ro(Of0<0<0*oa>a)a>*
-M
if- -M O
^ O ^O
UJ O) 0)
O OS >
t »-« r»- co ^a- co CMcom
• m tn *-H co «—• r*. co «—«
,_ -'v^' ^f ^" CO ^3" CO CO CO
C3 ^3 ^3 ^3 ^3 CO ^3 CO ^3 «-H «-^ ^H «-H ^H *—t ^*H •—t *—t *—* »-i *—' »—< C3 CO O
O^C3OOOC3^^OO^C3^^O^COCDOC3^ OCOC3
.
•<3-p^c\joococnoo*3-ocotTinocococo -
-
COOCM cocMOrx-incoco
•*3" CO CO CM CNJ CM «—< «-H «—I r-H
COC3C3 I OOOOOOO
OOO O.O CO O O O O
ooo
ooooooo
in in m in in- inmininmininin 'in mtninmininmin
vvvvvvvvvvvvvvvvvvvvvv
m m mininminmtnin m in m m in
vvvvvvvvvvvvvvv
I—
2
UJ
Q£
^
oooooooo-
*r T *cr
CM CNJ CM
^j.^j-^a-^-^-^j-^t^a-^r^j-'*
CMCMCMCMCMCMCMCMCMCMCM
i£>
UD
^-i o co cMin^-incocor^co^-CMCMco O.CM CMP*»«-HCOO>O>CJ>CO oo^s-co ^- r-* *-< coininojcocor*.
CO cOtnCMf^OTtnc7)WcOCOCM^«OCOincOCOCMCOOC3CncOC^ OJOO5 I OOCM I CMCM^-HCOCM'i-Oi
^H ,-1^-tCOCOCOCOCOCOCOCOCOCOCOCOCO COCOCO CMCM^-i ^H^-I^H
0)
o
i
o
O CO CO CO CO CO O
...
, oo o CM •— i moojr-*.coinmr^ r-v, rv. co co *3~ r^.
»-i ^-t^-ICOCOCOCOCOCOCOCOCOCOCOCOCO
r4cM<— t i
incocM
COCOCO
*4-U^CO t COO5CO~HOCNJCO
CNJ C3 CD CO •—* CD O> CO r^» CO
CM CXI —« -H rt —<
inininooininotor*.cototococ\icococxro>tooooo
-
i i i i i i
i i i i i
o o o o
I I I I
o o o o
I I I I I I I I I I t
OOOLOOOCDC3OOO
•o
3
»f—
•!-»
o
6-35
-------
•o
0)
E
«0
f-t
so
t
Q.
-
§
•4-»
2
c
CU
u
c
o
u
3=
~
CO
CU
•<->
o
T3
j:
_a
•—
-
c=
o
to
CO
E
OJ
o
ac
'
°,E
U
CO
T3
0)
•U
£
J
5"S
.
CU
=
CO
"o
c-
O
X)
1
OJ
CU
E
cocooojino5CD
OOO«-i«-**-t<— )O
1 1 1 1 1 t 1 1
OOCDOOOOO
OOOO^HOOO
CD «"•< ^j" cn CD oj in 01
OOOO^H— <—•— 1
CD
^— 1
in
CO
o
o
8'
*- 1
1. t
o
s **-
r— O
t- CO
co
o o
in cn r*.
CO OJ OJ
o o o
O CD CD
CD CD CD
OJ OJ OJ
OJ OJ OJ
in in co
co in CM
co m in
cn oj CD
AO in in
CD U) CD
CD OJ CD
in CD oj
CD «-H »-*
1 1 1
CD CD O
CD CD CO
CD in CD
CD O — 4
*-H
^^
in
1 1 1
r-. co t^
OJ OJ CM
CD CD CD
CD O O
CD 0 CD
0 CD CD
CM OJ OJ
OJ OJ OJ
CO CD CO
OJ CD OJ
in in in
O CO CD
-H CO *-S
in -«^ in
o o o*
CD CD CD
in CD CD
«-H OJ O
1 1 1
CD O CD
CD CD CD
oj in CD
«-H »-l OJ
lift
^~ co cn cn
CM CM •-» »-<
o o o o
O O O CD
CD CD CD CD
OJ OJ OJ CM
OJ OJ OJ OJ
l^^'l^f^
to co to in
^r *»^H
^_
4-1
O
CU
"D
•a
CU
4-1
t-
1
1'
c
o
->
c
a>
u
o
u
^
z*
CO
2
o
*l^
CU
>
4-»
to
§
^
o
J_
o
4-*
U
O
r—
f-
*4-
a
s-
«1
B fc
CU
4J
3
c:
'i
CU
a.
•M
1
u
IS
3
U
5_
•a
CO
>,
C
a
u
^
u
to
•a
u
(
g
<£
o
CO
•a
. s
C^
X
JC
c
'i
CD
. CO
X
0
. — O
CO ~H
•— t
^— X
E co
o in
CO
CO
u
JC
-Q
*~~
O
-T-
t—
'' .
3?
C_>
CU
(O
E
CO
n)
JC
£'
t.
o
.c
.8.
CO
o
Q.
CU
2
o
CO
to
e**~
CJ
31
1—
-a
6-36
-------
o
73
o
QL
O
B
I
•o
in
CD
D)
CO
1
c
g
"8
"E
o>
O
op
co
2
3
O)
IT
OUOQ QH±
6-37
-------
6.5.2 Semivolatile Organics . .
Table 6-17 presents the sampling schedule, volume of air sampled, duration of
sampling, and sampling location for semivolatile organic emissions. Sampling wascon-
ducted on Reactors 1 and 2 for the first 4 days of operation. The main exhaust line
was sampled for the remainder of the program. Table 6-18 lists the semivolatile
organic analytes and their detection limits. Table 6-19 lists only the results of semivol-
atile organic emissions that were detected during the study. Once again, semivolatile
organic emissions (naphthalene, 2-methylhaphthalene, acenaphthylene, acenaphthene,
dibenzofuran, fluorene, phenanthrene, and anthracene) were detectable during the first
4 days of sampling. Beginning the sixth day of operation, very small quantities (at or
below detection) of semivolatiles were found. "
6.5.3 Volatile Organics
Table 6-20 presents the sampling schedule, duration of sampling, and sampling
location for volatile organic emissions. The sampling was conducted simultaneously
with the semivolatile organic sampling on Reactors 1 and 2 for the. first 4 days of op-
eration. The main exhaust line was sampled for the remainder of the program.
Table 6-21 lists the volatile organic analytes and their approximate detection limits.
Detection limits will vary with dilution requirements of each sample. Table 6-22 lists the
sampling runs during which volatile organics were detected and.the corresponding de-
tection limits. Samples again show that the-maj©rity-of emissions occurred during the
first few days of reactor operation. Samples analyzed by Air Toxics Lab (CAN 1-15,
2-16, 1-17, and 2-17) show four compounds that were not detected previously. These
detections are believed to be laboratory contaminants and not a result of reactor emis-
sions.
Copies of the analytical data for THC, semivolatile organic, and volatile organic
analyses provided by ITAS laboratory are included in Appendix N.
6-38
-------
a
Sample volume
XAD-l-l
XAD-2-1
XAD-1-2
XAD-2-2
XAD-1-3
XAD-2-3
XAD-1-4
XAO-2-4
XAD-1-5.C
XAD-2-5
XAO-1-6
XAO-2-6
XAD-1-7
XAD-2-7
XAO-1-8
XAD-2-8
XAD-1-9
XAD-2-9
XAO-1-10
XAD-2-10
XAO-1-11
XAD-2-11
XAD-1-12
XAD-2-1. 2
XAD-1-13
XAD-2-I3
XAO-1-14
XAO-2-14
XAD-1-15
XAD-2-15
XAD-1-16
XAD-2-16
XAD-1-17
XAD-2-17
late (1991)
5/8
5/9
5/10
5/11
5/14
5/15
5/21
5/22
5/28
5/29
6/3
6/6
6/10
6/12
6/17
6/26
7/10
Liters
348.006
283.105
363.189
271.200
289.075
319.469.
67.236
386.053
330.513
434.332
885.466
793.649
624.172
529.768
764.299
898.858
424.013
347.095
403.739
362.716
823.058
398.504
860.102
433.528
1419.919
1008.73
1257.265
'883.041
1314.93
989.644
1665.992
397.293
719.544
801.689
ft3
12.288
10.0
12.82
9.576
10.207
11.281
2.37
13.632
11.671
15.337
31.265
28.024
22.040
18.707
26.988
31.739
14.972
12.256
14.256
12.808
2'9.063
14.071
30.371
15.308
50.138
35.619
44.395
31.181
46.431
34.945
58.827
14.029
• 25.408
28.308
b
Air flow, dscfm
3
3
• 1.5
1.5
' 1.33
1.33
<1.33
<1.33
4.10
4.10
6.92
6.92
6.42
6.42
6.17
6.17
6.26
6.26
6.20
6.20
6.17
6.17
6.17
6.17
6.13
6.13
6.03
6.03
6.23
6.23
6.83
6.83
5.5
5.5
Approximate c
samolinq time, h
24
24
24
24
24
24 -
24
24
24
24
48
48
24
24
48
48
24
'24
24
24
24
24
24
• 24
48
48
48
48
48
48
24
24
48
48
Sampl i ng,.j
location
Reactor 1
Reactor 2
Reactor 1
Reactor 2
Reactor 1
Reactor 2
Reactor 1
Reactor 2 •
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Ma'in exhaust
Main exhaust
Main exhaust
Ma,in exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
3 Samplfi volume corrected to standard conditions.
b Biolift reactor exhaust air flow, dry standard cubic feet per minute.
C Sampling time either 1 day (24 h) or 2 days (48 h), usually depending on canister size. =
d Sampling for Runs 1 through 4 was conducted on Reactors 1 and 2. Runs 5 through 17 were conducted in
the main exhaust .serving all five reactors. • :
6 XAD-1-4 was void because the reactor overflowed.
f Runs 4 and 5 were sampled with the reactors venting directly to ambient air.
