United States Office of Research and EPA-600/R-01-056a
Environmental Protection Development July 2001
Agency Washington, DC 20460
&EPA Environmental
Impacts
of the Use of
Orimulsion®
Report to Congress
on Phase 1 of the
Orimulsion® Technology
Assessment Program
Volume 1: Executive
Summary, Report, and
Appendix A
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Foreword
The U.S. Environmental Protection Agency 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. To meet this mandate, EPA's research program is providing data and technical support
for solving environmental problems today and building a science knowledge base
necessary to manage our ecological resources wisely, understand how pollutants affect our
health, and prevent or reduce environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's
center for investigation of technological and management approaches for preventing and
reducing risks from pollution that threaten human health and the environment. The focus
of the Laboratory's research program is on methods and their cost-effectiveness for
prevention and control of pollution to air, land, water, and subsurface resources; protection
of water quality in public water systems; remediation of contaminated sites, sediments and
ground water; prevention and control of indoor air pollution; and restoration of ecosystems.
NRMRL collaborates with both public and private sector partners to foster technologies that
reduce the cost of compliance and to anticipate emerging problems. NRMRL's research
provides solutions to environmental probelms by: developing and promoting technologies
that protect and improve the environment; advancing scientific and engineering information
to support regulatory and policy decisions; and providing the technical support and
information transfer to ensure implementation of environmental regulations and strategies
at the national, state, and community levels.
This publication has been produced as part of the Laboratory's strategic long-term
research plan. It is published and made available by EPA's Office of Research and
Development to assist the user community and to link researchers with their clients.
E. Timothy Oppelt, Director
National Risk Managment Research Laboratory
EPA REVIEW NOTICE
This report has been peer and administratively reviewed by the U.S. Environmental Protection
Agency, and approved for publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information Service,
Springfield, Virginia 22161
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EPA-600/R-01-056a
July 2001
Environmental Impacts of the
Use of Orimulsion®
Report to Congress on
Phase 1 of the Orimulsion® Technology
Assessment Program
Volume 1. Executive Summary, Basic
Report, and Appendix A
By
C. Andrew Miller, Kevin Dreher, Randall Wentsell, and Royal J. Nadeau
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
National Health and Environmental Effects Research Laboratory
Research Triangle Park, NC 27711
National Center for Environmental Assessment
Washington, DC 20460
National Risk Management Research Laboratory
Environmental Response Team
Edison, NJ 08837
EPA Project Officer: C. Andrew Miller
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
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Abstract
Orimulsion, a bitumen-in-water emulsion produced in Venezuela, was evaluated to provide a better
understanding of the potential environmental impacts associated with its use as a fuel. A series of
pilot-scale tests were conducted at the U.S. Environmental Protection Agency's Environmental
Research Center in Research Triangle Park, NC, to provide data on emissions of air pollutants from
the combustion of Orimulsion 100 (the original formulation), Orimulsion 400 (a new formulation
introduced in 1998), and a No. 6 (residual) fuel oil. These results, and results of full-scale tests
reported in the technical literature, were evaluated to determine the potential air pollutant emissions
and the ability of commercially available pollution control technologies to adequately reduce those
emissions. Emissions of carbon monoxide (CO), oxides of nitrogen (NOX), sulfur dioxide (SO2),
sulfur trioxide, particulate matter (PM), and organic and metal hazardous air pollutants (HAPs) were
measured from each of these three fuels to provide a comparison between the "new" fuel
(Orimulsion) and a fuel that has been commonly used in the U.S. (the No. 6 fuel oil). Results
indicate that CO, NOX, and PM emissions are likely to be nearly the same as those from the No. 6 fuel
oil, that SO 2 emissions can increase if the fuel sulfur content increases, that the particles generated by
Orimulsion 100 and 400 are likely to be smaller in diameter than those generated by No. 6 fuel oil,
and that HAPs are also likely to be similar to those from No. 6 fuel oil. Both the full-scale results
found in the literature and the pilot-scale results measured at EPA indicate that conventional air
pollution control technologies can effectively reduce emissions to very low levels, depending upon
the type of technology used and the desired emission levels. Because the bitumen in Orimulsion is
heavier than water and due to the presence of a surfactant in the fuel, spills of Orimulsion are likely to
be more difficult to contain and recover than are spills of heavy fuel oil, especially in fresh water.
Additional study is needed before adequate containment and response approaches can be developed.
Little, if any, work has been conducted by the fuel producer or the scientific community to address
the remaining spill-related issues.
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Preface
This report is the result of a request by the U.S. Congress to receive scientific information regarding
the potential environmental impacts of the use of Orimulsion as a fuel. In the second half of the
1990s, there was considerable interest on the part of electric utilities in using Orimulsion, which was
promoted as a low-cost fuel that could replace heavy fuel oil or coal. There were also many concerns
raised by the environmental community regarding the environmental impact associated with
switching to Orimulsion. In 1997, the U.S. Congress requested that the U.S. Environmental
Protection Agency (EPA) conduct a study to evaluate the potential environmental impacts associated
with the use of Orimulsion. EPA's Office of Research and Development provided funds to the
National Risk Management Research Laboratory (NRMRL) to conduct this study, and a team of EPA
experts in air pollution control, spill response, health effects, and environmental assessment was
assembled to carry out the investigation. This report was prepared by EPA staff using data generated
at EPA facilities as well as data collected from the general literature.
In 1998, Bitumenes Orinoco (Bitor), the manufacturer of Orimulsion, changed the formulation of the
fuel. The original fuel, renamed Orimulsion 100, was replaced with a new formulation named
Orimulsion 400. Compared to the amount of information on Orimulsion 100, there is relatively little
data on the performance of Orimulsion 400. While this report provides as much data as possible on
the emissions and performance of Orimulsion 400, the bulk of the data are for the older formulation
(Orimulsion 100). Although Orimulsion 100 is no longer produced, the results presented here are
still believed to adequately describe the basic behavior of both formulations of Orimulsion. The key
question to be addressed in this study is, "Is Orimulsion significantly different from other fossil fuels,
and if so, how?" The differences between Orimulsion 100 and Orimulsion 400, as indicated both
from the available data and the information provided by the manufacturer, are substantially smaller
than the differences between Orimulsion and other fossil fuels. The report distinguishes between the
two formulations where appropriate, but uses the generic term "Orimulsion" where such distinction
is either unimportant or misleading. The recent reformulation is significant with respect to the
surfactant used (which will affect spill toxicity) and the use of a magnesium-based additive (which
will affect boiler tube deposition and particulate matter emissions). Other environmental issues
appear to be impacted only to a minor degree by the change in formulation.
The emphasis of this report is on generation and control of air pollutants from the combustion of
Orimulsion. Although there are other environmental issues associated with the use of Orimulsion,
particularly spills of the fuel into water, EPA and NRMRL were advised on several occasions that
questions related to air pollutant generation and control were the key unknowns associated with
understanding the environmental impact potential of Orimulsion. The initial step in EPA's research
activities was the convening of a workshop to discuss environmental issues related to Orimulsion use.
This workshop, held February 8, 1998, concluded that there was a lack of information on particle size
distribution and composition and on emissions and control of sulfur trioxide from Orimulsion
combustion. The workshop also concluded that enough data existed to allow a comparative risk
analysis for heavy fuel oil and Orimulsion, and therefore additional research in that area was not
immediately required. The workshop noted that a lack of data existed describing the behavior, fate,
and effects of Orimulsion spills in fresh water. However, the workshop concluded that investigations
into these areas should be the responsibility of Bitor in the event they sought to market the fuel to
users where spills into fresh water were possible. Considerable work has been conducted to quantify
behavior, fate, and effects of Orimulsion in saltwater environments under the oversight of the
International Orimulsion Working Group, of which Bitor is a member and the major source of
funding. Thus this report has as its focus the generation and control of air pollutants, although other
topics are also covered.
This focus was emphasized in the Orimulsion Technology Assessment Plan that was prepared to
guide EPA's research efforts. This plan was reviewed and approved, with modifying comments, by a
in
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panel of technical experts, mostly from outside the federal government. The only exception was one
member from the U.S. Coast Guard. The Plan was then reviewed by the Office of Management and
Budget (OMB), the U.S. Department of Energy, and the Office of Science and Technology Policy.
EPA responded to comments made by each of these organizations and revised the Plan, which was
approved by OMB on April 22, 1999.
The National Risk Management Research Laboratory was the lead organization for the study, and was
chiefly responsible for preparation of Chapters 1-5 and 9-12. Robert E. Hall was the overall program
lead, and C. Andrew Miller was the lead author of these chapters. Kevin Dreher of the National
Health and Environmental Effects Research Laboratory prepared Chapter 6, on toxicity testing, with
substantial assistance from Adriana Grain. Chapter 7, on spills, was prepared with assistance from
Royal J. Nadeau of EPA's Office of Solid Waste and Emergency Response. Randall Wentsel of the
National Center for Environmental Assessment prepared Chapter 8, on environmental assessment.
The conclusions stated in this report are scientific conclusions, and are not intended to provide
guidance relative to regulatory requirements that may or may not apply to the use of Orimulsion.
Acknowledgments
Many people contributed to the collection of data and preparation of this report. From EPA's Air
Pollution Prevention and Control Division, the following people provided notable input:
• Marc Calvi for preparation and analysis of SEM samples,
• Shirley Wasson for XRF analysis of PM samples, and
• Paul Groff, Richard Shores, and Nancy Adams for quality assurance support.
From ARCADIS Geraghty & Miller (under EPA contract 68-C-99-201), efforts of the following
people were critical to the completion of this project:
• Suh Lee, project lead,
• Charly King for sample collection and preparation,
• Christian Elmore and Daniel Janek for SMPS operation, and
• Dennis Tabor for analytical chemistry support.
The opportunity to observe full-scale operations at the Dalhousie and Asnaes Generating Stations was
also very useful, and we received considerable assistance from:
• Rod Eagles and Barry Irvine of New Brunswick Power, Dalhousie, New Brunswick, Canada,
• Kim Jonas, Niels Groth-Andersen, Thorkild Meyer, and Hans Christensen of SK Power,
Kalundborg, Denmark, and
• Morten Thellefsen Nielsen, Technical University of Denmark, Lyngby, Denmark.
Many of the reports from which full-scale data were taken were provided by Nelson Garcia Tavel of
Bitor America, Jason Miles of Bitor Europe, and independent consultant Ken Olen.
IV
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Nomenclature and Acronyms
APCS air pollution control system
API American Petroleum Institute
APPCD Air Pollution Prevention and Control Division
ARD Arizona road dust
ASTM American Society for Testing and Materials
BALF bronchoalveolar fluid
bbl barrels, U.S. petroleum
BTEX benzene, toluene, ethylene, and xylenes
Btu British thermal unit
CAA Clean Air Act
CAAAs Clean Air Act Amendments of 1990
CARB California Air Resources Board
CE Combustion Engineering
CEM continuous emission monitor
CO carbon monoxide
CO2 carbon dioxide
DAS data acquisition system
DQI data quality indicator
EDX energy dispersive x-ray
ENEL Italian Electricity Generating Board
EPA Environmental Protection Agency
ESP electrostatic precipitator
FETC U.S. Department of Energy's Federal Energy Technology Center
FGD flue gas desulfurization
FPL Florida Power & Light Company
GIS geographical information systems
HAP hazardous air pollutant
HEPA high efficiency particulate air
HFO heavy fuel oil
HQ health quotient
IOWG International Orimulsion Working Group
IURE inhalation unit risk estimate
LAPIO low API oil
LDH lactate dehydrogenase
LNB low NOX burner
LOEC lowest observable effects concentration
LOEL lowest observed effect level
LOI loss on ignition
MACS miniature acid-condensation system
MDL method detection limit
MEI maximum exposed individual
MIR maximum individual risk
NCEA National Center for Environmental Assessment
NHEERL National Health and Environmental Effects Research Laboratory
NO nitric oxide
NOEC no observable effects concentration
NOX nitrogen oxides
NRC National Research Council
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Nomenclature and Acronyms (Continued)
NRMRL National Risk Management Research Laboratory
NSPS New Source Performance Standard
O2 oxygen
OERR Office of Emergency and Remedial Response
OFA overfire air
ORD Office of Research and Development
ORI 100 Orimulsion 100
ORI 400 Orimulsion 400
OSWER Office of Solid Waste and Emergency Response
OTAP Orimulsion Technology Assessment Plan
PAH polycyclic aromatic hydrocarbon
PBS Package Boiler Simulator
PC pulverized coal
PDVSA Petroleos de Venezuela, S.A.
PEA performance evaluation audit
PM particulate matter
PM2.5 particulate matter smaller than 2.5 (jm in aerodynamic diameter
PM10 particulate matter smaller than 10 (jm in aerodynamic diameter
ppm parts per million
QA quality assurance
QAPP quality assurance project plan
QC quality control
ROFA 6 residual oil fly ash (No. 6 fuel oil)
RSD relative standard deviation
SASS source assessment sampling system
SCR selective catalytic reduction
SEM scanning electron microscope
SMPS scanning mobility particle sizer
SNCR selective noncatalytic reduction
SO2 sulfur dioxide
SO3 sulfur trioxide
SVOC semivolatile organic compound
TCLP toxicity characteristic leaching potential
THC total hydrocarbon
TSA technical systems audit
VOC volatile organic compound
VOST volatile organic sampling train
WLFO wet limestone forced oxidation
XRF X-ray fluorescence
VI
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Contents
Volume 1
Page
Abstract ii
Preface iii
Acknowledgments iv
Nomenclature and Acronyms v
List of Figures xiii
List of Tables xvi
Executive Summary ES-1
Conclusions of the Report ES-1
Recommendations of the Report ES-1
Purpose and Approach ES-2
Background ES-3
Air Emissions ES-3
Data from EPA Pilot-Scale Tests ES-3
Toxicity Testing ES-4
Spills ES-5
Risk Assessment ES-5
Potential Use of Orimulsion ES-6
1. Introduction and Background
Background
Overview of Orimulsion and its Use
Air Emissions
Spills
Objective
Approach
Report Structure
-1
-1
-2
-3
-4
-5
-5
-6
2. Properties and Characteristics of Orimulsion 2-1
Background 2-1
Properties of Emulsified Fuels 2-1
Combustion Behavior 2-1
Impact on Boiler Efficiency 2-2
Fuel Handling 2-3
Properties of Orimulsion 2-3
Fuel Composition 2-4
Fuel Handling 2-4
Temperature 2-4
Shear 2-4
Contamination 2-6
Evaluating Environmental Issues Associated With Orimulsion Combustion 2-6
Air Emissions 2-7
Solid Residues 2-9
3. Review of Previous Orimulsion Combustion Research and Demonstration 3-1
Fundamental Studies 3-1
VII
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Contents (Continued)
Page
Pilot-Scale Testing 3-2
Combustion Performance 3-2
Burner Development 3-4
Trial Tests 3-4
Reburning Development 3-6
Air Pollution Control Equipment Evaluation 3-6
Full-Scale Testing and Operation 3-7
Plants Currently Operating 3-7
New Brunswick Power Dalhousie Generating Station 3-8
Dalhousie Demonstration Tests 3-8
Conversion to Permanent Orimulsion Operation 3-11
Use of Orimulsion 400 3-12
Kansai Electric Power Company Osaka No. 4 3-14
Kashima-Kita Electric Power Company 3-14
SK Energy Asnaes Unit 5 3-14
Orimulsion 100 Use at Asnaes 3-14
Orimulsion 400 Use at Asnaes 3-18
ENEL Brindisi Sud Units 1 and 2 and Fiume Santo Plant 3-19
Past Operations 3-20
Florida Power & Light Company Sanford Plant 3-20
PowerGen Ince and Richborough 3-21
Energie-Versorgung Schwaben Marbach III Power Plant 3-23
Planned Operations 3-23
Reburning Development 3-24
Engineering Studies 3-25
Feasibility Studies 3-26
Pollution Control Equipment Analyses 3-27
Other Work 3-27
Diesel Engines 3-27
Gasification 3-27
Briquetting of Coal Fines 3-27
Cement Kilns 3-28
Desulfurization 3-28
Summary of Previous Work 3-28
Operational Issues 3-28
Fuel Handling and Atomization 3-28
Excess O2 3-28
Boiler Efficiency 3-28
Boiler Fouling 3-29
Air Emissions 3-29
CO 3-29
NOX 3-29
SO2 and SO3 3-30
PM 3-31
Hazardous Air Pollutants and Metals 3-31
C02 3-32
Air Pollution Control 3-34
NOX Control 3-34
Low NOX Burners 3-34
Reburning 3-34
Selective Catalytic Reduction 3-34
Vlll
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Contents (Continued)
Page
SO2 and SO3 Control 3-35
PM Control 3-35
ESPs 3-35
Baghouses 3-35
Solid Residue Disposal 3-36
4. EPA Pilot-Scale Experimental Approach and Equipment 4-1
Approach 4-1
Test Equipment 4-1
Package Boiler Simulator 4-1
Fuel Supply System 4-2
Instrumentation 4-2
Continuous Emission Monitors 4-3
Data Acquisition System 4-4
Dilution Sampling System 4-5
Scanning Mobility Particle Sizer 4-6
Scanning Electron Microscope 4-7
Sampling Methods 4-7
EPA Methods 5 and 29 4-7
EPA Methods 0010 and 0030 4-8
Modified CARB Method 501 4-8
5. EPA Pilot-Scale Test Results 5-
Test Conditions 5 -
Fuel Composition 5-
O2 5-
Fuel Feed 5-
Emission Measurement Results 5-3
CO 5-3
NOX 5-5
SO2and SO3 5-5
PM 5-7
Organic HAPs 5-10
Volatile Organic Compounds 5-10
Semivolatile Organic Compounds 5-11
Metals 5-14
Emission Factors 5-18
Scanning Electron Micrographs 5-21
6. Physicochemical Properties and Acute Pulmonary Toxicity of Orimulsion Fly Ash 6-1
Objective 6-1
Oil Fly Ash Production and Collection 6-1
Reference Particle 6-1
Physicochemical Properties of Oil Fly Ash Samples and Arizona Road Dust 6-1
Acute Pulmonary Toxicity of Oil Fly Ash and Arizona Road Dust Samples 6-2
Oil Fly Ash Health Effects Commentary 6-5
7. Spills 7-1
Introduction 7-1
Background 7-1
IX
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Contents (Continued)
Page
Reported Orimulsion Spill Studies 7-4
Saltwater Spills 7-5
Freshwater Spills 7-5
Data Gaps 7-7
8. Environmental Risk Assessment 8-1
Comparative Ecological Risk Assessment Evaluation 8-1
Introduction 8-1
Summary of Comparative Ecological Risk Assessment Reports 8-2
Scope of Harwell Work 8-2
Approach of Harwell Work 8-2
Conclusions of Harwell Work 8-2
Scientific Evaluation of the Comparative Ecological Risk Assessment
of Spills from No. 6 Fuel Oil and Orimulsion 100 8-3
Overview of Harwell Assessment 8-3
Assessment Methodologies 8-3
Portability of this Assessment to Other Sites 8-7
Fate and Transport Methods 8-8
Toxicity Test Methods 8-8
Suggested Improvements for the Tampa Bay Risk Assessment 8-9
Toxicology 8-9
Benthic Community 8-10
Modeling 8-10
Mitigation 8-10
Assessment of Risk from Air Emissions 8-10
Conclusions 8-12
9. Comparison of Orimulsion with Other Fossil Fuels 9-1
Fuel Properties 9-1
Coal 9-1
Fuel Oil 9-2
Natural Gas 9-3
Fuel Use 9-4
Coal 9-5
Fuel Oil 9-5
Natural Gas 9-8
Air Pollutant Emissions and Control 9-8
CO Emissions and Control 9-8
NOXEmissions and Control 9-9
SOX Emissions and Control 9-11
PM Emissions and Control 9-13
Hazardous Air Pollutants Emissions and Control 9-16
Transition Metals Emissions and Control 9-18
CO2 Emissions 9-18
Summary of Air Pollutant Emissions 9-19
10. Quality Assurance 10-1
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Contents (Continued)
Page
Data Reported in Literature 10-1
In-House Combustion Testing 10-1
Data Quality Indicator Goals 10-1
Calculation of DQI Values 10-3
Sampling Goals 10-3
Analytical Data Quality Indicators 10-3
Volatile Organic Compounds 10-3
Semivolatile Organic Compounds 10-4
Metals Analyses 10-9
Audits 10-10
Audit Summary 10-10
Findings and Observations 10-12
EPA Performance Evaluation and Systems Audits 10-12
Flue Gas Flow 10-12
Fuel Input Flow 10-13
CEM Calibrations 10-13
Other Discrepancies 10-13
ARCADIS Technical Systems Audit 10-14
Other Discrepancies 10-14
Data Limitations 10-14
QA Review of Sampling and Measurement Activities at Asnaes 10-15
Flue Gas Concentration Measurements 10-15
PM Sampling Program 10-16
Toxicity Testing 10-17
11. Conclusions and Recommendations 11-1
Responses to Questions of the Peer Panel 11-1
Further Conclusions 11-3
Orimulsion Properties 11-3
Air Pollutant Emissions 11-3
Air Pollution Control Technologies 11-3
Solid Waste Disposal 11-3
Toxicity 11-3
Spills 11-3
Ecological Risk 11-3
Potential for Orimulsion Use 11-4
Data Reported in the Literature 11-4
Recommendations 11-4
12. References 12-1
APPENDIX A. Conversion of English System to SI System Units A-l
Volume 2
APPENDIX B. Continuous Emission Monitoring Data for EPA Pilot Scale Tests B-l
APPENDIX C. Volatile Organic Compound Analysis Laboratory Reports C-l
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APPENDIX D. Semivolatile Organic Compound Analysis Laboratory Reports D-l
APPENDIX E. Metal Analysis Laboratory Reports E-l
APPENDIX F. Orimulsion Spill References Cited by the NRC, U.S. Coast Guard,
and Environment Canada Reports F-l
APPENDIX G. Additional Ecological Risk Assessment Studies G-l
APPENDIX H. Comparative Risk Methodology Synopsis of Harwell et al. (1995) H-l
xn
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List of Figures
Volume 1
Page
1-1. Orinoco region of Venezuela 1-4
2-1. Types of instabilities in bitumen-in-water emulsions 2-6
3 -1. Emissions of CO, NOX, and PM measured during
pilot-scale tests of Orimulsion 100 combustion 3-3
3-2. F-jet and advanced F-jet atomizers used in Orimulsion combustion
tests at PowerGen's Power Technology Centre 3-5
3-3. Photograph of Dalhousie Generating Station, Dalhousie, New Brunswick, Canada .... 3-8
3 -4. Particle size distribution for PM emitted from the
combustion of heavy fuel oil and Orimulsion 100 during
demonstration testing at NB Power Dalhousie Generating Station 3-10
3-5. Carbon in ash in PM emitted from the combustion of
heavy fuel oil and Orimulsion 100 during demonstration testing
at NB Power Dalhousie Generating Station 3-11
3-6. CO as a function of stack O2 levels measured during
combustion testing of heavy fuel oil and Orimulsion 100
at the NB Power Dalhousie Generating Station 3-12
3-7. Relationship between the acid dewpoint and SOj,
emissions measured during Orimulsion 100 demonstration
testing at the NB Power Dalhousie Generating Station 3-13
3-8. Relationship between stack and acid dewpoint
temperature for each day during Orimulsion 100
demonstration testing at NB Power Dalhousie Station 3-13
3-9. CO, NOX, and SO2 emissions at Kansai Electric Company Osaka No. 4 plant 3-15
3-10. Emissions of PM, unburned carbon, and SO3 at
Kansai Electric Company Osaka No. 4 plant 3-16
3-11. Particle size distribution for PM from the combustion of
Orimulsion 100 measured at SK Energy Asnaes Unit 5 3-17
3-12. NOX emission rates as a function of load measured during testing
of Orimulsion 100 at the Florida Power & Light Sanford Plant 3-21
3-13. Average PM emission rates as a function of test condition measured
during testing of Orimulsion 100 at the Florida Power & Light Sanford Plant 3-22
3-14. NOX emissions measured during the reburning demonstration at Hennepin Station . . 3-25
3-15. NOX emissions measured during the reburning demonstration
at Hennepin Station using natural gas and Orimulsion 100
as reburn fuel, as a function of % reburn fuel input 3-26
4-1. Schematic of Package Boiler Simulator 4-3
4-2. Schematic of fuel feed system for heavy fuel oil 4-4
Xlll
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List of Figures (Continued)
Page
4-3. Schematic of fuel feed system for Orimulsion 100 and Orimulsion 400 4-5
4-4. Schematic of continuous emission monitoring system 4-6
4-5. Schematic of high volume dilution sampling system 4-7
5-1. Average CO emissions from the three fuels tested 5-4
5-2. CO vs. O2 for selected runs with Orimulsion 100, Orimulsion 400, and No. 6 fuel oil . 5-4
5-3. Average NO emissions from the three fuels tested 5-5
5-4. NO vs. O2 for selected runs with Orimulsion 100, Orimulsion 400, and No. 6 fuel oil . 5-6
5-5. Average SO2 emissions as measured by CEM from the three fuels tested 5-6
5-6. Average PM emissions from the three fuels tested 5-8
5-7. Cascade impactor results for the three fuels tested 5-9
5-8. Scanning mobility particle sizing results for the three fuels tested 5-10
5-9. Average detected concentration of volatile organic compounds 5-13
5-10. Average detected emission factors of volatile organic compounds 5-14
5-11. Average detected concentrations of semivolatile organic compounds 5-16
5-12. Average detected emission factors of semivolatile organic compounds 5-16
5-13. Concentrations of metals measured in the flue gases of the three fuels 5-17
5-14. Scanning electron micrograph of untreated blank filter at 700x magnification 5-22
5-15. Scanning electron micrograph of untreated filter loaded with PM
from No. 6 fuel oil at 700x magnification 5-23
5-16. Scanning electron micrograph of untreated filter loaded with PM
from Orimulsion 100 at 700x magnification 5-23
5-17. Scanning electron micrograph of untreated filter loaded with PM
from Orimulsion 400 at 700x magnification 5-24
6-1. Particle-induced acute lung injury 6-4
7-1. Movement, spill volumes, and spill rates of heavy oils
in U.S. domestic waters between 1991 and 1996 7-2
7-2. Spill of nonfloating oil in low-current fresh water 7-3
7-3. Spill of nonfloating oil in high-current fresh water 7-4
7-4. Spill of nonfloating oil in high-current salt water 7-5
9-1. Estimated recoverable reserves of coal in the U.S. by sulfur content 9-2
9-2. U.S. electricity generation in 1997 by fossil fuel 9-4
9-3. U.S. utility and industrial coal consumption in 1997 by state 9-6
9-4. U.S. fuel oil consumption by the commercial, industrial,
oil company, and utility sectors in 1997 by state 9-7
xiv
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List of Figures (Continued)
Page
9-5. U.S. natural gas consumption by the commercial,
industrial, and utility sectors in 1997 by state 9-10
9-6. Comparison of particle size distributions from the
combustion of pulverized coal before and after an ESP 9-15
9-7. Particle size distributions for a No. 6 fuel oil and the same fuel oil
in a 90% oil/10% water emulsion 9-17
Volume 2
B-l. CEM data for O2, CO, NO, and SO2 taken May 18, 1999 during
EPA's pilot scale testing of Orimulsion 400 B-2
B-2. CEM data for O2, CO, NO, and SO2 taken May 19, 1999 during
EPA's pilot scale testing of Orimulsion 400 B-3
B-3. CEM data for O2, CO, NO, and SO2 taken May 20, 1999 during
EPA's pilot scale testing of Orimulsion 400 B-4
B-4. CEM data for O2, CO, NO, and SO2 taken May 21, 1999 during
EPA's pilot scale testing of Orimulsion 400 B-5
B-5. CEM data for O2, CO, NO, and SO2 taken May 24, 1999 during
EPA's pilot scale testing of Orimulsion 100 B-6
B-6. CEM data for O2, CO, NO, and SO2 taken May 25, 1999 during
EPA's pilot scale testing of Orimulsion 100 B-7
B-7. CEM data for O2, CO, NO, and SO2 taken May 26, 1999 during
EPA's pilot scale testing of Orimulsion 100 B-8
B-8. CEM data for O2, CO, NO, and SO2 taken May 27, 1999 during
EPA's pilot scale testing of Orimulsion 100 B-9
B-9. CEM data for O2, CO, NO, and SO2 taken June 3, 1999 during
EPA's pilot scale testing of No. 6 fuel oil B-10
B-10. CEM data for O2, CO, NO, and SO2 taken June 4, 1999 during
EPA's pilot scale testing of No. 6 fuel oil B-l 1
B-l 1. CEM data for O2, CO, NO, and SO2 taken June 7, 1999 during
EPA's pilot scale testing of No. 6 fuel oil B-12
B-12. CEM data for O2, CO, NO, and SO2 taken June 8, 1999 during
EPA's pilot scale testing of No. 6 fuel oil B-l 3
xv
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List of Tables
Volume 1
Page
ES-1. Summary of air pollutant concentrations reported in the
literature for Orimulsion and heavy fuel oil ES-4
2-1. Typical properties of Cerro Negro bitumen 2-3
2-2. Typical values and ranges of Orimulsion 100 properties and constituents 2-5
2-3. Radioactive elements present in Orimulsion 2-6
2-4. Metals and radioactive elements present in Orimulsion fly ash 2-9
2-5. Toxicity characteristic leaching procedure (TCLP)
results for Orimulsion 100 and coal fly ashes 2-10
3-1. Flue gas composition for pilot-scale tests using a burner from
Dunamenti Power Station 3-3
3-2. Plants that have operated or are were operating commercially as of
December 2000 using Orimulsion 3-7
3-3. Emissions measured during Dalhousie Station Unit 1 Demonstration 3-9
3-4. Stack trace metal emissions in mg/Nm3 measured at Asnaes Unit 5 3-17
3-5. Trace metal concentrations in Orimulsion 100 fly ash
in mg/kg measured at Asnaes Unit 5 3-18
3-6. Trace metal concentrations in dry scrubber sludge samples
taken during operation with coal and Orimulsion 100 from Asnaes Unit 5 3-19
3-7. Emissions of trace metal compounds during tests of Orimulsion 400
at ENEL Fiume Santo Plant 3-20
3-8. Comparison of long-term contributions to ambient concentration or deposition
of pollutants from the combustion of Orimulsion 100 at Marbach III Power Plant . . . 3-24
3-9. CO emissions measured during pilot- and full-scale tests
for heavy fuel oil and Orimulsion 100 3-29
3-10. NOX emissions measured during pilot- and full-scale tests for
heavy fuel oil and Orimulsion 3-30
3-11. Reported SO3 emissions measured during pilot- and full-scale tests
for heavy fuel oil and Orimulsion 3-31
3-12. Reported PM emissions measured during pilot- and full-scale tests
for heavy fuel oil and Orimulsion 3-32
3-13. Reported PM size distributions measured during pilot- and
full-scale tests for heavy fuel oil and Orimulsion 3-33
3-14. Emissions of selected hazardous air pollutants from
coal, heavy fuel oil, and Orimulsion 3-33
4-1. Test matrix for EPA pilot-scale tests of Orimulsion air pollutant emissions 4-2
5-1. Elemental analyses (as received) of the three fuels tested 5-2
5-2. Average O2 stack concentrations for each test run, and average of four test runs 5-2
5-3. Average fuel flows for each test run, and average of four test runs 5-3
xvi
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List of Tables (Continued)
Page
5-4. SO2 concentrations for the three fuels tested as measured by CEM and MACS
methods, and as calculated based on complete conversion of fuel sulfur to SO2 5-7
5-5. Volatile organic compounds for which samples were analyzed 5-11
5-6. Semivolatile organic compounds for which samples were analyzed 5-12
5-7. Semivolatile organic compounds detected in the flue gases of the three fuels 5-15
5-8. Measured and calculated emission factors and percent recoveries for 12 metals 5-19
5-9. Results of XRF analyses of untreated filters and samples 5-20
5-10. XRF analyses of untreated and treated filters loaded with PM from the three fuels .... 5-21
5-11. Emission factors for CO, NO, SO2, and PM from the three fuels tested 5-21
6-1 Physicochemical characterization of collected PM2 5 oil fly ash
samples and Arizona road dust particles 6-2
6-2 Biomarkers of pulmonary acute toxicity or injury 6-3
6-3 Relative toxicity of oil fly ash and dust exposures at the lowest
observed effect level (LOEL) for each endpoint 6-3
8-1. Summary of risk estimates from inhalation exposure to
priority HAPs for 137 oil fired utility boilers in the U.S 8-12
9-1. Ranges of trace element concentrations in coals 9-2
9-2. Range of selected average trace element concentrations for U.S. coals
from different regions of the country, and maximum and minimum
concentrations from individual samples 9-3
9-3. Range of averages and reported typical values of trace element
concentrations in residual fuel oils from different sources 9-3
9-4. CO emission factors for coal, fuel oil, and natural gas 9-9
9-5. SO2 emission factors for three coal types and for No. 6 fuel oil 9-12
9-6. Filterable PM emission factors for different fuels
and different combustion system designs 9-13
10-1. Data quality indicator goals for critical measurements 10-2
10-2. CEM full-range and mid-range span check results 10-3
10-3. CEM system bias check results 10-4
10-4. VOC target analytes and method detection limits 10-5
10-5. VOC surrogate recovery results 10-6
10-6. VOC matrix spike and matrix spike duplicate results 10-6
10-7. SVOC matrix spike and matrix spike duplicate results 10-7
10-8. SVOC pre-extraction surrogate recovery levels 10-8
10-9. Pre-sampling surrogate recovery/XAD samples 10-10
10-10. Internal laboratory QC summary 10-11
10-11. Spiked metal sample recoveries 10-13
XVII
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Executive Summary
Conclusions of the Report
• Orimulsion is physically and chemically an emulsified heavy fuel oil with elevated sulfur,
vanadium, and nickel content.
• Emissions of air pollutants from Orimulsion are not fundamentally different in character from
those from other fossil fuels. Orimulsion will in general emit more pollutants than natural gas,
about the same as heavy fuel oil, and less than pulverized coal. These comparisons do not hold
for all cases, and are based on emission levels without air pollution control systems.
• Results from both full- and pilot-scale tests indicate that emissions from the combustion of
Orimulsion can be adequately controlled using commercially available air pollution control
technologies that are properly designed and operated.
• Previous experience with Orimulsion indicates that conversion to the fuel may require significant
changes to existing equipment, including air pollution control systems, fuel supply and handing
systems, and boiler internal components.
• In general, Orimulsion generated PM emissions that were capable of producing significant adverse
acute pulmonary toxicity, very similar to the No. 6 fuel oil tested. In all cases, PM from both
Orimulsion formulations and the No. 6 fuel oil showed measures of toxicity greater than or equal
to either Arizona road dust or saline solution.
• The behavior of Orimulsion in a spill is significantly different than that of most other fossil fuels.
• A review by an EPA-chosen expert panel of a utility-funded ecological risk assessment of a
potential spill in the Tampa Bay, Florida marine environment agreed with the assessment's
conclusion that a spill of Orimulsion 100 likely poses a similar or lower risk to Tampa Bay biota
than does an equivalent spill volume of No. 6 fuel oil. This review was limited to the scope of the
original report, and did not examine other factors that may have significant adverse ecological and
health impacts.
• The most likely use of Orimulsion in the U.S. in the short term is as a replacement for heavy fuel
oil, due to similarity in handling and combustion properties, the price differential between the two
fuels, and the readiness of plants using heavy fuel oil to accept tanker shipments of Orimulsion.
These factors would indicate that Orimulsion is most likely to be used along the Atlantic and Gulf
coasts in the U.S.
• The major gaps in understanding Orimulsion behavior are in freshwater spill response and effects.
Further work in this area should primarily be the responsibility of the fuel's suppliers and users,
and should not be considered as part of the Congressional directive to provide improved scientific
information on the environmental impacts of Orimulsion use. EPA and the U.S. Coast Guard have
requested the National Academy of Sciences to conduct a study on Orimulsion to evaluate what
additional information is required to effectively respond to freshwater spills. EPA should continue
to evaluate spill effects, behavior and response as appropriate in support of their legislated
responsibility for spill prevention, preparedness, and response.
Recommendations of the Report
The following recommendations are made with regard to Orimulsion behavior, its potential
environmental impacts, and EPA's role in further studies:
1. Based on the results of Phase I of the Orimulsion Technology Assessment Plan, it is not
necessary for EPA to proceed with Phases II and III.
2. From the perspective of air pollutant formation and control, Orimulsion should be considered
to be a heavy fuel oil, albeit with some properties that require special attention.
3. Studies of Orimulsion behavior in freshwater spills are needed in the event that Orimulsion is
transported along fresh waterways or used in situations where spills can reach fresh water, even
indirectly. This research should evaluate the effects and behavior of Orimulsion under
different conditions (water density, presence of silt or other solids, energy level of waves) and
should evaluate means of containing and responding to spills. Bitor or the end user should be
responsible for the cost of any such work that directly supports efforts to market Orimulsion
ES-1
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in the U.S. EPA should continue to follow any work conducted by others on the behavior and
fate of Orimulsion spills, and should conduct the research necessary to support their legislated
responsibility for spill prevention, preparedness, and response, outside the scope of the
Congressional directive to provide improved scientific information on the environmental
impacts of Orimulsion use.
4. Research recommended in a review by an EPA-chosen panel for improvements to a utility-
funded ecological risk assessment of a potential spill in the Tampa Bay, Florida marine
environment is considered to be the responsibility of Bitor.
Purpose and Approach
The purpose of this report is to address the request by Congress that the U.S. Environmental
Protection Agency (EPA) "provide better scientific data on the qualities and characteristics of this
product [Orimulsion*] and the potential environmental impact of its introduction" into commerce.
To address this request, a team led by EPA's National Risk Management Research Laboratory
(NRMRL) conducted research to examine the potential environmental impacts associated with the use
of Orimulsion as a fuel and prepared this report. The EPA research team included Office of
Research and Development (ORD) staff from NRMRL, the National Health and Environmental
Effects Research Laboratory (NHEERL), the National Center for Environmental Assessment (NCEA),
and Office of Solid Waste and Emergency Response (OSWER) staff from the Office of Emergency
and Remedial Response (OERR).
It is not the objective of this report to address possible regulatory requirements or to estimate the
costs associated with meeting such requirements. In each case, there are many site-specific factors
that are determined by local regulatory requirements and that can significantly impact the cost of
converting to Orimulsion. The data and the conclusions presented in this report should not be
considered as endorsing or discouraging the use of Orimulsion. The conclusions of this report
cannot be considered as identifying specific approaches for meeting regulatory requirements.
In response to reviews of Orimulsion research needs by an interagency panel and a panel of external
technical experts, EPA prepared an Orimulsion Technology Assessment Plan (OTAP) to guide its
research efforts. The reviewers identified the generation and control of air pollutant emissions and
the toxicity of those emissions as the key areas of needed research. Orimulsion spill response,
containment, and recovery, and the ecological effects of such spills (particularly in fresh water) were
considered to be less critical, and could be addressed as needed by the appropriate party or parties.
The OTAP outlined a phased approach, with the need for subsequent phases to be determined by any
significant questions identified during preceding phases. This report describes the efforts, results, and
conclusions of Phase I of the OTAP.
The key questions addressed by this report are:
1. Are the emissions from the combustion of Orimulsion significantly different than those from
other fossil fuels, and if so, how?
2. Can the emissions from the combustion of Orimulsion be adequately controlled using existing
air pollution control technologies? If not, are there modifications to existing technologies that
can be made to adequately control emissions, or are new control technologies required?
3. Is the behavior of Orimulsion during a spill significantly different than the behavior of other
fossil fuels, and if so, how?
4. What gaps in understanding the behavior of Orimulsion exist, based on the behavior of other
fossil fuels and the known properties of Orimulsion? Are these gaps serious with respect to
understanding the potential environmental impacts, and if so, what research should be
conducted to address these gaps?
*Orimulsion is a registered trademark of Bitumenes Orinoco, S.A.
ES-2
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Background
Orimulsion is a liquid fossil fuel consisting of an emulsion of approximately 70% bitumen (a
naturally occurring heavy petroleum material) from the Orinoco region of Venezuela, approximately
30% water, and a small amount of surfactant to ensure stability of the emulsion. The fuel consists of
small (8-24 (am diameter) droplets of bitumen emulsified in water and the surfactant. Orimulsion is
produced by Bitumenes Orinoco, S.A. (Bitor), a subsidiary of the Venezuelan national oil company
Petroleos de Venezuela, S.A. (PDVSA), and derives its name from the combination of "Orinoco"
and "emulsion."
In recent years, Orimulsion has been proposed as a fuel to replace either coal or heavy fuel oil in
utility power plants throughout the world. Orimulsion is currently being used as the primary fuel at
nine power plants in Canada, Denmark, Italy, Japan, and Lithuania, representing 3,866 MW of electric
power generating capacity and approximately 7.5 million tons of fuel consumption per year. To
date, no plant in the U.S. has used the fuel for other than short-term testing.
Air Emissions
Available technical literature (24 references describing air pollutant emissions at 9 full-scale sites and
3 pilot-scale facilities) was reviewed to determine what problems and issues were believed to be most
important with respect to air pollutant emissions and control, and to evaluate the levels of emissions
experienced by full-scale systems using Orimulsion. Table ES-1 presents a summary of data
reported in the literature for Orimulsion and heavy fuel oil. SO2 and PM data are for pollutant
concentrations upstream of any control device.
The reports indicated that CO emissions could be easily controlled by increasing combustion air
levels. In general, the conventional techniques used to reduce NOX emissions from oil combustion
(staged combustion, reburning, selective catalytic reduction) were reported to be applicable to
Orimulsion. CO and NOX were dependent upon boiler O2 and the combustion system design, similar
to other fossil fuels. SO2 concentrations from Orimulsion [upstream of any flue gas desulfurization
(FGD)] were consistent with SO2 concentrations from other fuels with similar sulfur contents. The
literature reported that conventional FGD systems could remove up to 95% of SO2 generated by the
combustion of Orimulsion. This would result in controlled emissions of approximately 125 ppm.
Full-scale results demonstrated that electrostatic precipitators (ESPs) can be used to control PM
emissions to a level similar to those of other fossil fuels.
Emissions of hazardous air pollutants were similar for both Orimulsion and fuel oil. Due to the
elevated levels of metals in Orimulsion, metal emissions were higher than organics, with nickel and
vanadium being found in the highest concentrations. Although vanadium is not listed as a hazardous
air pollutant under Title III of the Clean Air Act Amendments of 1990, it is of concern because of its
potential for causing acute pulmonary damage when inhaled. Nickel concentrations in Orimulsion
flue gas were higher than those from heavy fuel oil, but both iron and zinc concentrations were
higher in heavy fuel oil flue gases than in those from Orimulsion. Processes have been designed to
allow recovery of Ni and V in Orimulsion. At least two plants are currently sending Orimulsion ash
to facilities for recovery of one or both metals, thereby reducing solid waste streams.
Data From EPA Pilot-Scale Tests
Two formulations of Orimulsion (one commercially available [Orimulsion 400] and one
discontinued [Orimulsion 100]) and a No. 6 fuel oil were individually tested in a pilot-scale
combustor located at EPA's Environmental Research Center to allow direct comparison of emissions.
Concentrations of CO, NO, SO2, SO3, and PM were measured, as were concentrations of volatile and
semivolatile organic compounds and metals. Measurements of emissions from the different fuels
were compared to determine any differences in the amount or character of emissions. The tests were
conducted following NRMRL Quality Assurance Level II procedures, which included audits of
measurement equipment and review of data by outside organizations.
ES-3
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Table ES-1. Summary of air pollutant concentrations reported in the literature for Orimulsion and heavy fuel oil (SO2
and PM values are upstream of any control device).
Pollutant
CO
NOX
S02<3)
so3<5>
PM®
PM size
Literature
OrimulsionO)
30-100ppm(2)
(4 tests)
80-400 ppm
(10 tests)
2500 ppm
2-15 ppm
(6 tests)
160-350 mg/Nm3
(8 tests)
98-100% < 10 urn
80-97% < 1 urn
Literature
Heavy Fuel Oil
30-100 ppm
(4 tests)
180-420 ppm
(6 tests)
1200 ppm<4)
4-12 ppm
(2 tests)
100-41 5 mg/Nm3
(4 tests)
75-87% < 10 urn
45-51% <1 urn
Notes:
1. Most data reported in the literature are for Orimulsion 100, although there are several data points for Orimulsion
400.
2. Concentrations of all pollutants are as measured, and are not corrected to account for differences in O2
concentration.
3. Concentrations are measured upstream of any control device.
4. No SO2 values for fuel oil were reported in the Orimulsion literature. The 1200 ppm value is calculated based on
2% sulfur in the fuel. SO2 concentrations are strongly dependent upon the amount of sulfur in the fuel.
5. Measured using mini acid condensation sampling (MACS) method.
EPA's pilot-scale results were similar to those reported in the literature in terms of comparison of
Orimulsion to heavy fuel oil, with data showing little difference in CO, NOX, or PM furnace exit
concentrations, and smaller particles for Orimulsion than for heavy fuel oil. The pilot-scale data
differed most from the full-scale data for NOX, but were not unreasonable given the difference in
combustor system design. The pilot-scale tests provided further valuable confirmation of the
similarity between Orimulsion and heavy fuel oil, and also generated samples for use in inhalation
toxicity testing. The pilot-scale data were not intended to be directly comparable to full-scale
performance data, but were intended to identify fundamental differences between the fuels.
Toxicity Testing
NHEERL conducted tests measuring the pulmonary toxicity in laboratory animals of PM generated
by the combustion of Orimulsion 100, Orimulsion 400, and No. 6 fuel oil. Laboratory rats were
exposed by intratracheal instillation of different doses of PM from each of the fuels burned in the
NRMRL combustion tests, as well as Arizona road dust (ARD) and a saline solution as control
measurements. Five biomarkers of pulmonary toxicity or injury (bronchial alveolar fluid [BALF]
neutrophil/mL, BALF protein, albumin, lactate dehydrogenase [LDH], and eosinophil/mL) were
measured at 24 hours post-exposure. Each sample was ranked according to its lowest observed effect
level (LOEL) for each of the five biomarkers. The relative toxicity rankings for each biomarker
were:
BALF protein No. 6 fuel oil > Orimulsion 400 > Orimulsion 100 > ARD = Saline
albumin No. 6 fuel oil > Orimulsion 100 > Orimulsion 400 > ARD = Saline
LDH Orimulsion 400 > Orimulsion 100 = No. 6 fuel oil = ARD = Saline
neutrophil Orimulsion 100 = Orimulsion 400 = No. 6 fuel oil = ARD > Saline
eosinophil Orimulsion 100 = Orimulsion 400 = No. 6 fuel oil > ARD > Saline
ES-4
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The conclusion drawn by the toxicity tests is that, under the combustion conditions employed in these
studies, both Orimulsion formulations generated particulate emissions that were capable of producing
significant adverse acute pulmonary toxicity. In addition, particles derived from the combustion of
Orimulsion 100 and Orimulsion 400 were found to be very similar to No. 6 fuel oil fly ash particles
in their ability to induce acute pulmonary toxicity. Different results are possible for particles from
full-scale units with different operating conditions, for animals exposed via direct inhalation rather
than instillation, or for health-compromised animals. Tests of toxicity related to exposure by routes
other than inhalation, or of ecological toxicity, were not conducted under this study.
Spills
Orimulsion is considered to be a "non-floating" oil. Once spilled, the bitumen fraction of
Orimulsion is likely to either sink or remain neutrally buoyant, rather than forming a coherent
surface slick, which can have significant implications for contamination of drinking water supplies,
since many inlets to drinking water treatment systems are located below the surface of water bodies.
Special equipment is required to effectively contain and recover Orimulsion spills in saltwater
environments, and such equipment is currently used at shipping terminals where Orimulsion is off-
loaded.
Data gaps remain in the understanding of the behavior and fate of Orimulsion spilled in fresh water.
This is important because most spills occur at stationary facilities rather than during shipment. As
noted in the Orimulsion Technology Assessment Plan, if Bitor does begin to develop U.S. customers
at sites accessible only by fresh water, at a site near bodies of fresh water, or at a site where fresh water
can be contaminated by a spill, even indirectly, Bitor should be responsible for the research to address
the data gaps as they have done for marine environments. Such research does not fall under the
Congressional directive for this report, and should not be considered to be EPA's responsibility
under that directive. However, since EPA is responsible for responding to spills in certain situations,
the Agency should continue to investigate Orimulsion spill behavior and response as appropriate.
EPA (in collaboration with the U.S. Coast Guard) has requested the National Academy of Sciences to
conduct a study on Orimulsion to evaluate what additional information is required to effectively
respond to freshwater spills. EPA is currently conducting smaller studies on spill behavior modeling,
and will address the data gaps identified by the NAS as appropriate. EPA should remain aware of
any research conducted by others regarding freshwater spill research.
Risk Assessment
The potential ecological risk associated with the use of Orimulsion was evaluated by a panel of
independent reviewers chosen by EPA, who examined the work carried out by a U.S. utility to
estimate the ecological risk associated with a potential spill in the Tampa Bay, Florida marine
environment. The utility-funded study compared a hypothetical spill of Orimulsion 100** to a
hypothetical spill of an equal volume of heavy fuel oil. The comparative assessment examined
transport and fate of both fuels, including potential effects on shorelines and aquatic biota under a
range of different spill locations, seasonal variations, and wind and current conditions.
The independent reviewers agreed with the major conclusion of the Bitor study that a spill of
Orimulsion 100 likely poses a similar or lower risk to Tampa Bay biota than does an equivalent spill
volume of No. 6 fuel oil. However, the reviewers noted that parts of the assessment, such as risk
characterization, population modeling, and impacts to benthic (sea-, river-, or lake-bottom)
communities, were identified as assessment topics that could be improved. The reviewers felt that
these improvements would enhance the Tampa Bay report, but did not feel that the improvements
would impact the report's conclusions. The conclusions of the reviewers may differ for different
"Orimulsion 100 and Orimulsion 400 differ in the formulation of their respective surfactants
and in the use of a magnesium-based compound in Orimulsion 100 that is not found in Orimulsion
400. The two formulations are similar enough with respect to spill behavior that the spill assessment
conducted for Orimulsion 100 would be expected be only slightly different if Orimulsion 400 were
evaluated. No similar study has yet been conducted for Orimulsion 400.
ES-5
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conditions associated with other combinations of variables such as location, weather conditions, level
of fuel use, and diversity and number of biota in the locality.
The review did not examine other factors beyond the scope of the original assessment that may have
significant adverse ecological and health impacts, such as physical effects of an Orimulsion spill on
biota. In addition, the review examined only the utility-funded assessment, and did not examine
other literature on Orimulsion or heavy oil spill behavior, fate, and effects.
A study of cancer risk associated with air emissions from the combustion of heavy fuel oil in electric
utility steam generating units was used as the basis for comparing cancer risks due to the use of
Orimulsion with those from the use of heavy fuel oil. The original study evaluated the risk to human
health associated with exposure to HAP emissions from electric utility steam generating units, and
estimated that 0.4 additional incidences of cancer were estimated to be caused by exposure to Ni
emissions from all 137 oil-fired plants in the U.S. This value was estimated to be a conservative
estimate of the potential cancer risk associated with the use of Orimulsion, based on the Ni emissions
from both fuels.
Potential Use of Orimulsion
Orimulsion can be used in applications similar to coal or heavy fuel oil. Orimulsion is readily used in
plants designed to use heavy fuel oil, due to the fuels' similar handling and use characteristics. The
difference in fuel prices between fuel oil and coal may also favor fuel oil as being more likely to be
replaced with Orimulsion. The states with the highest fuel oil use are (in order of consumption)
Florida, New York, Massachusetts, Connecticut, and Hawaii, all of which are oil consumers and not oil
producers. They are also located on the coast, and may be more suitable markets for Orimulsion
than states with high coal consumption.
Previous experience with Orimulsion indicates that conversion to the fuel may require significant
changes to existing equipment, including air pollution control systems, fuel supply and handing
systems, and boiler internal components.
ES-6
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Chapter 1
Introduction and Background
Orimulsion* is a liquid fossil fuel consisting of an emulsion of 70% bitumen (a naturally occurring
heavy petroleum material) from the Orinoco region of Venezuela, 30% water, and a small amount of
surfactant (see Chapter 2). In recent years, Orimulsion has been proposed as a fuel to replace either
coal or heavy fuel oil in utility power plants throughout the world. However, there has not been a
comprehensive evaluation of the fuel by an independent organization that would provide an overview
of the fuel, its current and proposed uses, or its potential environmental impact. The objective of this
report is to provide such an overview based on the information available in the open literature and
from the results of limited testing of the fuel by the U.S. Environmental Protection Agency's
(EPA's) National Risk Management Research Laboratory (NRMRL).
Background
Orimulsion was first used commercially in 1991 at two plants in the U.K. and one in Japan. The first
commercial use of Orimulsion in North America was in 1994 at New Brunswick Power's Dalhousie
Generating Station, located in Dalhousie, New Brunswick, Canada. Since that time, eight other sites
have converted to Orimulsion, with several other plants either converting or considering its use.
Because of the rapid growth in Orimulsion use, concern over the environmental impacts associated
with using Orimulsion has increased. These concerns include environmental exposures of toxic or
harmful materials to the environment by accidental spills and by stack emissions and disposal of ash
generated by the combustion of Orimulsion.
In the mid-1990s, Orimulsion was proposed as the fuel for one power plant in the U.S., but to date no
plant in the U.S. has used the fuel other than in short-term testing. Because of the interest in and
concern about using Orimulsion as a fuel for utility and industrial boilers, the U.S. Congress
requested that EPA initiate a study to evaluate the environmental impacts associated with using
Orimulsion. In Fiscal Year 1998 the Congress added the following language to the Conference
Report on Bill H.R. 2158 appropriating funds for EPA operations:
The conferees are aware that orimulsion, a mixture of bitumen and water, is being considered
for generating electricity in the United States. While orimulsion has been used in several
countries including Japan, China, Italy and Canada's maritime provinces, it has not been
utilized within the United States. Because little is known about the risks associated with the
introduction of this new product, the conferees direct EPA to initiate a research activity to
provide better scientific data on the qualities and characteristics of this product and the
potential environmental impact of its introduction. (U.S. House of Representatives 1997)
In response to this request, NRMRL's Air Pollution Prevention and Control Division (APPCD) led an
effort by EPA's Office of Research and Development to prepare a technology assessment plan to
evaluate the environmental impacts associated with the use of Orimulsion in utility and industrial
boilers (EPA 1999a). This plan was reviewed by an external panel of experts, and revised to address
their concerns. The plan's focus is on the air emissions, as it was the panel's opinion that issues
associated with spills had been addressed by a number of studies and that a review of these studies
could provide the information necessary to adequately determine the environmental impact
associated with a spill of Orimulsion in salt water (Freedman et al. 1998).
The Orimulsion Technology Assessment Plan was developed as a three-phase approach to allow
results generated during the initial testing to be used as guidance in the later phases. The emphasis of
the first phase was on the pilot-scale testing at NRMRL and the toxicology tests using the fly ash
generated during those tests. The second phase would expand the emissions testing to include field
sampling of full-scale units, preferably sampling the flue gases from both Orimulsion and the
*Orimulsion is a registered trademark of Bitumenes Orinoco, S.A.
1-1
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preconversion fuel (expected to be heavy fuel oil). This phase would also include toxicological tests,
with the samples being taken from the field tests instead of the pilot-scale tests. Phase III would
expand the field tests and include a more detailed environmental assessment which would include the
toxicology data from Phases I and II. Phase I was funded by EPA; however, the need for subsequent
phases was deemed to be contingent upon the findings of Phase I.
Phase I of the NRMRL Technology Assessment Plan included four major components. The first of
these was a review of the available literature, including a number of test reports made available to
NRMRL by Bitor America Corporation (Bitor). The second component was a set of pilot-scale tests
to evaluate the basic combustion behavior and emissions characteristics of Orimulsion and a heavy
fuel oil* in a single pilot-scale combustor. This approach was intended to allow a comparison of the
emissions and combustion performance of both fuels. The third component was a series of
toxicological tests to be conducted by EPA's National Health and Environmental Effects Research
Laboratory (NHEERL), co-located with APPCD in Research Triangle Park, NC. These tests would
evaluate the acute toxicity of the collected fly ash generated by the combustion of Orimulsion and
compare it to that of heavy fuel oil. The fourth component was an assessment of the environmental
impacts of Orimulsion use, including exposure to fly ash generated by Orimulsion combustion and to
Orimulsion spills. This component was conducted by EPA's National Center for Environmental
Assessment (NCEA), located in Research Triangle Park, NC (EPA 1999a).
Although spills of Orimulsion into bodies of water pose a potentially significant environmental threat,
this topic was determined not to be an area in which research was immediately required. There has
been considerable work conducted under the guidance of the International Orimulsion Working
Group (IOWG). The IOWG is composed of interested parties from Bitor, the fuel's U.S. marketer, the
National Oceanic and Atmospheric Administration, the U.S. Coast Guard, Environment Canada,
Fisheries and Oceans Canada, and the Canadian Coast Guard. This work has focused on spill
behavior, effects, and response primarily in saltwater (marine) and to a lesser extent in freshwater
environments, and has been funded largely by Bitor. A study of non-floating oil spills conducted by
the National Research Council (NRC) was recently completed, and also touched on spills of
Orimulsion in both freshwater and marine environments (National Research Council 1999).
Discussions within EPA, and further confirmed by interagency reviews of the Orimulsion Technology
Assessment Plan, concluded that, although there remains a significant gap in the understanding of the
behavior, fate, and effects of Orimulsion in fresh water, the bulk of the research in this area should be
the responsibility of Bitor rather than of EPA. Further, there are currently no near-term plans for
using Orimulsion at sites which would receive the fuel via freshwater routes. Therefore the decision
was made to focus this study on air pollutant emissions and rely on existing spill data to provide an
understanding of the risks associated with spills of Orimulsion in marine environments. However, this
decision did not preclude the potential for further EPA research on Orimulsion to address needs
identified by EPA's regulatory offices.
This document reports on the results of Phase I of the Orimulsion Technology Assessment Plan.
Overview of Orimulsion and its Use
Orimulsion is a bitumen-water emulsion produced from bitumen extracted from the Cerro Negro
field of the Orinoco Belt of eastern Venezuela (see Figure 1-1). Total Orinoco bitumen reserves have
The terms residual fuel oil, heavy fuel oil, and No. 6 fuel oil are used interchangeably
throughout this report. Residual fuel oils typically refer to the petroleum products that remain after
removal of distillate products from the crude oil. "Bunker C" is also often used as a term to
describe residual fuel oil. No. 6 fuel oil is a grade of residual oil that has a Saybolt Universal
viscosity range between 900 and 9000 s and requires preheating for handling and burning (Reed,
1998a). Heavy fuel oil can refer to either No. 6 fuel oil or a "heavy" No. 5 fuel oil, and usually
(but not always) requires preheating for handling and burning.
1-2
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been estimated at approximately 1.2 trillion (1012) barrels* (oil equivalent), with 267 billion (109)
barrels (oil equivalent) in economically recoverable reserves using current technology (U.S.
Department of Energy 1998a). These figures compare to 1.02 trillion barrels of world recoverable
crude oil reserves, 22.5 billion barrels of U.S. recoverable crude oil reserves, and an energy
equivalent of 995 billion barrels of crude oil in U.S. recoverable coal reserves (U.S. Department of
Energy 1998b). Orimulsion is produced by a subsidiary of the Venezuelan national oil company
Petroleos de Venezuela, S.A. (PDVSA), Bitumenes Orinoco, S.A. (PDVSA-Bitor), and derives its
name from the combination of "Orinoco" and "emulsion." PDVSA is exploring other areas within
the Orinoco Belt as possible bitumen extraction sites, and PDVSA-Bitor has long-term plans for three
additional Orimulsion production facilities. In 1998, long-term plans estimated exports of
Orimulsion to be as high as 20 million tons per year by 2000 (U.S. Department of Energy 1998a).
However, those plans have been scaled back, and current plans call for approximately 6 million tons
to be exported in 2000 (Garcia 1999).
The primary market for Orimulsion to date has been as a fuel for electric utility boilers, with 3,866
MWe of generating capacity world-wide using Orimulsion as a primary fuel. Plants are currently
operating with Orimulsion in Canada, Denmark, Italy, Japan, and Lithuania, and two plants have
operated in the United Kingdom (Quig and Woodworth 1997). Orimulsion has replaced both heavy
fuel oil and pulverized coal as primary fuels at these plants. The wider price difference between
Orimulsion and heavy fuel oil compared to coal makes replacement of fuel oil more economically
attractive. Further, most plants designed for using heavy fuel oil can be converted to Orimulsion
without major modifications, and many of these plants are located near seaports. The latter
consideration is important because Orimulsion is normally transported to plants using ocean-going
tankers, with additional transport expense making supply of plants without direct seaport access less
cost-effective.
Plans for additional conversions to Orimulsion from other fossil fuels or for new plants have been
announced for Italy and possibly in Guatemala (Power Generation 1998). Firms in Korea and
Taiwan have also undertaken reviews of the fuel for potential future use (U.S. Department of Energy
1998a). In the U.S., feasibility studies have been conducted on the potential costs of converting to
Orimulsion for at least three power plants, but only one utility has sought to convert to the fuel
(Energy and Environmental Research Corporation undated, Lentjes Bischoff 1997). Florida Power &
Light Company's application for a permit to convert its Manatee Power Plant from heavy fuel oil to
Orimulsion was denied in 1998, and as of early 1999 there has not been any further attempt to use
Orimulsion in the U.S.
Air Emissions
Air emissions from fossil fuel combustion may be of concern for several reasons. Some compounds
emitted into the atmosphere from these sources are considered carcinogenic, while others may lead to
different health problems or to unacceptable environmental damage. Acute exposure to elevated
levels of a compound may be of concern, while chronic exposures at lower levels may be the primary
concern associated with other compounds. These considerations have led to different regulatory
approaches to limiting emissions of air pollutants.
Criteria pollutants are those for which National Ambient Air Quality Standards (NAAQS) have been
established, and include carbon monoxide (CO), nitrogen dioxide (NO2), ozone (O3), sulfur dioxide
(SO2), particulate matter (PM) less than 10 (jm in aerodynamic diameter (PM10), PM less than 2.5 (am
in aerodynamic diameter (PM2.5), and lead (Pb). Nickel (Ni) and magnesium (Mg) are listed along
with 187 other compounds and compound classes as hazardous air pollutants (HAPs) under the 1990
CAAAs (Clean Air Act 1990). Vanadium (V) is not listed as a HAP, but [along with other transition
metals such as copper (Cu), iron (Fe), Ni, and zinc (Zn)] has been hypothesized as playing a key role
in causing acute adverse health effects associated with exposure to PM2 5 (Dreher et al. 1996a, 1996b,
1997).
*See Appendix A for conversions to SI units.
1-3
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Caribbean Sea
D Production Block
— Pipeline
• Flow Station
jose i Export Terminal
Figure 1-1. Orinoco region of Venezuela (adapted from Bitor undated).
Compared to some other fossil fuels, Orimulsion has elevated levels of sulfur, nitrogen, Ni, and V (Mg
levels for Orimulsion 100 were also elevated due to the Mg additives that are not in Orimulsion 400).
The presence of sulfur in fuels leads to emissions of SO2, and elevated nitrogen levels contribute to
higher emissions of oxides of nitrogen (NOX). NOX is composed of NO2, a criteria pollutant, and
nitric oxide (NO), which plays a key role in the formation of Oj, in the presence of ambient
concentrations of volatile organic compounds (VOCs) and sunlight. Orimulsion also behaves like
other emulsified fuels in producing PM that is largely composed of PM2 5. For these reasons, the air
emissions generated by the combustion of Orimulsion may be of concern if not properly controlled.
However, as noted above, it is important to compare these emissions with those from other fuels, as
Orimulsion will be used in lieu of other fuels and not in isolation. Air pollutants are generated and
emitted from the combustion of all fossil fuels, and can be reduced by applying appropriate air
pollution control methods and technologies. Therefore it is important to understand the effects on
emissions associated with the change in fuel distinct (to the extent possible) from the effects of system
design and operation.
It is also important to evaluate Orimulsion emissions both before and after any treatment by pollution
control equipment to the extent possible. Measurement of uncontrolled pollutant concentrations
from Orimulsion provides a consistent basis for comparison that is not influenced by the different
design and performance characteristics of pollution control equipment. Measurement of controlled
emissions allows one to evaluate how well current air pollution control technologies are able to reduce
emissions generated by the combustion of Orimulsion. If it is not possible to measure emissions both
before and after any pollution controls, knowledge of the uncontrolled emissions and the efficiency
and applicability of pollution control equipment can be used to estimate controlled emissions.
Spills
Orimulsion has two characteristics that significantly impact its behavior when spilled in water. First,
Orimulsion falls into a category of fuels termed by the American Petroleum Institute (API) as "low
API oils" (LAPIOs), whose densities are greater than that of fresh water and very close to that of salt
water. This characteristic results in a fuel's tending to settle or sink in fresh water and remain
1-4
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neutrally buoyant in salt water (water containing more than 20 ppt salt). Sinking or settling spill
plumes are difficult to track and recover with conventional spill containment and recovery
technologies (National Research Council 1999). Second, the presence of a surfactant in Orimulsion
and other emulsified fuels prevents the coalescence of hydrocarbon particles, leading to higher
particle dispersion and further complicating containment and response measures. Thus, spills of
Orimulsion require the use of special equipment and techniques during spill containment and
response.
Similar to the air emissions issue, the issue of Orimulsion spills cannot be viewed in isolation, since the
transport and use of other liquid fuels (heavy fuel oil in particular) also pose a risk of environmental
damage due to spills and subsequent environmental exposure. Understanding changes (both
increasing or decreasing) in risk associated with the use of Orimulsion compared to practices that are
currently accepted is of greatest importance to objectively evaluating risks associated with use of the
fuel. This is true for potential spills as well as for air emissions or other environmental issues related
to Orimulsion use.
Objective
The Orimulsion Technology Assessment Plan is designed to address the main issue raised by
Congress, that is, to provide better scientific data on the qualities and characteristics of Orimulsion
and the potential environmental impact of its introduction. The key questions addressed by this
report are:
1. Are the emissions from the combustion of Orimulsion significantly different from those from
other fossil fuels, and if so, how?
2. Can the emissions from the combustion of Orimulsion be adequately controlled using existing
air pollution control technologies? If not, are there modifications to existing technologies that
can be made to adequately control emissions, or are new control technologies required?
3. Is the behavior of Orimulsion during a spill significantly different than the behavior of other
fossil fuels, and if so, how?
4. What gaps in understanding the behavior of Orimulsion exist, based on the behavior of other
fossil fuels and the known properties of Orimulsion? Are these gaps serious with respect to
understanding the potential environmental impacts, and if so, what research should be
conducted to address these gaps?
The objective of this document is to answer these questions to the fullest extent possible and to
provide appropriate conclusions regarding the use of Orimulsion and how it may impact the
environment.
It is not the objective of this report to address possible regulatory requirements or to estimate the
costs associated with meeting such requirements. In each case, there are many site-specific factors
that are determined by local regulatory requirements and that can significantly impact the cost of
converting to Orimulsion. The data and the conclusions presented in this report should not be
considered as endorsing or discouraging the use of Orimulsion. The conclusions of this report
cannot be considered as identifying specific approaches for meeting regulatory requirements.