6-39
-------
TABLE 6-18.
HAZARDOUS SUBSTANCE LIST OF SEMIVOLATILE OR6ANICS AND
THEIR DETECTION LIMITS
CAS No.
Descri pti on
ug/tube
CAS No.
Description '
fjg/tube
108-95-2 Phenol 10 51-28-5
111-44-4 bis(2-ch1oroethyl)ether 10 100-02-7
95-57-8 2-Chlorophenol 10 132-64-9
541-73-1 1,3-Dichlorobenzene 10 121-14-2
106-47-7 1,4-Dichlorobenzene 10 606-20-2
100-51-6 Benzyl alcohol 10 84-66-2
95-50-1 1,2-Dlchlorohenzene 10 7005-72-34
95-48-7 2-Methylphenol 10
39638-32-9 bis(2-Chloroisopropyl) 10 86-73-7
ether 100-01-6
106-44-5 4-Methylphenol 10 534-52-1
621-64-7 N-nitrosodi-n-propylamine 10
67-72-1 Hexachloroethane 10 534-52-1
98-95-3 Nitrobenzene 10 101-55-3
78-59-1 • Isophorone 10
88-75-5 2-Nitrophenol 10 118-74-1
105-67-9 2,4-Oimethyl phenol 10 87-86-5
65-85-0 Benzole acid ' 50 85-01-8
111-91-1 bis(2-Chlorethoxy) methane 10 120-12-7
120-83-2 2,4-Oichlorophenol 10 84-74-2
120-82-1 1.2,4-Trichlorobenzene 10 206-44-0
91-20-3 Naphthalene 10 . 129-00-0
106-47-8 4-Chloroaniline 10 85-68-7
87-68-3 Hexachlorobutadiene 10 91-94-1
59-50-7 4-Chloro-3-methylphenol 10 56-55-3
91-57-6 2-Methylnaphthalene 10 117-81-7
77-47-4 Hexachlorocyclopentadiene 10
88-06-2. 2.4.6-Trichlorophenol 10 218-01-9
95-95-4 2,4,5-Trichlorophenol 50 117-84-0
91-58-7 2-Chloronaphthalene 10 205-99-2
88-74-4 2-Nitroanaline „ 50 . 205-08-9
131-11-3 Dimethyl phthalate . 10 50-32-8
208-96-8 Acenaphthylene 10 193-39-5
99-09-2 3-Nitroaniline 50 53-70-3
83-32-9 Acenaphthene 10 191-24-2
2,4-Di ni trophenol 50
4-Nitrophenol 50
Dibenzofuran 10
2,4-Dinitrotoluene 10
2,6-Dinitrotoluene 10
Diethyl phthalate 10
Chlorophenyl phenyl 10
ether
Fluorene . ; • 10
4-Nitroaniline • 50
4,6-Di ni tro-2-methyl- 50
phenol
N-nitrosodiphenylamine 10
4-Bromophenyl phenyl 10
ether
Hexachlorobenzene ; 10
Pentachlorophenol . 50
Phenanthrene 10
Anthracene 10
Oi-n-butyl phthalate 10
Fluoranthene 10
Pyrene ; 10
Butyl benzyl phthalate " 10
3,3'-Dichlorobenzidine 20
Benzo(a)anthracene 10
bis(2-ethylhexyl) 10
phthalate
Chrysene 10
Di-n-octyl phthalate 10
Benzo(b)f 1 uoranthene 10
Benzo(k)f1uoranthene 10
Benzo(a)pyrene 10
Indeno(l,2,3-cd)pyrene 10
Dibenzo(a,h)anthracene" 10
Benzo (g, h, i) peryl ene 10
6-40
-------
CO
~
Q
CO
CO
CO
S
LLJ
O
O
cc
o
LU
_J
I
o
1
LLJ
CO
O>
CO
LU
_J
CD
CD
O
X
CD
i
Q
^
X
in
I
CM
Q
X
in
5
^
X
CM
O
^
X
cp
CM
O
^
X
2
5
x
CM
Q
X
•*>"
5
^
X
5
o
^
X
1
5
X
CD
CD
E
CO
CO
Q.
•o
1
CO
g
o
0
o
0
CM
o
0
CO
O
O
CM
0
O
CO
O
o
Tf
o
0
5>
0
^
CM
O
^.
Q
CO
en
CM
o
CD
CO
ex
CO
z
o
o
o
0
CM
o
0
CO
0
O
CO
0
o
8
o
^^
o
0
8
•f—
in
in
o
in
in
CO
"*
CD
CD
CO
t—
r~
Q.
CO
O
E
CM
o
o
o
o
eg
o
0
CO
o
0
CO
T—
o
CM
o
CM
0
in
CM
o
in
o
in
CM
o
CM
CM
0
CD
C
CD
.C
I
CD
<
0
o
o
o
in
0
o
8
o
CM
CO
^ —
in
^_
in
CO
T~
in
in
••"
en
a>
0
CO
CO
^.
in
en
o
0
CD
ex
CO
CD
o
<
0
•o
o
o
CM
O
O
8
o
0
CO
0
CO
co
0
CO
o
O)
in
o
^
•«^-
0
s
0
0>
•«*
o
I
C
CD
Q
O
O
0
o
^_
o
o
8
o
h-
in
0
CO
in
0
CO
o
*
o
o
CO
0
en
CO
0
••s-
CO
o
uorene
LL.
o
0
0
0
CM
O
0
CO
O
O
CO
O
CM
CM
O
^^
T—
O
o
CM
0
^_
i —
O
CM
O
0)
0
O
CD
C
CD
r~
'c
to
CD
°-
o
0
o
0
CM
O
0
CO
O
o
co
0
o
s
o
CO
o
o
s
0
CM
0
o
in
CM
o
CM
0
o
CD
C
CD
1
'c
6-41
-------
TABLE
6-20.
Start
Run No.
CAN-1-1
CAN-2-1
CAN-1-2
CAN-2-2
CAN-1-3
CAN-2-3
d
CAN-1-4
CAN-2-4
CAN-1-5
CAN-2-5
CAN-l-6d
CAN-2-6
CAN-l-7d
CAN-2-7
CAN-1-8
CAN-2-8
d
CAN-1-9
CAN-2-9
CAN-1-10
CAN-2-10
CAN-1-11
CAN-2-11
e
CAN-l-12e
CAN-2-12
f
CAN-l-13f
CAN-2-13
f
CAN-l-14f
CAN-2-14
CAN-l-15f
CAN-2-15
f
. CAN-1-16
CAN-2-16
CAN-1-17
GAN-2-17
Time
(24-h)
1535
1556
1433
1520
1402
1430
1121
1156
v 1418
1424
1253
1306
1027
1033
1400
None
1210
1210
•1125
1125
1504
1509
None
None
1300
1310
1422 .
1422
1405
1405
1023
1023
1452
1455
Date
(1991)
5/8
5/8
5/9
5/9
5/10
5/10 •
5/11
5/11
5/14
5/14
5/15
5/15
5/21
5/21
5/22
-
5/28
5/28
.5/29
5/29
6/3
6/3
-
-
. 6/10
6/10
6/12
6/12
6/18
6/18
6/26
6/26
7/10
7/10
VOLATILE
ORGANIC
SAMPLE
ID AND LOCATION
• Stop
Time
(24-h)
1417
1436
1354
1403
1106
1135
1035
1117
1340
1255
1130
1130
1345
1348
1420
-
1050
1050
1055
1055
1243
1244
'
-
1342
1343
1452
1251
1339
1339
0948
0948
1422
1422-
Date
(1991)
5/9
5/9 •
5/10
5/10
5/11
5/11
5/12
5/12
5/15
5/15
5/17
5/17
5/22
5/22
5/24
- .
5/29
5/29
5/30
5/30
6/4
6/4
-
-
6/12
6/12
6/14
6/14
« 6/19
6/19
6/27
6/27
7/12
7/12
Airflog.
dscfm
3
3
1.5
1.5
1.33
1.33
<1.33
<1.33
4.1
4.1
6.92
6.92
6.42
6.42
6.17
6.17
6.26
6.26
6.20
6.20
6.17
6.17
6.17
6.17
6.13
6.13
6.03
6.03
6.23
6.23
6.83
6.83
5.5
5.5
Approximate ^
sampling time, h
24
24
24
24
24
24
24
' 24
24
24
48
48
24
24
48
•
24 '
24
24
24
24
24 i
-
-
48
48
48 :
48 ;
24
24
24
24
48
48 .
Samp! i ngc
location
Reactor 1
Reactor 2 -.
Reactor 1
Reactor 2
Reactor 1
Reactor 2
Reactor 1
Reactor 2
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Main exhaust
Biolift reactor exhaust airflow, dry standard cubic feet per minute.
Sampling time either 1 day (24 h) or 2 days (48 h), usually depending on canister size.
Sampling for Runs 1 through 4 was conducted on Reactors 1 and 2. Runs 5 through 7 were sampled in
the main exhaust line serving all five reactors.
i
Canisters did not fill because of slurry in the flow regulator. Condition was not discovered until
analysis showed no sample volume. Flow regulator was replaced and sample flow was rechecked.
No canisters available for sampling. .
Canisters inadequately emptied and cleaned by laboratory prior to analysis. ;
6-42
-------
TABLE 6-21. VOLATILE ORGANIC LIST AND
APPROXIMATE DETECTION LIMITS
Volatile organic Detection limit,- ppb
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
1,1-Dichl oroethene
Carbon disulfide
Methyl ene chloride
t-1, 2-Dichl oroethene
1,1-Dichl oroethene
c-1 , 2-Dichl oroethene
Chloroform
1,1,1 -Tri chl oroethane
Carbon tetrachloride • '
Benzene
1, 2-Dichl oroethane
Tri chl oroethene
1,2-Dichloropropane
Bromodi chl oromethane
c-l,3-Dichloropropene
Tol uene
t- 1 , 3-Di chl oropropene
1 , 1 , 2-Trichl oroethane
Tetrachl oroethene
Di bromochl oromethane
Chlorobenzene
Ethyl benzene
m- and/or p-Xylene
o-Xylene
Styrene
Bromoform
1 s 1 , 2 , 2-Tetrachl oroethane
0.5
0 3
w * <•/
03
w • *j r
0.5
0.3
.0.2
0.2
0.3
0.3
0 3
V • w
0.3
0 3
V • tj
0 2
"'C • !