Approach
The approach taken in addressing the above questions was to conduct independent testing of
Orimulsion to the greatest extent possible and to compare the results from those tests to existing data.
Substantial data on the behavior of Orimulsion in combustion applications and in spills have been
presented in the open literature, and these data were used where appropriate.
Most of the data in the open literature have been collected under test programs funded by Bitor or
utility companies interested in using Orimulsion. Although concerns have been expressed regarding
the objectivity of these data, this information can and should be used in developing conclusions as to
the environmental impacts of Orimulsion use if the data are of sufficient quality to make such use
1-5
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appropriate. Determining whether these data are of sufficient quality to be used is a matter of
technical judgement, and a discussion of data quality for results generated by EPA under this
program and of those in the literature will be discussed in detail in the chapter on Quality Assurance.
The use of data from the literature allows a broader range of experience to be evaluated in
determining the behavior or Orimulsion. While it may be desirable to conduct a completely
independent set of tests ranging from bench to full scales over a range of conditions, it is much more
effective to evaluate results from a variety of sources, critically review those results, and incorporate
the data that are determined to be suitable for use. The factors that determine whether data from the
literature should be used include: the quality assurance data reported in the test reports or articles (are
replicates, calibrations, and similar measurements included?); the consistency of the results with other
Orimulsion tests and with tests of other fossil fuels (do the results make sense in relation to other
results?); and the consistency of the results with fundamental physical and chemical behavior (do the
results make sense in relation to what is expected based on an understanding of other fuels with
similar physical and chemical characteristics?). Finally, even those data from the literature that
appear to be inconsistent with other results and with expected behavior should be noted. In such
cases, these "outlier" results may indicate different measurements, different processes, incorrect
results, or in some cases an unexpected result may indicate important, but previously unrecognized,
changes in fundamental behavior. Whatever the reason for the inconsistency, it is important to
identify such results and bring the inconsistency to the notice of the technical community.
Report Structure
In Chapter 2, this report discusses the general properties and characteristics of Orimulsion. Chapter 3
presents a review of previous work, including pilot- and full-scale emissions tests of Orimulsion
combustion and comparison to emissions from heavy fuel oil. Chapter 4 presents the experimental
approach and equipment used in the pilot-scale combustion tests conducted at APPCD. Chapter 5
presents the results of the APPCD pilot-scale tests. Chapter 6 presents the results of the toxicity testing
conducted for this project. Chapter 7 addresses spills, and Chapter 8 reviews an environmental risk
assessment conducted to evaluate the potential environmental impact of a spill of Orimulsion in a
saltwater environment. Chapter 9 compares Orimulsion to other fossil fuels from an environmental
perspective. Chapter 10 presents the quality assurance procedures and measures taken during this
project, and Chapter 11 presents conclusions and recommendations drawn from this study.
References are given in Chapter 12, and Appendices providing unit conversions, raw data, and
detailed technical reports follow the report chapters.
1-6
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Chapter 2
Properties and Characteristics of Orimulsion
Background
Orimulsion fits into the general category of emulsified fuels, which broadly includes emulsified fuel
oils, coal-water slurries, and coal-oil slurries. Orimulsion is typical of an oil-in-water emulsion,
meaning that the water is the continuous phase and the Orinoco bitumen is the dispersed phase. This
chapter will discuss the properties and characteristics of Orimulsion that influence its combustion
behavior and the emissions generated by its use in combustion systems. To better understand the
behavior of Orimulsion in combustion systems, properties of emulsified fuels (particularly emulsified
heavy fuel oils) and their combustion behavior in general will first be discussed, followed by a more
detailed discussion of Orimulsion as a fuel.
Properties of Emulsified Fuels
Hydrocarbon fuels emulsified with water* have been studied for many years as means to improve
operating efficiency and reduce combustion-generated pollutant emissions (Dryer 1976). The
addition of water can increase the performance of internal combustion systems such as piston engines
and gas turbines by taking advantage of the water's expansion to steam during heating. The lower
combustion temperatures associated with water addition can also reduce emissions of nitrogen oxides
(NOX). The presence of water vapor can also enhance the production of hydroxyl radicals, which
increases the reaction rate of carbon monoxide (CO) to carbon dioxide (CO?), promoting more rapid
completion of the combustion process (Dryer 1976).
Combustion Behavior
Early water addition tended to be in the form of water injection into the engine cylinder or turbine
combustor can. Mixing the water and fuel (usually distillate oil) together allowed a single injection,
but also required the use of a surfactant to ensure the mixture did not separate prior to injection.
Most oil-water emulsions used as fuels tend to be water-in-oil emulsions, in which the oil is the
continuous phase and the water forms the dispersed phase. These emulsions exhibit physical
behavior that also contributes to improved performance through the phenomenon of "micro-
explosions." Dryer (1976) discussed the work of Ivanov and Nefedov (1962) which postulated that
when heated, the small droplets of water (surrounded by a fuel oil of higher boiling point) would
rapidly and disruptively vaporize and expand, shattering the original emulsion droplet into many
smaller droplets. Further work by Dryer et al. (1976) has demonstrated this secondary atomization
resulting in very fine fuel droplets that can devolatilize and burn out more quickly and more
completely than the much larger fuel droplets produced by mechanical atomization. The findings of
Ivanov and Nefedov were summarized as follows (Dryer 1976):
" 1 . Emulsified fuels burn faster than anhydrous ones.
"2. Water in emulsified fuels does not impair, but improves the combustion process,
owing to the additional simultaneous breaking of the droplets, and to a better mixing
of the burning substances in air.
" 3 . The reduction of the combustion time of emulsified fuels has a favorable influence
on the burning of sooty residue, thus improving the completeness of combustion
and reducing the deposition of soot (scale) on the working surfaces."
The secondary atomization and the presence of water allow heavy fuels to be combusted at lower
peak temperatures and lower excess air levels than would be possible with non-emulsified or "neat"
fuels, often with increased fuel burnout. Studies of emulsified fuel combustion in practical systems
indicated that water-in-oil emulsions could reduce PM (as measured by smoke number) at constant
*Emulsified fuels are fuels that are composed of a mixture of a solid and liquid phase, where
the solid phase is suspended as particles in the liquid phase.
2-1
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excess air, with little change in either CO or NOX (Hall 1975, 1976). Using an emulsified oil allowed
an operator to reduce excess air to a point where the smoke number was equal to that under baseline
excess air using neat fuel oil, thereby resulting in reductions of NOX without increases in PM. These
results were verified in two separate studies of emulsified heavy fuel oil and two emulsified light fuel
oils in a small commercial boiler (Miller 1996, 1998).
Impact on Boiler Efficiency
The disadvantage to using oil-water emulsions is the additional mass of water that is heated and
carried out of the boiler, representing an energy loss from the perspective of boiler efficiency. In
addition, the change in heat release characteristics due to the added water may also have significant
impacts on where within a boiler the heat transfer occurs. For instance, a slower heat release rate
within the boiler may shift a substantial portion of heat transfer from the radiant waterwalls and
superheater to the convective section. Changes in heat transfer surface areas may be required to
minimize the overall impact on boiler operation. The impact on boiler efficiency depends largely
upon the amount of water that is added to the oil.
One method of determining boiler efficiency is the heat loss method as defined by the American
Society of Mechanical Engineers (ASME) in their Performance Test Code (PTC) 4.1 (American
Society of Mechanical Engineers 1991). This method relies on measurements of the input energy
(the energy flowing into the system with the fuel and air) and energy losses; i.e., energy that is not
absorbed by the steam. Such losses include energy carried out of the system by the flue gases and
unburned fuel, energy radiated from the boiler skin to the surroundings, and energy escaping the
boiler from leaks. The ASME PTC 4.1 defines efficiency through the heat loss method as:
r, =100%- f Heat losses \ x100o/0 (2-1)
(Heat in fuel + Heat credits j
where heat credits involve energy inflow through the boiler feedwater and combustion air. The heat-
in-fuel term is the product of the fuel's higher heating value and the flow rate of the fuel to produce
energy per unit time.
The major heat loss is through the sensible heat in the flue gases; however, other heat losses may also
be significant, depending upon the operating characteristics of the particular boiler. In addition to
flue gas heat loss, energy may also be lost through leaks of boiler water or combustion gases; the
presence of CO, unburned hydrocarbons, and/or unburned carbon in the flue gases; or the presence
of water in the fuel. The total heat loss is simply the sum of those losses, calculated in Btu/hr.
The changes in heat losses for an oil-water emulsified fuel will be most pronounced in the losses
through the sensible heat and the losses through the presence of water in the fuel. The heat loss
through the sensible heat in the flue gases is a product of the flue gas flow rate, specific heat, and
difference in temperature from ambient. Thus, at a given exit temperature, as more mass flows out of
the boiler due to the added water, the more heat is lost through the sensible heat and the lower the
thermal efficiency.
The heat loss due to the moisture in the flue gases is the sum of the loss associated with the moisture
in the fuel and the loss associated with the conversion of hydrogen to water in the combustion
process. For oil-water emulsified fuels, the major change to the thermal efficiency is due to the
increased moisture in the fuel. This loss is calculated from
MF
(2-2)
where LMF is the heat loss due to moisture in the fuel, fMF is the percent moisture content of the fuel,
hwo is the enthalpy of the water vapor in the flue gases at the stack temperature and vapor partial
pressure (generally assumed to be 1 psia) in Btu/lb, href is the enthalpy of saturated liquid water at the
2-2
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reference temperature (68 °F) in Btu/lb, and WF is the flue gas mass flow rate in Ib/hr. hWG and href
are determined from standard ASME steam tables. As was the case for the sensible heat loss, the
change in loss due to moisture in the fuel is directly proportional to the change in the percent
moisture content of the fuel.
A 30% water content in an emulsified heavy fuel oil has been shown to reduce boiler thermal
efficiency by 2-3%, compared to the same neat heavy fuel oil with a moisture content of less than
0.05% (Miller 1998).
Fuel Handling
Fuel handling characteristics can impact emissions of pollutants in combustion systems, as poor
nozzle atomization or unsteady flows can lead to poor burner performance and higher emissions of
carbon monoxide (CO), oxides of nitrogen (NOX), and unburned hydrocarbons. Therefore, it is
important to be aware of the fuel handling characteristics of emulsified fuels that may lead to the
above problems.
Properties of Orimulsion
Orimulsion is an emulsion of bitumen and water, with the bitumen being the dispersed phase and
water being the continuous phase. The bitumen is produced in Venezuela's Orinoco Belt, degassed,
dehydrated, and desalinated and emulsified in water. An emulsifying agent is added to stabilize the
emulsion. The term "Orimulsion" is derived from the combination of "Orinoco" and "emulsion."
The bitumen used in Orimulsion is taken from wells in the Cerro Negro field in the Orinoco belt of
eastern Venezuela. Bitumen is a naturally occurring hydrocarbon with a viscosity greater than
10,000 mPa-s at ambient temperature. Table 2-1 presents typical properties of the Cerro Negro
bitumen.
Much of the information on Orimulsion properties and handling in this section is taken from the
Orimulsion Design and Operations Manual, Version 4.0 prepared by Bitor Europe (Bitor Europe,
1994) and from the Bitor America report, Physical and Chemical Characterization of Orimulsion-100
Fuel, its Constituents and ByProducts of Combustion (Bitor America 1997).
Table 2-1. Typical properties of Cerro Negro bitumen (Bitor America 1997).
Property
Carbon, %<1)
Hydrogen, %
Nitrogen, %
Oxygen, %
Sulfur, %
Ash, %
Sodium, ppm
Vanadium, ppm
Nickel, ppm
Iron, ppm
Value
85.3
9.7
0.54
0.30
4.04
0.12
40
440
110
12
Property
"API
Viscosity, mPa-s at 25 °C
Density, kg/m3 (at 15 °C)
Gross heating value, MJ/kg
Flash point, °C
Pour point, °C
Saturates, %
Aromatics, %
Resins, %
Asphaltenes, %
Value
8.0
8x1 04- 10s
1.019
42.8
120
38
10.7
58.0
19.3
11.9
1. Percentages are weight percentages, unless otherwise noted.
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Fuel Composition
There are currently data on two different formulations of Orimulsion, that differ with respect to the
surfactant used and to the use of a magnesium (Mg) additive to minimize boiler surface corrosion.
The original formulation was generally referred to as Orimulsion. When the new formulation was
introduced in late 1998, the two formulations were distinguished by referring to the original as
Orimulsion 100 and the new as Orimulsion 400. Bitor has replaced all Orimulsion 100 with
Orimulsion 400 and no longer produces the original formulation. The terms 100 and 400 refer to
the Bitor nomenclature for the emulsifying agents used in the different formulations. No Orimulsion
200 or Orimulsion 300 have been produced.
Orimulsion 100 consisted of approximately 70% by weight of Orinoco bitumen, 29.8% water, 0.2%
nonyl phenol ethoxylate as the surfactant and approximately 350 ppm (Mg equivalent) of
magnesium nitrate. Orimulsion 400 consists of approximately 70% Orinoco bitumen, 29.8% water,
and 0.13% tridecylalcohol ethoxylate and 0.03% monoethanolamine as surfactant.
Orimulsion 100 consisted of bitumen droplets with a single mode at approximately 17-18 (jm in
diameter, with a median size of 10-15 \\m in diameter, and with less than 1% of droplets larger than
150 (am in diameter. In some instances, the median droplet size and the percent of droplets larger
than 150 \\m may have increased under certain operating conditions, but this change was not linked
to any changes in boiler performance or operational problems. Orimulsion 400 is produced with a
bimodal bitumen size distribution, with the modes at approximately 8 (am and 24 (am in diameter.
The bimodal distribution allows for closer packing of the bitumen droplets and also results in lower
viscosity of the emulsion. There have been some suggestions that the bimodal distribution also
results in a "staging" effect in which the smaller droplets burn out more quickly than the larger
droplets, resulting in lower NOX emissions and better burnout.
The composition of both Orimulsion formulations are primarily dependent upon the composition of
the Orinoco bitumen from which they are produced. The bitumen is mixed with water to create an
emulsion of approximately 30% water and 70% bitumen, with small amounts of the emulsifying
agent. The Orinoco bitumen is generally high in sulfur (S), vanadium (V), and nickel (Ni), and
therefore Orimulsion also has high contents of these elements. Table 2-2 presents typical values and
ranges of Orimulsion 100 composition, including several trace elements (Bitor Europe 1994). In
addition, Orimulsion also contains several radioactive elements. Table 2-3 presents values of
radioactive elements found in Orimulsion (Bitor America 1997).
Fuel Handling
As with any emulsion, Orimulsion requires care in handling to ensure the bitumen and water phases
remain uniformly dispersed. Extremes of temperature, excessive shear, or contamination may result
in instabilities in the emulsion. The types of instabilities that can occur are illustrated in Figure 2-1.
An emulsion that does not remain uniform can lead to high levels of water passing through a burner
followed by high levels of hydrocarbons, which in turn can result in poor burner performance and
higher pollutant emissions.
Temperature
The effectiveness of the surfactant to maintain a stable emulsion diminishes at temperatures over 175
°F (80 °C). The emulsion begins to deteriorate at temperatures over 210 °F (100 °C) and is
completely destabilized at temperatures over 250 °F (120 °C). Although freezing has not been found
to cause destabilization of the emulsion, Bitor recommends maintaining the temperature of the fuel
above 40 °F (5 °C). Recommended storage temperature for Orimulsion is 85 °F (30 °C). Because of
the fuel's sensitivity to high temperatures, Bitor does not recommend the use of steam heating coils,
as the contact temperature of the heating coils can result in local temperatures well above the
recommended values.
Shear
Although the Orinoco bitumen exhibits Newtonian fluid behavior, Orimulsion does not. Orimulsion
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Table 2-2. Typical values and ranges of Orimulsion 100 properties and
constituents (Bitor Europe, 1994).
Property or Constituent
c, %<1)
H, %
S, %
N, %
O, %
V, ppm
Ni, ppm
Na, ppm
Mg, ppm
Cr, ppm
Fe, ppm
Chloride, ppm
Ash, %
Water Content, %
Specific gravity at 15° C
Average droplet size, urn
Droplets > 150 urn, %
Gross heating value, 106Btu/lb (MJ/kg)
Net heating value, 106 Btu/lb (MJ/kg)
Typical Value
60
7.3
2.7
0.5
0.2
300
65
30
350
1.1
13
92
0.2
29
1.0113
10
0.7
12,860(29.9)
11,870(27.6)
Typical Range
55-62
7-7.5
2.4-2.9
0.4-0.55
0.18-0.6
270-340
60-70
15-50
300-450
NA®
NA
NA
0.12-0.25
27-30
NA
8-15
0.5-1.5
12,480-13,340
(29-31)
11,620-13,340
(27-29)
1. Percentages are weight percentages, unless otherwise noted.
2. Not available.
must be pumped so as to avoid high shear regimes to minimize any separation or deterioration of the
emulsion. Bitor recommends limiting shear rates to less than 500 s-1 and velocities to less than 10 ft/s
(3 m/s). Because the emulsion is better able to resist degradation from shear at lower temperatures, it
is also recommended that fuel lines be maintained at temperatures less than 120 °F (50 °C).
The above limitations result in use of fuel heating systems that do not use steam, which can heat the
fuel to temperatures substantially higher than the recommended level in the near vicinity of the
heating coil. In addition, it is also recommended that screw pumps be used and that pump speeds be
maintained at 1800 rpm or less for Orimulsion 100 and 3000 rpm or less for Orimulsion 400. It is
also recommended that fuel recirculation be avoided, and that fuel flow control be based on pump
speed rather than on the throttling of control valves, again to avoid high shear situations in fuel lines.
Flow measurements should not be taken with devices using orifice plates or Venturis, but non-
intrusive, positive displacement, or turbine meters should be used instead to minimize regions of high
shear inside the fuel lines.
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Table 2-3. Radioactive elements present in Orimulsion (Bitor America 1997).
Isotope
Cobalt 60
Cesium 137
Uranium (natural)
Radium 226
Radium 228
Thorium 230
Thorium 232
Thorium 228
Lead 210
Polonium 210
pCi/g
<0.1
<0.1
<0.1
0.1
0.6
0.5
0.1
0.2
0.1
0.1
Bitumen Water
Creaming Sedimentation Inversion
Figure 2-1. Types of instabilities in bitumen-in-water emulsions (Bitor Europe 1994).
Contamination
Orimulsion is not compatible with other fuel oils, although contamination with small quantities (< 5%
by weight) of heavy fuel oils has not resulted in destabilization of Orimulsion 400. However,
distillate fuel oils and solid matter such as sand or rust may reduce Orimulsion stability. High
paraffmic materials are immiscible in Orimulsion, and contamination with such materials can lead to
filter plugging. Water can be used to clean Orimulsion from fuel lines or tanks, as Orimulsion is
designed to mix with water.
Evaluating Environmental Issues Associated With Orimulsion Combustion
The focus of this report is on emissions and control of air pollutants generated by the combustion of
Orimulsion in boilers and furnaces. While spills of Orimulsion into water bodies and generation of
2-6
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wastewater and solid residues are also important topics to consider when evaluating the environmental
impact of Orimulsion use, those issues are beyond the scope of this report. In evaluating
environmental issues associated with Orimulsion use in combustion systems, it is the differences
between Orimulsion and other fuels that are most critical, since Orimulsion will be used in lieu of
other fuels. Such an evaluation is most useful when one looks at the impacts of Orimulsion
compared to the fuel or fuels most likely to be displaced by it. This approach is relatively simple
when a conversion is made that does not significantly change the output of plants other than the one
being converted, but this is the most simple case. If, for example, an electrical generating station
converts from firing only heavy fuel oil to firing only Orimulsion and the total amount of electricity
produced in each instance does not change over the time periods measured, then the total mass
emissions from heavy fuel oil combustion can be directly compared to those from the use of
Orimulsion. However, if the output of the plant changes substantially, then the issue becomes more
difficult to evaluate.
Consider the case where an electrical generating station converts from firing only heavy fuel oil to
firing only Orimulsion, but doubles its output of electricity.** Orimulsion displaces the full amount
of heavy fuel oil use at the plant, but also displaces an unknown amount of other fuels that would
have been used to generate the remaining electricity at other plants. This electricity may have been
produced by the combustion of coal, distillate or heavy fuel oil, natural gas, biomass, or from other
sources that do not rely on combustion, such as hydro or nuclear power. The particular fuel or fuels
displaced will depend upon the relative costs of power generation at the other available plants, and
will change as electricity demand and plant availability change. In general, it would be expected that
electricity generated by firing Orimulsion would displace the most expensive fuel, but the specific
decision as to which fuel is displaced is a complex decision influenced by factors such as plant
availability, pollutant emissions, and maintenance of transmission system reliability.
It is therefore speculative at best to try to estimate the environmental impacts associated with firing
Orimulsion on a national or regional basis. One can, however, estimate the impacts of converting an
individual plant to Orimulsion from a different fossil fuel. Therefore, this report will focus on the
direct differences in environmental impacts due to converting from one fuel to Orimulsion at
individual plants.
It is important to note that all fossil fuel combustion results in some impact to the environment, and
that the impacts associated with Orimulsion use may be less than the impacts associated with a
different fuel. However, the environmental impacts of coal, oil, and natural gas have been studied for
many years, and the unknown quantity in this report is the possible impact associated with Orimulsion
use.
Air Emissions
The most apparent air emissions issues associated with the combustion of Orimulsion are those arising
from the composition of the fuel. Compared to many heavy fuel oils, Orimulsion exhibits increased
levels of S, Ni, and V. Increased levels of Mg were also likely with Orimulsion 100 due to the
addition of Mg-based compounds for minimizing boiler surface corrosion. Although Orimulsion
400 does not inherently contain an Mg-based additive, boiler operators may inject such additives for
corrosion control (this is a relatively common practice when using heavy fuel oils). Because of the
increased concentrations of these compounds in Orimulsion, it would be expected that emissions of
these compounds and their oxides are likely to be higher when using Orimulsion than when using
heavy fuel oil.
It is a simple procedure to calculate the emissions of SO2, Mg, Ni, and V from the combustion of
"This discussion does not consider regulatory actions such as the impacts of a "major
modification," but is rather intended to emphasize the complexity of determining actual
environmental impacts where Orimulsion use may displace other fuels. Issues associated with
regulatory actions and requirements are outside the scope of this report.
2-7
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Orimulsion, since the fuel is the only significant source of those compounds. Mass emission rates (in
lb/106 Btu) of Mg, Ni, and V can be determined by simply dividing the concentration of the
individual compounds (in ppm or (ig/g) by the energy content of the fuel per unit mass:
M. = c.-E (2-3)
11 v '
where M; is the mass emission rate of compound i per unit energy (in lb/106 Btu), C; is the
concentration of compound i in ppm or (Jg/g, and E is the energy content of the fuel in Btu/lb.
Likewise, the SC>2 emission rate can be calculated by similar means, but taking into account the
additional mass of the oxygen (02) required for combustion of the S to SC^:
M = (2xl06xc UE (2-4)
S02 \ S/
where MSO2 is the mass emission rate of SO2 in lb/106 Btu and cs is the fraction of S in the fuel
(measured on a wet or as-fired basis). The factor 2 accounts for the fact that the molecular weight of
S is 32 and the molecular weight of SO2 is 64, and the factor 106 converts from Ib/Btu to lb/106 Btu.
Predicting emissions of other combustion-generated pollutants is not as straightforward, as they are
significantly impacted by the combustion conditions in the boiler. For instance, NOX formation
depends upon the mixing of the fuel and the air, the amount of nitrogen in the fuel, and the peak
temperatures reached in the flame. Orimulsion tends to have somewhat higher levels of nitrogen in
the fuel, but also has lower flame temperatures, resulting in relatively little change in NOX emissions
when compared to heavy fuel oil.
CO emissions strongly depend upon the amount of Q^ available for completion of the combustion
reactions. The small size of the bitumen droplets in Orimulsion allows boilers to operate with less
excess O2 without significant increases in CO, compared with firing heavy fuel oil or pulverized coal.
This is because the time required for devolatilization and burnout of the bitumen particles is short
due to the small droplet size.
PM emissions can also be dependent upon the combustion conditions, particularly for fuels that have
relatively low ash contents. If combustion conditions are poor, increased PM emissions are expected
because of increases in unburned carbon or the formation of soot. The small bitumen droplet size
and the presence of water in the combustion zone tend to minimize the unburned carbon fraction
when burning Orimulsion, and the water tends to assist in suppressing the formation of soot. In
addition, the high levels of V in the fuel also acts as a catalyst for improved carbon burnout, further
promoting the conversion of the carbon in the fuel to carbon dioxide (CO2).
The "microexplosions" that characterize emulsified fuels assist in promoting carbon burnout and
combustion efficiency, but also result in the formation of very small fuel particles. This behavior, in
combination with the small bitumen droplet sizes of Orimulsion, promotes the formation of
submicron particles (particles with aerodynamic diameters < 1 (am). For fuel oils, high carbon
burnout results in the release of inherently bound metals that form submicron particles through
nucleation, condensation, and coagulation mechanisms. In addition to their small size, these particles
also tend to contain high levels of metals and sulfur (Linak et al. 1999). Similarly, the PM generated
by the combustion of Orimulsion is expected to be characterized by high percentages of submicron
particles.
The presence of V in Orimulsion not only affects carbon burnout, but also acts as a catalyst for the
formation of SOj, in higher levels than for other high S fuels that do not have such high levels of V.
SOj, emissions are of concern for several reasons. First, SOj, is difficult to capture, since it acts as a
particle in flue gas desulfurization (FGD) systems and as a gas in particulate capture systems.
2-S
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Second, SO3 forms acid aerosols in the stack plume, adding to the total particle emissions of a plant.
Finally, SO3 emissions tend to form visible plumes that can have a significant impact on the public's
perception of how well a plant is controlling emissions.
Solid Residues
In addition to the direct emissions of pollutants to the atmosphere, the combustion of fossil fuels
often generates solid residues that require disposal. In particular, boilers that use particle control
equipment can collect large quantities of fly ash. In some instances, fly ash can be used in
production of cement or other building materials. In cases where disposal is necessary, the trace
element content of the ash becomes important. Table 2-4 presents the concentrations of metals,
halogens, and radioactive elements measured in fly ash generated by Orimulsion combustion. These
results, reported by Bitor America (1997), show that Orimulsion fly ash has detectable levels of lead,
nickel, vanadium, and the radioactive elements lead 210, thorium, and natural uranium.
In characterizing solid residues for disposal suitability, an important measure is the toxicity
characteristic leaching procedure (TCLP), which follows a standard EPA procedure (EPA 1997).
TCLP values for As, Ba, Cd, Cr, Hg, Se, and Pb in Orimulsion 100 fly ash were reported as
significantly less than the acceptance criteria presented in the Resource Conservation and Recovery
Act (RCRA), and in the same range as TCLP values for coal fly ash (Bitor America 1997), as shown
in Table 2-5.
Table 2-4. Metals and radioactive elements present in Orimulsion fly ash (Bitor America 1997).
Element
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Concentration
(M9/9)
<0.5
<5
<5
<5
34
<0.02
25980
<0.2
<5
90730
Element
Lead 210
Radium 226
Radium 228
Total Thorium
Uranium (natural)
Concentration
(pCi/g)
0.4
<1.2
<1.9
4.0
0.9
2-9
-------
Table 2-5. Toxicity characteristic leaching procedure (TCLP) results for Orimulsion 100
and coal fly ashes (Bitor America 1997).
Metal
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
RCRA
Criterion
(mg/L)
5
100
1
5
5
0.2
1
Orimulsion 100 fly ash (mg/L)
BDL<1)-0.64
BDL-0.66
BDL-0.05
0.62-1.6
BDL-1.01
BDL-0.04
BDL-0.13
Coal fly ash (mg/L)
BDL-2.68
0.11-1.61
BDL-0.58
BDL-4.64
BDL-2.94
BDL
BDL-0.15
1. Below detection limit
2-10
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Chapter 3
Review of Previous Orimulsion Combustion Research and
Demonstration
Considerable work has previously been conducted to evaluate Orimulsion's combustion behavior at
different scales, from fundamental combustion studies to long-term operational testing. Fundamental
combustion and analysis studies, pilot-scale testing, and full-scale demonstrations and operations have
been reported in the technical literature, conferences, and trade magazines. In addition, there are a
number of internal company reports and studies that have been made available to EPA as part of its
efforts to evaluate the environmental effects of Orimulsion use. Many of these have been
summarized in a recent review paper (Miller and Srivastava 2000). There are also several references
describing Orimulsion studies and applications that have been posted to the World Wide Web. This
chapter will discuss the studies that have been done related to the combustion and gasification of
Orimulsion, primarily as it relates to air emissions, but with some discussion of wastewater and solid
waste disposal as well.
A number of overview papers have been presented that provide basic information about Orimulsion
and how it compares to other fuels, what modifications are required to use it, and issues of cost
associated with conversion of units to Orimulsion use (Olen 1998a, Quig and Woodworth 1997).
Some of these papers do not have detailed information concerning emissions, but rather provide
more general information about the fuel, combustion and emissions characteristics, and where it is
being (or has been) used.
The majority of reported results are for Orimulsion 100. In some respects, such as for fundamental
combustion behavior, little difference is expected between Orimulsion 100 and Orimulsion 400. For
issues such as formation of PM and NOX, predicting the effect of the change in Orimulsion
formulation is more difficult. Where data are presented, a distinction is made between Orimulsion
100 and Orimulsion 400. In cases where the text discusses Orimulsion use in general, no distinction
is made between the two formulations.
Fundamental Studies
Several studies of the fundamental combustion behavior of Orimulsion have been carried out over the
past ten years, primarily at the University of Leeds. Drop tube reactor studies conducted by Williams
and Pourkashanian (1987) on bitumen-in-water mixtures concluded that the mixtures exhibited
combustion characteristics that were better than coal-water slurries but worse than medium fuel oil, as
measured by ignition temperature, maximum fuel droplet temperature, flame lifetime and measured
burning rate. The bitumen-in-water mixture was different than the Orimulsion produced currently,
but used the same Orinoco bitumen and roughly the same water content. This study concluded that
the bitumen-in-water mixture would produce a flame that was more stable than a flame using coal-
water slurry as the fuel (Williams and Pourkashanian 1987).
Results of a study of single droplets in a drop tube reactor were reported by Marcano et al. (1991). In
these experiments, Orimulsion, Orinoco bitumen, and medium fuel oil, and a hard-bitumen-in-water
emulsion were tested (Orinoco bitumen is considered a soft bitumen). The Orimulsion exhibited
lower internal temperatures during combustion than the other fuels due to the presence of the water
in the fuel. The lower temperatures are believed to lead to the lower emissions of NOX noted when
using Orimulsion. The study concluded that Orimulsion behaved similarly to the fuel oil, while the
hard-bitumen-in-water emulsion exhibited behavior that was between the fuel oil and coal-water
slurries (Marcano et al. 1991).
This similarity between Orimulsion and heavy fuel oil was further demonstrated by Hampartsoumian
et al. (1993) in their study of the burning rate of heavy fuel oil and Orimulsion chars. This study
found that the burning behavior of Orimulsion chars was very similar to that of heavy fuel oil, with
Orimulsion exhibiting slightly more reactivity than the heavy fuel oil.
3-1
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Maki and Miura (1997) developed a computer simulation of Orimulsion pyrolysis that calculated a
distribution of pyrolysis products. These products may be combustion process intermediate
products, and the simulation may provide data for the development of further models of Orimulsion
combustion. A two-step model was developed, using a relatively fast primary reaction and a slower
secondary gas phase reaction. The simulation modeled a decomposition of the gas phase products to
methane (CH4) and inorganic materials, and a solid phase decomposition to coke.
In addition to the work conducted to evaluate the fundamentals of Orimulsion combustion, research
has been conducted in the area of fuel analysis, primarily to determine content of trace metals such as
Fe, Mg, Na, Ni, and V (Platteau and Carrillo 1995, Kamiura et al. 1996).
Pilot-Scale Testing
Pilot-scale tests have been conducted at several facilities to evaluate Orimulsion's combustion
performance, different burner designs for Orimulsion use, and the use of Orimulsion as a reburning
fuel.
Combustion Performance
Test results of Orimulsion 100 combustion performance on a test rig using a single full-scale burner
were reported in 1996 (Allen and Beal 1996). These tests evaluated CO, NOX, and PM emissions as a
function of stack O2 levels for both heavy fuel oil and Orimulsion 100. Uncontrolled CO emissions
were lower for Orimulsion 100 at O2 levels of less than 0.8%, but were lower for heavy fuel oil at
higher O2 levels. NOX emissions were consistently lower for Orimulsion 100 than for heavy fuel oil,
with the lower flame combustion temperatures being attributed for most of the difference. PM
emissions were consistently and significantly higher for Orimulsion 100 than for heavy fuel oil, but
whether a portion of the PM was due to SO3 aerosols is not reported. Figure 3-1 shows the CO, NOX,
and PM results reported in this study. The authors also noted that Orimulsion had a higher reactivity,
and therefore better combustion properties, than the heavy fuel oil tested (Allen and Beal 1996).
A different burner was tested using Orimulsion 100 and heavy fuel oil on the same test rig as above.
The burner was the same as that used in the Dunamenti Power Station operated by the Hungarian
Power Company. The emissions results from the tests are presented in Table 3-1. These results are
similar to the emissions measured in the tests above, with CO emissions slightly higher for Orimulsion
100 than for heavy fuel oil under the reported conditions, and with NOX being approximately 20%
lower for Orimulsion 100 than for heavy fuel oil. Interestingly, the PM emissions for Orimulsion
100 were less than 40% of the PM emissions for heavy fuel oil, but the PM content as determined by
Bacharach smoke number would indicate higher emissions for Orimulsion 100. However, the report
noted that the smoke number samples appeared yellow in color, and suggested that this was due to
very high levels of sulfates or SO2 captured on the filter when burning Orimulsion. The report stated
that the higher smoke number is due primarily to the higher sulfur content. However, the
significantly higher sulfur content of Orimulsion 100 compared to heavy fuel oil was considered to
result in either increased formation of sulfate particles in the stack plume or increased stack emissions
of SO3 aerosols (Barta et al. 1996).
The tests of the Hungarian Power Company burner also noted that the Orimulsion flame was not only
cooler than the heavy oil flame, but also was longer than the heavy oil flame. This may account for
the higher CO emissions in the test rig, which will have less volume for the fuel to complete
combustion. The report suggested that the lower measured Orimulsion PM emissions may have been
due to deposition of ash in the flame tunnel, since mass balance calculations would predict PM
emissions of approximately 500 mg/Nm3, roughly 20% higher than those measured from heavy fuel
oil (Barta et al. 1996).
Tests were also conducted in Canada on a fuel very similar to Orimulsion (Wong et al. 1989, Whaley
et al. 1991). A water-continuous emulsion of western Canada bitumen was tested by the CANMET
laboratories of Energy, Mines, and Resources Canada in the late 1980s. This fuel was nominally
composed of 35% water and 65% bitumen. No information was provided as to the use of surfactants
3-2
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45
40-
35-
£30-
£25
0-20
O 15-
10-
0
500
0^450
^ 400-
« 350
<§) 300.
E 250
a. 200
°: ^50
0*100
z 50
0
0.40
3 0.35
S 0.30
"o °-25
i 0.20
~ 0.15^
I 0.10
0.05-
0.00
1
1
•
1
0
' _
• 1
• (
1
,
Irimnl
1
0
~IIJ=L| f*l
;inn 1(
•
i
0
1
•
•
1
0
•
0.2 0.4 0.6 0.8
Stack O2, %
1.2
Figure 3-1. Emissions of CO, NOX, and PM measured during pilot-scale tests of Orimulsion 100 combustion (Allen
and Beal 1996).
Table 3-1. Flue gas composition for pilot-scale tests using a burner from Dunamenti Power Station (Barta et al.
1996).
02 (%)
CO (ppm as measured)
NOX (ppm @ 3% O2)
S02 (ppm)
S03 (ppm)
Bacharach smoke number
PM (mg/Nm3)
Heavy Fuel Oil
1.0
40
273
1605
8.5
1-2
415
Orimulsion 100
0.95
61
217
2228
13.2
2-3
160
or emulsifying agents. The western Canadian bitumen was 83.4% carbon, 10.5% hydrogen, and 5%
sulfur, compared to the Orinoco bitumen composition of 85.3% carbon, 9.7% hydrogen, and 4%
sulfur noted in the previous chapter. The flame from the Canadian fuel was reported to be bright and
3-3
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stable, and shorter and more intense than a No. 6 fuel oil flame. The study concluded that the fuel
appeared to be "an acceptable alternative to No. 6 fuel oil" (Wong et al. 1989).
Burner Development
Tests of different atomizer designs were conducted in 1988 using Orimulsion (Tombs 1996). These
tests evaluated a mechanical pressure jet atomizer and three dual-fluid atomizers in a full-scale burner
installed at a pilot-scale test facility. The tests sought to develop a burner-atomizer combination that
did not exert excessive shear and that created good mixing of the fuel and atomizing fluid (steam).
The dual-fluid atomizers tested were Y-jet, F-jet, and advanced F-jet, with the advanced F-jet design
found to be suitable for full-scale operation. Figure 3-2 presents the F-jet and advanced F-jet
designs. Different burner configurations were tested using Orimulsion 100 and Orimulsion 400 in
the spring of 1998 by DB-Riley for SK Power of Denmark (DB-Riley 1998). The tests also evaluated
a number of spray atomizer designs and compared performance of the Orimulsion formulations with
the performance of heavy fuel oil. The tests concluded that Orimulsion 400 had similar combustion
performance to Orimulsion 100 (Hall 1998).
Trial Tests
Pilot-scale tests were conducted by the Italian Electricity Generating Board (ENEL) at their research
and development facility using a 50 MWth full-scale burner in a single burner test rig (De Santis et al.
1996). These tests compared the combustion and emissions characteristics of Orimulsion 100 with a
high sulfur (2.8%) No. 6 fuel oil using two burners and several different atomizing nozzles.
Measurements of CO, NOX, SOX, volatile organic compounds (VOCs) and polycyclic aromatic
hydrocarbons (PAHs) were made during the combustion trials. In addition, the conversion of SO2 to
SO3 was also measured.
SO2 values ranged from 5750 to 6250 mg/Nm3 for Orimulsion 100, with SO3 emissions less than 5
ppm. These SO2 concentrations correspond to approximately 2200 to 2380 ppm (at 77°F). The SO3
emissions are lower than those reported in other tests, with the difference attributed to lower levels of
vanadium having deposited on the test facility's surfaces than is typical for full-scale systems.
The ENEL tests compared emissions from two types of burners, a three fuel (coal/oil/gas) Babcock &
Wilcox XCL low NOX burner and a dual-fuel (oil/gas) ENEL/Ansaldo TEA Mark 2 low NOX burner.
For the XCL burner, NOX emissions were approximately 30% lower when burning Orimulsion 100
compared to operation with No. 6 fuel oil. NOX emissions from the XCL burner ranged from
approximately 190 mg/Nm3 (150 ppm) at 3% O2 to about 320 mg/Nm3 (260 ppm) at 4.5% O2 when
burning Orimulsion 100 and from 300 mg/Nm3 (240 ppm) at 1.8% O2 to approximately 390
mg/Nm3 (320 ppm) at 3.8% O2 when burning No. 6 fuel oil. When using the TEA burner, NOX
emissions from Orimulsion 100 ranged from approximately 350 mg/Nm3 (280 ppm) at 1.5% O2 to
approximately 570 mg/Nm3 (460 ppm) at 4% O2, and from about 250 mg/Nm3 (200 ppm) at 2% O2
to about 320 mg/Nm3 (260 ppm) at 4.5% O2 when burning No. 6 fuel oil.
The O2 level at which CO emissions exceeded 100 mg/Nm3 (87 ppm) when using the XCL burner was
approximately 2% when burning No. 6 fuel oil and approximately 3.5% when burning Orimulsion
100. Because it was expected that the CO "knee"* would be at a lower O2 level for Orimulsion 100
than for No. 6 fuel oil, further investigation was undertaken. It was determined that the Orimulsion
was incorrectly heated during these tests, leading to the higher CO levels when burning Orimulsion
100 compared to No. 6 fuel oil. Further tests using several different atomizing nozzle designs found
that only one nozzle design could achieve CO emissions lower than 50 ppm at O2 levels less than 1%,
but that atomizer also resulted in the highest NOX emissions of the four atomizers tested. It was not
clear which atomizer of those tested produced the lowest CO and NOX emissions, but the study
concluded that NOX emissions for Orimulsion 100 would be 15-30% higher than for No. 6 fuel oil.
The study also concluded that Orimulsion responded to low NOX firing techniques in a manner
*Nearly all combustion systems exhibit a rapid and substantial increase in CO below a certain O2
level. This point is often termed the "CO knee," and will vary from one unit to another.
3-4
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Oil Port
Annular
Mixing
Chamber
Exit Port
Atomizing Fluid
Inner Body
Turbulent Recirculating Flow
F-Jet Atomizer
ap Nut
Atomizer
Inner
Body
_
Passage
Steam Passage
Mixing Chamber
Advanced F-Jet Atomizer
Figure 3-2. F-jet (top) and advanced F-jet atomizers used in Orimulsion combustion tests at PowerGen's Power
Technology Centre (Tombs 1996).
similar to No. 6 fuel oil, but that additional atomizer testing was needed to determine the optimal
design for the particular burners they were testing.
PM emissions from Orimulsion 100 were measured at between 220 and 260 mg/Nm3. The particle
size distribution (as determined using scanning electron microscope) showed 73.1% of the particle
mass being less than 10 (jm and 21.2% < 1.0 (am for Orimulsion 100. The PM from Orimulsion 100
3-5
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combustion had 84% unburned carbon (percent of the ash as measured by SEM-EDX). For No. 6
fuel oil, the distributions showed 87.1% < 10 (jm and 51.3% < 1.0 (am, and the unburned carbon
value was 78.5% (De Santis et al. 1996). The unburned carbon values for these tests were
significantly higher than those reported in other studies, suggesting that site-specific factors
influenced these results.
VOC emissions were measured at 277 (ig/Nm3 when burning Orimulsion 100 and 350 (jg/Nm 3 when
using No. 6 fuel oil. PAH emissions were measured at 7.9 (ig/Nm3 when using Orimulsion 100,
compared to 5.2 (jg/Nm3 when using No. 6 fuel oil (De Santis et al. 1996).
Reburning Development
Bertacchi et al. (1997) conducted tests of Orimulsion 100 as a reburn fuel** in a 6 MWth pilot-scale
test facility. These tests showed baseline NOX emissions when using Orimulsion 100 as a reburn fuel
were approximately 50 mg/Nm3 (40 ppm) lower than for a heavy fuel oil under similar conditions.
These tests concluded that Orimulsion performed better than heavy fuel oil as a reburn fuel, but that
the behavior of Orimulsion was somewhat different than heavy fuel oil. While the NOX emissions
tended to decrease with increasing levels of reburn fuel for heavy fuel oil, increasing the level of
reburn fuel with Orimulsion resulted in a decrease followed by an increase in NOX emissions. Thus,
at higher reburn zone stoichiometries, NOX emissions using Orimulsion as the reburn fuel were higher
than those at the same reburn zone stoichiometries, but at lower reburn zone stoichiometries, using
Orimulsion 100 as the reburn fuel resulted in lower NOX emission than using heavy fuel oil as the
reburn fuel. The optimum reburn condition using Orimulsion 100 on this pilot-scale unit was about
15% reburn fuel*** in a reburn zone stoichiometry of approximately 0.85, which resulted in NOX
emissions of 240-250 mg/Nm3 (195-205 ppm), compared to baseline emissions of 600 mg/Nm3 (490
ppm).
Additional testing was conducted in a 1 MW combustion test facility by Irons and Jones (1996), who
also concluded that Orimulsion 100 had properties that would make it suitable for use as a reburn
fuel.
Air Pollution Control Equipment Evaluation
During full-scale demonstration of Orimulsion 100 operation at Florida Power & Light's Sanford
Plant in 1991, two pilot-scale baghouses were evaluated for their effectiveness in controlling PM from
Orimulsion combustion (Olen et al. 1991). A 5,000 acfm pulse jet cleaned baghouse and a 10,000
acfm reverse gas cleaned baghouse were tested. The pulse jet unit had 48 bags, and a range of fabric
materials were tested on this unit, including Huyglas, Tefaire, P84, and Ryton/Rastex. The larger
reverse gas cleaning unit used 80 bags of Gore-Tex membrane laminated to a fiberglass fabric
supplied by W.L. Gore and Associates, Inc. The larger unit had an air to cloth ratio of 3.8 at a
maximum gas flow rate of 14,000 acfm.
The study concluded that a pulse jet baghouse can be used to control PM emissions from the
combustion of Orimulsion. However, several conditions apply to the successful application of this
technology. The bags required coating with a sorbent material prior to startup to protect the bags
from the high SOj, levels typical of Orimulsion 100 emissions. In addition, it was determined that
maintaining a low acid dewpoint through high baghouse inlet temperature and low excess Q^ (typical
high load conditions) was necessary to ensure adequate bag life. The tests also concluded that
prolonged operation would not be feasible at high acid dewpoint conditions such as those that would
be present during low load operation, unless adequate sorbent material was co-injected into the flue
**Reburning is a method of NOX control that injects a fraction of the fuel heat input at a point
downstream of the main burners to create a fuel-rich zone in the furnace, followed by injection of
burnout air to allow complete burnout of the hydrocarbons. Reburning can achieve NOX emissions
reductions of 40-60% (Meadows et al. 1996).
***15% of the total heat input to the boiler is injected into the reburn zone.
3-6
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gases to protect the bags from degradation from SO3.
Testing of the reverse gas cleaned baghouse was not able to determine whether such a design would
be appropriate for use in Orimulsion applications. While evaluation of the filter media indicated
normal wear patterns (compared to other fossil fuel applications), the tests were discontinued before
adequate data could be gathered to determine effectiveness of additives or long-term operation (Olen
etal. 1991).
Full-Scale Testing and Operation
Plants Currently Operating
A number of boilers are currently using Orimulsion as their primary fuel (in most cases the sole fuel)
in commercial operations. Table 3-2 lists those plants that were commercially operating or have
commercially operated using Orimulsion as of November 1999. In addition to these plants,
Orimulsion is also being used at a 770 MWe coal-fired power plant in Germany as fuel for the plant's
auxiliary boilers. The Ibbenbiiren plant will use up to 22,000 tons of Orimulsion annually for
startup and fuel support when coal volatile content drops below a given point (Bitor Europe 1998).
Table 3-2. Plants that have operated or are were operating commercially as of December 2000 using Orimulsion
(Olen 1998b, Quig and Woodworth 1997, Quig 1999, Garcia 1999, Miles 1999, Garcia 2000).
Country
Canada
Denmark
Italy
Japan
Lithuania
United
Kingdom
Plant Name
NB Power Dalhousie#1
NB Power Dalhousie #2
SK Power Asnaes #5
ENELBrindisiSud#1
ENEL Brindisi Sud #2
ENEL Fiumesanto #3, #4
Mitsubishi Kasei
Kashima-Kita #1
Kashima-Kita #2
Kansai Osaka #4
Hokkaido Electric
Shiriuchi
Lietuvos Energija
PowerGen Ince "B" (4)
PowerGen Richborough^
Operation
DateO)
1994
1994
1995
1997
1999
1999
1992
1991
1994
1994
1997
1995
1991
1991
Original Fuel
Design
Heavy fuel oil
Pulverized coal
Pulverized coal
Pulverized coal
Heavy fuel oil
Orimulsion
Pulverized coal
Heavy fuel oil
Heavy fuel oil
Heavy fuel oil
Heavy fuel oil
Pulverized coal
Orimulsion
Heavy fuel oil
Heavy fuel oil
Pulverized coal
Boiler
Design
T-fired
T-fired
Opposed
wall-fired
Opposed
wall-fired
Opposed
wall-fired
T-Fired
T-fired
T-fired
T-fired
T-fired
NA<3>
Wall-fired
Wall-fired
NA
Plant/Unit
Rating (MW)
105
215
640
660
660
2x320
70 + steam
95 + steam
125 + steam
156
350
150+steam
500
3x120
Orimulsion
Consumption, tons/yr
700,000(2)
1,400,000
1,500,000
1,500,000
1,300,000
(total for 2 units)
300,000
375,000(2)
200,000
100,000
150,000
1,300,000
300,000
1. Initial commercial operation date using Orimulsion.
2. Combined consumption, Units 1 and 2.
3. Information not available.
4. Retired, May 1997.
5. Retired, 1996.
3-7
-------
New Brunswick Power Dalhousie Generating Station
New Brunswick Power Corporation's Dalhousie Generating Station has been in operation using
Orimulsion since the fall of 1994 (Mulholland 1996). The Dalhousie plant, shown in Figure 3-3, is
located in Dalhousie, New Brunswick, Canada, and has two units. Unit 1 is a tangentially-fired unit,
rated at 103 MWe, and originally designed to burn a 2.6% S No. 6 fuel oil when it began commercial
operation in 1967. The unit was designed by Combustion Engineering (CE) as a three-level, 12-
burner unit (New Brunswick Power 1989). Unit 2 was originally designed to burn an indigenous
New Brunswick coal with sulfur content of 8%, and is rated at 212 MWe. Unit 2 began commercial
operation in 1978 (Kennedy and Sainz 1992). Conversion of the plant to burn Orimulsion began in
1991, following an 18-month demonstration of Orimulsion operation on Unit 1.
Dalhousie Demonstration Tests
A comprehensive report of the 1988 Orimulsion demonstration program at Dalhousie was
summarized in a report on the demonstration prepared by NB Power (New Brunswick Power
1989).At the time the report was written, the Dalhousie Station had approximately 2,500 hours of
equivalent full load operation, with plans for a further 1,700 hours of equivalent full load operation.
Measurements of fuel handling characteristics, boiler thermal efficiency, carbon in ash, ESP
performance, and pollutant emissions were made during the demonstration. The results of those tests
are summarized below and in Table 3-3.
Figure 3-3. Photograph of Dalhousie Generating Station, Dalhousie, New Brunswick, Canada.
3-8
-------
Unit 1 burners used CE internal mix atomizers with steam as the atomizing fluid. The burners were
originally designed for mechanical atomization, but were retrofit for steam atomization for the
Orimulsion tests. The nozzle fuel ports were increased in size to provide an increased flow capacity
of approximately 20% over that used during No. 6 fuel oil operation. The unit was able to achieve
98 MWe using all 12 burners when using Orimulsion, compared to a maximum load of 104 MWe
when using No. 6 fuel oil.
During testing, the boiler thermal efficiency dropped from 87.2% using No. 6 fuel oil to 82.6%
using Orimulsion 100. The reduction in efficiency was due to the effect of the high water content of
Orimulsion 100 as well as the increase in boiler tube fouling associated with Orimulsion 100
compared to the No. 6 fuel oil. Carbon in ESP ash levels were consistently very low (near 1%), while
those for the No. 6 fuel oil ranged from over 45% at 0.7% excess O2 to 35% at 2.5% excess O2.
The ESP was in operation during all tests. At less than 50% load, the ESP collection efficiency was
greater than 95%, but dropped to approximately 86% at full load. This drop in efficiency was
attributed to an increase in the flue gas volume (and higher particle velocities) due to higher ESP inlet
temperatures (450 °F during the demonstration compared to approximately 340 °F when using No. 6
fuel oil). A further contributing factor was believed to be the lower ash density when using
Orimulsion 100 compared to No. 6 fuel oil. The report concluded that the ESP could effectively
collect Orimulsion ash at higher efficiencies if the flue gas mass flow, temperature, ash density,
particle resistivity, and particle size were properly taken into account.
PM loading at the economizer exit was approximately 250 mg/m3 at 70 °F and 0.5% O2 (at the
economizer exit) when using Orimulsion 100 compared to an estimated 105 mg/m3 at 70 °F and
0.8% O2 for No. 6 fuel oil, again at the economizer exit.
The particle size distribution of Orimulsion ash was considerably smaller than that of ash from No. 6
fuel oil. PM generated by the combustion of Orimulsion 100 during the Dalhousie demonstration
was found to be 98% by weight (wt%) less than 10 um in diameter and 50 wt% less than 0.3 um in
diameter, as seen in Figure 3-4. This compares to approximately 75 wt% less than 10 um in diameter
and 35 wt% less than 0.3 um in diameter for PM from No. 6 fuel oil. This resulted in an ash of much
lower density (5-10 lb/ft3 for Orimulsion 100 compared to 25 lb/ft3 for No. 6 fuel oil). The ash from
Orimulsion 100 combustion consisted of 16% S, 11% V, 2% C, and 1% Fe, with the majority (55%)
being reported as "Other" (oxygen, hydrogen, nitrogen, and trace metals including magnesium).
Ash from No. 6 fuel oil combustion consisted of 36% C, 13% V, 6% S, and 1% Fe, with 36%
"Other." The Orimulsion 100 ash had substantially less carbon in the ash than did the heavy fuel oil
ash over the range of O2 levels tested. Figure 3-5 shows the carbon in ash measurements for
Orimulsion 100 and heavy fuel oil as a function of stack O2 level.
Table 3-3. Emissions measured during Dalhousie Station Unit 1 Demonstration (New Brunswick Power 1989).
CO(at0.7%O2)
NOX (at 3% O2, 90 MWe)
PM (at economizer exit)
Particle Size Distribution
SO2 (at 3% O2, uncontrolled)
SO3
Orimulsion 100
30 ppm
180-215 ppm
250 mg/m3 at 70 °F
98% < 10 urn
50% < 0.3 urn
2270-2350 ppm
2-15 ppm
HFO
60 ppm
180-190 ppm
105 mg/m3 at 70 °F<1)
75% < 10 urn
35% < 0.3 urn
1540-1560 ppm
MA®
1. Reported estimated value of PM loading
2. Not available
3-9
-------
CO emissions were consistently lower than those from No. 6 fuel oil. At 0.7% O2, the boiler exit CO
level using Orimulsion 100 was measured at approximately 30 ppm, while the boiler exit CO level
using No. 6 fuel oil was measured at approximately 60 ppm. CO emissions were influenced by the
temperature of the Orimulsion and the atomizing steam and by the differential pressure between the
fuel and the steam. At a load of 90 MWe and 0.5% excess O2, CO emissions were reduced from 20
ppm to less than 10 ppm as the Orimulsion temperature changed from 125 °F to 150 °F. Figure 3-6
shows the variation in CO emissions with changing O2 levels at different loads and compared to heavy
fuel oil. Changing the atomizing steam temperature from 424 °F to 500 °F resulted in a reduction of
CO from approximately 50 ppm to approximately 30 ppm. As the differential pressure was changed
from +10 psig to +4 psig (steam to fuel), the CO emissions increased from 50 ppm to approximately
95 ppm.
At the time the demonstration was conducted, the Dalhousie Station did not use an FGD system or
NOX controls, so NOX and SOX emissions in this report reflect uncontrolled emissions. Uncontrolled
SO2 emissions when using Orimulsion ranged from 2270 to 2350 ppm at 3% O2, compared to 1540
to 1560 ppm at 3% O2 for No. 6 fuel oil. NOX emissions at 90 MWe load ranged from 180 to 215
ppm when firing Orimulsion compared to 180 to 190 ppm when firing No. 6 fuel oil.
SO3 emissions from the combustion of Orimulsion were measured at between 2 and 15 ppm during
optimized operation, with the lower value being measured under clean boiler conditions and the
higher value measured after the boiler internal surfaces had been fouled due to continuous operation
with Orimulsion. SO3 emissions as high as 35 ppm were noted during initial test runs, but as
operators became more familiar with Orimulsion operation and were able to reduce the excess O2
levels, SOj, emissions were consistently in the lower range (New Brunswick Power 1989). Figures 3-7
and 3-8 show the relationship of SOs emissions to acid dewpoint temperature and the variation of
daily acid dewpoint temperature in the stack over the demonstration test period, respectively.
on :
57U
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• •,-,«,,
™~ ~~ Heav
ulsion 100
, . ^_ _ .-.i ^\' i
y Fuel ON
0.1
100
1 10
Particle diameter, |jm
Figure 3-4. Particle size distribution for PM emitted from the combustion of heavy fuel oil and Orimulsion 100
during demonstration testing at NB Power Dalhousie Generating Station (New Brunswick Power 1989).
3-10
-------
£
O en
^* A.(\
£1 4U
a :
c :
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re 1U
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y Fuel (
ulsion '
DM
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Stack O2, %
2.5
Figure 3-5. Carbon in ash in PM emitted from the combustion of heavy fuel oil and Orimulsion 100 during
demonstration testing at NB Power Dalhousie Generating Station (New Brunswick Power 1989).
Boiler efficiency was measured at 82.4% during Orimulsion 100 firing and 87.4% during HFO
firing. The unit's net heat rate was determined to be 10,972 Btu/kW-hr when using Orimulsion 100
and 9,743 Btu/kW-hr when using HFO (Hidalgo et al. 1989).
Conversion to Permanent Orimulsion Operation
Conversion of the Dalhousie plant to permanent Orimulsion operation was completed in 1994. As
part of the conversion, the plant installed new fuel transfer, handling, and storage facilities, new
burner tips for Unit 2 (the No. 6 oil burners in Unit 1 were not changed), a new common flue gas
desulfurization (FGD) system, and a new common wastewater treatment facility (Kennedy and Sainz
1992). The FGD system was designed to reduce SO2 emissions by 90% compared to the
preconversion levels. The FGD system is a wet limestone system, using a single absorption tray and
five spray headers in a counter-current design. The system was designed to produce wallboard grade
gypsum with a minimum of 92% CaSO4*2H2O at a Ca to S stoichiometric ratio of 1.03 (Kennedy and
Sainz 1992).
During commercial operation with Orimulsion 100, CO emissions were reported to be 30 ppm or less,
at boiler O2 levels of less than 1%. NOX emissions were measured at 290 ppm (corrected to 3% O2)
during the same test program. These NOX values compare to the roughly 200 ppm measured during
demonstration testing. SO2 emissions were measured at just under 200 ppm (corrected to 3% O2) in
the stack. This compares to the uncontrolled concentrations of 2300 ppm measured during the
demonstration testing, giving a reduction of approximately 91% (Janati 1997). PM emission rates
when using Orimulsion 100 over long-term operation have been reported as being consistently
around 0.015 Ib/lO* Btu (Janati 1997, Irvine and Eagles 1998).
The wastewater treatment plant was designed to reduce the bitumen content of any wastewater from
levels as high as 10,000 mg/1 to less than 10 mg/1 to meet applicable government requirements. In
addition, the treatment plant was also designed to remove trace metals such as vanadium. Bench scale
testing of the treatment process indicated that vanadium could be reduced from levels as high as
7,000 mg/1 to less than 0.5 mg/1 to meet the applicable government regulations. Efforts were also
made to increase the density of the collected fly ash and pelletize it to allow it to be used as a
feedstock for a vanadium recovery process and minimize the landfill requirements of the ash
3-11
-------
300
250
200
E
Q.
a-150
o~
O
100
50
90 MWe
75
50
MWe
MWe
300
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Stack 02, %
200
E
Q.
O
O
100
50
H
eavj
Fuol
O
Orimiblsioln 100
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Stack O2, %
Figure 3-6. CO as a function of stack O2 levels measured during combustion testing of heavy fuel oil and
Orimulsion 100 at the NB Power Dalhousie Generating Station. The top plot shows CO at different
loads when burning Orimulsion 100 and the bottom figures compares CO emissions from heavy fuel oil
and Orimulsion 100 at 90% load (New Brunswick Power 1989).
(Kennedy and Sainz 1992). The collected fly ash was quite low in density compared to fly ash from
heavy fuel oil or coal, resulting in mechanical problems in maintaining flow of the ash in the ESP
hoppers. These problems were solved by lining the ESP hoppers with stainless steel, removing
surface irregularities in the ash flow path, and wetting the ash after removal from the hopper to
stabilize it and increase the density. As of late 1998, the collected fly ash was being prepared and
sold for vanadium recovery (Irvine and Eagles 1998).
Use of Orimulsion 400
The Dalhousie plant converted from the original formulation (Orimulsion 100) to Orimulsion 400 in
3-12
-------
September 1998. The formulation of Orimulsion 400 that was being used had significantly lower
viscosity than the original formulation of Orimulsion, resulting in some operational changes to
achieve optimum fuel pressure at the burners and to the burner tip port sizes. During the initial six
weeks of operation with Orimulsion 400, the plant noted lower emissions of CO and NOX and less
unburned carbon than was measured with Orimulsion. CO emissions were reported as near zero with
stack O2 at 0.5%, and NOX emissions had dropped from 125 ng/J to 105-110 ng/J (Irvine and Eagles
1998).
Plans have been made to install a wet ESP on the common stack at Dalhousie to reduce the level of
280
275
^265
0250
•ja
'o
<
235
230
SO3, ppm
10
20
Figure 3-7. Relationship between the acid dewpoint and 863 emissions measured during Orimulsion 100
demonstration testing at the NB Power Dalhousie Station (New Brunswick Power 1989).
310
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0 290
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tS 9RO
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M
•
•
tac
DIC
•
•
k
•
JW
•
•
po
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•
nt
Ml
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•
Figure 3-8. Relationship between stack and acid dewpoint temperature for each day during Orimulsion 100
demonstration testing at NB Power Dalhousie Station (New Brunswick Power 1989).
3-13
-------
SO3 emissions and eliminate any visible plume, even though there is no regulatory requirement for
installing the system (Irvine and Eagles 1998). This approach may be necessary in cases where other
means of SOs reduction have not been successful.
Kansai Electric Power Company Osaka No. 4
The Osaka No. 4 boiler of Japan's Kansai Electric Power Company (Kansai) was converted to operate
using Orimulsion in 1994, and results of emission and performance testing were reported in 1996
(Kaneko et al. 1996). The 156 MWe boiler was originally designed for coal and oil firing in 1960,
and has burned only oil since 1970.
Reported CO emissions from both Orimulsion 100 and heavy fuel oil (HFO) were consistently less
than 100 ppm for O2 levels ranging from 0.6 to 3.0%. CO emissions from Orimulsion 100 appeared
to be slightly higher than for HFO at O2 levels less than 1%, but were otherwise nearly the same for
both fuels.
NOX emissions ranged from approximately 120 ppm at 0.6% O2 to approximately 200 ppm at 3% O2
when using Orimulsion 100 and from approximately 80 ppm at 0.8% excess O2 to approximately
120 ppm at 3% O2 when firing HFO (all values corrected to 4% O2). Uncontrolled SO2
concentrations from Orimulsion 100 combustion were reported as approximately 2500 ppm,
corrected to 1% O2. CO, NOX, and SO2 concentrations for Orimulsion 100, heavy fuel oil, and
nonemulsified Orinoco bitumen during testing at Osaka No. 4 are shown in Figure 3-9.
PM emissions and unburned carbon in the ash at the Osaka No. 4 boiler measured during operation
with Orimulsion 100, heavy fuel oil, and Orinoco bitumen showed that emissions decreased as stack
O2 levels increased. PM emissions were slightly higher and unburned carbon levels were
approximately the same when using Orimulsion compared to firing with heavy fuel oil. Unburned
carbon levels were measured as slightly higher for heavy fuel oil than for Orimulsion 100 at O2 levels
less than about 1%, and slightly lower than for Orimulsion for higher O2 levels. Reported SO3
emissions increased as O2 level increased for both Orimulsion 100 and heavy fuel oil, with emissions
during Orimulsion firing being consistently higher than those measured during heavy fuel oil firing.
Figure 3-10 shows emissions of PM, unburned carbon, and SO3 from Orimulsion 100, heavy fuel oil,
and Orinoco bitumen at the Osaka No. 4 plant.
Kashima-Kita Electric Power Company
The Kashima-Kita Electric Power Company of Japan is also using Orimulsion for electric power
generation. Olen and Alcantara (1993) noted that the plant made extensive modifications to the ESP
to handle the ash generated by the combustion of Orimulsion. A third field was added to the existing
ESP to handle the greater ESP particle loading. Part of the increased particle loading was due to the
injection ammonia for conversion of SOs to particulate ammonium sulfate. This approach has also
been applied to the Osaka No. 4 boiler. Long spiked discharge electrodes are also used in the
Kashima-Kita ESP to overcome current suppression due to space charge effects. These modifications
have resulted in PM emissions of less than 0.013 lb/106Btu or 20 mg/Nm3 at full load, with an inlet
loading of 550-650 mg/Nm3. This inlet loading compares with roughly 280 mg/Nm3 without
ammonia injection (Olen and Alcantara 1993).
SK Energy Asnaes Unit 5
Orimulsion is also being used in Denmark by SK Energy at the Asnaes Generating Station, Unit 5.
Unit 5 is a 700 MW opposed wall fired unit originally designed to burn coal (Quig and Woodworth
1997).
Orimulsion 100 Use at Asnaes
Emissions testing was conducted when firing Orimulsion 100 in this unit in 1995 (SK Energy
undated). Measurements of CO, CO2, NOX, O2, and SO2 were taken using CEMs, and extractive
samples of SO3, trace elements, and PM were also taken. In addition, measurements of trace elements
in the plant wastewater and scrubber sludge were made. CO measurements for these tests were not
reported in the literature. NOX emissions were reported to be 150-180 ppm, or 30-40% lower than
3-14
-------
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Stack O2, %
Figure 3-9. CO, NOX, and SO2 emissions at Kansai Electric Company Osaka No. 4 plant (Kaneko et al. 1996).
those measured during operation using coal at the same plant. SC>2 emissions were measured at 315
mg/Nm3, and SO3 emissions at 7.2 mg/Nm3. Across the heat exchanger (air preheater), SC>2
concentrations dropped from 7,228 to 6,672 mg/Nm3, with the FGD system reducing SO2
concentrations by 95%. SO3 emissions dropped from 301 mg/Nm3 upstream of the heat exchanger
to 16.6 mg/Nm3 downstream, with the scrubber reducing SO3 concentration by less than 57%. PM
emissions were measured at 12.1 mg/Nm3, with a mass emission rate of 16.6 kg/hr. O2 levels were
measured at 5.6% during these tests (SK Energy undated).
The tests conducted at Asnaes also measured particle size distributions using a cascade impactor.
Less than 1% of the total particle mass captured during these tests was larger than 1.3 pn in diameter,
3-15
-------
and 75% were smaller than 0.35 (im. These measurements are shown in Figure 3-11.
Measurements of trace metal concentrations in the flue gas, the captured fly ash, in wastewater, and in
scrubber sludge were also made during the tests at Asnaes. These effluent streams were analyzed for
concentrations of Al, As, Cd, Cr, Cu, Ca, Hg, Mn, Mg, Ni, Pb, Se, V, and Zn. Concentrations of these
metals in the stack gas are presented in Table 3-4. The reported stack emission concentrations are
somewhat surprising, since both Ni and V concentrations are reported as below detection limits, while
measurable quantities of Mg and Se are reported with relatively high levels of Se in both the solid and
gas phase fractions. These results are in contrast to the reported trace element concentrations in the
fly ash, shown in Table 3-5. The fly ash Ni and V concentrations are very high, at 14,000 mg/kg for
Ni and 59,000 mg/kg for V (measured in dry samples). The Mg level is also quite high, as would be
expected because of the Mg content of the fuel. The measurement of the Asnaes stack sample and
the fly ash suggest that in this case the Ni and V emissions are primarily in the collected fly ash and
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Figure 3-10. Emissions of PM, unburned carbon, and SO3 at Kansai Electric Company Osaka No. 4 plant
3-16
-------
(Kanekoetal. 1996).