0 2
W o £_
0 3
v • *j
0.2
0.3
0.2
0.4
0 2
V o <_
0.4
03
V/ *
02
** • t_
0.2
02
V • C.
0 2
v * &_
0.2
0.2 !
6-43
-------
I
V)
0
«/)
co
i— i
LU
O
«t
a*
o
LU
_J
i— i
g
t
•
CM
CSJ
(O
LU
_l
ff\
£
in
i
^
t
CM
CO
1
CSJ
CO
1
»— 1
OJ
1
CO
OJ
1
*— 1
1—4
1
OJ
»— 1
«-H
_J
0
-£2
CL
_J
Q
J3
O.
0
ja
Q.
a
J2
CL
_I
Q
0.
CL
O
fl
Q.
O
_Q
CL
(O
Q
.Q
a.
Compound P
*f*ftOiO*f*3-*3-T*3-'*t*t^'
OOOOOOOOOOOO
CO O> CO OJ
oj oj oir^cD co o"> r-. -«3-
.-) OJ 1 O O OJ t 1 O *-H O O
*3-*3-COCO^3-'3-^-^-*3-^r^f-a-
OOOOOOOOOOOO
r-* *-4 in
*H r-. co CM oj cj>o^-^-
O *-4 O *•*< — < CO 1 1 O CO — < O
- oj
OOOOOOOOOOOO
"co m
r-.ojooco^ro»
**- 1— o 4-> a> x
•— _C r— O) £= 0) 1
i3 o -c o a> c o.
M S 0 UNO)
••- CD f- -r- O C N J-
•DCOt- . — CUCOO)
0)14-1— 0) 0)jr_Q 0)-*^C Q)
C r— O 1 CCOO-Q-OQ)C
O>^t--HQJ(lJfDi-r— Cr— OJ
_Q _C O -N3(-O>in3>)U
03 QJ J3 - I 1 4->
OS:O»-*CQ»— 1— CJUJ E O01
«— i
O
1
OJ
c?
*-<
1
«— 1
C7>
OJ
CO
I
r*»
t
CO
i
~H
m
i
OJ
__i
o
f!
a.
_i
C3
_a
o.
CL
Q
^
Q_
CL
Q
JD
a.
Q
Q.
CL
Q
J3
a.
£3
J3
CL
^
jQ
Q.
Compound P
cococnococococococococo
ooooooooocsoo
^ CO
^H o oj r*. co co
<-4OJI<-lOOJ1 1 1 O 1 1
cococncncocococococococo
C5C3OOC3OOOOC3C3C3
co " a>
o oj m oo oj in ^r
^-t r-^ 1 -H O ^J- I | 1^-HOI
COCOC7>O>COU3COCOCOCOCO(O
OOOOOOOOOCDOO
en r*. co
o oj co co 05 t^-.
C3OJ1»-iCD^-ii 1 IOI 1
cococnocococococotococo
OOOOC3OC5OOOOO
CO
oj co ^* *-* in co o
»-<^ri--<'-t^riojioi t
-«r^rtotO'^r'«3-i r-»
cor^. r^.cocNi'cr^r^rojco
O OJ I <-HOOJOOO--4O 1
^•^rcoco^-^-^-^r^tTr^r^r
C3C3C3OOOOC3OCJOCD
OJ CO
oj co o co oj • LO T± m
*-H«-II^-(C3CNJI 1 O «-H O 1
0)
c
(O
OJ JZ 0)
•o -M a> c
0) .^- »
«*- •— o 4-» a> x
r— jc . — a> c eu i
3 o .c o _cja (U^^C O)
. c f— o i ccoo-atJOJc
O >i t- *-H CU 0)(Q (-1 — C r— 0)
JD ^: o -Mnuo>iit-
(OOJ.£= - OJ O QJ JC 4-» 1 1 -M
CJ 3E CJ »-« CQ 1— 1 — CJ LjJ E O CO
c
o
u
6-44
-------
•o
0)
O
O
CM
CM
I
LU
_l
CO
«c
O —I "~^ *"•* ""* *""' *•"* «—' «-J &) O O O O O
j» """ ~"~
-Q •—i »-i CM OO
Q. ....
Q_ | i _i _< ._, ^ , , l^^lto
Q ^. .~ ^ CM CM CM CM CM CM — -=- CM 01 05 03 CM
JD.
-Q CJ ^< CD to
a • '2-d- • • -22-s. -2
°- °- °- ° CM CM ° 0. 0. ^ r¥ °. °. °. ° °
OJ CM CM CM
'O
I
ja
Q-
i i i totoi i i;£
-C O
4-1 i—
<
C 0) I
-------
-------
SECTION 7
QUALITY ASSURANCE/QUALITY CONTROL MEASURES
This section describes the quality assurance/quality.control (QA/QC) measures
associated with the sampling and analysis activities. Sample tracking information was
provided in Table 6-1. Analytical methods were listed in Table 4-6 and references for
these were footnoted at the bottom of this table. Subsection 7.1 describes the
QA/QC performed on pre- and posttreatment samples to ensure the quality of the
data produced by the pilot-scale testing. Subsection 7.1.1 describes the process for
determining the detection limits used in the study. Accuracy and precision data are
presented in Subsections 7.1.2 and 7.1.3, respectively. Results of analyses of blanks
associated with the treatment samples and surrogate recoveries, are presented in
Subsections 7.1.4 and 7.1.5. Problems encountered during the analysis of the treat-
ment samples and modifications to established analytical methods are discussed in
Subsection 7.1.6. Subsection 7.1.7 presents the results of the systems audit and
laboratory audit performed during the course of the study. Subsection 7.2 describes
the laboratory QC results for air sampling. Subsection 7.3 describes the QA/QC
procedures used by the ECOVA laboratory. .
7.1 Pretreatment and Posttreatment Samples
7.1.1 Detection Limits
The following subsections describe how method detection limits and practical
quantitation limits were determined and the effect they have on the data.
7-1
-------
Method Detection Limits for Semivolatile Organics
Method detection limits (MDLs) represent the minimum concentration of a
substance that can be measured and reported (with 99 percent confidence) at a value
above zero. These limits were calculated by using the Instrument Detection Limits
(IDLs), matrix spike and matrix spike duplicate recoveries from the posttreatment soil
matrix, and dilution factors from extraction procedures and sample preparation.
The IDLs for the semivolatile organics were determined by injecting seven repli-
cate samples spiked with 5 jug/L of each critical contaminant. The standard deviation
for each compound's recovery was calculated and multiplied by 3 to give ;the com-
pound a specific IDL. Table 7-1 presents the results of the IDL study performed on
the Extrel 400 GC/MS. ,
The MDLs were calculated by the following equation:
- MDL = [(IDL/AR) * OF] * 100
'where MDL = method detection limit for the contaminant i
IDL = instrument detection limit for the contaminant
AR = average percent recovery calculated from MS/MSD
samples
DF = dilution factor of samples calculated from extraction
process and sample preparation
The MDLs are based on individual analytical methods; therefore, the extraction
process and efficiency are important in determining the detection limits. For this study,
the extraction efficiency of the soil was determined by the percent recovery values for
the critical contaminants, which were spiked at predetermined values into the post-
treatment test soil matrix, extracted, and analyzed by GC/MS. The extraction process
affects the detection limits by the amount of sample that is used during the extraction
procedure. Typically, 30 g of soil is used in the extraction process. This results in a
dilution factor of approximately 34, as the results are converted to the concentration of
contaminants per kilogram. Because of the nature of the matrix involved, only 1 g of
pretreaitment soil was extracted. The treatment soil samples also underwent a Gel
Permeation Chromatography (GPC) cleanup procedure to make them more amenable
7-2
-------
Q
ID
CO
111
IE
LU LU
QZ
LU CO
CC <;
LUuj
X —I
1-P
II
-co
LU
CO
£
f^ ^*
C c
ocr
ei <°
vj
C c
o 3
ODC
ci10
c c:
O 3
O DC
C c.
0 §
OCC
6"
C r-
o §
ODC
r-i CM
U
O 3
ODC
6 ^
0 §
ODC
<» ^
i.E
CO w
"5
.£
Critical contam
co
CO
0
CO
^
•«—
^
in
^j.
^j-
-^j-
•*3-
^j.
Tfr
in
CD
_CD
I
CO
Z
CM r-~
CO T-
•<* o
o en
•* co
h~ 0
^t ^f
-* o
0 •*
CM O
^t ^
CO i-
.co •*
en o
co **•
«
CM O
in in
CD
m
•Methylnaphthall
cenaphthylene
CM <
CM
0
in
o
co
^3.
V-
Tj-
Tj-
CO
,3-
co
^J-
Tfr
in
cenaphthene
<
CO
CO
T~
^
CM
••i1
^j.