45%
40%
35%
30%
I 25%
o 20%
+J
§ 15%-
n*
10%
5%
0%
0.01
0.1 1
Particle Size, jam
10
Figure 3-11. Particle size distribution for PM from the combustion of Orimulsion 100 measured at SK Energy
Asnaes Unit 5 (SK Energy undated).
Table 3-4. Stack trace metal emissions in mg/Nm3 measured at Asnaes Unit 5 (SK Energy undated).
Al
As
Cd
Cr
Cu
Ca
Hg
Mn
Mg
Ni
Pb
Se
V
Zn
Solid Phase
< 0.178
< 0.685
< 0.0071
< 0.0214
< 0.0214
0.0294
< 0.443
< 0.0178
< 0.0045
< 0.0712
< 0.0712
1.30
< 0.712
0.0116
Gas Phase
0.0356
< 0.0356
< 0.0004
< 0.0018
< 0.0018
< 0.0535
2.00
0.0047
0.0445
< 0.0035
< 0.0035
4.71
< 0.0356
< 0.0039
Total
< 0.214
< 0.721
< 0.0075
< 0.0231
< 0.0231
0.0294<1)
<2.45
< 0.0225
< 0.0491
< 0.0747
< 0.0747
6.01
< 0.747
< 0.0155
No. of non-detects (of 4
solid and 4 gas phase
measurements total)
4 solid, 0 gas
3 solid, 2 gas
4 solid, 4 gas
4 solid, 4 gas
4 solid, 4 gas
0 solid, 2 gas
4 solid, 0 gas
4 solid, 0 gas
1 solid, 0 gas
4 solid, 4 gas
4 solid, 4 gas
0 solid, 0 gas
4 solid, 4 gas
0 solid, 1 gas
1. The "Total" value may not add up to the sum of the
non-detects in individual runs.
Solid Phase" and "Gas Phase" values due to
3-17
-------
not in the emitted flue gas or PM.
Tests were also conducted to determine the levels of trace metals in the scrubber sludge.
Measurements were taken during operation using coal and Orimulsion to allow an evaluation of the
differences in trace elements in the sludge when using the two fuels. Table 3-6 presents the
concentrations of the 14 metals listed above plus iron (Fe) measured in the scrubber sludge. As
would be expected, the concentrations of Mg, Ni, and V are significantly higher during Orimulsion
100 operation compared with coal, while slightly higher levels of Hg and Se were found in the
samples taken during operation with coal. The Cd concentration was also somewhat higher in the
Orimulsion sludge sample than in the coal sludge sample, although it is not clear why this difference
occurred.
Orimulsion 400 Use at Asnaes
Additional testing was conducted in spring 1999 at Asnaes Unit 5 following conversion of the plant
to Orimulsion 400 (Gibb 1999). NO, O2, SOs, and trace element concentrations were measured, as
were particle size distributions. NO measurements showed an increase from 100 mg/Nm3 (80 ppm) at
320 MW load to about 200 mg/Nm3 (160 ppm) at 620 MW load during Orimulsion 400 firing. O2
levels were maintained between 2.0 and 2.5% for these tests. SO3 concentrations were reported at 15-
20 ppm at the ESP inlet during full load operation. Reported SO3 concentrations dropped to 4-7
ppm at the ESP outlet and to about 1 ppm at the stack, indicating substantial levels of reduction by
the ESP and the FGD system at Asnaes.
PM concentrations were reported to average 87 mg/Nm3 at the ESP inlet during Orimulsion 400
firing, although the two measurements reported indicated a substantial variation, at 61 and
114 mg/Nm3. Measurements at the ESP outlet averaged 2.83 mg/Nm3, resulting in an ESP efficiency
Table 3-5. Trace metal concentrations in Orimulsion 100 fly ash in mg/kg (unless otherwise noted) measured at
Asnaes Unit 5 (SK Energy undated).
Al
As
Cd
Cr
Cu
Ca
Hg
Mn
Mg
Ni
Pb
Se
V
Zn
Fly Ash, As-
supplied, mg/kg
0.065%
12
0.99
42
12
NIVK1)
1.1
0.011%
11%
12,000
9.8
22
51,000
44
Fly Ash, Dry,
mg/kg
0.075%
13
1.1
49
14
NM
1.3
0.013%
13%
14,000
11
26
59,000
51
Wastewater,
mg/L
0.1082
0.0025
0.016
0.0066
0.0042
NM
0.0004
0.87
NM
0.055
0.03
0.14
0.812
0.018
1. Not measured.
3-18
-------
of 96.7%. Stack emissions were measured slightly higher than ESP emissions, possibly due to mist
from the FGD system. Stack PM emissions averaged 3.3 mg/Nm3 for 3 test runs.
PM size distributions were also measured at the ESP inlet and outlet and at the stack using cascade
impactors during Orimulsion 400 firing. Approximately 79% of the PM mass was smaller than 2.5
(jm in diameter at the ESP inlet, compared to 41% at the ESP outlet and 87% at the stack. The total
mass concentration of particles less than 2.5 (jm in diameter averaged 69 mg/Nm3 at the ESP inlet,
1.16 mg/Nm3 at the ESP outlet, and 2.87 mg/Nm3 at the stack. Based on the reported values, the ESP
removed 98% of particles less than 2.5 (jm in diameter and 91% of the particles larger than 2.5 (jm in
diameter. Reentrainment of larger particles was hypothesized as one reason for the lower removal
efficiency of the ESP for the particles larger than 2.5 (jm in diameter (Gibb 1999).
PM composition was also measured at the same three locations during the Orimulsion 400 tests at
Asnaes. Gibb (1999) reported percentages of several oxides and SO3 in the collected PM for each of
the test runs. The majority of PM entering the ESP was vanadium pentoxide (X^Os), at 47%. SO3
made up 38.7% of the PM mass at the ESP inlet, and the remainder was composed of nickel oxide
(NiO) and oxides of calcium, magnesium, sodium, and Fe. The percentage of SOj, in the PM
increased and that of V2O5 decreased as the PM passed through the pollution control system. PM at
the stack was 0.7% V2O5 and 75.7% SO3. NiO made up 0.13% of the PM at the stack, with the rest of
the PM being composed of the remaining oxides noted above.
ENEL Brindisi Sud Units 1 and 2 and Fiume Santo Plant
Brindisi Sud Units 1 and 2 are 660 MWe wall-fired boilers operated by the Italian utility, ENEL.
Brindisi Sud Unit 1 was originally designed to burn coal, and is equipped with low NOX burners, OFA,
Table 3-6. Trace metal concentrations
Orimulsion 100 from Asnaes
in dry scrubber sludge samples taken during operation with coal and
Unit 5 (SK Energy undated).
Al
As
Cd
Cr
Cu
Ca
Hg
Mn
Fe
Ni
Pb
Se
V
Zn
Mg
Sludge, coal
operation, mg/kg
7.7%
13
91
120
130
15%
21
1.3%
3.2%
330
130
290
220
1300
3.3%
Sludge,
Orimulsion 100
operation, mg/kg
7.6%
14
130
130
130
11%
10
1.9%
3.7%
1500
110
180
3300
1500
5.7%
3-19
-------
flue gas recirculation, selective catalytic reduction, and a limestone-gypsum absorber FGD system.
Planned modifications made for Orimulsion use included adding new sootblowers and installing an
MgO injection system in the economizer to protect boiler surfaces from SOj, condensation (Bertacchi
et al. 1997). The Fiume Santo plant, located in Sardinia, was also converted to Orimulsion in 1999.
This plant was converted directly from heavy fuel oil to Orimulsion 400. Measurements of trace
metal emissions were made following conversion of the plant to Orimulsion 400, and the results of
these measurements are shown in Table 3-7 (ENEL 1999).
Past Operations
Orimulsion has been used at several plants under normal operating conditions either as short-term test
programs over a period of a few weeks or as longer-term evaluations lasting as long as several years
to examine the performance of plants when using Orimulsion. In each case, Orimulsion 100 was
used and no testing was conducted using Orimulsion 400.
Florida Power & Light Company Sanford Plant
A short-term demonstration test of operation using Orimulsion 100 was conducted at the Florida
Power & Light (FPL) Sanford Plant in 1991. The tests were conducted primarily to evaluate the
combustion characteristics and potential pollutant emissions when using Orimulsion. During the tests,
multi-cyclone PM controls were used, and were determined to be ineffective in removing the small
PM generated from Orimulsion 100 combustion (Olen and Alcantara 1993).
The tests took place over a 10 day period, with CEM and extractive samples taken during steady state
operation and during operation with sootblowing. The test results were well documented, including
reporting of quality assurance and quality control measurements, in a report describing the results
(Entropy 1991). NOX emission rates measured during these tests ranged from 0.463 to 0.576 lb/106
Btu when using Orimulsion 100, with the emission rate increasing with load as shown in Figure 3-12.
SO2 emission rates remained relatively constant between 4.15 and 4.23 lb/106 Btu, with no significant
variation due to load or sootblowing. PM emission rates for individual tests ranged between 0.128
and 0.215 lb/106 Btu and did not change appreciably with load. As would be expected, PM emission
rates did indicate an increase during sootblowing operation, as seen in Figure 3-13 (Entropy 1991).
Note that fewer tests were conducted both at high (90-100%) load and during sootblowing operation
than were conducted at medium (50-90%) load, resulting in less certainty with respect to the
Table 3-7. Emissions of trace metal compounds during tests of Orimulsion 400 at ENEL Fiume Santo Plant
(ENEL 1999).
Element
As
Be
Cd
Co
Cr(lll)
Cr(VI)
Cr (total)
Cu
Hg
Mn
Ni (total)
Concentration, ug/Nm3
2.7
0.1
0.2
0.6
7.7
7.7
15.4
6.8
0.9
7.3
14.1
Element
Pb
Pd
Pt
Rh
Sb
Se
Sn
Te
Ti
V
Concentration, ug/Nm3
5.5
2.9
1.4
1.0
0.1
6.1
0.8
0.1
1.2
7.2
3-20
-------
Oca
.90
3 n EC
4_> U.9U
CD :
*° 0 54
aT
-a n 50
(Q U.9U
o
W A >,e
(/) 0 46
mn AA
X !
° 042
2 U.*rA
n An
• Stc
• Stc
n So
o So
ady St<
ady St<
Dtblowi
jtblowi
ite, Medium Lo
ite, High Load
ig, Medium Lo
ig, High Load
B
n
.
•
ad
ad
•
"
%
•
250 270
290 310 330
Load, MW
350 370
Figure 3-12. NOX emission rates as a function of load measured during testing of Orimulsion 100 at the Florida
Power & Light Sanford Plant (Entropy 1991).
measurements taken at high load and during sootblowing than those taken during steady state,
medium load conditions.
The reported PM emission rates at the Sanford plant were similar to the ESP inlet (uncontrolled)
levels reported during the Dalhousie Orimulsion demonstration tests. NOX emissions were reported as
being essentially the same as those from the combustion of heavy fuel oil in the same plant under
similar conditions of excess air and air preheat levels. The heavy fuel oil was mechanically atomized
and the Orimulsion was steam atomized during these tests (Olen and Alcantara 1993).
In addition to measurements of NOX, SO2, and PM, measurements of total hydrocarbons (THCs),
metals, and sulfuric acid mist (including SO3) were also taken during the Orimulsion 100 tests (CO
was not measured). THC emissions were less than 7 ppm for all but one of the conditions tested, with
an average of 5.2 ppm. The single condition exceeding 7 ppm found THC stack concentrations of
15.9 ppm. One set of metals emission rate measurements were taken during steady state operation
at high load. Three measurements were taken during a single test day under similar conditions.
Metals measured were antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead,
manganese, mercury, Ni, phosphorus, selenium, silver, thallium, V, and zinc. Emission rates of all
metals except for Ni and V were less than 36 lb/1012 Btu, with mercury emission rates measured at
0.21 lb/1012 Btu. Ni emission rates averaged 3,650 lb/1012 Btu and V emission rates averaged 14,500
lb/1012 Btu. In each case, the PM control device in use was a multiclone. Sulfuric acid mist emission
rates were also measured during a single test day, with an average emission rate of 0.00719 lb/106 Btu
being reported (Entropy 1991).
PowerGen Ince and Richborough
Two plants, both operated by PowerGen pic in the United Kingdom, have operated using Orimulsion
3-21
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0.25
0.00
O)
If
O)
if
(0
•a
(0
O)
_c
o
o
o
o
Figure 3-13. Average PM emission rates as a function of test condition measured during testing of Orimulsion
100 at the Florida Power & Light Sanford Plant (Entropy 1991). PM control was multi-cyclone for
these tests.
100 as their primary fuel, but are no longer using the fuel. Their experience with the fuel and the
emissions associated with its use remain relevant, however. Ince Generating Station is a 2-unit plant,
each unit rated at 500 MWe, originally designed to use fuel oil. Ince used approximately 4.8xl06
tons of Orimulsion between 1991 and the end of 1995, with an average load factor of 70% and
availability of 94% during that period. Richborough Generating Station is a 3-unit plant, with each
unit rated at 120 MWe, originally designed to burn coal, but later converted to burn oil. The
Richborough plant began commercial operation using Orimulsion in 1991, and used approximately
1.65x106 tons of Orimulsion 100 between 1991 and the end of 1995 (Tombs 1996).
Initial operation with Orimulsion at Ince required the use of a propane support burner due to
excessive shearing and subsequent breakdown of the fuel. Development and application of new
atomizers for use with Orimulsion and other liquid fuels resulted in stable combustion, allowing for
the use of Orimulsion without need for support fuel. These tests were among the first to use
Orimulsion, and subsequent reports of operations at other facilities have not indicated any need for
auxiliary fuel during normal operation.
The Ince unit was operated at very low Q^ levels, below 0.1% excess Q%, with negligible carbon-in-ash
3-22
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(< 0.5%). Operation at such low O2 levels resulted in high CO emissions, on the order of 1000 ppm,
which was allowable in the U.K. during the period of Orimulsion use at the plants. The low O2 level
was desired to minimize formation and emissions of SO3. PM emissions at Ince were typically 30
mg/m3 or less, with approximately 3,300 tons/yr (3,000 tonnes/yr) of low density ash collected. The
ash had a median diameter of less than 1 (jm and a resistivity of 1010 to 1011 ohm-cm, which is within
the range in which collection by ESP is feasible. As is currently being done at the Dalhousie plant,
the ash generated at Ince was mixed with water to increase the density and to improve the handling
characteristics. PowerGen also evaluated the potential for recovering the V present in the ash through
a process that was tested in Germany (Tombs 1996). The ESP at Ince was specifically designed to
collect the fly ash generated by Orimulsion combustion. The ESP was designed to reduce full load
PM emissions from about 350 mg/Nm3 to approximately 35 mg/Nm3, a 90% reduction (Olen and
Alcantara 1993).
Use of Orimulsion at Ince resulted in a thin deposit of ash building up on the boiler tube surfaces and
changes in the boiler temperature distribution. Modifications to the boiler to minimize the impacts of
the changed heat transfer characteristics included removal of the radiant superheater originally above
the front wall, increasing the number of sootblowers in the convective section from 10 to 32, and
converting several of the sootblowers from compressed air to steam operation (Tombs 1996).
Richborough Generating Station was closed in March 1996, and Ince Generating Station was closed
in March 1997, both due to financial considerations (PowerGen 1998a, 1998b).
Energie-Versorgung Schwaben Marbach III Power Plant
Trial testing of Orimulsion operation was conducted at the Energie-Versorgung Schwaben AG
Marbach III Power Plant in Marbach, Germany in 1993. The emissions tests associated with the trials
were different than those conducted in other locations, as they focussed on the impacts on ambient
pollutant concentrations. The trials lasted for 16 days, with ambient measurements of CO, NO2, SO2,
HC1, PM, metals, and dioxins and furans being taken during that period. Calculations were made to
estimate the contribution of the plant to the background during operation with Orimulsion.
Contributions to the ambient pollutant concentrations were determined to be significant if they were
greater than 1% of the limit, guide, or target value (collectively referred to as appraisal value) set by
the local air pollution authority or if they were 10% of the background or "preliminary" pollution
level. Table 3-8 shows the appraisal value, the maximum contribution from emissions during
Orimulsion operation, the percent contribution from Orimulsion emissions, and the background
ambient pollutant concentration. As seen in the table, only Ni and V reported to be from Orimulsion
operation were of concern in terms of the criteria noted above, and only SO2 and precipitated PM, Ni,
and V were greater than 0.1% of the appraisal value (TUV Sudwest 1993).
Planned Operations
This section describes testing or studies conducted for plants that have planned for use of Orimulsion.
In some cases, these plans were not carried out, but the information presented here remains relevant to
evaluating the differences between Orimulsion and other fossil fuels. Plans were made to convert the
Florida Power & Light Company Manatee Plant from heavy fuel oil to Orimulsion in 1998. The
Manatee Plant consists of two 800 MWe units designed for firing heavy fuel oil. Changes in the heat
transfer characteristics due to the higher fuel water content and the nature of the ash deposited on
boiler surfaces would have required modifications to the boiler and to the fuel receiving, storage, and
handling system. These changes would have resulted in a derating of the unit by approximately 8%
(Blum et al. 1998).
Additional pollution controls were also planned for the plant. The existing multicyclone particle
collectors were to be replaced with ESPs for PM control, and a wet limestone scrubber was to be
added as an FGD system. The ESP was designed to remove approximately 94% of the PM generated
by Orimulsion 100 combustion to meet an emission rate of 0.02 lb/106 Btu. The FGD system was
designed to control approximately 95% of the uncontrolled SO2 concentrations, with a target
emission rate of approximately 0.22 lb/106 Btu. NOX controls for the units were to consist of low
3-23
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Table 3-8. Comparison of long-term contributions to ambient concentration or deposition of pollutants from the
combustion of Orimulsion 100 at Marbach III Power Plant to appraisal values and background
concentrations or deposition during trial tests of Orimulsion combustion (TUV Sudwest 1993).
Pollutant
CO
NO2
SO2
Suspended PM
Precipitated PM
PCDD/F
HCI
Hg
As in suspended PM
Cd in suspended PM
Cr in suspended PM
Co in suspended PM
Ni in suspended PM
Pb in suspended PM
V in suspended PM
Cd in precipitated PM
Pb in precipitated PM
Unit
ug/m3
ug/m3
ug/m3
ug/m3
g/(m2 d)
pg/m3
ug/m3
ng/m3
ng/m3
ng/m3
ng/m3
ng/m3
ng/m3
ng/m3
ng/m3
ug/(m2 d)
ug/(m2 d)
Appraisal
Value
10,000
80
140
150
0.65
0.016
100
1000
5
40
7
5000
11
2000
.(1)
250
5
Maximum
contribution from
Orimulsion
operation
0.002
0.024
0.22
0.009
0.0007
0.00009
0.0002
0.00018
0.00028
0.00019
0.0019
0.0011
0.21
0.0037
0.94
0.0003
0.018
% contribution of
Orimulsion
emissions to
appraisal value
0.00002
0.03
0.16
0.006
0.11
0.056
0.0002
0.00002
0.0056
0.0005
0.03
0.00002
1.9
0.0002
13.4(2)
0.006
0.007
Background
concentration
1000
40
20
50
0.18
0.01-0.02
10
3
7
1
5
1
4
12
7
<0.5
20
1. No value set.
2. % of background concentration.
NOX burners in combination with reburning. The reburning system was designed to use Orimulsion
100 as the reburning fuel and to achieve an additional 47% reduction over the baseline emissions
with LNBs alone. The NOX control technologies were designed to achieve an emission rate of 0.1255
lb/106 Btu (Blum et al. 1998).
Reburning Development
Full-scale testing of Orimulsion 100 as a reburn fuel was conducted at Illinois Power Company's
Hennepin Power Station in 1997 (Rostorfer et al. 1997, 1998). Hennepin Unit 1 is a 74 MWe
tangentially-fired unit burning an Illinois #6 coal. The unit became operational in 1953, and had
been the site of a U.S. DOE Clean Coal Technology project to demonstrate natural gas reburning as a
NOX control technology (Folsom 1995). The Orimulsion reburn project required several
modifications to the plant to allow Orimulsion to be used on Unit 1, since the unit was not designed to
use liquid fuels. The barge used to transport the Orimulsion was used as the storage tank, and
temporary heat-traced insulated fuel lines were installed to move Orimulsion from the barge to the
plant. A Moyno positive displacement pump was used as the fuel supply pump. Four Orimulsion
injectors were installed in three corners of the boiler, with the fourth corner having only three
3-24
-------
The Orimulsion reburn tests achieved a 64% NOX reduction at the Hennepin Station at a 16% reburn
fuel injection rate. NOX emissions were reduced from a baseline value of 0.75 lb/106 Btu to a level of
0.27 lb/106 Btu during continuous testing over nearly one full day. This compares with a reduction
of 67% (to 0.24 lb/106 Btu) when using natural gas as the reburn fuel. OFA capacity at the plant
limited the reburn rate to 16% for Orimulsion, but modeling predictions indicated further reductions
were possible at higher reburn rates if additional overfire air capacity could be obtained. Loss on
ignition values were noted as being "within the range of typical plant experience" (Rostorfer et al.
1997, 1998). Figure 3-14 shows the results of short-term reburn testing at Hennepin, and shows NOX
emission rates during baseline operation, use of OFA only, and reburning with natural gas and
Orimulsion. Figure 3-15 presents NOX emission rates as a function of % reburn fuel injection for
natural gas and Orimulsion.
A general overview of reburning with Orimulsion was discussed by Schimmoller (1998). This article
states that the capital costs associated with reburning are estimated at between $15 and $20/kW, which
was noted as being cost effective in comparison with other NOX control technologies. The use of
Orimulsion as a reburning fuel was estimated as being more cost effective than natural gas and to
provide greater NOX reductions than coal. Depending upon the price differential between Orimulsion
and natural gas, annual costs can be similar to overfire air or selective noncatalytic reduction
(Schimmoller 1998).
Engineering Studies
Several engineering and feasibility studies have also been conducted to evaluate the use of
Orimulsion in existing plants and to evaluate potential performance of pollution control systems for
Orimulsion applications. These studies are primarily analytical in nature as opposed to experimental,
but provide additional information on the potential for emissions control in Orimulsion-fired plants.
0.8
go-7
<°0 0.6
1 0.5
o 0>
'55
I 0.3
LU
xO.2
O
Z 0.1
• Bas
• OF4
. Nati
A Reb
Orin
. 4 Art
* 100
Reb
jline
iral Gas
Liming
lulsion
urning
"I
• •
A A
" r
•
0
* <**r
10 15
% Excess Air
20
25
Figure 3-14. NOX emissions measured during the reburning demonstration at Hennepin Station. Baseline
emissions, emissions with overfire air only, and emissions using natural gas and Orimulsion 100 as
reburn fuels are shown (Rostorfer et al. 1997).
3-25
-------
0.35
S 0.30
(O
o
0.25
0.20
(/>
| 0.15
UJ
ox 0.10
0.05
0.00
I
n l»
• C
i
[
atural i
)rimuls
9
ID [
J
(
3as
on 100
u
4
i i
P
• • <
; ••
t
c
i~i
*
8 10 12 14 16 18
Reburn Input, % of Total Heat Input
20
Figure 3-15. NOX emissions measured during the reburning demonstration at Hennepin Station using natural gas
and Orimulsion 100 as reburn fuel, as a function of % reburn fuel input (Rostorfer et al. 1997).
Feasibility Studies
Energy and Environmental Research Corporation (EERC) conducted a feasibility study with Intevep,
the research arm of the Venezuelan petroleum company Petroleos de Venezuela, S.A. (PDVSA) to
evaluate the technical and cost aspects of converting a small utility plant to Orimulsion. The study
evaluated the conversion of a two-unit plant firing heavy fuel oil to Orimulsion. The plant evaluated
had two 105 MWe tangentially-fired boilers, designed and built in the late 1950s, with ESPs installed
for PM control.
The study evaluated operational, economic, and environmental impacts of the conversion, and
concluded that the conversion could be made without reducing the plant's rating while meeting all
applicable environmental regulations, and with a return on investment of 27.8%. The conversion
specified the installation of a wet FGD system to meet the applicable SO2 emissions limits,
modification of the burner atomizers, increased sootblowing capacity, new induced draft fans to meet
the greater volume of flue gas and the higher pressure drop with the FGD system, and improved
instrumentation and control systems (EER/Intevep undated).
An in-depth feasibility study evaluating the conversion of New England Electric Company's Salem
Harbor Station to Orimulsion was conducted, and evaluated a number of different alternatives from
conversion of a single unit to conversion of all four units at the plant. Several alternative pollution
control configurations were also considered in the study. For a conversion of the 440 MWe Unit 4
alone, it was determined that a wet limestone FGD system would eventually be required to achieve a
93% reduction in SO2 emissions and a selective catalytic reduction (SCR) system would be required
to achieve 76% NOX reductions (both reductions based on uncontrolled levels). In addition, a wet
ESP was recommended for control of any visible plumes associated with emissions of SQ^. The final
proposed design also included wastewater treatment facilities, production of gypsum from the
scrubber solids, and extensive boiler modifications to maintain unit rating and heat rate. Other
options included the installation of a reburning system upstream of the SCR to reduce the cost of
NOX controls and modification of the ash handling system to allow for the different characteristics of
Orimulsion fly ash. The feasibility study determined that applicable air pollutant emission limits
3-26
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could be met when using Orimulsion if appropriate pollution control equipment were installed
(Lentjes Bischoff 1997). Currently, the Salem Harbor Station is not actively considering conversion
to Orimulsion.
A more general overview of issues associated with conversion to Orimulsion was conducted by
Bechtel Corp. (Khan 1996). This study found that converting to Orimulsion from heavy fuel oil
would result in an economic break-even for a plant that had a 33% capacity factor if the capital cost
of conversion was $167/kW. For a capital cost of $250/kW, the break-even capacity factor was
estimated at 48%. For capacity factors above these points, the plant would generate a net savings.
The study also noted that more effective environmental controls were likely to be required when
using Orimulsion than when using heavy fuel oil, but that emissions regulations could be met with
proper pollution control equipment. The study also noted that a plant that converted to Orimulsion
would be likely to face more stringent emissions limits, since units that repower may be required to
meet new source performance standards or controls for prevention of significant deterioration (Khan
1996).
Pollution Control Equipment Analyses
All of the Orimulsion-fired plants reporting a reduction of SO 2 emissions by FGD employ wet
limestone forced oxidation (WLFO) systems, with the exception of the Mitsubishi unit, which uses a
Wellman-Lord process that was in place prior to conversion to Orimulsion (Olen 1998b). The
extensive industrial experience with WLFO scrubbers and the ability of these systems to produce
gypsum as an end product have made them the preferred system for application to Orimulsion-fired
boilers. However, an analysis of lime spray dryer FGD designs indicate they may be competitive on a
cost basis with WLFO systems for units with high sulfur emissions over the life of a plant. One of the
difficulties associated with spray dryer designs is the production of calcium sulfite, which has no
commercial value and must be landfilled, in contrast to the salable gypsum produced by WLFO
systems. Mixing Portland cement with the spray dryer solid waste was evaluated to determine whether
such a mixture could stabilize the wastes physically and chemically. At 10% mixture of cement with
spray dryer waste was determined to result in the best physical characteristics (density, hardness) and
the lowest leachability of constituents such as Ca, V, and sulfates (Kuchibotla et al. 1998). To date,
no plants are known to be considering spray dryers for FGD.
Other Work
The studies below do not have direct application to Orimulsion use in utility boilers, but are included
to demonstrate the range of work that has been conducted on applications of Orimulsion.
Diesel Engines
Orimulsion has been tested in diesel engines, but no emissions data are currently available from these
tests. The tests were intended to evaluate whether Orimulsion could be used as a diesel engine fuel,
and were tested in three different low- and medium-speed engines (Marruffo and Sarmiento 1997).
Gasification
Orimulsion has been evaluated by researchers in the U.S. and Japan as a feedstock for gasification
processes. In the U.S. study, Orimulsion was found to be a better feedstock than coal-water slurries,
as measured by the volume of product gas per unit fuel or per unit O2 required (Quintana and Davis
1990). The U.S. tests were conducted over a 9-day period, with 144 tons of Orimulsion gasified
(Marruffo and Sarmiento 1997). Few details were available regarding the Japanese work, but no
significant problems in using Orimulsion as a gasification feedstock were reported (Inumaru et al.
1993).
Briquetting of Coal Fines
Coal cleaning operations produce a waste product consisting of water and relatively high levels of
fine coal particles. It is desirable to recover these coal fines for use as a fuel. However, the large
surface areas and high water contents make it difficult to dewater the fines in preparation for
production of pellets. Orimulsion has been evaluated as a binding agent, and the results of these tests
3-27
-------
indicate that it can be effectively used in the coal fine dewatering and pelletizing process (Kan et al.
1998). This process of adding a bitumen to the coal fines before dewatering, called GranuFlow™,
was developed by the Department of Energy's Federal Energy Technology Center (FETC), and has
been demonstrated at FETC and several commercial-scale coal cleaning plants. (Wen and Killmeyer
1996, Zitron et al. 1998).
Cement Kilns
Tests were conducted at the Arawak Cement Company in Barbados to evaluate the use of Orimulsion
as a fuel in cement kilns. One evaluation of the tests stated that Orimulsion could be used without
additional emissions control equipment because the higher SO2 generation of the fuel would be offset
by the reaction of the sulfur with the cement clinker (Marruffo and Sarmiento 1997). The cement
company has since begun commercial operation using Orimulsion (Bitor America 2000).
Desu Ifurization
A study of hydrodesulfurization of both Orinoco bitumen and Orimulsion was conducted using
several Ni and molybdenum catalysts. The catalytic treatments removed up to 75% of S in the
bitumen and up to 58% of S in Orimulsion (Sharma and Olson 1995).
Summary of Previous Work
This section will summarize the results reported from the various studies discussed above to provide
an overall view of the performance of Orimulsion related to operations and emissions. Summary
plots and tables for several pollutants are included for as much of the existing data as possible.
Operational Issues
Fuel Handling and Atomization
As noted in the previous chapter, Orimulsion is highly sensitive to extremes of temperature and
excessive shear rates during handling. Exceeding the recommended storage and handling limits on
these parameters may lead to a breakdown of the emulsion and poor combustion performance. The
characteristics of the fuel make it important to select the proper atomizing nozzle and approach to
ensure the fuel does not degrade. While many units that fire heavy fuel oil use mechanical
atomization, plants that have converted from heavy fuel oil to Orimulsion have also converted their
fuel atomizers to use steam rather than mechanical pressure. Poor atomization may lead to poor
burnout or flame instability and increased emissions of CO, unburned carbon, or NOX.
Excess O2
In general, plants using Orimulsion tend to operate at somewhat lower excess O2 levels than plants
using heavy fuel oil, and at significantly lower excess O2 levels than plants using pulverized coal. For
example, Ince Generating Station was able to consistently operate at O2 levels less than 0.1% in the
stack with carbon-in-ash levels of less than 0.5%. O2 levels are reduced to the lowest point consistent
with acceptable CO and unburned carbon to minimize the amount of SO3 formation and to improve
boiler thermal efficiency.
Boiler Efficiency
Boiler efficiency depends upon several factors, including the efficiency of converting carbon in the
fuel to CO2, the heat transfer efficiency of the boiler tubes, and the mass of flue gas exiting the boiler.
Each of these can be affected by converting to Orimulsion from other fuels. Carbon conversion
efficiency when firing Orimulsion tends to be very high and, based on unburned carbon in ash
measurements, tends to be higher than for heavy fuel oil. For both fuels, however, carbon conversion
efficiency is usually greater than 99% and may approach 99.9% in well-operated systems.
Orimulsion has been shown to result in reduced boiler tube heat transfer and reduced efficiency due
to more solid deposits than are typically observed during heavy fuel oil use. The high water content
of Orimulsion significantly impacts boiler thermal efficiency by adding a substantial mass of a
chemically inert compound to the flue gas mass, resulting in greater levels of heat being carried out
of the boiler rather than being transferred to the steam. While Orimulsion usually requires less excess
O2 and therefore less air into the boiler to maintain acceptable CO and unburned carbon, the resulting
3-28
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O2 and therefore less air into the boiler to maintain acceptable CO and unburned carbon, the resulting
reduction in flue gas mass is not great enough to overcome the increase from the water in the fuel.
Boiler efficiency changes measured during the Dalhousie Orimulsion 100 demonstration tests showed
a reduction of boiler efficiency from 87.2% when firing heavy fuel oil with a clean boiler to 84.5%
when burning Orimulsion 100 with a clean boiler. When operating with a fouled boiler, the boiler
efficiency dropped from 86.4% when using heavy fuel oil to 82.6% when using Orimulsion 100
(New Brunswick Power 1989). This efficiency drop may increase total mass emissions from a plant if
it must operate at a higher fuel input rate to maintain output.
Boiler Fouling
As noted above, boiler fouling appears to be greater with Orimulsion 100 than when using heavy fuel
oil, which can lead to reduced boiler efficiency. In addition, increased sootblowing to minimize the
buildup of deposits can result in higher PM emissions during the sootblowing periods if the PM
control equipment is not adequately designed to handle the increased inlet PM loadings. Finally,
Orimulsion may use a Mg-based compound to help reduce the fouling properties of the fuel. In
Orimulsion 100, this was mixed with the fuel prior to shipping, and with Orimulsion 400, the Mg
compound is injected into the fuel just prior to its entering the burners. In both cases, this results in
additional Mg emissions that are not associated with the hydrocarbon fuel itself.
Recent data indicate that the fouling associated with Orimulsion 100 use may be significantly reduced
when using Orimulsion 400. The Asnaes Power Station has experienced reduced levels of boiler
fouling when using Orimulsion 400, and has thus been able to achieve long term operation at 625
MW versus the 610 MW achievable using Orimulsion 100. Unit 5 is currently limited to 625 MW due
to reheater temperature limitations rather than due to boiler tube fouling. The plant planned to cease
any injection of Mg-based reagents based on the results of several months of operation with
Orimulsion 400 (Miller and Shores 1999).
Air Emissions
CO
CO emissions are strongly influenced by the excess O2 levels at which a plant is operated. Emission
concentrations as low as 30 ppm have been reported during full-scale operation. Significantly higher
CO emission concentrations are likely as O2 levels drop below those generally reported in the
literature, with one instance of emission concentrations as high as 1000 ppm reported. Table 3-9
presents a summary of reported CO emission concentrations from both full- and pilot-scale tests. In
general, CO emission concentrations seem to be the same or slightly lower when using Orimulsion
than when using heavy fuel oil, although conditions and equipment differences at individual plants
may result in Orimulsion CO levels being higher than those from heavy fuel oil.
NOX
NOX emissions measured when firing with Orimulsion are reported to be slightly higher than those
measured when firing with heavy fuel oil and lower than those measured when firing coal at full
Table 3-9. CO emissions measured during pilot- and full-scale tests for heavy fuel oil and Orimulsion 100.
Plant or test
Dalhousie #1 Demonstration Tests
(New Brunswick Power 1989)
Osaka No. 4 (Kaneko et al. 1996)
PowerGen (Allen and Beal 1996)
Hungarian Power (Barta et al. 1996)
Scale
Full
Full
Pilot
Pilot
O2 Level During Test
0.7%
0.7-3.0%
0.3-1.2%
1%
CO (using Heavy
Fuel Oil)
60 ppm
100 ppm
30-45 ppm
40 ppm
CO (using
Orimulsion 100)
30 ppm
100 ppm
33-36 ppm
61 ppm
3-29
-------
scale. Reported NOX measurements taken during firing of Orimulsion 400 indicate that use of
Orimulsion 400 may result in slightly lower NOX emissions than those from the firing of Orimulsion
100. Pilot- scale studies tended to indicate Orimulsion firing reduces NOX emissions compared to
those from firing heavy fuel oil. These results are summarized in Table 3-10. Differences in
operating conditions and burner performance can significantly impact NOX emissions. Conditions
that are appropriate for heavy fuel oil or coal firing may not be optimum for operation using
Orimulsion. Further discussion of NOX emissions and the use of low NOX burners will be presented
below.
SO2 and SO3
Uncontrolled SO2 emissions are primarily dependent upon the sulfur content of the fuel.
Orimulsion's high sulfur content results in uncontrolled SO2 emissions of approximately 2500 ppm,
consistent with uncontrolled SO2 emissions from other fuels with similar sulfur contents. Once
formed, control of SO2 is fundamentally the same for Orimulsion as for other fuels, and there has
been no report of any difference in achieving adequate SO2 control when using Orimulsion
compared to other fuels.
SO3 emissions are a consequence of the fuel sulfur content and the high level of V, which acts as a
catalyst to promote formation of SO3 from SO2 particularly when there is adequate O2 for the
reaction to occur. SO3 emissions are reduced to some degree by operating at low excess O2 and by
Table 3-10. NOX emissions measured during pilot- and full-scale tests for heavy fuel oil and Orimulsion. Unless
otherwise noted, the post-conversion fuel is Orimulsion 100 and all values are corrected to 3% C>2-
Plant or test
Dalhousie #1 Demonstration Tests
(New Brunswick Power 1989)
Dalhousie #1 and #2, using
Orimulsion 400 (Irvine and Eagles
1998)
Osaka No. 4 (Kaneko et al. 1996)
Asnaes Unit 5 (SK Energy undated)
Asnaes Unit 5, using Orimulsion 400
(Gibb1999)
Sanford Unit 4 (Entropy 1991)
PowerGen (Allen and Beal 1996)
Hungarian Power (Barta et al. 1996)
ENEL (XCL burner) (De Santis et al.
1996)
ENEL (TEA burner) (De Santis et al.
1996)
Scale
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pilot
Pre-conversion NOX
and fuel
180-190 ppm
Heavy fuel oil
125ng/J
Orimulsion 100
120 ppm
Heavy fuel oil
250 ppm(1)
Coal
150-180 ppm
Orimulsion 100
NM
420 ppm
Heavy fuel oil
270 ppm
Heavy fuel oil
410 mg/Nm3
Heavy fuel oil
240 mg/Nm3
Heavy fuel oil
Post-conversion NOX
180-215 ppm
105-110ng/J
(Orimulsion 400)
200 ppm
(uncontrolled)
150-180 ppm
80-160 ppm
Orimulsion 400
400 ppm
390 ppm
220 ppm
190 mg/Nm3
320 mg/Nm3
1. 02 level not reported.
3-30
-------
the use of Mg-based additives. Table 3-11 shows the reported SO3 emissions from full- and pilot-
scale tests.
PM
Particulate matter emissions from Orimulsion depend upon the ash content of the fuel, the carbon
burnout, and to a slight degree the formation of SOj, aerosols. The PM generated by the combustion
of Orimulsion tends to be very small, with the majority of the particle mass less than 1 (am in
diameter, and in some cases with the majority of particle mass less than 0.3 (am in diameter.
Orimulsion PM contains substantial levels of Mg, Ni, and V that have been reported as being highly
water soluble, resulting in potential difficulties in disposal in landfills due to subsequent leaching of
these metals. The captured fly ash has been reported as being much less dense than the fly ash
generated from the combustion of heavy fuel oil, resulting in problems in solid handling and
transport. In some cases, the addition of water to the ash after collection has been shown to
substantially increase the ash density and its potential for high wind-borne fugitive emissions during
transport and storage. Orimulsion PM has resistance sufficient to allow it to be controlled using ESPs
(discussed in more detail below).
Comparisons of PM emissions from Orimulsion operation with those from heavy fuel oil or coal will
be highly dependent upon the characteristics, particularly the ash content, of the other fuel being
used. Table 3-12 presents the PM emissions reported from full- and pilot-scale tests of Orimulsion
use. Comparisons of PM size distributions is also highly dependent upon operating parameters such
as fuel atomization (a function of fuel flow and temperature and atomizing method), making general
comparisons between different fuels difficult if not impossible. Table 3-13 presents reported PM size
distributions for Orimulsion and heavy fuel oils burned in the same units.
Hazardous Air Pollutants and Metals
Substances considered to be hazardous air pollutants (HAPs) are listed in Title III of the 1990 Clean
Air Act Amendments (CAAAs), which includes 189 compounds and compound classes (Clean Air
Act 1990). As seen in the above discussions, the emphasis on HAP measurements has been oriented
Table 3-11. Reported SO3 emissions measured during pilot- and full-scale tests for heavy fuel oil and Orimulsion.
Unless otherwise noted, the post-conversion fuel is Orimulsion 100.
Plant or test
Dalhousie #1 Demonstration Tests
(New Brunswick Power 1989)
Osaka No. 4 (Kaneko et al. 1996)
Asnaes Unit 5 (SK Energy undated)
Asnaes Unit 5, using Orimulsion 400
(Gibb1999)
Sanford Unit 4 (Entropy 1991)
Hungarian Power (Barta et al. 1996)
ENEL (De Santis et al. 1996)
Scale
Full
Full
Full
Full
Full
Pilot
Pilot
P re-conversion SO3
and fuel
NM<1)
4-12 ppm (uncontrolled)
Heavy fuel oil
NM
NM
NM
8.5 ppm
Heavy fuel oil
NM
Post-conversion SO3
2-15 ppm
44-68 ppm (uncontrolled)
7.2 mg/Nm3
Orimulsion 100
1 ppm
Orimulsion 400
0.0072lb/106Btu<2)
13.2 ppm
<5 ppm
1. Not measured.
2. Sulfuric acid mist (including SO3)
3-31
-------
toward metals. This is consistent with the findings of EPA's Report to Congress on HAP emissions
from utility boilers, which found that organic HAPs are not likely to be emitted from large utility
boilers in significant amounts (EPA 1998). In addition to the measurements presented above, one
study reported measurements of As, Cd, Pb, Hg, Ni, and V (not listed as a HAP in the 1990 CAAAs)
and emissions of organic compounds including polycyclic aromatic hydrocarbons (PAHs), dioxins
and furans, benzene, and formaldehyde. This study compared emissions from coal, heavy fuel oil,
and Orimulsion, and concluded that HAP emissions from Orimulsion were lower than those for heavy
fuel oil for all 10 compounds reported, and were lower than those for coal for 7 of the 10 reported
compounds. Table 3-14 shows the measurements reported in this study (Allen and Beal 1997).
In general, HAP and metal emissions are generally low, even when uncontrolled. Emissions of V are
consistently the highest trace element emission associated with Orimulsion. Concentrations of Ni and
V in fly ash may result in difficulties in landfilling due to their high levels (10,000 ppm and higher)
and the reported high water solubility of these compounds in the fly ash. Several efforts have been
made to use the ash as a feedstock for V recovery, and this is currently being done by the Dalhousie
Plant (Irvine and Eagles 1998).
CO2
Emissions of CO2 are important from the perspective of global climate change, but are not currently
Table 3-12. Reported PM emissions measured during pilot- and full-scale tests for heavy fuel oil and Orimulsion.
Unless otherwise noted, the post-conversion fuel is Orimulsion 100.
Plant or test
Dalhousie #1 Demonstration Tests
(New Brunswick Power 1989)
Osaka No. 4 (Kaneko et al. 1996)
Kashima-Kita (Olen and Alcantara
1993)
Asnaes Unit 5 (SK Energy undated)
Asnaes Unit 5 using Orimulsion 400
(Gibb1999)
Sanford Unit 4 (Entropy 1991)
lnce"B" (Tombs 1996)
PowerGen (Allen and Beal 1996)
Hungarian Power (Barta et al. 1996)
ENEL (De Santis et al. 1996)
Scale
Full
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pre-conversion PM and
fuel
105mg/Nm3
(uncontrolled)
1 00-220 mg/Nm3
(uncontrolled)
Heavy fuel oil
NM(1)
NM
NM
NM
NM
0.05-0.1 lb/1Q6Btu
Heavy fuel oil
415mg/Nm3
Heavy fuel oil
NM
Post-conversion PM
250 mg/Nm3
(uncontrolled)
1 80-300 mg/Nm3
(uncontrolled)
280 mg/Nm3
(uncontrolled^2)
12.1 mg/Nm3 (controlled)
Orimulsion 100
3.3 mg/Nm3 (controlled)
Orimulsion 400
0.16 lb/1Q6Btu
(uncontrolled)
350 mg/Nm3
(uncontrolled)
0.3-0.35 lb/1Q6Btu
(uncontrolled)
160 mg/Nm3
(uncontrolled)
220-260 mg/Nm3
(uncontrolled)
1. Not measured.
2. Measured without ammonia injection.
3-32
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Table 3-13. Reported PM size distributions measured during pilot- and full-scale tests for heavy fuel oil and
Orimulsion.
Plant or test
Dalhousie #1 Demonstration Tests
(NB Power 1989)
Asnaes Unit 5 (SK Energy undated)
lnce"B" (Tombs 1996)
ENEL(DeSantisetal. 1996)
Scale
Full
Full
Full
Pilot
Pre-conversion PM size
distribution and fuel
% (by mass)
< 10 urn
75
% (by mass)
< 1 urn
45
Heavy fuel oil
NM<1)
NM
87.1
NM
NM
51.3
Heavy fuel oil
Post-conversion PM size
distribution
% (by mass)
< 10 urn
98
100
% (by mass)
< 1 urn
80
97
Median diameter < 1 urn
73.1
21.2
1. Not measured.
Table 3-14. Emissions of selected hazardous air pollutants from coal, heavy fuel oil, and Orimulsion, in lb/1012 Btu
(Allen and Beal 1997).
Arsenic
Cadmium
Lead
Mercury
Nickel
Vanadium*3)
PAH
Dioxins/Furans
Benzene
Formaldehyde
Coal
2.4
1.0
3.7
6.4
21
NA
6x1 0-4
2.5x1 0-6
5.2
3.8
Heavy Fuel Oil
NA(1)
0.2
3.9
5
123
141
0.013
1.3x10-5
1.1
32
Orimulsion
ND(2)
ND
0.18
ND
3.7
125
ND
3.5x1 0-6
4.6
4.7
1. Not available
2. Not detected
3. Not on the list of HAPs in the 1990 Clean Air Act Amendments
regulated. Nevertheless, given the level of concern regarding the potential for global climate change,
Orimulsion has been evaluated for its potential for CO2 emissions compared with coal and heavy fuel
oil. Because Orimulsion has a higher hydrogen to carbon ratio than coal, the amount of CO2 emitted
during combustion of Orimulsion will be lower than that emitted during the combustion of coal.This
characteristic of Orimulsion has been exploited at the Asnaes Power Station. Asnaes staff report that
the plant emits 16% less CO2 using Orimulsion 400 than was emitted when burning pulverized coal.
This difference, in combination with the plant size, is large enough to account for 1/20 of the Danish
government's national goal of 20% CO2 reduction (Miller and Shores 1999).
An extensive study of the use of Orimulsion in integrated gasification combined cycle (IGCC) power
3-33
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and chemical plants and the capture of CO2 in these systems was carried out by Parsons (1997) for
the International Energy Agency (IEA). This study compared CC>2 emissions for several scenarios of
gasification and combined cycle operation using Orimulsion as a feedstock, and did not compare
Orimulsion to other fuels. An IEA summary of the study noted that the emissions of CCVkWh
generated from Orimulsion in an IGCC were lower than those of coal but higher than those of natural
gas (Parsons 1997).
Air Pollution Control
The pollutant concentrations generated by the combustion of Orimulsion are such that some degree
of air pollution control will be required, although the level of control is likely to vary according to
the requirements of individual locations. It is important, then, to understand whether available control
technologies can be used to reduce emissions from the combustion of Orimulsion to an acceptable
level. This section will discuss the reported experience with applying air pollution control
technologies to plants firing Orimulsion.
NOX Control
NOX concentrations can be controlled using a number of technologies, divided into two main types -
combustion controls and post-combustion controls (Muzio and Quartucy 1997). The combustion
controls are those that rely on alteration of the combustion conditions to minimize formation of NOX
in the combustion zone, while post-combustion technologies convert NOX already formed to nitrogen
or other products. Combustion controls are much more sensitive to changes in fuel properties,
although the presence of specific compounds can also adversely impact the performance of post-
combustion NOX controls.
Both low NOX burners (LNBs) and reburning have been evaluated for use in plants using Orimulsion,
while the only reported post-combustion technology used at Orimulsion-fired plants is selective
catalytic reduction (SCR). Reported results indicate that each of these technologies can be
successfully applied to control NOX from Orimulsion combustion, although the designs of the
technologies must account for the specific characteristics of the fuel. In this respect, Orimulsion is
similar to other fuels in that fuel-specific and site-specific factors must be taken into account when
designing and operating NOX control equipment. The particular technology or combination of
technologies used at a specific plant will depend upon factors such as cost and required NOX emission
level.
Low NOX Burners
Pilot-scale tests have verified that NOX emissions from Orimulsion combustion can be controlled
using the same techniques used for low NOX combustion with other fuels. Staged combustion
methods used in low NOX burners (LNBs) for other fuels have been demonstrated for Orimulsion,
resulting in NOX reductions similar to those measured using other fuels (De Santis et al. 1996, Allen
and Beal 1996, Quig and Woodworth 1997). In general, LNBs can achieve 30-50% reduction of NOX
from baseline emissions.
Reburning
Reburning has been demonstrated at a full-scale plant, using Orimulsion as a reburn fuel. Emission
reductions of greater than 60% were demonstrated on a unit burning coal as the base fuel. Reported
pilot-scale testing of reburning using Orimulsion as the reburn fuel have confirmed its ability to be
used as a reburn fuel, and measurements of Orimulsion reactivity also support its use in such
applications. Orimulsion reburn installation costs have been estimated at approximately $15/kW
(Rostorfer et al. 1997).
Selective Catalytic Reduction
In cases where very high NOX reductions are required, selective catalytic reduction (SCR) may be
used on Orimulsion-fired units. This type of system was installed at the Osaka No. 4 boiler in Japan,
allowing the unit to reduce its uncontrolled emissions to less than 30 ppm, an 85% reduction from the
uncontrolled NOX emissions reported in Table 9 (Hall and Lee 1998). One issue associated with SCR
3-34
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use in Orimulsion-fired systems is the interaction between the ammonia (NH3) injected for NOX
control and the SO3 present in the flue gas. These can react to form particulate ammonium bisulfide,
which can significantly increase the loading on the PM control equipment.
SO2 and SO3 Control
Control of SC>2 is achieved using conventional wet limestone forced oxidation scrubbers by all units
currently burning Orimulsion. Several of these systems produce gypsum from the spent scrubbing
liquor, minimizing the mass of solid waste that must be landfilled. 862 reductions of 90% or greater
are typical of these systems, allowing controlled emissions of approximately 200 ppm to be achieved
with conventional control methods. There have been no problems with scrubber operation unique to
Orimulsion use that have been reported in the literature. The major issue associated with Orimulsion
use when using scrubbers is the higher Ni and V contents of the scrubber sludge and gypsum. The
Ni and V contents of these by-products have not been found to prevent either the sale of gypsum
from Orimulsion or the safe disposal of scrubber sludge.
PM Control
In general, PM control can be achieved by using either ESPs or baghouses (fabric filters), although
there have been no long term evaluations of baghouse performance on an Orimulsion-fired power
plant. In general, however, either type of system should be applicable to Orimulsion, provided that
the equipment is appropriately designed and operated.
ESPls
Uncontrolled PM levels of between 250 and 1,000 mg/Nm3 are likely in units using Orimulsion, with
the higher levels caused by the use of additives such as ammonia to the flue gas for neutralization of
SOs. PM from Orimulsion combustion is small in size, with 80-90% being less than 4 (am in
diameter. Particle size distributions of Orimulsion PM (without flue gas additives) have typically
been measured as having a bimodal distribution, with approximately 65% of the particle mass having
a mean diameter of 0.4 (jm and the remaining 35% having a mean diameter of 4.0 (am. Sootblowing
tends to increase the amount of the larger size particles (approximately 4.0 (am in diameter) to result
in roughly equivalent mass percent of the larger and smaller particle sizes (Olen 1998b).
PM control for utility plants burning Orimulsion has been demonstrated to be as high as 97% at the
Kashima-Kita plant in Japan (Olen and Alcantara 1993). PM removal efficiencies of between 86 and
94% have been measured at other plants, with outlet emission rates ranging from 20 to 35 mg/Nm3
(Irvine and Eagles 1998, Olen and Alcantara 1993). In some cases, existing ESPs have been
modified by increasing the number of ESP fields or installing different discharge electrodes. These
changes have improved performance over the original systems designed primarily for collection of
PM from heavy fuel oil combustion. Other design and operational issues include an increase in flue
gas volume due to higher water content of the fuel and higher furnace exit temperatures, increased
ash resistivity, and higher inlet particle loading due to injection of ammonia or to boiler surface
fouling. The low density of the collected ash requires some preparation of the ash to increase density
and reduce fugitive dust; addition of water is usually adequate to solve these problems (Irvine and
Eagles 1998, Tombs 1996). The reported data indicate that the design and operational problems can
be addressed so that adequate PM control is achieved by ESPs, even in cases where high particle
loadings result from injection of ammonia.
Baghouses
Pilot-scale tests of baghouse performance concluded that pulse jet baghouses may be suitable for use
with Orimulsion if adequate protection of the bag materials was ensured. Such protection included
the pre-coating of the bags with a sorbent material for low acid dewpoint operation, and co-injection
of a sorbent material during high acid dewpoint operation. Similar tests of a reverse gas baghouse
were inconclusive, primarily because of limited testing due to cessation of tests prior to completion of
the expected test matrix. No full-scale operating unit currently uses baghouses for control of PM
from Orimulsion.
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Solid Residue Disposal
The ash generated by the combustion of Orimulsion and collected by PM control equipment tends to
be less dense than that generated by the combustion of heavy fuel oils. In some instances, the
procedures used to handle the captured ash required modification to improve handling capabilities.
This typically involved the addition of a slight amount of water to the ash to increase density and
improve ash particle agglomeration (Irvine and Eagles 1998).
The Ni and V contents of the captured ash are relatively high, and the ash can be processed to recover
these elements. Ash from the Dalhousie Plant and from the Asnaes Generating Station is shipped to
plants in the U.S. and Germany, respectively, for V recovery (Irvine and Eagles 1998, Miller and
Shores 1999).
3-36
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Chapter 4
EPA Pilot-Scale Experimental Approach and Equipment
A series of combustion tests were conducted at the NRMRL combustion research facilities in Research
Triangle Park, NC to provide data on emissions from Orimulsion and heavy fuel oil generated in a
single combustion system under controlled conditions.
Approach
The approach chosen for the test program was to measure emissions from the two formulations of
Orimulsion and a commercially available heavy fuel oil in a single test combustor. This approach
was believed to result in data that would allow direct comparison of the impact of the different fuels
on air pollutant formation and emissions. By using this approach, changes in emissions due to
different burner or combustor design parameters would be eliminated, and the only significant
factors remaining would be the combustion conditions and the fuels.
Each test condition was run four times to allow the repeatability of the test condition and results to be
quantified. Flue gas constituents and properties to be measured were CO, CO2, NOX, O2, PM, SO2,
SOs, and THC concentrations; particle size distributions; concentrations of As, Be, Cd, Cr, Cu, Fe, Mn,
Mg, Ni, Sb, V, and Zn; and concentrations of volatile and semivolatile organic compounds. Table 4-
1 shows the test matrix developed for the test program, with the number of measurements of each of
the above constituents or parameters and the methods used in quantifying each constituent or
parameter.
Test Equipment
All tests were conducted on a single research combustor under test conditions that were held as
constant as possible. Some differences were anticipated due to differences in combustion
characteristics between Orimulsion and heavy fuel oils. Operating at conditions appropriate to each
fuel was viewed as more desirable than maintaining a single condition, since real world operation
would adjust combustion conditions to achieve optimum performance based on the particular fuel.
In particular, O2 level was intended to be set based on the minimum O2 that could be achieved without
generating excessive CO. "Excessive" CO was defined to be approximately 50-100 ppm for these
tests. To the extent possible, all other test conditions were intended to remain constant for all fuels.
Package Boiler Simulator
The package boiler simulator (PBS) is a 3xl06 Btu/hr horizontally-fired unit capable of burning
natural gas or liquid fuels in an environment that simulates a water wall boiler. A schematic of the
unit is shown in Figure 4-1. The PBS burner has an air-atomizing nozzle that is capable of handling
the unit's full load heat input, based on No. 6 fuel oil. Since the PBS was operated at heat input rates
well below full load, it was adequate to handle the higher volume of Orimulsion required to maintain
a steady heat input rate. The PBS has a 10 in. inside diameter refractory lined burner section
connected to a water cooled transition section of the same inside diameter. The transition section
allows staged air or fuel injection through radial or axial ports or through two ports on the horizontal
axis aligned 45° from the unit centerline. The transition section connects to the Dowtherm cooled
boiler section, which has a 24 in. inside diameter and is 110 in. long. The combustion gases pass out
of the boiler section to the vertical stack, where sampling ports are located for taking extractive
samples. Inspection and access ports for injection probes or optical sampling are located along the
boiler wall and at the stack end of the boiler.
Flue gases from the PBS are ducted to the facility's air pollution control system (APCS), which
consists of a 4xl06 Btu/hr secondary combustion chamber, a fabric filter, and a wet acid gas scrubber.
The APCS allows the PBS to operate under poor combustion conditions that intentionally generate
higher than normal pollutant emissions during research studies without emitting those excessive
pollutants to the environment. The PBS has been used in studies of low NOX combustion and
reburning for control of NOX (Linak et al. 1985, Miller et al. 1998).
4-1
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Table 4-1. Test matrix for EPA pilot-scale tests of Orimulsion air pollutant emissions.
Condition
Fuel
Boiler Load (Btu/hr)
Excess O2 (%)<1)
MgOH Injection
Number of test runs
CO, CO2, NOX, O2, SO2, THC
(CEMs)
PM concentration (Method 5)
Particle Size Distribution
(cascade impactor)
Particle Size Distribution
(SMPS)
Metal concentration
(Method 29)
Volatile Organic
concentration (Method 0010)
Semivolatile organic
concentration (Method 0030)
SO3<2) (MACS train)
1
Orimulsion 100
1,000,000
3
No
4
Continuous during test
3 tests
3 tests
1 test (5 or more runs
per test)
3 tests
3 tests
3 tests
3 tests
2
Orimulsion 400
1,000,000
3
Yes
4
Continuous during test
3 tests
3 tests
1 test (5 or more runs
per test)
3 tests
3 tests
3 tests
3 tests
3
No. 6 Fuel Oil
1,000,000
3
No
4
Continuous during test
3 tests
3 tests
1 test (5 or more runs
per test)
3 tests
3 tests
3 tests
3 tests
1. Actual test ©2 level was intended to be set based on the
ppm.
2. Miniature acid-condensation system (DeVito and Smith
minimum ©2 at which CO remained less than 50-100
1991)
Fuel Supply System
The fuel supply system can influence the stability of emulsified fuels such as Orimulsion. The
system should minimize shear rates through pumps, piping, and fittings as much as possible, and
should be able to maintain the appropriate temperature range during operation. The original fuel
supply system used by the PBS was designed for heavy fuel oil and required modification before
Orimulsion could be fed to the boiler. During operation with heavy fuel oil, the original fuel supply
system (shown schematically in Figure 4-2) was used.
For operation with Orimulsion 100 and Orimulsion 400, the fuel supply system was modified to use a
lower shear Moyno pump rather than the original gear pump and to eliminate the pressure relief
valves and the continuous circulation loop used in the original supply system. The modified fuel
supply system is shown in Figure 4-3.
A Mg-based additive was injected into the boiler during testing of Orimulsion 400. The additive was
Mg(OH)2, and was injected into the flame at a rate of between 0.35 and 0.54 g/min during operation
at IxlO6 Btu/hr. This injection rate resulted in a molar ratio of between 2.1 and 3.8 mol Mg to 1 mol
V in the fuel.
Instrumentation
The PBS has continuous emission monitors (CEMs) for measurement of combustion gas
composition. Concentrations of CO, CO2, NOX, O2, SO2, and THC are measured by CEMs and
4-2
-------
Fuel Pump
To Rue Gas Cleaning System
Extractive
Sampling
Ports
Axial
Injection
Port
Dowtherm
Oulet
Combustion
Air Blower
Radial
Injection
Port
Burner
Section
Transition
Section
Date
Aquisifon
System
Figure 4-1. Schematic of Package Boiler Simulator.
continuously recorded using a computerized data acquisition system (DAS). Stack gases are
extracted through a fixed stainless steel probe into Teflon® tubing and transported to the CEM
sample conditioning system. The sample gases are dried using a Hankeson® dryer and particles are
removed by a filter. A portion of the sample is then diverted to the NOX analyzer, with the remaining
sample passing through a Dryrite® canister and then to the other gas analyzers. THC measurements
use a heated stainless steel sampling line that is maintained at 350 °F. The CEM system is shown
schematically in Figure 4-4.
Continuous Emission Monitors
The CO and CC>2 analyzers were Rosemount® model 880A infrared analyzers. Two CO analyzers
were used, one having an operating range of 0 to 1000 ppm (CO low) and one having an operating
range of 0 to 5% (CO high). The CO2 analyzer has an operating range of 0 to 20%. A Rosemount®
model 951A chemiluminescence NOX analyzer was used to measure concentrations of NO and NO2
in the range of 0 to 1000 ppm. The analyzer can be used to measure either NO or NOX. In the NOX
operating mode, the unit converts any NO2 to NO prior to porting the gas to the detector. The
analyzer was operated in NO mode during the test program
The O2 analyzer was a Rosemount® model 755R paramagnetic analyzer, with a measurement range of
0 to 25%. SO2 concentrations were measured using a Du Pont photometric model 400 analyzer.
THC was measured using a Rosemount® 402 hydrocarbon analyzer, which operates using a flame
4-3
-------
Combustion Air
-XL
v
Return
Atomizing
Air
Package Boiler Simulator
Pressure
Regulator
Solenoid
Valve
Totalizer
Pressure
Regulator
To Other Units
Relief
Valve ""/K
Temperature
Regulator
Supply
Pump
From
Orimulsion
Supply
MQpen Ball
Valve
M Closed Ball
Valve
Fuel Line
Wiring
©Temperature
Sensor
©Pressure
Gauge
Figure 4-2. Schematic of fuel feed system for heavy fuel oil.
ionization detector. The THC measurement is given as equivalent methane (CH4), and has an
operating range of 0 to 50,000 ppm.
Data Acquisition System
The DAS is a computer-based system separate from the CEMs. It uses a Macintosh® computer and
Strawberry Tree® data acquisition cards, and logs inputs from each of the CEMs at constant intervals
4-4
-------
Package Boiler Simulator
From
Oil
Feed
System
Pressure Solenoid
Regulator valve
Pressure
Regulator
A
-©
Moyno Pump
Drum Heater
NX| Open Ball Valve
^ Closed Ball Valve
Fuel Line
Wiring
(l) Temperature Sensor
(PJ Pressure Gauge
Figure 4-3. Schematic of fuel feed system for Orimulsion 100 and Orimulsion 400.
that can be adjusted according to the needs of each experiment. Selected data are shown on the
screen during operation, and all data are stored on the unit's hard disk drive for later retrieval and
reduction. Data logging is conducted only during testing or calibration.
Dilution Sampling System
A dilution sampling system (shown schematically in Figure 4-5) was used to collect samples for use
in toxicity testing by EPA's National Health and Environmental Effects Research Laboratory
(NHEERL). This system collects large quantities of PM for the toxicological studies. The system is
capable of sampling 10 ft3/min of flue gas. The sample passes through a modified Source
Assessment Sampling System (SASS) cyclone and is then diluted with 100 fWmin of clean ambient
4-5
-------
Sample
Pump A To Vent
To Air
Pollution
Control
System
PBS
Stack
Package
Boiler
Simulator
\Calibration
Gas Valves
Sample
Pump
Sample
Probe
Line Filter
Figure 4-4. Schematic of continuous emission monitoring system.
air using a perforated cone assembly. Rapid uniform dilution cools the sampled gases and PM to
nearly ambient temperature within a residence time of approximate 3 s. Isokinetic sampling
conditions were not possible for these large dilution samples. Further details regarding the dilution
sampler's construction and operation are presented by Steele et al. (1988).
The SASS cyclone preseparator produces 50 and 95% particle collection efficiencies at
approximately 1.8 and 2.5 (am aerodynamic diameter, respectively, at standard conditions. The small
fraction of PM that passes through the cyclone is collected on large (25.5 in. diameter) Teflon coated
glass fiber filters for subsequent analysis (Linak et al. 1999).
Scanning Mobility Particle Sizer
A Thermo Systems, Inc., scanning mobility particle sizer (SMPS) was used to measure particle size
4-6
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Non-iso kinetic
Sampling
Probe
Filler
H EPA/Activated
Carbon Filter
Flow
ample Control
Blower
Pressure Gauge
Temperature Sensor
Figure 4-5. Schematic of high volume dilution sampling system.
distributions for particles with diameters in the range of 0.01 to 1.0 (jm diameter. The SMPS
classifies and counts particles using principles of charged particle mobility through an electric field.
The SMPS was configured to yield 54 channels evenly spaced (logarithmically) over the operating
size range. SMPS samples were extracted from the PBS stack isokinetically and diluted with filtered
nitrogen (N2) to a ratio of approximately 5 parts N2 to 1 part stack gas. Dilution flow was controlled
using a mass flow controller and total sample flow measured with a laminar flow element. Both
devices were calibrated using a Gilabrator® bubble flow meter. Additional details of the system
design and operation are described by Scotto et al. (1992) and Linak et al. (1994).
Scanning Electron Microscope
Samples were also collected on silver membrane filters and analyzed using a SEM equipped with an
energy dispersive x-ray (EDX) spectrometer. These analyses provided morphological information of
individual particles. Particles were extracted from the stack location using the same sampling system
and dilution as used by the SMPS described above. However, these particles were directed through a
stainless steel filter holder containing a 47 mm silver membrane filter. Sampling times of
approximately 30-60 s provided a sufficient quantity of particles for analysis. Silver filters were used
to improve conductivity and minimize particle charging caused by the electron beam.
Sampling Methods
EPA Methods 5 and 29
Particle concentrations were determined using EPA Method 5 (EPA 1994); EPA Method 29 was used
to determine metal concentrations in the flue gases (Garg 1990). The particle concentration option
4-7
-------
was used during the Method 29 operation, but the mercury option was not used, meaning that the
Method 5 procedure used the same train as Method 29, allowing a single sampling train to be used to
determine both PM mass and metal concentrations.
A blank Method 29 sampling train was prepared and set up at the sampling location, and remained at
that location for the duration of sampling. The blank train filter was weighed, and the solutions were
recovered and analyzed with the remaining Method 29 sampling trains to identify possible
contamination. Two Method 29 trains were spiked with known concentrations of target metals and
subsequently analyzed with the other samples to determine laboratory recovery of known
concentrations. Chapter 11 (Quality Assurance) provides additional details concerning the blanks
and spiked samples. The Method 29 samples were analyzed for As, Be, Cd, Cr, Cu, Fe, Mn, Mg, Ni,
Sb, V, and Zn.