CO
•^f
CO
^f
Tf
Tj-
CM
ry
CM
in
ibenzofuran
Q
in
o
CO
co
CO
CO
CO
CO
en
co
oo
CO
oo
CO
in
luorene
u_
CM
CO
O
in
CO
CM
T^
CO
T^-
CM
^3-
0
^J-
CM
^j-
CM
"
in
henanthrene
Qi
co
T~
CM
CM
CO
CM
CO
CO
CO
CO
co
r~-
CO
CO
CO
in
nthracene
<
en
CM
o
en
CM
CO
CM
en
CM
o
co
oo
CM
f~-
CM
CO
.CM
in
luoranthene
u.
oo r>-
co m
i- O
o o
1— ^
en -t
CM CO
O CO
CO CO
T- co
CO CO
en co
CM CO
o oo
co co
•^ r^
CO CO
in in
CD
C
yrene
enzo(a)anthrace
Q. m
en •*
en co
CM 0
CO i-
T- CM
Is- CM
CO CM
CM CO
CO CM
O i-
•sf CM
O i-
Tf CM
en o
CO i-
T- in
Tf CM
in in
CD
CD
hrysene
enzo(b)fluoranth
O OQ
co co
co in
O CM
CO T-
T- O
CM T-
CM CM
CM 0
CM CM
CM CM
"3- CO
CM CM
in co
CM CM
co co
CM CM
in in
CD
C
CD
enzo(k)fluoranth
enzo(a)pyrene
OQ OQ
7-3
-------
to analysis. This resulted in a dilution factor of 2 because the sample volume was
split. Another dilution factor of 2 resulted from performing a pesticide split on the
sample,-which entailed dividing the sample into two equal portions so a pesticide
extraction could be performed. Although no pesticides were analyzed for in the
posttreatment samples, pesticide splits were performed in an attempt to clean up the
matrix to make it more amenable to analysis. The final dilution factor for the treatment
soil was 4000, based on the extraction aliquot and the GPC cleanup procedure.
Posttreatment samples were originally analyzed as medium-level soils with a
dilution factor of 4000. Since the MDLs for the samples were above 1 ppm (the
QA/QC criteria for the CS&D program), the samples were reextracted and reanalyzed
as low-level soils to lower the MDLs. For the reextracts, 30 grams of soil were
extracted (as opposed to 1 gram for medium level). The resulting extract underwent
GPC to clean up the extract and make it more amenable for analysis. Serial dilutions
were performed on the samples to bring the analytes within the instrument's curve
range resulting in a dilution factor of 2664. However, MDLs for the majority of the
compounds were still above 1 ppm. This could be due to the presence of high con-
centrations of petroleum hydrocarbons in the soil which may have resulted in poor
extraction efficiencies and matrix interferences for the target analytes. The analytical
data for the low-level soil analyses was used to evaluate the treatment technology.
The low-level analyses allowed for detection of compounds present in the soil in
small concentrations but diluted out during the medium-level extraction. Table 6-5 and
6-6 present the analytical data for the low-level extractions, while Appendix N presents
the analytical data for all analyses provided by -the ITAS laboratory on the soil, includ-
ing medium-level extraction data and low-level extraction data. For liquids, 1 liter of
sample is generally extracted. The volume of sample that could be obtained from the
reactors was limited; therefore adjustments had to be made in the volume of sample
extracted. For the samples from Week T9, 300 mL of liquid was extracted from the
samples; whereas 500 mL of liquid were extracted from the samples from Week T12.
This resulted in dilution factors of 3.3 and 2 for Weeks T9 and T12 respectively.
Because liquid extractions are divided into acid fractions and base-neutral fractions,
7-4
-------
another dilution factor of 2 results when the two fractions are combined to form the
analytical sample. The final dilution factor for the treatment liquid was 6.7 and 4 for
Weeks Tg and T12 respectively. The MDLs calculated for treatment soil and liquid sam-
ples are presented in Table 7-2 and 7-3 respectively.
Practical Quantitation Limits for Semivolatile Organics
Practical Quantitation Limits (PQLs) are limits at which the concentration of a
substance can be quantitated accurately (with 99 percent confidence). The PQLs
were determined from the values listed in Table 2 of Method 8270 in SW-846. The
PQLs in this table are based on an IDL of 10 ppb, a 30-g extraction aliquot, and a
GPC cleanup procedure for soil samples; and on an IDL of 10 ppb, a 1-L extraction
aliquot, and the combination of base-neutral and acid fractions for liquid samples. The
treatment soil samples used a 1-g extraction aliquot and underwent a pesticide split;
therefore, the PQLs for the treatment soil matrix are raised by a factor of 60. The
treatment, liquid samples used 300 mL and 500 mL of sample for the extraction
process during Weeks T9 and T12 respectively; therefore, the PQLs for the treatment
liquid matrix are raised by a factor of 3.3 and 2 for Weeks T9 and T12 respectively.
Table 7-4 presents the PQLs reported by the ITAS laboratory for this study.
Data Interpretation
The calculations used to determine MDLs and PQLs are similar in nature. The
main difference is the laboratory and instrument specificity of the MDLs compared with
the PQLs, which were compiled and averaged from studies performed in many dif-
ferent labs. Therefore, the PQLs reported in the Certificate of Analysis for semivolatile
organic data should not be used for this study. Instead, the method- and soil-specific
MDLs calculated for this study should be used in evaluating the data. Where critical
constituents are not detected, the concentrations are reported as being below the
i
detection limit specific to the constituent and the sample.
7-5
-------
LU
§
UJ
DC
O
u.
§
LO
~m
co
COH
HUJ
So
ri-OC
ujO
_i
m
CM
t-
> 0
CD
cr
3"
Q-
.^^
i
Q
-> F
Q QL
^> O^
c >_
0 0
*"* o
— CD
>,
. CD
D»
> O
CD
o:
co^
Q.
J
Q
CO
c
CO
<5
CO
O
in
"
CO
co
CM
o
f-
CD
on
CO
o
^
"
CO
CO
CM
CM
^>
f^
co
CO
o
Naphthalene
O
"
CO
co
CM
0
CT>
CO
CM
CO
•^j.
O
?
CO
CO
CM
CM
ro
co
CM
CO
•<3-
CD
C
m
CO
2-Methylnaph
rn
in
o
CO
co
CM
CO
co
fs^.
Y—
o
1 —
o
CO
co
CM
cn
ro
CD
jv.
^ —
o
0
cz
Acenaphthyle
0
£
CO
co
CM
in
CD
CM
o
in
o
cn
••a-
CO
CO
CM
o
CSU
c~
CM
O
in
cn
Acenaphthen
o
CD
CO
co
CM
en
0
00
CO
co
Y_
CO
CO
CO
CM
CO
co
ro
co
t—
Dibenzofuran
CO
T—
CO
CO
CM
cn
o
CO
0
in
o
CO
"
CO
CO
CM
CO
ro
o
in
o
Fluorene
in
CM
CO
co
CM
cn
ID
00
CM
co
o
o
CO
CO
CO
CM
CO
ro
CM
CO
o
m
Phenanthren
•^i-
in
CO
co
CM
on
CO
on
Y—
CO
^
CO
CO
CM
^J.
CM
CD
CO
^
T—
Anthracene
on
CO
0
CO
co
CM
f-
f^.
CO
cn
CM
o
"
CO
CO
CM
(V,
At
cn
CM
o
Fluoranthene
co
CO
CO
co
CM
CO
CO
O)
on
CO
Y.
**
CO
CO
CM
CO
on
co
co
CO
Y—
CD
C
Si
CD
T—
CO
CO
CM
CO
CO
CJ5
j^.
in
o
o
CM
CO
CO
CM
CO
co
[^
in
o
CD
cz
Benzo(a)anth
CM
CD
CO
CO
CM
O
^
CO
-------
UJ
>O
LLl
CO
Q
111
OLLI
Oo
rr ^~
£ O
CD
CC
CO
.O
C
a
.
Q
c
TO
i
TO
C
8
TO
O
•*-*
0
o
CO
CM
i in
• CD
> l~~-
3 CM
} CO
5 ^
i- cr
6 cd
*i^
vj r^*
O CD
X> CM
•o co
D ^
O
—
j
_f~
«
0
,_
"*
f\]
o
r-.
2
CD'
in
co
£
o
(
o
1
CM
"*
^
3
\
r
-
cd
^.^
T-
CM
O
in
o
,_
"*
CM
CD
CO
CO
CO
,—
CO
CD
in
^-
^
CO
co
T—
^
l_
r
o
CO
"*
CO
CO
cp
0
0
in
"*
CD
Tt
C
o
c
r
(•
"*
in
o
CM
CO
o
CM
CO
CO
in
CM
00
o
a
en
"
0
D
D
1—
_
^
co'
in
o
co
T-
co
T-
CM
in
CO
en
CM
o
co
CM
CD
in
CO
en
c\
o
o
co
CO
O)
CO
CO
T-
_
"
CD
CO
C\
CO
CO
f-
c
o
CO
0
--
n
o
^
XT
CD
CD
c
CO
L^
O
^
c
CD
2
^
CC
o
CD
m
^
en
en
CM
o
in
CM
CO
^
o
c
CM
C
CM
--
CO
r^
CM
CO
•>—
Q
in
CD
CO
CO
CM
CO
»-
CD
C
(
X.
1
^r
_
I
O
cu
in
co
co
CO
in
M
o
CM
CO
in
T-
co
in
CM
Q
jf,^
—
l
c.
0
g
is
c
CD
H
^2
CO
II
Q
7-7
-------
LU
lo
§5
IX
LUOC
bo
cc w
vx
QU.X
Q_
S
M
•O
IS
Is.
S
I
0)
0
Q-
05 *c\
"1 "2
" «
S *
if
o —
0.
co
i?
C "ffi
0) ^
E g
i=
o>
Q.
d^
s- E
c «-
-i= ^w
_„.!
IS
"5
Q"oi
r—
e
g'l
§2
H *^
Q-
_j
E o
OJ II
'jy CT"
B
-'"'a
S E
d"I
°- E
•Is
i-s
0,0.
II
03 "5
^J B
9 E
. OJ
ot
In
Q-
-i^r^r-r--^-t~-
COJC\I
ooooooooooooooo
ooooooooooooooo
NCM» 03 -^ § CD fl;
2:c\j<
-------
Critical Constituents With Detection Limits Greater Than 1 mg/kg
The treatment soil sample had to be extracted as a medium-level soil because
of the high levels of PAHs that were present. The medium-level extraction resulted in
detection limits greater than 1 mg/kg and ranging as high as 29 mg/kg.