EPA Methods 0010 and 0030
EPA Method 0030 was used to sample the concentration of volatile organic compounds (VOCs) in
the flue gases of all three fuels (EPA 1986a). EPA Method 0010 (sometimes referred to as a
Modified Method 5) was used to sample semivolatile organic compounds for all three test conditions
(EPA 1986b). Three samples were taken for the semivolatile organic compounds and triplicate VOC
samples were taken.
Both EPA Method 0010 and 0030 sampling trains were prepared, set up at the sampling location, and
analyzed to identify possible contamination.
Modified CARB Method 501
Particle size distributions were also measured using an in-stack cascade impactor. An Anderson®
impactor was used in a modified California Air Resources Board (CARB) Method 501 (CARB 1990).
This method allows size-segregated samples to be collected for determining either the relative mass
fractions in each size range or the concentration of trace elements in each size range. These tests
modified the CARB method slightly to allow for use in the research combustor. The CARB method
places the impactor precutter in the stack. However, the PBS stack is too small to allow in situ
placement of the impactor, so a buttonhook nozzle is used rather than the straight nozzle specified in
the CARB method. Fewer runs are conducted during research testing than are called for in the CARB
method, with only three runs used during research testing rather than the seven runs specified by the
CARB method.
A blank CARB 501 impactor was also prepared and set up at the sampling location, and its filters
subsequently weighed, to evaluate any contamination of the filters during the sampling procedures.
4-8
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Chapter 5
EPA Pilot-Scale Test Results
Tests measuring air pollutant emissions were conducted on EPA's Package Boiler Simulator during
May and June 1999. The tests measured emissions from the combustion of Orimulsion 100,
Orimulsion 400, and a No. 6 fuel oil. Samples of Orimulsion 100 and Orimulsion 400 were obtained
from Bitor America for the test program, and were shipped from Venezuela as part of normal
shipments to the Dalhousie Generating Station in New Brunswick, Canada.
Test Conditions
To the extent possible, the tests followed the test matrix in Table 4-1. Actual operating conditions
varied from the nominal test conditions in two ways. First, the O2 levels specified in Table 4-1 were
difficult to maintain. Second, the fuel feed system illustrated in Figure 4-2 required modification
before either formulation of Orimulsion could be fed into the PBS over a period required for testing.
These two problems are discussed in more detail below, and in Chapter 10 (Quality Assurance).
Fuel Composition
The composition of the fuel is important for several reasons. First, the fuel energy content will
determine the fuel flow rate required to achieve a given load. Second, the sulfur content of the fuel
will largely determine the SO2 concentration. Third, the fuel nitrogen content can have a significant
impact on NOX formation. And finally, the trace metal content of the fuel will strongly influence the
flue gas concentrations of those metals. Table 5-1 presents the analyses of the three fuels (No. 6 fuel
oil, Orimulsion 100, and Orimulsion 400) supplied to EPA for these tests. Samples were taken from
the fuel drums prior to testing.
02
Maintaining steady levels of O2 at the nominal 3% specified in the test matrix was very difficult, if not
impossible, for the duration of each test run. The PBS was influenced by changes in the stack draft
level and by variations in air flow thought to be due to changes in the atomizing air pressure. Stack
draft level is an issue for this unit because it is connected to the air pollution control system (APCS)
along with several other test combustors. The APCS requires control of the inlet pressure, and
therefore strongly influences the stack draft level of the PBS. Due to leaks in the PBS, changes in
stack draft result in changes in the measured stack O2 level independent of the inlet air flow.
Combustion air flow settings were based both on theoretically determined levels as well as stack O2
measurements to provide a degree of confidence that the O2 level at the burner was adequate.
However, considerable variability in stack O2 levels remained. There appeared to be continuous
fluctuations in atomizing air pressure, probably due to fluctuations in the air compressor (see Figures
4-2 and 4-3). Nevertheless, the flame appeared to maintain good stability and was not observed to
fluctuate or generate significant levels of unburned fuel droplets for any of the three fuels. Several
days of operation provided adequate confidence that the unit was operating well enough to allow
testing to proceed, even though the stack O2 levels varied more than desirable.
O2 levels typically remained below 5%, except for several instances where recorded values exceeded
20% during CEM system failures. Values recorded during such excursions were not included in
calculations of run or condition averages. Average values for the 12 test runs ranged between 2.3
and 4.6%. O2 levels at the burner are believed to be slightly lower than these averages due to leakage
of air into the PBS. Table 5-2 presents the average O2 concentration for each test run and the average
of the four test runs per condition. Plots of the CEM measurements are also presented in Appendix B
for each test run.
Fuel Feed
Initial operation of the PBS and the fuel feed system shown in Figure 4-2 indicated that Orimulsion
100 could be fed through the same system used for heavy fuel oil, despite concerns over excessive
shear rates (See Chapter 2). However, these initial operating periods were too short in duration to
5-1
-------
Table 5-1. Elemental analyses (as received) of the three fuels tested.
Water, %
Carbon, %
Hydrogen, %
Nitrogen, %
Sulfur, %
Ash, %
Oxygen, % (by difference)
Antimony, ug/g
Arsenic, ug/g
Beryllium, ug/g
Cadmium, ug/g
Chromium, ug/g
Copper, ug/g
Iron, ug/g
Lead, ug/g
Magnesium, ug/g
Mercury, ug/g
Nickel, ug/g
Selenium, ug/g
Vanadium, ug/g
Zinc, ug/g
Energy content, Btu/lb
No. 6 Fuel Oil
0.7
86.45
10.23
0.26
2.07
0.08
0.90
0.78
2.6
<0.005
<0.005
0.58
0.76
51
1.8
7.6
<0.005
47
0.13
221
8.9
18,121
Orimulsion 100
23.32
64.20
8.13
0.25
3.05
0.17
0.88
0.57
2.9
<0.005
<0.005
0.235
<0.005
12
1.9
342
<0.005
69
2.9
324
0.90
13,919
Orimulsion 400
28.92
58.12
7.14
0.17
2.23
0.07
3.35
0.35
2.2
<0.005
<0.005
0.20
<0.005
22
1.4
1
<0.005
59
0.04
262
0.37
12,596
Table 5-2. Average O2 stack concentrations for each test run, and average of four test runs, in percent. Values in
parentheses indicate standard deviation for each test run.
Fuel
Orimulsion 100
Orimulsion 400
No. 6 Fuel Oil
Run 1
2.74%
(0.31)
3.96%
(0.58)
4.63%
(0.52)
Run 2
2.62%
(0.73)
3.40%
(0.20)
2.49%
(0.77)
Run 3
3.47%
(0.90)
2.33%
(0.54)
3.88%
(0.78)
Run 4
2.57%
(0.43)
4.37%
(0.62)
2.42%
(0.45)
Average
2.85%
(0.42)0)
3.51%
(0.89)
3.36%
(1.08)
1. Standard deviation values for the condition averages are calculated using the four individual run average
concentrations.
5-2
-------
result in degradation of the Orimulsion, and subsequent operation for longer periods resulted in
clogging of the fuel lines with bitumen that had separated from the water and in unstable and poor
quality flames. The fuel feed system was modified as described in the previous chapter, and this
resulted in much improved operation as well as elimination of the fuel degradation.
Some drift in the fuel flow rate remained, however, although incorporation of an additional pressure
regulator in the fuel line minimized changes during individual test runs. Some variability in fuel flow
remained, resulting in slightly different load levels from one test run to another. These changes were
slight, however, and were not likely to have significantly influenced the measured emissions. Table 5-
3 presents the fuel flows measured during each test run and the average fuel flow for each test
condition.
Calculated load of the PBS during the test runs, based on fuel heat content and measured fuel flow,
was on average, 1,037,000 Btu/hr with Orimulsion 100, 968,000 Btu/hr with Orimulsion 400, and
915,000 Btu/hr with No. 6 fuel oil.
Emission Measurement Results
CO
Average CO emissions were between approximately 15 and 40 ppm (corrected to 3% O2) for all runs.
The average CO emissions for No. 6 fuel oil were slightly lower than for either Orimulsion, but as
Figure 5-1 shows, CO emissions were measured at below 20 ppm for at least one test run for both
Orimulsion formulations. As noted above, CO emissions are strongly dependent upon O2 level, and
much of the variation in CO may be due to changes in O2 levels during the test runs. Average O2
levels for the three conditions were 2.8% for Orimulsion 100, 3.5% for Orimulsion 400, and 3.4% for
No. 6 fuel oil. The Orimulsion tests also showed higher variability in both O2 and CO levels than did
the No. 6 fuel oil tests. Much of this variation was believed to be due to more and larger changes in
O2 level during the Orimulsion test runs than were seen during the No. 6 fuel oil runs.
CO increased significantly for all three fuels as O2 levels dropped below a certain level.
Unfortunately, the variation in O2 levels and the air leakage into the PBS noted above make it
impossible to accurately determine the O2 level at which CO concentrations begin to increase. CO
concentrations typically stayed below 50 ppm until O2 dropped below a threshold value, then
increased rapidly to greater than 1000 ppm. The threshold value differed for different test runs, and
sometimes within a test run. For Orimulsion 100, the threshold O2 value ranged from approximately
1.1 to 2.5% and for Orimulsion 400, the threshold value ranged from 1.8 to 3.5%. For No. 6 fuel
oil, the threshold O2 level ranged from 0.6 to 2.4%. Figure 5-2 plots CO against O2 for each of the
test runs.
CO concentrations also increased to relatively high levels for short periods during testing. These
short-duration spikes occurred at apparently random intervals, and were believed to be caused by
variations in fuel and air flows resulting in transient periods of low excess air. The relatively small
Table 5-3. Average fuel flows for each test run, and average of four test runs. Values in parentheses indicate
standard deviation for each test run.
Fuel
Orimulsion 100
Orimulsion 400
No. 6 Fuel Oil
Run 1
0.1396 gpm
(0.0364)
0.1426 gpm
(0.0633)
0.1013 gpm
(0.0416)
Run 2
0.1418 gpm
(0.0652)
0.1520 gpm
(0.0460)
0.1006 gpm
(0.0332)
Run 3
0.1526 gpm
(0.0199)
0.1641 gpm
(0.0678)
0.1035 gpm
(0.0299)
Run 4
0.1540 gpm
(0.0559)
0.1513 gpm
(0.0781)
0.0972 gpm
(0.0440)
Average
0.1470 gpm
(0.0736)0)
0.1525 gpm
(0.0882)
0.1006 gpm
(0.0264)
1. Standard deviation values for the condition averages are calculated using the four individual run average
concentrations.
5-3
-------
Orimulsion 100 Orimulsion 400 No. 6 Fuel Oil
Figure 5-1. Average CO emissions from the three fuels tested in ppm, corrected to 3% O2. Average values for
each of the 12 test runs and average for each condition are shown.
1200-
0^1000-
* Qrimuteion 100
• Orimufeion 400
-I- No. 6 Fuel Oil
Figure 5-2. CO vs. O2 for selected runs with Orimulsion 100, Orimulsion 400, and No. 6 fuel oil.
5-4
-------
700-
500-
400-
300-
|200-
100-
0-
i
Orimulsion 100 Orimulsion 400 No. 6 Fuel Oil
Figure 5-3. Average NO emissions from the three fuels tested in ppm, corrected to 3% O2. Average values for
each of the 12 test runs and average for each condition are shown. Error bars represent 1 standard
deviation about the average.
size of the combustor makes this unit more sensitive to small fluctuations in fuel and air flows than
would be seen in a full-scale unit.
NOX
Only concentrations of nitric oxide (NO) were measured during EPA's pilot-scale testing. NO
emissions averaged near 500 ppm (corrected to 3% O2) for each of the three fuels. Here, the NO
values were much steadier across test runs for Orimulsion 100 and Orimulsion 400 than for No. 6
fuel oil. Given the range of uncertainty in the average values (indicated by the ±1 standard deviation
error bars in Figure 5-3), it is not possible to discern any significant difference in NO emission levels
between the three fuels. There was a slight drop in NO with decreasing stack O2, similar to what one
would observe from other hydrocarbon fuels. Figure 5-4 shows typical levels of NO concentrations
for the range of O2 levels in the PBS.
SO2andSO3
Likewise, average SO2 emissions as measured using CEMs (presented in Figure 5-5) were found to be
essentially the same for each of the three fuels, at 1000 ppm (corrected to 3% O2). Although the
average SO2 measurement for the No. 6 fuel oil is slightly lower than either of the Orimulsion
formulations, the measured variability in the average value for the fuel oil makes it impossible to state
that there is any significant difference between SO2 emissions from the No. 6 fuel oil used in these
tests and either of the two Orimulsion formulations.
Using the MACS sampling train, SO2 concentrations were measured at 1220 ppm for the No. 6 fuel
oil, 1640 ppm for Orimulsion 100, and 2010 ppm for Orimulsion 400. Based on the analyses of the
fuels' sulfur contents, if 100% of the sulfur were to be emitted as SO2, one would expect SO2
concentrations to be roughly 1000 ppm for the No. 6 fuel oil, 2400 ppm for Orimulsion 100, and
1800 ppm for Orimulsion 400. These values, as well as the CEM measurements, are presented in
Table 5-4.
5-5
-------
700
• Qrimufeion 100
o Orimulsion 400
No. 6 Fuel Oil
Figure 5-4. NO vs. O2 for selected runs with Orimulsion 100, Orimulsion 400, and No. 6 fuel oil.
1200
0^1000
Run 1
Run 2
Run 3
Run 4
| | Average
C/3
Orimulsion 100 Orimulsion 400 No. 6 Fuel Oil
Figure 5-5. Average SO2 emissions as measured by CEM from the three fuels tested in ppm, corrected to 3% O2.
Average values for each of the 12 test runs and average for each condition are shown. Error bars
represent 1 standard deviation about the average.
While the CEM measurements are consistently lower than the MACS measurements, the differences
are not consistent across the fuels. Neither measurement method is consistently higher or lower than
5-6
-------
the corresponding calculated value.
It is unclear why these discrepancies exist. One hypothesis is that the "missing" sulfur (the
differences between the calculated concentrations and the concentrations measured by CEMs) is due
to SO3 formation. However, this would result in SO3 concentrations between 800 and 1400 ppm for
the two Orimulsion formulations, which would be substantially higher than anything reported in the
literature or than what would be expected based on the properties of the fuel. While these values are
slightly higher than the SO2 concentrations measured by CEMs, SO3 concentrations that are roughly
equivalent to SO2 concentrations are not unreasonable. Although the MACS system measured SO3
concentrations of only 1 ppm on two occasions, these measurements are difficult to take correctly,
and may be the source of the error.
A second hypothesis is that the fuel analyses were incorrect. This could account for the differences
between the measured and calculated SO 2 concentrations, but not for the differences between the two
measurement methods. A third hypothesis is that the measurements were incorrect. While this could
explain the discrepancies, both the CEM and the MACS results would have to be in error for this to
explain the differences. The CEMs were calibrated before and after each test run, providing some
indication of CEM data reliability (see Chapter 10 for further discussion of calibration procedures).
There were no indications of problems to such a degree that would satisfactorily explain the
difference between CEM and calculated SO2 concentrations.
A fourth possible reason for lower measured SO2 concentrations could be a reaction with the Mg
additives on the filter of the sampling equipment. Mg additives were not used during testing of the
No. 6 fuel oil, but were used (in different forms) for both Orimulsion formulations.
A comparison of data from full-scale plants reported in Chapter 3 shows that uncontrolled SO2
concentrations ranged between 2200 and 2400 ppm when burning Orimulsion 100. This is
consistent with the calculated value for Orimulsion 100 in Table 5-4. Given the consistency between
CEM and calculated SO2 concentrations for the No. 6 fuel oil, it is reasonable to conclude that the
CEM measurements reported for these pilot-scale tests are probably low, particularly for the
Orimulsion tests. There may have been some interference between flue gas components and the
CEM's SO2 measurements during the Orimulsion tests, although there have been no indications of
such interferences discussed in the literature.
The available evidence does not suggest that the differences in SO2 concentrations for the No. 6 fuel
oil and the two Orimulsion formulations are due to differences in the fuels other than sulfur content.
Full-scale results and understanding of combustion behavior would indicate that uncontrolled SO2
concentrations from Orimulsion will in practice be quite close to the calculated values based on fuel
sulfur content.
PM
PM emissions do show some differences between the three fuels (see Figure 5-6). The Orimulsion
400 and No. 6 fuel oil had PM concentrations that were approximately 25% lower (at 150 mg/Nm3)
than those from Orimulsion 100 at approximately 200 mg/Nm3. The analysis of Orimulsion 100
showed both higher ash levels and higher amounts of magnesium than were present for either of the
other two fuels. These differences are likely to have accounted for the difference in PM
Table 5-4. SO2 concentrations for the three fuels tested as measured by CEM and MACS methods, and as
calculated based on complete conversion of fuel sulfur to SO2.
No. 6 Fuel Oil
Orimulsion 100
Orimulsion 400
CEM Measurements
910
990
1020
MACS Measurements
1220
1640
2010
Calculated Concentrations
960
2400
1820
5-7
-------
concentrations between the three fuels. Loss on ignition (LOI) values were determined for PM
samples from each of the fuels. The samples were collected on the large dilution sampler filter,
downstream of a cyclone designed to remove particles larger than 2.5 (jm in diameter. Of the three
fuels, only the No. 6 fuel oil had any measurable amount of mass in the cyclone catch. The cyclone
catch and samples of the large filters for each fuel were subject to LOI analyses. The filters all
indicated no measurable LOI (above that measured for a blank filter), and the No. 6 fuel oil cyclone
catch had an LOI value of 59%. The high LOI measurement is not unexpected, as the larger particles
in the No. 6 fuel oil sample are likely to be largely unburned carbon.
Particle size distributions show a marked difference between Orimulsion and the No. 6 fuel oil. The
fraction of total particle mass collected on an Andersen cascade impactor is plotted versus particle
size for the three fuels in Figure 5-7. Approximately 80% of the total particle mass captured was
smaller than 1 (jm in diameter for both Orimulsion 100 and Orimulsion 400, compared to 50% of the
particle mass for the No. 6 fuel oil. Approximately 90% of the particle mass was smaller than 2.5 (jm
in diameter for both Orimulsion formulations, compared with approximately 75% for the No. 6 fuel
oil. All three fuels have a bimodal particle size distribution to at least a slight degree, with Orimulsion
400 and the No. 6 fuel oil showing a larger coarse (particles > 6 (am in diameter) mode than the
Orimulsion 100. The coarse mode is likely to be due to incomplete combustion of the bitumen
droplets in the case of Orimulsion and of the fuel spray droplets in the case of the No. 6 fuel oil.
Results from the scanning mobility particle sizing system (SMPS) provide more detail regarding the
particle size distributions for particles smaller than 1 (jm in diameter, as shown in Figure 5-8. Even in
this size range, there are differences in the size distributions. The Orimulsion 400 and No. 6 fuel oil
are quite similar, with modes between 0.06 and 0.08 (am, while the Orimulsion 100 has a smaller
mode at just larger than 0.1 urn. The SMPS measurements for the No. 6 fuel oil show a slight
indication of the mode near 1 (jm, as dV/d(log D p) begins to curve upward for particles larger than
about 0.3 jm.
250-
200-
o
DJ
§ 100-
50-
0-
Orimulsion 100 Orimulsion 400 No. 6 Fuel Oil
Figure 5-6. Average PM emissions in mg/dscm from the three fuels tested. Average values for each of the 12 test
runs and average for each condition are shown. Error bars represent 1 standard deviation about the
average.
5-S
-------
w
"ro
fif)%
50%
90%-
10%
O0/
70%-,
R0%-
40%
90%
lU/o
7 no/.-,
fiO%-
90%
Orimulsion 100
^
1
1 1
Orimulsion 400
'
No. 6 Fuel Oil
r — 1 l~
0.1 1 10 100
Particle Size, |am
Figure 5-7. Cascade impactor results for the three fuels tested.
The SMPS data reflect volume distributions and the cascade impactor data are mass distributions,
making it necessary to transform volume distributions to mass distributions using size-specific
5-9
-------
particle density. The difference between mass and volume may explain the similarity of particle size
distributions for Orimulsion 400 and No. 6 fuel oil as measured by SMPS compared to the difference
as measured by mass using the impactor.
Organic HAPs
Both volatile and semivolatile organic compounds were sampled during the test program. Each
sample was analyzed for a total of 33 volatile organic compounds (VOCs) and 96 semivolatile
organic compounds (SVOCs). Three samples were collected for each fuel. The compounds for
which the samples were analyzed are given in Tables 5-5 (VOCs) and 5-6 (SVOCs).
Volatile Organic Compounds
In general, very low levels of VOCs were detected. Only 9 of the 33 VOCs were detected (the highest
detection level for all the VOCs was 0.259 (ig/dscm), with two of those compounds (iodomethane and
dichloromethane) being present as laboratory contaminants. Of the remaining 7 VOCs, carbon
disulfide, benzene, and toluene were detected in 9 of the 9 samples, m,p-xylenes and styrene were
detected in 8 of the 9 samples (both compounds in 2 of 3 Orimulsion 100 samples and 3 of 3 of the
other fuels), ethylbenzene was detected in 5 of 9 samples (in 1 of 3 samples of Orimulsion 100 and
Orimulsion 400 and in 3 of 3 samples of No. 6 fuel oil), and o-xylenes were detected only in 3 of 3
o Orimulsion 100
• Orimulsion 400
1E-1
0.01
Dp, urn
Figure 5-8. Scanning mobility particle sizing results for the three fuels tested.
5-10
-------
Table 5-5. Volatile organic compounds for which samples were analyzed.
1,1 Dichloroethene
1,1,1-Trichloroethane
1 , 1 ,2-Trichloroethane
1,1-Dichloroethane
1,2-Dibromoethane
1,2-Dichlorobenzene
1,2-Dichloroethane
1,2-Dichloropropane
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
c-1 ,2-Dichloroethane
c-1 ,3-Dichloropropene
Carbon Disulfide
Carbon Tetrachloride
Chlorobenzene
Chloroform
Dibromochloromethane
Dibromomethane
Dichloromethane
Ethylbenzene
lodomethane
m,p-Xylenes
o-Xylene
Styrene
t-1,2-Dichloroethene
t-1 ,3-Dichloropropene
Tetrachloroethene
Toluene
Trichloroethene
No. 6 fuel oil samples. Figure 5-9 shows the average detected concentrations of the VOCs in the
three fuels in (ig/dscm, and Figure 5-10 presents the average emission factors of the 7 detected VOCs
in Ib/lOi2 Btu. Both average concentrations and average emission factors are calculated using only
detected values, and do not use 0 or other value to reflect samples with concentrations below the
detection limit. For m,p-xylenes, styrene, and ethylbenzene, the average concentrations of VOCs in
Orimulsion 100 and Orimulsion 400 shown in Figure 5-9 are high, since incorporation of the method
detection level or zero in the average would reduce the reported value. The concentrations of VOCs
in No. 6 fuel oil flue gases would not be affected, since each of the 7 VOCs was detected in each of
the 3 samples for No. 6 fuel oil.
There are no significant differences in VOC emissions between the three fuels, even if variability in
measurements is not considered. The largest difference in concentrations of a particular compound
between the three fuels was for benzene, with roughly 2.4 (ig/dscm difference between Orimulsion
400 (at 3 (ig/dscm) and No. 6 fuel oil (at 0.6 (jg/dscm). This difference may be high on a percentage
basis, but in absolute terms is very small. As an illustration, the annual mass emissions of benzene
from a 500 MW power plant operating 24 hrs/day, 365 days/yr with a 10,000 Btu/kW-hr heat rate
would result in 72 Ib (32.8 kg) of benzene emissions when burning Orimulsion 400 if emissions were
at the concentration measured in these tests. Each of the other compounds would be emitted at lower
annual levels for either Orimulsion 400 or the other two fuels. These values can be calculated from
the emission factors presented in Figure 5-10.
Semivolatile Organic Compounds
Flue gases from each of the three fuels were sampled and analyzed for 98 semivolatile organic
compounds, including 16 polycyclic aromatic hydrocarbons (PAHs). Of these 98 compounds, only
9 semivolatile organic compounds were detected. Of these 9, 4 were phthalates, a common laboratory
contaminant. The semivolatile organic compounds detected were 1,4-dichlorobenzene, 2-
5-11
-------
Table 5-6. Semivolatile organic compounds for which samples were analyzed. PAHs are underlined.
1 ,2,4,5-Tetrachlorobenzene
1 ,2,4-Trichlorobenzene
1,2-Dichlorobenzene
1,3 Dinitrobenzene
1,3,5-Trinitrobenzene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
1 ,4-Naphthoquinone
1-Naphthylamine
1-Nitrosopiperidine
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dichlorophenol
2,6-Dinitrotoluene
2-Acetylaminofluorene
2-Chloronaphthalene
2-Chlorophenol
2-Methyl-4,6-dinitrophenol
2-Methylnaphthalene
2-Methylphenol
2-Naphthylamine
2-Nitroaniline
2-Nitrophenol
3,3'-Dichlorobenzidine
3,3'-Dimethylbenzidine
3-Methylcholanthrene
3-Nitroaniline
4-Aminobiphenyl
4-Bromophenyl phenyl ether
4-Chloro-3-methyl-phenol
4-Chloroaniline
4-Chlorophenyl phenyl ether
4-Methylphenol
4-Nitroaniline
4-Nitrophenol
5-Nitro-o-toluidine
7,12-
Dimethylbenz(a)anthracene
Acenaphthene
Acenaphthvlene
Acetophenone
Aniline
Anthracene
Benzofatenthracene
Benzo(a)pvrene
Benzo(b)fluoranthene
Benzo(ghi)pervlene
Benzo(k)fluoranthene
Benzyl Alcohol
Benzyl butyl phthalate
Bis (2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl)ether
Chlorobenzilate
Chrvsene
Di-n-butyl phthalate
di-n-octyl phthalate
Diallate
Dibenz(a.h)anthracene
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
Dinoseb
Diphenylamine
Ethyl methanesulfonate
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachloropropene
Indenod .2.3-cd)pvrene
Isodrin
Isophorone
Isosafrole
Methyl Methanesulfonate
n-Nitrosodi-n-butylamine
N-nitrosodi-n-propylamine
n-Nitrosodiethylamine
n-Nitrosomethylethylamine
n-Nitrosospyrrolidine
Naphthalene
Nitrobenzene
p-Dimethylaminoazobenzene
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
Pvrene
methylnaphthalene, acetophenone, benzyl butyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate,
diethyl phthalate, naphthalene, and phenol.
The semivolatile organic compound analysis method (Method 8270) analyzes the sampling train
condensate, the filter, and the XAD resin for presence of the compounds. Thus there are 3 samples to
be analyzed for each test run. Since each fuel was sampled 3 times, a total of 9 samples were
analyzed for each fuel. Table 5-7 shows the semivolatile compounds with concentrations measured
above the detection level of 1 (jg in the analyte (corresponding to a maximum flue gas detection level
of 0.47 (jg/dscm), and the number of times each compound was detected in the 9 samples per fuel.
None of the 9 compounds were detected in all samples, and 2 compounds (1-4 dichlorobenzene and
2 methylnaphthalene) were detected in only 1 sample of the No. 6 fuel oil. Benzyl butyl phthalate
was not detected in any of the No. 6 fuel oil samples, in only 1 of the Orimulsion 100 samples, and 2
of the Orimulsion 400 samples. The remaining semivolatile organic compounds were detected in
5-12
-------
each of the three fuels, with samples registering detection ranging from 1 of 9 (naphthalene in
Orimulsion 100) to 7 of 9 (di-n-octyl phthalate in No. 6 fuel oil). The number of times detected
gives an indication of the likelihood of measuring these compounds as existing in the flue gases, as
opposed to being laboratory contaminants. The more samples a compound is detected in, the more
likely it is to be present in the flue gas and not simply a laboratory contaminant.
The concentrations of semivolatile organic compounds in the flue gases of the three fuels were
relatively low. The compound with the minimum concentration detected in all three fuels was
naphthalene, at a level of just over 2 (jg/dscm in Orimulsion 400 flue gases (see Figure 5-11). The
highest concentration of the semivolatile organic compounds was the 9.3 (jg/dscm of di-n-butyl
phthalate measured in No. 6 fuel oil flue gases. Emission rates in lb/1012 Btu are presented in Figure
5-12 for the three fuels. Using the same scenario as for the VOCs, the maximum annual mass
emissions would be of di-n-butyl phthalate, at about 680 Ib/yr. Total mass emissions of PAHs in this
scenario would be 92 Ib/yr (assuming the nondetect values were zero). Differences in semivolatile
organic compound emissions between the three fuels are slight. Measurement variability (not shown
in Figure 5-12) was high for these measurements, making it difficult to determine any significant
differences.
0
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Figure 5-9. Average detected concentration of volatile organic compounds in the flue gases of the three fuels
tested. Concentration values for ethylbenzene, m,p-xylenes, and styrene do not reflect the samples
for which these compounds were not detected in Orimulsion 100 and Orimulsion 400 flue gases.
5-13
-------
Metals
The concentration of metals in the flue gases from the three fuels are shown in Figure 5-13. This
figure is divided into 3 sections to better show the differences in metal concentrations. Each sample
was analyzed for 12 metals: Sb, As, Be, Cd, Cr, Cu, Fe, Mg, Mn, Ni, V, and Zn. Each metal was
detected in each sample, except for Sb, which was detected only in the No. 6 fuel oil. Sb, As, Be, Cd,
Cr, and Mn were each measured at concentrations near 10 (jg/dscm, with minor differences between
the fuels.
In several instances, the percent recovery of several metals was relatively poor. Recovery is defined
here as the percent of metal mass emissions measured in the flue gas divided by the metal mass
emissions calculated based on the amount of metal in the fuel. Table 5-8 presents the percent
recovery for each of the metals for which analysis was conducted in these tests. Recovery values over
100% indicate that more metal was measured in the stack than would have been expected, based on
100% emissions of that metal in the fuel. Recoveries below 100% indicate that less metal was emitted
in the stack gases than would have been expected, based on 100% of that metal in the fuel being
emitted.
Recoveries for the two major metals of concern from Orimulsion and heavy fuel oil, Ni and V, were
near 100%. Recoveries ranged from just under 80% to just over 102%, with an average for all the
fuels being 94.2%. Recoveries for Be and Cd were on the order of 1000% for each of the three fuels.
Both of these metals were not found in any of the three fuels, and the values used to calculate a
maximum emission factor were the fuel analysis detection limits. It is likely that the detection levels
2.5
CM
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B
15
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Figure 5-10. Average detected emission factors of volatile organic compounds in the flue gases of the three
fuels tested. Emission factor values for ethylbenzene, m,p-xylenes, and styrene do not reflect the
samples for which these compounds were not detected in Orimulsion 100 and Orimulsion 400 flue
gases.
5-14
-------
reported for the fuel analyses were somewhat low, resulting in calculated emission factors that were
well below the value the method could in fact detect. Measured emission factors for both Be and Cd
were quite low for all three fuels, with a maximum value of 8.45 lb/1012 Btu.
The results for Cu are similar to those for Be and Cd. Cu was not detected in either Orimulsion
formulation, but was detected in the No. 6 fuel oil. Recoveries of Cu were again on the order of
1000% for the Orimulsion formulations, but were within a factor of 2 for the No. 6 fuel oil (59%).
The other remaining recovery significantly greater than 100% was for Mg from Orimulsion 400. In
this case, the fuel analysis did not account for the injection of Mg(OH)2 into the fuel immediately
prior to burning, and it was expected that the stack gas concentration of Mg would be substantially
higher than would be predicted based on fuel content of Mg alone.
There were also several metals that exhibited very low recoveries, on the order of 1%. Arsenic (As)
was measured at less than 2% of the levels that would be expected based on the As level in each of the
three fuels. Sb was measured at less than 1% of the calculated level for Orimulsion 100 and
Orimulsion 400, and at just over 22% for No. 6 fuel oil. Orimulsion 100 and Orimulsion 400 also
showed very low recoveries for Fe, at less than 4% for both fuels, while over 45% of Fe was recovered
from the No. 6 fuel oil. The low recovery of Fe from both Orimulsion formulations makes the
differences in measured emissions shown in Figure 5-12 somewhat less severe, although the No. 6
fuel oil would still be the highest Fe emitter of the three if 100% of the Fe measured in the fuel were
emitted through the stack. If 100% of Fe were recovered in the stack gases of all three fuels, each
would emit on the order of 1000 lb/1012 Btu, rather than No. 6 fuel oil measured in 1000s and
Orimulsion measured in 10s. Zn was also recovered at relatively low rates, particularly for
Orimulsion 100. Again, the low recovery rates magnify the apparent differences between Orimulsion
and the No. 6 fuel oil, although the No. 6 fuel oil would still emit roughly an order of magnitude
more Zn than either of the Orimulsion formulations if 100% recovery were achieved. Mg recovery
for Orimulsion 100 was also quite low, at only 3.3%.
Low recovery rates may reflect a buildup of deposits in the combustor. However, there was no
indication of significant deposition in the PBS during or following the test campaign. Other reasons
for low recovery include sampling, preparation, and analysis errors. While these problems are quite
possible, the recovery of metals in samples spiked with known amounts of metals was quite good (see
Chapter 11), and did not indicate widespread problems in sample collection, handling, or analysis.
Table 5-7. Semivolatile organic compounds detected in the flue gases of the three fuels and the number of times
each compound was detected in the 9 samples collected for each fuel.
Compound
1-4 Dichlorobenzene
2 Methylnaphthalene
Acetophenone
Benzyl butyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Naphthalene
Phenol
Number of Detects,
Orimulsion 100
0
0
3
1
6
3
3
1
5
Number of Detects,
Orimulsion 400
0
0
3
2
5
2
2
2
4
Number of Detects,
No. 6 Fuel Oil
1
1
3
0
6
3
3
2
4
5-15
-------
Figure 5-11. Average detected concentrations of semivolatile organic compounds in the flue gases of the three
fuels tested.