No phenolic compounds were detected. They may have been diluted out as a
result of the medium-level extraction; however, data interpretation would not have been
possible with a low-level extraction of a pretreatment sample because of the PAH
levels. Overlapping of isomer peaks as well as peaks of different compounds would
have compromised the .data because the contaminants could not be accurately
quantified.
7.1.2 Accuracy Data
Accuracy data were calculated from the analysis of matrix spike/matrix spike
duplicate samples. Accuracy is expressed as the percent recovery of the constituents
spiked into the sample in known amounts. The equation for calculating percent
recovery is as follows:
(C — C)
Percent Recovery = 100 —• — '•
ct ;
where C = value of unspiked aliquot
Cj = value of spiked aliquot
pt = value for spike added
As stated in the SAP, the QA objective for accuracy (percent recovery) is in the
range of 20 to 200 percent. Tables 7-5, 7-6, and 7-7. present the percent recoveries
calculated from matrix spike/matrix spike duplicate samples for the pretreatment soil
matrix, the soil matrix after 9 weeks of tpeatment, and the soil matrix after 12 weeks.of
treatment, respectively. Tables 7-5, 7-8, and 7-9 present the percent recoveries
calculated from matrix spike/matrix spike duplicate samples for the pretreatment liquid
7-9
-------
TABLE 7-5. MATRIX SPIKE DATA FOR CRITICAL SEMIVOLATILE
CONTAMINANTS, UNTREATED MATRIX
(percent recovery)
Bioreactor-001
sludge
Constituent
Naphthalene :
2-Methyl naphtha! ene
Acenaphthylene
Acenaphthene
Diberizofuran
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a) anthracene
Chrysene
Benzo (b')fluoranthenec
Benzo(a)pyrene
MSa
32.9
39.8
52.4
-2.9
11.4
-12.4
-93.8
-20.8
-74.2
-7.2
38.4
34.6
35.6
24.4
MSDb
46.9
44.4
44.2
-91.4
-41.7
-110
-318
-153
- -243
-111
-29
-33.1
16.5
2.2
Bioreactor-001
liquid
MS ;
28.5,
22.9;
31.9
28.7
29.5;
30
30.2
27.6
25.4
28.9
27.5
26.5
22.3
19.9
MSD
26.1
21.3
32.5
29.1
29.6
30.5
34.1
29.2
26.3
28.4
26.3
25.6
22.2
16.7
a MS = Matrix spike sample.
MSI) = Matrix spike duplicate sample."
0 Benzo(b) and benzo(k)fluoranthene were found to co-elute; therefore,
a total amount was given under benzo(b)fluoranthene. * ,
7-10
-------
O
O
111-
o
>
UJ
CD
a
CD
Q.
cncD
COCDh-
•^CDlOCOOI^-inCMOOOCDi- CM
CO
S
oj h* o> ^ o) .r*^- c
co CM i— to r- •*£ "o ci co cvi r^ cJ
oor-~-cococooocDcocococoLO
CD CM
•>* t-~- en CD oj co co co in en co c\j CM
o o o o o o
o
5°
en
CO
CO
OCMO
IT)
CD
_CD
CO
.
a>
S
°CD
c
zcvj<
~:3.ec:.2>, J3
-------
C/D
^
•^
^«
2
<
P
~z.
o
ULJ
pZ
<;
_^j
o
>
12
LLJH-
03^^-.
_ILU ><
< LU CD
_ 5 O
— ^T 03
OC pr >-
o o -»±
DC 03
op. "
Ml LU CD
1— Q.
r^ h^ I1*- co co co co co co *— o co ^ CD
'"
o^r^cn^^ocoooocnco co
8$££c8§§c£222§8 ff
rfCO'^tCDCOO'^t'COinOOCDO O)
CD^t-^-^-COOCOlOCOOOCVlO i—
tncDcocnooT— i— ococooco ,—
ocMocncvicnoco^cocMi^co co
m-r-oooooot-ooocvi in
i-^coooooi-^oinoooc» o
COT-OCOCOCVJCOCOOO'COOCO t^
o oj to 1/5 CD o> CM h^> ^~ r^ o r^ ^ ^ —
cDh-t^t~-r--h-cococooocicor^ en
u5-^coi~--*cocncocMincoin-^- h~
ScDi^f^S^ScnScocococo en
O CJ1 T — ^ — IO CM C7> CO IO O O> CO ^" f*^
0)OOCO-=tOCMT-CDCOCOCOCO CM
i^-cococococococncocnoocor^ o>
COO^h-l^rfl^COCvJlOOOO CO
cDcncNjcDcocDcoiocOi— o-i— o **•
t^t^COCOOOCOCOOJCOOOO CD
T- 1— T—
^cn-r-cni-.T-cocoomooo co
^5 CO F*** ^3 ^~ CD ^f tO CO *•" ^5 •*• ^5 Tf
o
? .CD c
55 C CD
— • CC
Zc\i< -Q
<» x -o
•- ~ w
"55 2 2s
^ " "S"
n Q N
CO CO fe
2 2 m
CO -Q o
7-12
-------
o
o
HI
§
o
I?
UJ^
COLU
_jUJ
<
0
~
HI
^
a.
co
x
DC
op
1^-
UJ
CQ
co
CO
CO
CO
co
CO
CO
CO
c
o
o
OJ CO ••*
IO
CD CM
t^ CO
a*.'*? •*)• •>—
CVI ITI CO CD OCI C\j CO 1^-
I T-; CO CO i-;
• - u) cn cn
-------
C/D
<
O
o
LLJ
o_
> CM
UJ v*
^s —
I LLJ £^
< > 0)
Q^S
tg §
DC^ £i
OOHE
DCZi 9?
2^
"j-LLJ
f'fe
2S
LLJH
51
co
x
cc
05
CO
0)
Q.
in
CO
CO
CO
co
CO
co
co
0
^cMinin^fcncocicnr^-tnin co
COCOCQCOCOCOCDCOmcOI-^h-CO CO
co o f^- co co r*~ *~~ ^— co ^— co co o>
CO" i^ C\i CD CD 1-^ f^ CO' i-^ O) O CD OJ Co"
COCDCDCOCDf^CDCDCDCOCDCDh-
•>d;oif--cococ\jT-t— cnt^pcvico in
o'cvii— c\jcoQi*^inojcdoa>co' co
C\J p O> in CT) •* F-; p O CO CO •* 00 in
CO O t"~.' co' CO' -r-1 CO' in O CO' O CD O in
co
.
CDt-^CDCOCDCDCOCOCOr~-COr^-t--- CD
ocoincoinmcnorfcDcncocM
CDCDCDCOCD
-------
matrix, the liquid matrix after 9 weeks of treatment, and the. liquid matrix after 12 weeks
of treatment, respectively.
Recoveries in the pretreatment samples, were generally low. In addition, the soil
matrix showed the phenomenon of having negative recoveries for critical constituents.
This means that critical constituents were being detected at lower concentrations in
the MS/MSD samples than in the unspiked sample. There are two possible reasons
for this phenomenon. The poor recoveries may have been caused by matrix inter-
ferences resulting from overloading the soil and analytical system with PAHs. The
original levels of PAHs in the soil may have been close to saturating the extraction fluid
with contaminants, and the additional spiking of each contaminant into the soil may
have oversaturated the extraction fluid and resulted in the poor extraction efficiency.
The other possible explanation for the poor recoveries may be layering of PAHs in the
soil due to the centrifuging process. Because centrifuging partitions mixtures out by
weight, the PAHs may have been layered out in the soil, which would result in a
nonhomogeneous sample. A thorough remixing of the soil sample may not have been
done in the laboratory. Thus, analytical results would present data of varying
concentrations depending on where.the sample aliquot was obtained. The recoveries
for the liquid sample, although low, were still within the acceptable limits established in
the SAP except for benzo(a)pyrene. !
Although recoveries in the posttreatment samples were better, problems still .
existed in some samples. The MS sample from Bioreactor 1 during Week T9 showed
0 percent recovery for many of the compounds. This may have been due to an error
»
in spiking the sample during the extraction process. The recovery for
benzo(b)fluoranthene was below 20 percent in the MS sample from.Bioreactor 6 for
Week T9. The MS/MSD set from Bioreactor 5 showed the most inconsistency; the MS
sample showed very poor recoveries, and the MSD sample showed very good
recoveries. Again, the inconsistencies may be due to possible layering of the PAH
compounds during the centrifuge process.
7-15
-------
Recoveries of the critical constituents in the treated liquid matrices from
Weeks Tg and T12 were good. Recoveries ranged from a low of 40.7 percent to 99.5
percent. All recoveries were within the acceptable limits established in the SAP.
7.1.3 Precision Data
Precision data were calculated from the analysis of matrix spike/matrix spike
duplicate samples. Precision is expressed as the relative percent difference (RPD)
between the matrix spike and the matrix spike duplicate concentration values. The
equation for calculating relative percent difference is as follows:
- (D, - D9) 100
RPD = J-J *L
Pi * OJ /2
where RPD' = relative percent difference
D.J = larger of the two observed values
Dp = smaller of the two observed values
As stated in the SAP, the QA objectives for precision (RPD) were ±20 percent
for concentrations greater than 200 M9/kg and ±100 percent for concentrations less
than or equal to 200 /*g/kg. Tables 7-10 and 7-11 present the precision data
calculated from the matrix spike and matrix spike duplicate samples for the soil fraction
and liquid fraction respectively. . ;
The RPD values for the pretreatment soil fraction were generally outside the
acceptable limits of ±20 percent established for concentrations greater than 200
Mg/kg. Because of the poor recovery in the Week T9 MS sample for Bioreactor 1, the
RPD values for jnany of the compounds were outside the acceptable limits of
± 100 percent for concentrations less than 200 M9/kg. The Week T12 MS/MSD
samples from Bioreactor 5 also showed RPDs greater than 100 percent. The RPDs
for the other MS/MSD sets were generally good; most values were less than 20
percent. The RPDs for Bioreactor 4 from Week T12 showed values of 30 percent.
The RPDs for the MS/MSD samples in the liquid fraction were all within the
acceptable limits established in the SAP. The RPD values in the liquid fraction were
7-16
-------
03
O
O
c
w^
CMo'— , co co
J2f£ =
CD
C CO
2 ® S
*- e- ,<»-«= co
Zc\i<
-------
z
<
O
O
O
CD ^-,
OC
o
c:
P
i-^cMcr>-.-eoinini-o;t-cocn-r-
••*<*'^-"3--'*eOCMCO'^--<*'
Igiiis
o § ?££ =
CO
l«|
CD
C
s
CO
eo
c
CO
«
7-18
-------
generally less than 20 percent. The MS/MSD set for Bioreactor 4 during Week T9 of
sampling showed the worst precision; the RPD values ranged frorn 25,9 percent for
phenanthrene to 65.5 percent for anthracene.
7.1 A Blank Data for Soil Analyses
Equipment blanks were collected during the premilling, postmilling, and
centrifuging operations. Trip blanks were also collected for each major sampling event
in Weeks T0> T9> and T12 in the study. These blanks were analyzed for possible semi-
volatile organic contamination. The analyses of these samples showed no sign of
contamination in the sampling procedures. In addition, method blanks were extracted
for each set of samples submitted to the lab. These samples were also analyzed for
semivolatile organic contamination, and results were negative. .
During the premilling and postmilling sampling operations, field blanks were
collected to determine possible volatile organic contamination. Daily blanks were also
analyzed prior to sample analysis to ensure that the instrumentation was free of any
major volatile organic contamination. Volatile organic compounds detected in the
analysis of these blanks are presented in Table 7-12. All compounds detected were
less than the maximum control limits established for blanks in SW-846 Method 8240.
7.1.5 Surrogate Recoveries Data
In addition to the preceding quality assurance procedures, all samples analyzed
for volatile and semivolatile organics were spiked with surrogates as a means of
a
checking recovery efficiency. The results for surrogate recoveries during semivolatile
and volatile organic analyses are presented in Tables 7-13 and 7-14 respectively. Of
particular importance are the recoveries of terphenyl-d14 in the semivolatile organic
analyses and toluene-d8 in the volatile organic analyses. Terphenyi-d14 is the
surrogate most representative of the complex PAHs present in the treatment soil.
Recoveries for this surrogate ranged from a low of 38 in the pretreatment soil to a high
of 130 percent in the posttreatment soil samples. Poor recoveries of this surrogate
7-19
-------
TABLE 7-12. BLANK DATA FROM ANALYSIS OF BIOSLURRY SAMPLES
Field blank,
mg/L
Methyl ene chloride 0.014 B
Acetone 0.020.-B
Carbon disulfide
Chloroform
2^Butanone
1,1, 1-Tr.i chl oroethane
Trichloroethene 0.002 JB
To! uene
1,2, 3-Tri chl oropropane
VBLKJ3,
mg/L
0.005
0.024
0.01
0.002 J
0.002 J
VBLKJ4, VBLKJ6,
mg/kg mg/L
0.018
0.013 ' •
0.003 J ;'
' 0.001 J
0.007 J ' •
0.002 J
0.002 J
0.001 J
B = Target analyte detected in method blank as well as the sample.
J = Estimated value for analyte detected below established detection limit.
7-20
-------
CO
UJ
Q.
CO
O
^-
O
DC
O
LLJ
j=
_1
O
5^
-y O
^- O
CD
co ^
— — C
DC CD
L1J.E
> CD
OS
o
UJ
DC
LLJ
H-
CD
O
DC
DC
ID
CO
.
CO
r-i-
LLJ
_i
CD
h-
o
c
CD
Q.
O
2
.Q
H
co
CM
"o
C
CD
Q_
O
O
3
LL.
CM
CO
"U
"o
CD
_c
Q.
tp
c
CD
.C
Q.
CD
h-
C
CD
Q.
lo
0
3
ul
CM.
7
CD
CD
N
C
CD
.a
S
2
LO^LoScococncocM^'^co
%
•
T-^-OCOCOT-OOCOCOC)CDO
COCOLOLOCOCOCOCOCOCOCOLO
SS318S3fcBfe5E5!|
SSSgS^PlD5SgfSg
OOr^-T— C3>LOC3>OO>'— OOOO
^
-^ c o *
-2 3 S 2 i -^ "c ^"l
"o.-9-SmPi-s""^
°o> a>O)CO-gS c ^"- O> C "^ CO D> C CD O O
M = ^'J § -^ "^ :§ § E « m
£J5*^ £^ -
CD
•S5!
^ —
si
0 0
o o
CO (0
CD CD
o o
in CD
O CM
CO T-
m o
•* CO
o t^
1^ (0
^ LO
CO CO
CO CO
00 CO
CO -
-------
.
-r
"c
8,
CO
i
LU
1
CD
1
1 —
0
c
CD
Q.
O
O
.Q
H-
CO
CM
"5
c
CD
Q.
0
O
iZ
CM
CO
"O
'
O
C
CD
Q.
TJ
C
CD
r"
Q.
CD
I —
C
CD
Q.
_Q
o
0
LU
CM
in
-a
CD
c.
CD
N
C
CD
.a
S
CM ir> in o OCD or- o-r- in co m f-- or-- o ••- o "'o00
o r- co Ti- r^ CM [•— co r-~ T- coco cor-- r-— CD " f*- :^L co ^i CD
"*
•
co co in re ore ore mre in re ocoini^or^incotnco
CD -vt* p— CM i — • co r~— co r— o r*— i~ F*~ CD co m co ^t" co CM co to
•»-
re
"*cowro inre ore ore inro tncoh-r^moocoinco
co co to o co o CD o r^- o r— o co to co m t^* ^* CD T~ r^ to
v *—
t^COI--O CD-r- T-CM CO03 COO5 CO^tO^^^Q^LO S1^.
re
CM"*oa> cn-i— ocn <35r~- T-IO oco cno co-* co CM^I —
h— ^i* co co f*~ r*— co CD t^ ^— o^ r— • t^> CD r*— CD CT> to r*— co CT> m
"~
**
re
a>coc\ji-~- OOCM intn-t-co coo coco men OCM to coco-r-
tncococo r^-i-~ r~~co cot^- coco i^to com com.co CMCOIO
•
•*
0
CO
Ij ^
CU C ^^ ^f ^^ ^f ^^ ^f ^^ ^f ^^ ^f
CO ^ ^f ^f ^f ^f ^f ^^ ^^ ^i, ^^ ^t ^^ ^^ ^^ ^t ^«
•& ~° $ "Z. ^ 'Z. 7^ $ "Z. ^2 Sm m CQ mffi m^ mffl
c -4— j^ 03 « m iSr m ^: rn ^ m , « , i *^ ^t , t ™ ,1
re *— ™3 ^i u-i i^ tu ^i uj _i UJ ^i *rt <^ ^rt ^^ ^rt ^^ ^rt <^ jrt ^5
J3 2w^ CO? "^? "•*? ^" i T--A CMCM •^••^- toin coco
^Q.T~'~e^c^Ti'T5'tn1otoc°OCCCCCCCCCCCCCOCDCQC
^UUH-PPPPPPPPPl-l-l-t-h-l-l-l-l-l-
OT
'1
i^
_CD
a.
s
o
re
CD
S
o
r*
CD
I
CD
^
CD
"5
O)
Q
3
CO
re
7-22
-------
TABLE 7-14.
SURROGATE RECOVERIES IN VOLATILE ORGANIC SAMPLES
(percent recovery)
Premilling soil
Postmilling soil'
Field blank
Method blank VBLKJ3
Method blank VBLKJ4
Premi 11 i ng soi 1 TCLP
Postmilling soil TCLP
Method blank VBLKJ6
Method blank VBLKJ9
TC'LP blank VBLK294
1 , 2-Di chl oroethane-d4
100
91
104
98
92
94
93
94
92
96
Tol uene-d8
113
93
104
103
109
104
104
103
102
105
Bromof 1 uorobenzene
115
90
102
104
110
109
101
103
100 f
103 :
7-23
-------
were obtained in the liquid fractions. All of the pretreatment liquid samples and four of
the live posttreatment samples showed recoveries below the acceptable limits
established in SW-846. Reextraction and reanalysis of these samples verified a matrix
interference problem in the analysis of these samples.
Recoveries for toluene-dS, the surrogate most representative of the volatile
organic contaminants possibly present in the soil, were all within the acceptable limits
established in SW-846.
Standard reference solutions were analyzed for metals and inorganics to
evaluate the efficiency of the analytical method. The results of the analyses of the
standard reference solutions are presented in Table 7-15.
7.1.6 Analytical Problems l
Because of the complex nature of the matrix under evaluation, several analytical
problems occurred during their analyses that may have an effect on the data.
The holding times for extraction of the premilling, postmilling, and Week T0
samples were exceeded. The samples were originally extracted as low-level soils,
which resulted in a thick oily extract that was not amenable to analysis., The samples
had to be reextracted as medium-level soils, which resulted in missed holding times.
In addition, the liquid fractions from Week T0 and the sludge from Bioreactor 1 from
Week T0 were extracted a third '|ime so a matrix interference could be proven for the
liquids and the proper MS/MSD spiking solution could be used on Bioreactor 1
sludge. It is believed that the missed holding times should not affect the data because
the samples were preserved with concentrated hydrochloric acid in the hope of inhib-
iting further biological activity. In addition, the samples were stored at 4°C, which also
would impair biological activity and help to ensure sample integrity.
The detection limits for many of the critical constituents were greater than
1 mg/kg as a result of the medium-level extractions being performed on the soil
fractions. Medium-level extractions were performed on the soil because of the high
level of total petroleum hydrocarbons detected in the soil matrix. The posttreatment
samples from Weeks Tg and T12 produced data with many nondetections of critical
7-24
-------
TABLE 7-15. STANDARD REFERENCE SOLUTION RESULTS
FROM ANALYSIS FOR METALS AND INORGANICS
(percent recovery)
Metals and inorganics
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Cadmi urn
Calcium
Chromium
Chromium VI
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Chloride
Cyanide
Fluoride
Total phosphorus
Sulfate
Total analysis TCLP analysis
109
97
80.7 94.5
111 108
104
96.6 95.7
103
106 97.5
100 '-.-.
98.9 ]
,100
98.6
110 94.6 ;
101 ',
108
102, 100, 99, 100 102 !
102
97.6
91.9 85.2
112 104 ,
99.1 '
104
101
99.1
105
102
88.8
98.6
94.7
(continued) 7-25
-------
TABLE 7-15 (continued)
Metals and inorganics
Sulfide
TOC
TOX
Total analysis
123
99.4
91.8
TCLP analysis
!
contaminants. The contaminants present in low concentrations may have been diluted
out in the medium-level extraction process. As a result, the soil fractions from Weeks
T9 and T12 were reextracted and reanalyzed as low-level soils. The holding times for
the reextractions were exceeded; however,-the integrity otthe-data should not be '
^affected because the samples, were preserved with concentrated hydrochloric acid.
The reextraction data are important because of the effect they may have on the eval-
uation of the treatment efficiency of the bioslurry system. The low-level extracts use a
larger sample aliquot which allows for a more representative sample of the soil being
studied and allow for detection of contaminants at lower concentrations that were not
available in the medium-level extracts due to dilution effects, thereby enabling a better
evaluation of the treatment technology.
The data for this treatment study should be used with caution, based on the
analysis of the MS/MSD samples and the surrogate recovery results. Although
recoveries of the spike compounds were better in the treated samples than in the
untreated samples (which indicates a cleaner matrix free of interferences), the
inconsistencies in recoveries shown by the RPD values indicate that the samples may
not have been homogeneous. As stated previously, the centrifuge process may have
caused layering of the soil samples, with the heavier PAH-contaminated fraction
settling at the bottom and the less contaminated fraction settling at the top. As a
result, the final analytical data may be affected by the place where the extraction
aliquot was obtained. .
The surrogate recoveries for terphenyl-d14 in the liquid fraction indicate a matrix
interference that may have affected the ability to extract PAHs out of the matrix.
7-26
-------
In addition to the problems concerning the critical contaminants, a few minor
analytical problems were also observed in the analysis of the remaining CS&D
constituents. For example, the holding time for cyanide was exceeded during the
study. Because cyanide was not a critical contaminant, however, the integrity of the
soil data was not affected. The holding time for the extraction of pesticides was also
exceeded during the study. Again, because pesticides were not critical contaminants,
the integrity of the soil data was not affected.
I
7.1.7 Audits
Audits were performed by S-Cubed, a subcontractor of the U.S. EPA, on the
treatment system sampling procedures and on the laboratory's analytical procedures.
Conditional ratings for QA/QC procedures were given to both the sampling and analy-
tical methods IT followed during the study. Copies of the Corrective Action Recom-
mendation Forms and the final report for both audits are presented in Appendix O.
7.2 Air Samples
Routine Standard Reference Method QC procedures were followed throughout
this test series. These included, but were not limited to, the following:
Calibration of field sampling equipment.
Sampling train configuration and calculation checks.
Onsite quality assurance checks, such as sampling train leak checks.
Use of designated analytical equipment and sampling reagents.
Laboratory analytical procedures.
The field sampling equipment, reagents, and analytical procedures used during
this test series met all the necessary guidelines set forth for accurate test results. The
laboratory quality control samples included blanks, matrix spikes, and duplicate
analyses. Laboratory QC results are discussed by analysis type in the following
subsections. • .. • '
7-27
-------
7.2.1 Analyses of Total Hydrocarbon (THC) Emission Monitoring
Method 25A was used for continuous monitoring of THC concentrations, and all
calibrations and system checks were well within the guidelines for this method. Table
7-16 presents example calibration data from this test program. All other calibration
data are contained in Appendix N. .
TABLE 7-16. EXAMPLE METHOD 25A THC CALIBRATION DATA
Contaminant
Date monitored
5/7 THC
5/8 THC .
5/9 THC
a Drift % of span
= (Posttest calib.
Drift,
% of span
1.6C
-1.4
-0.8
response - initial
Linearity..
% of span
-0.2C
-0.2
0.2
calib. response) ..
Correlation
coefficient
0.9999
0.9999
0.9999
i nn
Span value, ppm
Based on predicted concentrations from linear regression equation and the
span value as follows:
•. Q, .. _ (Gas concentration - predicted concentration) v inn
Linearity - $pan valu^ ppm , x 100
c Drift and linearity present maximum errors based on four calibration
standards.
7.2.2 Analyses for Hazardous Substance List (HSL) Semivolatile Organics
All analyses for semivolatile organics were conducted by gas chromatography/
mass spectrometry (GC/MS) in accordance with SW 846 Method 8270.
Table 7-17 is an example of surrogate recoveries on sample tubes and field
blank tubes. Table 7-18 presents the acceptable recovery limits for surrogates in
Method 8270. AH other blank data and surrogate recoveries data are included in
Appendix N. All semivolatile laboratory data met Method 8270 requirements.
7-28
-------
CO
LLJ
CD
H
1
CD
Q
^^1
UJ
u_
Q
z
UJ
Q_
fl^~
.>
CO
0
CO
LLJ
CC
LLJ
O
0
LLJ
CC
LLJ
O
O
CC
DC
~")
CO
LLJ
P
O
LLJ
CO
m"
r-.
LLJ
CD
\-
„
0
CD
JC
r»
0
E
0
_Q
£
CO
"o
C
CD
jr
Q.
2
0
j2
CM
"o
C
CD
<—
o.
1
CO
T3
C
CD
Q.
CD
-t
"°
>>
CD
0
O
LL
CM
CD
o o
co to co
O CO CM
cn to to
o> co •>*•
co co in
"
co co in
oo co in
tO 1 — TT
CO CO f^
o> oo o>
to Is** •^-
CM
—1 — 1
00
o o o
2
LL.
i
V—
6
•
-* LO
h^ to
Sg
r-N.
h- 1~-
CT) Kf
Is- CO
O i-
co t^
T— CO
CO to
o
o o
m
i
T—
6
X
to co in
CO CO •*
cn co i-
co to to
to co o>
S- to "^f
^. 00 OO
oo to ••*
o in in
to r*- to
-* in -*
in co in
CM
OO
CVJ C\J C\J
000
'c
2
LL.
^7
CM
i
X
r> to
h- to
co at
O CO
O) CO
t~- to
i- to
00 CO
CM CM
to r-~
*
« CO
to in
O
O 0
1
m
•*7
CM
6
X
O Is- O
co to r*-
,
o •*!• rr
O> OO O)
r-- Is- in
to to Is**
to to co
oo oo oo
oo tn CM
in in to
CM 0 00
to to in
3
m
o
Sen ^C
0 X
c c
J5 J2 v;
CD CD c
•o -o J5
CD CD CQ
LL. LL. -o
i i O
0= 0-g £
< S. < m &
XU. XCQ 2
7-29
-------
TABLE 7-18. ACCEPTABLE SURROGATE RECOVERY LIMITS
Surrogate compound
Nitrobenzene-D5
2-Fluorobiphenyl
p-Terphenyl-D14
Phenol -D6
2-Fluorophenol
2 , 4, 6-Tri bromophenol
QC recovery
Solids
23-120
30-115
18-137
24-113
25-121
19-122
limits, percent
Waters
35-114 .
43-116
33-141
10-94
21-100
10-123
7.2.3 Volatile Organic Analyses
AH of the canister samples were analyzed for volatile organics by concentrating
aliquots cryogenically and analyzing by gas chromatography/mass spectrometry.
•Table'7-19 lists the volatile organics which is an example canister blank and their
corresponding detection limits. Table 7-20 is an example of surrogative recoveries in
canisters and method blanks. All other blank data and surrogate recoveries are
included in Appendix N.
7.3 Bioreactor Monitoring Samples
As samples were collected by an ECOVA Research Associate at the T&E
Facility in Cincinnati, each group of samples was given a number corresponding to the
central sample log book at ECOVA's laboratories in Redmond, Washington. This
number was assigned when the Research Associate called ECOVA's labs. Upon
their receipt at ECOVA's lab, the samples were checked, the Chain of Custody was
signed, and a Sample Group Worksheet was begun that followed each sample group
through its testing protocol at ECOVA. The sample group numbers for all 12 weeks of
analysis are presented in Table 7-21.
7.3.1 Analytical Methods
Table 7-22 lists the methods used in monitoring the reactors in the pilot-scale
phase of this project.
7-30
-------
TABLE 7-19. VOLATILE CANISTER BLANK RESULTS
Compound
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
1 , 1 -Di chl oroet hene
Carbon disulfide
Methyl ene chloride
t-1 , 2-Di chl oroethene
1,1-Di chl oroethene
c-1 , 2-Di chl oroethene
Chloroform
1 , 1 , 1 -Tri chl oroethane
Carbon tetrachloride
Benzene
1, 2-Di chl oroethane
Tri chl oroethene
1, 2-Di chl oropropane
Bromodi chl oromethane
c-1 ,3-Dichl oropropene
To! uene
t- 1 , 3-Dtchl oropropene
1,1, 2-Tri chl oroethane
Tetrachl oroethene
Di bromochl oromethane
Chlorobenzene
o Ethyl benzene
°m +/or p xylene •
o- xylene
Styrene
Bromof orm
1,1,2, 2-Tetrachl oroethane
Blank
NDa
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Detection limit
0.5
0.3
0.3
0.5
0.3
0.2
0.2
0.3
0.3
0.3
0.3
0.3
0.2
0.2
0.3
0.2
0.3
0.2
0.4
0.2
0.4
0.3
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
ND = None detected.
7-31
-------
TABLE 7-20. EXAMPLE SURROGATE VOLATILE ORGANIC RECOVERIES
Surrogate organic volatile recoveries,
percent
Sample ID',
Can 1-1
Can 2-1
Method blank
Method blank
Method blank
Lab No.
04
04 DL
05
05 DL
VBLKQ4
VBLKQ5
VBLKQ6
d4-l,2-
Diqhloro-
ethane
99
99
105
119
106
106
97
d8-Toluene
101
99
95
115
99
94
102
p-Bromo-
fluoro-
benzene
107
102
106
88
97
106
98
TABLE 7-21. SAMPLE GROUP NUMBERS ASSIGNED BY ECOVA LABS
Test Week
0
1
2
3
4
6
9
10
11
12
Date
May 8
May 15
May 22
May 29
June 5
June 19
" • July 10
July 17
July 24
July 31
Sample Group
277-122
277-127
277-133 ;
277-142 •
277-146 :
277-162
277-184
214-1
214-11
214-30
7-32
-------
TABLE 7-22. METHOD USED TO MONITOR REACTORS
DURING PILOT-SCALE PHASE
Compound . Method
Semivolatiles (BNAs) EPA 8270 & ECOVA SSC-4
Oil and grease (O&G) EPA 413.1 :
Inorganic nutrients EPA 300.0
NH3 . EPA 350.2 ;
TPH EPA 418.1
Nitrate . ECOVA SSC-9
Ortho-phosphate P ECOVA SSC-14
Composited soil sample Microtox
The following is a synopsis of the methods used by ECOVA in this study:
Polvnuclear Aromatic Hydrocarbons fPAHs^ - The PAH analysis by HPLC (EPA
8310 Mod) was conducted at the ECOVA laboratory in Redmond, Washington.
This analysis generated the primary process monitoring data used to track the
degradation progress and to provide the necessary information for process
modifications, if required. The analytical results provided individual, quantitation
of specific PAH compounds, including those considered to be critical
contaminants. ;
=»
Oil and Grease (O&GyTotal Petroleum Hydrocarbon fTPH^ - The 6&G (EPA
413.1) and TPH by IR (EPA 418.1) analyses were performed by IT Corp. The
results are nonspecific,'but they provided good monitoring data for the general
organic content of the slurry.
Nutrients and Ammonia - The nutrient analysis (by EPA Method 300) and the
ammonia analysis (by the modified Nessler Method) were conducted at
ECOVA's laboratory. These analyses were used to track nutrient levels during
the pilot test and provided data necessary to insure optimal nutrient levels.
Total Heterotrophs and PAH Degraders - The total heterotroph analysis (by SM
907) and PAH degrader analysis (by SM 907 Mod) were conducted at the
ECOVA laboratory in Redmond. These analyses were used to track the activity
of the heterotrophic and specific PAH degrading populations of microorganisms
during the pilot test.
Microtox - Microtox analyses were conducted at ECOVA's laboratories to
monitor the change in toxicity over the course of the study.
7-33
-------
Field Measurements - Four field measurements were made at the T&E Facility-
dissolved oxygen (DO), temperature, pH, and particle size distribution. The DO,
temperature, and pH measurements were made by lowering probes into the.
reactor. The particle size distribution was assessed by wet screening
techniques.
7.3.2 Analytical Problems and Deviations
A major problem with the analyses for polycylic aromatic hydrocarbons was the
efficient extraction of the PAHs from the soil matrix. During, both the bench-scale and
the pilot-scale phases of the project, despite exhaustive attempts to mill, sonicate, and
extract PAHs from virgin soil, concentrations of soil-bound PAHs increased after
several weeks in a bioreactor. The .most reasonable explanation, based on empirical
evidence and total suspended solids data, is that the shear forces within the reactors
comminuted the -larger soil particles to finer ones. This, in turn, diminished their
resistance to mass transfer effect (e.g., smaller particles exhibited a shorter surface-to-
center path length) and allowed a higher PAH extraction efficiency because PAH
residues could more easily diffuse to the particle surface.
Although this phenomenon was noted in the bench-scale phase and resulted in
having to subject the soil to ball milling three times during the pilot-scale test, the
comminution effect was still readily apparent.
No other major deviations from standard procedures were noted.
7.3.3 Detection Limits
Table 7-23 reflects the current limits of detection (LOD) of individual PAHs at the
ECOVA laboratories. These limits were derived by serially diluting standards until the
HPLC could no longer quantitate the results. This lowest standard concentration was
then run 10 times to develop a statistical universe. The values from the next-to-the-last
standard dilution were used to calculate an LOD by the following equation:
LOD = Standard amount + 3 standard deviations !
7-34
-------
TABLE 7-23. CURRENT LIMITS OF DETECTION (LOD)
OF INDIVIDUAL PAHs AT THE
ECOVA LABORATORIES3
a
PAH
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene •
Anthracene
Fluoranthene
Pyrene
Benzo[a]anthracene
Chrysene
Benzo[b]fluoranthene
Benzo{k]fluoranthene
Benzo[a]pyrene
Dibenz[a,h]anthracene/
Benzo[g,h,i]perylene
lndeno[1 ,2,3-cd]pyrene
Lowest standard,
ppm
0.3908 ± 0.0528
0.7894 ± 0.1347
0.2691 ± 0.0717
0.0870 ± 0.0053
0.0401 ± 0.0029
0.0378 ± 0.0025
0.0594 ± 0.0151
0.2280 ± 0.0846
0.0411 ± 0.0038
0.0379 ± 0.0026
0.0769 ± 0.0059
0.0355 ± 0.0061
0.0395 ± 0.0117
0.0374 ± 0.0094
0.0338 ± 0.0079
LOD,
ppm
0.5492
1.1935
0.4842
0.1029
0.0488
0.0453
0.1047
0.4818
0.0525
0.0457
0.0946
0.0538
0.0746
0.0656
0.0575
All other methods have detection limits < 1 ppm.
7-35
-------
-------
SECTION 8
CORRESPONDENCE
Table 8-1 presents the activities and correspondence that were critical to the
outcome of this study.
TABLE 8-1. CRITICAL ACTIVITIES AND CORRESPONDENCE
Date and Type of
Activity or
Correspondence
11/7/89
Site Visit
11/20/89
Site Visit
7/90
Meeti ng
10/1/90
Tel ephcme
10/5/90
Tel ephcme
10/15/90
Site Visit
11/90
Tel ephone
12/14/90
Meeti ng
2/91
Reporting
2/22/91
Transport
Contact
Jim Brown
ReTec
Jim Brown
ReTec
Richard Lauch
U.S. EPA
Richard Trax
ReTec
Jim Brown
ReTec
Jim Brown
ReTec
ECOVA
R. Lauch
R. Lewis
U.S. EPA
ECOVA
G. Simes
U.S. EPA
ECOVA
Subject/Action
ITEP sent sampling team to characterize BN
soi 1 .
ITEP sent sampling team to drum up
potential soil for treatment studies;
drums stored at site.
BN soil chosen as test soil for Bioslurry
study.
Discussed ITEP's plan to collect more
soil. R. Trax relayed that BN would not
allow ITEP to reopen their soil liner.
ITEP will sample from drums stored at
site.
Verified ITEP's plan to travel to BN site
on 10/15/90, dump and repackage soil from
3 drums, and transport drums to
Cincinnati.
ITEP sent team to dump and repackage soil
from 3 drums for treatment studies. •
Bench-scale work began on BN soil.
Visited ECOVA to observe bench-scale work,
discussed pilot-scale study.
Pilot-scale SAP submitted to EPA for
review.
Additional drum of soil shipped to ECOVA
for further studies.
(continued)
8-1
-------
TABLE 8-1 (continued)
Date and Type of
Activity or
Correspondence
2/25/91
Transport
4/17/91
Reporting
4/26/91
Reporti ng
• 5/8/91
Treatment Test
5/10/91
Treatment Test
6/91
Analytical
7/1/91
Meeting
7/10/91
Treatment Test
7/11/91
Treatment Test
7/31/9:i
Treatment Test
9/91
Reporting
9/91
Reporting
10/91
Reporting
Contact
U.S. EPA T&E Facility
G. Simes
U.S. EPA
G. Simes
U.S. EPA
ECOVA
IT
U.S. EPA
ECOVA
IT
U.S. EPA
B. Blackburn
S-Cubed
R. Lauch
U.S. EPA
J. Herrmann
R. Lauch
E. Grossman
U.S. EPA .
A. Jones
B. Mahaffey
C. Krauskopf
ECOVA
C. Krauskopf
ECOVA '
C. Krauskopf
ECOVA
Mike Smith
ITEP
L. Tomassoni
ITAS-Cincinnati
9
L. Jones
U.S. EPA
R. Lauch
U.S. EPA
Additional drums of soil shipped to
Cincinnati for pilot-scale test.
Letter submitted to EPA responding to QA
comments on SAP.
Letter submitted to EPA responding to
further QA comments on SAP.
Pilot-scale work began on BN soil with
screening and milling processes.
Reactors charged with slurry and spike
with inoculum. i
B. Blackburn performed audit on analytical
laboratory. Conditional pass given on
basis of holding time for critical I
contaminants being exceeded.
Discussed bioslurry results through Week
6. ITEP to collect T samples on 7/10/91
(Week 9): ECOVA to affiend slurries and .
ITEP to collect T samples on 7/31/91
(Week 12). lz
T samples collected from reactors.
Reactors 2, 4, 5, and 6 were respiked with
inoculum. Reactors 5 and 6 had surfactant
added to them.
T samples collected from reactors.
Reactors shut down.
All data pertaining to bioslurry study
reported- to ITEP.
Data summary form for bioslurry study
submitted to U.S. EPA.
OER for bioslurry study submitted to U S
EPA.
8-2
------- |