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rimulsion 100
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Figure 5-12. Average detected emission factors of semivolatile organic compounds in the flue gases of the three
fuels tested. Emission factor values for each of the 9 compounds shown do not reflect the samples
for which these compounds were not detected.
5-16
-------
Figure 5-13. Concentrations of metals measured in the flue gases from the three fuels. The concentrations are
shown on three different scales (from bottom to top): 0-100, 0-1600, and 0-30,000 ug/Nm3.
5-17
-------
Even with the high range of recovery rates, the summary picture of trace element behavior for
Orimulsion is that it behaves very similarly to the No. 6 fuel oil. Both Orimulsion formulations
demonstrated higher concentrations of Mg, Ni, and V than the fuel oil, as one would expect. The fuel
oil demonstrated higher concentrations of Cu, Fe, and Zn, again as would be expected. The metals
for which recoveries were either very high or very low (As, Be, Cd) demonstrated roughly the same
behavior in terms of recovery rates for all three fuels. Based on the current data, there is no
indication that trace elements behave significantly differently in an Orimulsion-fired system than in
the same system firing No. 6 fuel oil.
X-ray fluorescence (XRF) analyses of filter samples were also conducted as a further measure of the
behavior of metals. These analyses were conducted by APPCD staff, and examined portions of filters
from the dilution sampler (discussed in Chapter 4). XRF analyses were made of blank filters and
filters with PM from each of the three fuels. In addition, filters that had originally been loaded with
PM from each of the three fuels were washed with deionized distilled water (ddH2O), and with ddH2O
and 1 M hydrochloric acid (HC1) were also analyzed. One of the key questions associated with the
toxicity study was, "How soluble are the metals, particularly the transition metals Cu, Fe, Ni, V, and
Zn, in the PM?"
Table 5-9 presents the results from the XRF analyses for a blank filter and filters loaded with PM
from each of the three fuels. Values in the table are kilocounts per second, and represent relative
amounts of each metal (higher counts are measured for higher metal concentrations). The results
presented in Table 5-7 indicate that the PM captured on the dilution sampler filters (after passing
through a cyclone designed to remove particles larger than 2.5 (jm in diameter) contained relatively
little Cu or Zn, since the XRF analyses were roughly the same for the blank filter and the filter-bound
PM samples for these two metals. There were significant levels of S and lesser amounts of Fe, Mg, Ni,
and V present in the PM samples, as would be expected. The Orimulsion 400 tended to have higher
amounts of each of these (with the exception of Mg) than did the Orimulsion 100, and only Fe was
higher for the No. 6 fuel oil compared to Orimulsion 400. These results are similar to those
presented earlier from the Method 29 samples, with Fe being higher for the No. 6 fuel oil and Ni and
V being higher for Orimulsion 400.
Table 5-10 presents the results for samples washed with ddH2O alone or a sequence of ddH2O and
HC1. These results show that S is removed quite readily from the filters using ddH2O alone for all
three fuels. Minor differences in solubility of Fe, Mg, and Ni between the three fuels are indicated,
with ddH2O removing both Fe and Mg to a relatively constant level for each of the fuels. Further
washing with HC1 did not appear to remove any further Fe or Mg. These results indicate that Ni is
removed from the No. 6 fuel oil PM sample somewhat more readily with ddH2O than from either
Orimulsion formulation, and that the 1 M HC1 solution is required to remove Ni from the Orimulsion
ash to the level attained by ddH2O washing of the No. 6 fuel oil filter. The greatest difference in
behavior is seen for V. About 80% of the V in the untreated filters containing PM from No. 6 fuel
oil and Orimulsion 100 are removed using only ddH2O, while removing only 46% of the V in the
case of Orimulsion 400. Further treatment with 1 M HC1 removed essentially all of the remaining V
for all three fuels. This difference indicates that the PM from Orimulsion 400 may contain V in a
different form than in the PM from the other two fuels, which may impact the solubility and therefore
the toxicity of Orimulsion 400 PM. In general, one would expect that higher solubility would result
in higher toxicity.
Emission Factors
Emission factors for CO, NO, SO2, and PM in terms of mass per energy input are calculated from the
concentrations of the respective compounds, flue gas flow, and fuel flow measured during testing on
the PBS. Table 5-11 presents the emission factors for each of these pollutants, for the three fuels
tested, in lb/106 Btu. These values reflect the difference both in emission concentrations as well as
fuel heat content. Some differences are noticeable when emission factors are compared to emission
concentrations. CO emission factors follow the same trend as did concentrations, with relatively
5-18
-------
Table 5-8. Measured and calculated emission factors and percent recovery for 12 metals
measured in the flue gases of the three fuels.
Measured Emission
Factor,
lb/10i2Btu
Calculated Emission
Factor,
lb/1012 Btu
Recovered
Orimulsion 100 Average
Arsenic
Antimony
Beryllium
Cadmium
Copper
Chromium
Iron
Manganese
Magnesium
Nickel
Vanadium
Zinc
2.53
0
7.06
2.67
3.83
2.76
33.71
7.55
812
4,600
18,612
3.77
208
41
< 0.36<1)
< 0.36<1)
< 0.36<1)
17
862
17
24,571
4,957
23,278
65
1.21%
0.00%
1960.%
741.%
1070.%
16.3%
3.91%
45.7%
3.30%
92.8%
80.0%
5.84%
Orimulsion 400 Average
Arsenic
Antimony
Beryllium
Cadmium
Copper
Chromium
Iron
Manganese
Magnesium
Nickel
Vanadium
Zinc
3.19
0.19
8.45
2.46
4.99
7.92
26.48
7.77
1,185
4,452
19,932
12.70
175
27.79
< 0.40<1)
< 0.40<1)
< 0.40<1)
15.88
1,747
18.26
79.39(2)
4,684
20,800
29.37
1.83%
0.68%
2130.%
621.%
1260.%
49.9%
1.52%
42.6%
1490.%
95.1%
95.8%
43.3%
(continued)
5-19
-------
Table 5-8 (Continued). Measured and calculated emission factors and percent
recovery for 12 metals measured in the flue gases of the three
fuels.
Measured Emission
Factor,
lb/1Qi2Btu
Calculated Emission
Factor,
lb/1012 Btu
Recovered
No. 6 Fuel Oil Average
Arsenic
Antimony
Beryllium
Cadmium
Copper
Chromium
Iron
Manganese
Magnesium
Nickel
Vanadium
Zinc
2.35
9.65
5.21
3.06
24.82
8.34
1,290
12.59
53.98
2,575
12,446
316
143
43
< 0.28<1)
< 0.28<1)
42
32
2,814
NA<3)
419
2,594
12,196
491
1.64%
22.4%
1890.%
1110.%
59.2%
26.1%
45.8%
NA
12.9%
99.3%
102.%
64.3%
1. The given emission factor is calculated based on the detection level of the fuel analysis method.
2. The injection of Mg additive is not included in the calculated emission factor.
3. Not available.
Table 5-9. Results of XRF analyses of untreated filters and samples, in kilocounts/second for selected metals.
Filter
Blank
No. 6 Fuel Oil
Orimulsion 100
Orimulsion 400
S
0.5
34.0
18.6
59.9
Cu
0.1
0.2
0.2
0.2
Fe
2.6
4.7
2.7
3.2
Mg
0.3
0.5
2.5
1.3
Ni
0.1
4.4
3.0
13.3
V
0.0
12.2
7.6
31.8
Zn
27.7
27.5
27.1
24.4
small differences between the two fuels, and with Orimulsion 400 slightly higher than either
Orimulsion 100 or No. 6 fuel oil. For NO, the differences again are small, but the emission factor for
No. 6 fuel oil is somewhat higher than for either Orimulsion formulation. Likewise, SO2 emission
factors show a slightly different pattern, with the No. 6 fuel oil having the highest emission factor, in
contrast to emission concentrations where the No. 6 fuel oil had the lowest SO2 concentration. The
PM emission factor also is highest for the No. 6 fuel oil, whereas Orimulsion 400 had the highest PM
mass concentration. In each case, the difference is relatively minor, and the variability in
measurements makes it impossible to conclude that these differences are significant.
5-20
-------
Table 5-10. XRF analyses of untreated and treated filters loaded with PM samples from the
three fuels. Values are in kilocounts/second.
Filter
No. 6 Fuel Oil
(untreated)
No. 6 Fuel Oil (ddH2O)<1)
No. 6 Fuel Oil (HCI)<2)
Orimulsion 100
(untreated)
Orimulsion 100 (ddH2O)
Orimulsion 100 (HCI)
Orimulsion 400
(untreated)
Orimulsion 400 (ddH2O)
Orimulsion 400 (HCI)
S
34.0
1.3
0.7
18.6
0.8
0.8
59.9
2.2
1.1
Fe
4.7
3.9
3.0
2.7
2.8
2.8
3.2
2.8
3.0
Mg
0.5
0.6
0.6
2.5
0.7
0.6
1.3
0.6
0.6
Ni
4.4
0.3
0.3
3.0
1.5
0.2
13.3
3.0
0.6
V
12.2
2.3
0.1
7.6
1.7
0.0
31.8
17.2
0.2
1. Deionized distilled water.
2. 1 M hydrochloric acid.
Table 5-11. Emission factors for CO, NO, SO2, and PM from the three fuels tested in the PBS, in
lb/106 Btu.
Orimulsion 100
Orimulsion 400
No. 6 Fuel Oil
CO
0.0079
0.0104
0.0081
NO
0.46
0.47
0.54
SO2
0.85
0.93
1.02
PM
0.69
0.75
0.82
Scanning Electron Micrographs
In addition to measurements of pollutants, samples were also collected on silver membrane filters for
evaluation under a scanning electron microscope (SEM) to provide morphological information of
individual particles. Particles were extracted from the stack location using the same sampling system
and dilution as used by the SMPS described above. However, these particles were directed through a
stainless steel filter holder containing a 47 mm silver membrane filter. Sampling times of
approximately 30-60 s provided a sufficient quantity of particles for analysis. Silver filters were used
to improve conductivity and minimize particle charging caused by the electron beam.
The micrographs taken of samples at 700x magnification are shown in Figures 5-14 through 5-17.
Figure 5-14 is an SEM micrograph of a blank filter, and clearly shows the filter fibers with little
material on the filter. The fibers are 1 (jm in diameter or smaller, and have no consistent orientation.
Figure 5-15 is an SEM micrograph of a filter loaded with PM from the combustion of the No. 6 fuel
oil, again at 700x magnification. Very few filter fibers are visible, and the filter appears to be almost
completely coated with PM. The material appears to be largely composed of small hollow spheres,
many with numerous pores. There also appears to be a substantial amount of ash particles similar to
flakes, again with the material appearing to be quite porous. In this sample, the majority of particles
appear to be smaller than 5 ^m in diameter, although there are several spheres that are slightly larger,
such as those at the top center and bottom center of the image.
5-21
-------
Figure 5-16 is an SEM micrograph of a filter loaded with PM from the combustion of Orimulsion
100 at 700x magnification. The filter is again nearly completely covered with PM, although there
seem to be slightly more fibers visible than was the case for the No. 6 fuel oil. The material appears
to be somewhat less porous than the No. 6 fuel oil, but does have several spherical particles near the 5
(jm diameter size. The spheres show some porosity, but generally less than that for the No. 6 fuel oil
PM. For both the Orimulsion 100 and the No. 6 fuel oil, the PM appears to form a crust over the
filter fibers, but it is impossible to say whether this crust is merely an appearance or is actually
present.
Figure 5-17 is an SEM micrograph of a filter loaded with PM from the combustion of Orimulsion
400 at 700x magnification. This image appears significantly different than for either the No. 6 fuel
oil or Orimulsion 100. There do not appear to be significant amounts of individual particles in this
image, but more of a continuous crust or slag-type of material. There are still numerous pores in the
solid, but the material appears to have solidified from a liquid rather than being deposited as many
individual solid particles that later agglomerated into a crust, as was the case for the No. 6 fuel oil and
the Orimulsion 100. It is not clear what differences account for the change in appearance, but the
Orimulsion 400 did use a different form of Mg than did the Orimulsion 100. Whether this led to
formation of different species in the particles is not known.
Figure 5-14. Scanning electron micrograph of untreated blank filter at 700 x magnification.
5-22
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Figure 5-15. Scanning electron micrograph of untreated filter loaded with PM from No. 6 fuel oil at 700 x
magnification.
Figure 5-16. Scanning electron micrograph of untreated filter loaded with PM from Orimulsion 100 at 700 x
magnification.
5-23
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Figure 5-17. Scanning electron micrograph of untreated filter loaded with PM from Orimulsion 400 at 700 x
magnification.
5-24
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Chapter 6
Physicochemical Properties and Acute Pulmonary Toxicity of
Orimulsion Fly Ash
Objective
Orimulsion represents a fuel made of natural bitumen emulsified in water that could be an
economical substitute for fuel oils currently used in utility and other types of commercial boilers. No
utilities in the United States are currently using Orimulsion, therefore, the potential public health
impact associated with emissions derived from the combustion of Orimulsion has not been
documented. The present study compares the physicochemical properties and acute pulmonary
toxicities of fly ash obtained from the combustion of two Orimulsion formulations (Orimulsion 100
and 400) with similar properties of fly ash obtained from the combustion of a conventional fuel, No.
6 residual oil.
Oil Fly Ash Production and Collection
The production and collection of Orimulsion 100, Orimulsion 400 and No. 6 residual oil fly ash
particles was performed by W.P. Linak and C.A. Miller at the National Risk Management Research
Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, NC, as described in
Chapter 4. Briefly, Orimulsion 100, Orimulsion 400 and No. 6 residual oil fuels were burned using a
package boiler simulator as previously described (Chapter 4, pages 4-1 to 4-6). Fine (PM2 5 mass
mean aerodynamic diameter) oil fly ash particles were obtained using a dilution sampler and PM2 5
SASS cyclone collection system as previously described (Chapter 4, pages 4-6 to 4-7). Oil fly ash
particles were collected on Teflon-coated glass fiber filters. Filter samples containing Orimulsion 100
(OFA100), Orimulsion 400 (OFA400) and No. 6 residual oil fly ash (ROFA#6) were obtained for
subsequent physicochemical and toxicological analyses performed by K. Dreher, Experimental
Toxicology Division, National Health and Environmental Effects Research Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC.
Reference Particle
Arizona road dust (ARD) was included as a surrogate particle representing particles that may be
present in the ambient air arising from mechanical processes. ARD was obtained from Andrew Ohio,
Human Studies Division, National Health and Environmental Effects Research Laboratory, U.S.
Environmental Protection Agency, Chapel Hill, NC. Fine ARD was produced by grinding ARD
particles using a ball mill. The size of fine ARD employed in these studies was 1.491 (am mass mean
aerodynamic diameter with a 1.535 geometric standard deviation.
Physicochemical Properties of Oil Fly Ash Samples and Arizona Road Dust
OFA100, OFA400, ROFA#6, and ARD samples were characterized for the following physicochemical
properties: acidity; acid (1.16M HC1) soluble transition metal, lead and sulfate content; water soluble
transition metal, lead and sulfate content. A summary of these physicochemical analyses is shown in
Table 6-1. ROFA#6 was found to be the most acidic oil fly ash sample with the overall order of
particle acidity being: ROFA#6 > OFA400 > OFA100 > ARD. Under the acid hydrolysis conditions
employed, no lead (Pb) or zinc (Zn) was detected in any of the oil fly ash samples examined.
Vanadium (V), nickel (Ni), and iron (Fe) were the predominant transition metals present in each of
the oil fly ash samples. OFA400 contained the highest 1.16 M HC1 acid soluble metal and sulfate
content. The overall order of particle 1.16 M HC1 acid soluble metal and sulfate content was found to
be: OFA400 > OFA100 > ROFA#6 > ARD. Finally, ROFA#6 was found to contain the highest
percentage of total water soluble or bioavailable metal content. OFA100 and OFA400 contained very
similar and low percentages of total water soluble or bioavailable metals.
Under the combustion conditions employed in these studies, both Orimulsion formulations produced
particles of higher total metal and sulfate content when compared to similar particulate emissions
derived from No. 6 fuel oil. However, the water solubility or bioavailability of the various
6-1
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Table 6-1. Physicochemical characterization of collected PM2.5 oil fly ash samples and Arizona road dust particles
Sampled)
OFA100
OFA400
ROFA#6
ARD
Metal Content (|jg/mg of sample/2)
Zn
BDL<4)
BDL
0.72
(100)
0.03
(2.8)
Pb
BDL
BDL
0.01
(0)
NDO
Ni
11.43
(15)(5)
16.79
(75)
3.40
(100)
0.19
(0.12)
Mn
0.03
(21)
0.03
(100)
0.03
(100)
ND
Fe
0.96
(2.0)
0.94
(19)
1.76
(4.6)
7.01
(0.03)
V
53.84
(45)
83.91
(15)
18.38
(64)
0.01
(3.7)
Cu
0.01
(9.0)
0.01
(100)
0.04
(100)
0.08
(0.26)
Total
metal
(HQ/mg)
66.27
(39)(6)
101.68
(35)
24.34 (68)
7.32
(0.04)
Total
sulfate
(HQ/mg)
87.8(100)
169 (100)
47.8(100)
0.26
(50)
pH(3)
4.45
3.25
2.9
4.97
1. Sample designations: OFA100, Orimulsion 100 fly ash; OFA400, Orimulsion 400 fly ash; ROFA#6, No. 6 residual
oil fly ash; ARD, Arizona road dust, a surrogate for a non-combustion-derived particle.
2. Metal content obtained from 1.16 M HCI hydrolysis of filter samples. All values are expressed as ug/mg PM based
on estimated theoretical mass deposition on filters. All metal values were corrected for filter contribution of metals.
3. pH of an aqueous solution containing equivalent concentration of 7.0 mg/mL for each sample. For comparative
purposes: acidity of deionized-distilled H2O, pH = 4.98; acidity of an equivalent amount of Teflon filter, pH = 5.53.
4. Below detectable limits.
5. Values in parentheses represent the percent of each metal that was water soluble. The water solubility of each
metal is a measure of its bioavailability.
6. The total percent water soluble metal content for each oil fly ash sample was derived from the individual
experimental data obtained for each metal.
7. Not determined.
metals were found to be lower for both Orimulsion formulations when compared to fine ROFA#6
particles. ARD particles, employed as a surrogate for non-combustion-derived particles, were not
acidic and contained very little metal. In addition, the metal contained within ARD was essentially
water-insoluble or non-bio-available.
Acute Pulmonary Toxicity of Oil Fly Ash and Arizona Road Dust Samples
Teflon glass fiber filters containing OFA400, OFA100, or ROFA#6 fine particles were extracted with
deionized-distilled water. Water extracts containing both soluble and insoluble constituents of each
oil fly ash sample were dried by lyophilization and the recovered material employed in subsequent
toxicological analysis.
The acute pulmonary toxicities of OFA400, OFA100, and ROFA#6 water extracted material were
examined using healthy, male, 65-75 day old, Sprague-Dawley rats. ARD was included in these
toxicology studies to serve as a surrogate particle to evaluate the acute pulmonary toxicity of particles
derived from non-combustion processes. Rats were exposed by intratracheal-instillation to various
doses of OFA400, OFA100, or ROFA#6 water-extracted material or ARD which had been re-
suspended in saline. Another group of rats were exposed to saline to serve as a control for potential
trauma arising from the intratracheal-instillation procedure. Animals were analyzed for acute
pulmonary toxicity by bronchoalveolar lavage at 24 hours post-exposure. Bronchoalveolar fluid
(BALF) samples were analyzed for biomarkers of acute pulmonary toxicity or lung injury as listed in
Table 6-2.
Results of the acute pulmonary toxicity assessments of each oil fly ash water extract and ARD are
shown in Figure 6-1 and Table 6-3. A lowest observed effect level (LOEL) was determined for each
sample and biomarker of acute toxicity examined in these studies. The LOEL in these studies was
6-2
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defined as the lowest statistically significant dose that elicited an effect above the corresponding
control saline level for each biomarker of pulmonary toxicity or injury (Table 6-2). Statistical
analysis was conducted at each LOEL for each oil fly ash sample in order to produce a general
relative toxicity ranking.
Intratracheal-instillation of saline was found to produce little if any detectable acute pulmonary
toxicity or injury. As shown in Figure 6-1, BALF macrophage/mL levels, a biomarker of pulmonary
inflammation, was not affected by any of the samples examined in this study. ARD was found to be
the least toxic particle for a number of biomarkers of acute pulmonary toxicity or injury (BALF
protein, albumin, eosinophil/mL) examined in these studies. ROFA#6 water-extracted material
induced more pulmonary edema than extracts of OFA100 and OFA400. OFA100 and OFA400 water
extracts were found to produce a similar extent of acute pulmonary toxicity or injury.
In general, under the combustion conditions employed in these studies both ROFA#6 and Orimulsion
Table 6-2. Biomarkers of pulmonary acute toxicity or injury.
BALF Endpoint
Protein concentration
Albumin concentration
Lactate dehydrogenase (LDH) activity
Macrophage concentration
Neutrophil concentration
Eosinophil concentration
Biomarker
Pulmonary Edema and/or Airway
Hypersecretion
Pulmonary Edema
Pulmonary Cellular Cytotoxicity
Pulmonary Inflammation
Pulmonary Inflammation
Pulmonary Inflammation
Table 6-3. Relative toxicity of oil fly ash and dust exposures at the Lowest Observed Effect Level (LOEL) for each
endpoint. Note that the rankings are not of LOEL values, but of relative toxicity (higher LOEL indicates
lower toxicity).
LOEL(1)
(mg/rat)
Endpoint
Relative Toxicity Ranking at the
Observed LOEL(2)
Pulmonary Injury
0.5
0.5
0.5
Pulmonary Edema/Secretory Activity
BALF endpoint: Protein (ug/mL)
Pulmonary Edema
BALF endpoint: Albumin (ug/mL)
Pulmonary Cellular Cytotoxicity
BALF endpoint: LDH (U/L)
ROFA#6 > OFA100 = OFA400 > ARD =
ROFA#6 > OFA100 = OFA400 > ARD =
ROFA#6 = OFA100 = OFA400 =ARD >
Saline
Saline
Saline
Pulmonary Inflammation
0.125
0.25
Cellular Inflammation
BALF endpoint: Neutrophil/mL
Cellular Inflammation
BALF endpoint: Eosinophil/mL
ROFA#6 = OFA100 = OFA400 = ARD >
ROFA#6 = OFA100 = OFA400 > ARD >
Saline
Saline
1). The LOEL was defined as the lowest dose of each oil fly ash sample which produced a specific biological
response that was statistically significantly (p<0.05) different from saline control animals.
2). Statistical analysis was conducted at each LOEL for each oil fly ash sample in order to produce a relative toxicity
ranking.
6-3
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1200
1OOOOOO-i
100000-
10000
10OOOOOni
100000-
I 10000^
_c
Q.
2 1000^
100-
0.125 0.25 0.5 1
Dose (mg/rat)
0.125
0.25 0.5
Dose (mg/rat)
0.125 0.25 0.5 1
Dose (mg/rat)
100^
0.125
0.25 0.5
Dose (mg/rat)
0.125
0.25 0.5 1
Dose (mg/rat)
Figure 6-1. Particle-induced acute lung injury. Results obtained from analysis performed on bronchoalveolar
lavage fluid samples recovered from animals at 24 h post-exposure. Animals were exposed by intratracheal
instillation to: saline (O); OFA100 (A); OFA400 (T); ROFA#6 (X); or ARD (• ). Various biomarkers of acute lung
injury were assessed such as: A) edema/secretory activity (protein/mL); B) edema (albumin/mL); C) cellular
cytotoxicity (LDH U/L); as well as inflammatory biomarkers such as: D) macrophage/mL; E) neutrophil/mL; and F)
eosinophil/mL N=6 for Orimulsion 100, Orimulsion 400, No. 6 fuel oil, and Arizona road dust; N = 12 for saline.
Values represent means ± standard errors of the mean.
6-4
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formulations generated participate emissions that were capable of producing significant adverse acute
pulmonary toxicity. In addition, particles derived from the combustion of Orimulsion 100 and
Orimulsion 400 were found to be very similar to No. 6 residual oil fly ash particles in their ability to
induce acute pulmonary toxicity.
Oil Fly Ash Health Effects Commentary
There are a number of comments that need to be made regarding the health effects of Orimulsion
100 and Orimulsion 400 fly ash as reported herein. First, results obtained in these studies reflect the
relative toxicities of the various oil fly ash samples, OFA100, OFA400, and ROFA#6, obtained from
the combustion of these fuels using an in-house boiler located at the National Risk Management
Research Laboratory, U. S. Environmental Protection Agency, Research Triangle Park, NC. It is
possible that the relative toxicities of OFA100 and OFA400 versus ROFA#6 may change under
different combustion conditions such as might be employed in larger utility boilers. Secondly,
intratracheal-instillation was employed as the method of exposing animals to the various oil fly ash
samples. This method of exposure was employed due to the small amount of material collected
following the in-house combustion of the various fuels. However, comparative studies examining the
relative distribution and level of acute pulmonary toxicity of oil fly ash following inhalation and
intratracheal-instillation exposures have been conducted within the Experimental Toxicology
Division, Pulmonary Toxicology Branch, National Health and Environmental Effects Laboratory,
U.S. Environmental Protection Agency, Research Triangle Park, NC. These studies have
demonstrated that at low doses (110 (ig/rat) similar pulmonary distribution and acute pulmonary lung
toxicity following oil fly ash exposure were achieved by either inhalation or intratracheal instillation
exposure methods (Costa et al. 1998). Finally, the relative toxicities of ROFA#6 OFA100, and
OFA400 were determined in these studies using young and healthy animals. The relative toxicity of
oil fly ash generated from the combustion of these fuels could be different when health-
compromised animals are examined. Therefore, results from this study do not provide any
information regarding the impact of Orimulsion 100 and Orimulsion 400 particulate emissions on
potential susceptible human sub-populations.
6-5
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Chapter 7
Spills
Introduction
As part of the initial activities to define the scope of this report, a workshop was held to identify the
state of understanding of the environmental aspects of Orimulsion use, including its behavior and
effects when spilled into water (EPA 1999a). The workshop noted that there was "an extensive body
of published information on spills," although most of it was based on research sponsored by Bitor.
The workshop concluded that very little information was available concerning the behavior and
effects of an Orimulsion spill in fresh water, but that the primary responsibility for conducting the
research necessary to supporting any application required for using Orimulsion in the U.S. rested
with Bitor. The recommendations of the workshop were that if Bitor does begin to develop U.S.
customers at sites accessible only by fresh water, at a site near bodies of fresh water, or at a site where
fresh water can be contaminated by a spill, even indirectly, Bitor should be responsible for the
research to address the data gaps as they have done for marine environments. Such research does not
fall under the Congressional directive for this report, and should not be considered to be EPA's
responsibility under that directive. However, since EPA is responsible for responding to spills in
certain situations, the Agency should continue to investigate Orimulsion spill behavior and response
as appropriate. EPA (in collaboration with the U.S. Coast Guard) has requested the National
Academy of Sciences to conduct a study on Orimulsion to evaluate what additional information is
required to effectively respond to freshwater spills. EPA is currently conducting smaller studies on
spill behavior modeling, and will address the data gaps identified by the NAS as appropriate. For
these reasons, the Orimulsion Technology Assessment Plan did not include research into the behavior
and effects of Orimulsion spills into fresh water.
Background
Spills are of concern when transporting any liquid material by ship, barge, or pipeline, when leakage
or accident has the potential to introduce the liquid into bodies of water near the site of material
transfer or use, or when the liquid contaminates runoff or enters other indirect routes to bodies of
water. Concerns about spills can be divided into two main areas: (1) spill response and cleanup; and
(2) impact of the spilled material on the environment. Orimulsion has two properties that distinguish
it from many other fuels from the perspective of spills. The first property that is of concern is that
the bitumen portion of Orimulsion is heavier than fresh water at ambient temperatures (see Chapter 2
for discussion of Orimulsion's properties). The second property is the presence of a surfactant in the
fuel, which acts to prevent the bitumen from coalescing into larger particles or spills that can be more
easily collected.
The bitumen in Orimulsion has a density greater than that of fresh water (see Table 2-1). This means
that Orimulsion is considered to be a "Group V oil" as defined by the U.S. Coast Guard (Federal
Register 1996). Group V oils are those that have specific gravities greater than 1.0, and generally do
not float on water. A committee of the National Research Council (NRC), the Committee on Marine
Transportation of Heavy Oils, recently evaluated the risks of nonfloating oil spills and methods of
responding to those spills (National Research Council 1999). This study included an evaluation of
emulsified oils and of Orimulsion as a special case of heavy emulsified fuels.
The term heavy oil in the NRC report was used to describe dense, viscous oils with low volatility (flash
point higher than 65 °C), very little loss by evaporation, and viscous to semisolid consistency. The
report gave examples of heavy oils as including Venezuela, San Joaquin, and Bunker crude oils,
residual oils (Nos. 5 and 6 fuel oil, Bunker C, and slurry oil), asphalt, coal tar, coke, carbon black, and
pitch. Nonfloating oils is the term used by the NRC Committee to describe oils, like some heavy oils,
that do not float on water. This includes oils that sink immediately, those that mix into the water
column and move with the water in suspension, and those that have a portion of the fuel that initially
floats, but mixes with sand or sediment and then sinks.
To date, there have been no significant spills of Orimulsion. One could estimate the probability of an
7-1
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Orimulsion spill during transport based on the reported frequency of transport-related heavy oil
spills; however, Bitor's policy to date has been to use double-hulled vessels for transport, which
reduces spill potential. Additionally, Orimulsion has not been transported by barge, which accounts
for the bulk of spill volume. The NRC study reported that the average annual movements of heavy
oils were 45.7xl09 ton-miles per year in the period 1991 through 1996. During the same time
period, the annual volume of heavy oil spills was 10,840 bbl/year, resulting in a spill ratio of 237 bbl
spilled per 109 ton-miles. Of the total, barge transport accounted for 19.6xl09 ton-miles per year,
9,765 bbl/year spilled, and a spill ratio of 499 bbl spilled per 109 ton-miles (see Figure 7-1).
Nonfloating oils were estimated to account for approximately 20% of the total heavy oil volume
(National Research Council 1999). The spills per 109 ton-miles rates are likely to be higher for
19.6(43%)
26.1 (57%)
Heavy oil movement, 10 ton-miles/year
1,074(10%)
,765 (90%)
Spill volume, bbl/year
499
Spill rate, bbl/10y ton-miles
Figure 7-1. Movement, spill volumes, and spill rates of heavy oils in U.S. domestic waters between 1991 and 1996
(data from National Research Council 1999).
7-2
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heavy oils than for Orimulsion due to the reliance on tankers versus barges, and the use of double-
hulled versus single-hulled tankers.
It should be noted that more spills occur at stationary facilities than during transport. These spills can
enter bodies of water through containment leakage, storm drains, sewers, or other indirect routes.
Such spills can also pose a greater threat to public drinking water supplies, since the facilities are
often located closer to populated areas and therefore nearer to water supply inlets.
The study found that nonfloating oils behave differently and have different environmental fates and
effects than floating oils. In contrast to floating oils, nonfloating oils when spilled can pose "a
substantial threat to water-column and benthic [sea, river, or lake bottom] resources, particularly
where significant amounts of oil have accumulated on the seafloor" (National Research Council
1999). Such spills do not quickly degrade, and can impact resources for a longer period of time than
do floating spills, although the effects and behavior of such spills are poorly understood. Spills of
nonfloating oils are difficult to track, since the spill plume is largely underwater. While a number of
tools and techniques have been developed for tracking such spills, the actual performance of these
tools is unknown either through controlled experiments or application to spills. In addition, there are
few technologies available for effectively containing and recovering spilled nonfloating oils. Those
methods that are currently used are often effective only in areas with very low currents and minimal
wave activity. Once the oil has deposited on the sea or river bed, recovery of the spilled oil can be
done manually by divers (a slow and labor intensive method) or by dredging. However, dredging
tends to collect substantial amounts of other sediments and materials, and proper disposal of the
collected materials can be problematic (National Research Council 1999).
The surfactants present in emulsified fuels will maintain their effectiveness in fresh water longer than
in salt water. Figure 7-2 shows the behavior of emulsified fuels in spills for low- and high-current
fresh water and for high currents in salt water. In low-current conditions in fresh water, the spilled
fuel will settle to the bottom of the water column, with low potential for mixing with bottom sediments
in the short term (National Research Council 1999).
In fresh water with high currents, the bitumen particles will settle toward the bottom down-current of
the spill (see Figure 7-3). The surfactant will remain effective for a limited period of time, preventing
Gravitational
Spreading
Figure 7-2. Spill of nonfloating oil in low-current fresh water (adapted from National
Research Council 1999).
7-3
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recoalescence of the fuel particles. The deposition rate of the particles may increase if the bitumen
particles (which are highly adhesive) interact with fine-grain sediments, increasing the particles'
density. In addition, many freshwater riverine systems are high in suspended solids to which the
bitumen is likely to adhere. Usually, the suspended materials occur close to the bottom as a "floe."
This floe once mixed with bitumen will be changed in physical/chemical character. These materials
are deposited in the more quiescent submerged regions of a river.
In saltwater spills, emulsified oils will form clouds of dispersed particles in the upper 1-2 meters of
the water column, as shown in Figure 7-4. In such instances, the surfactants lose their effectiveness
more quickly than in fresh water, allowing the bitumen particles to coalesce and rise to the surface,
forming tarry slicks. In open water, the particles are likely to disperse, resulting in increased
difficulty in containing and recovering emulsified fuels as the time from the spill increases (National
Research Council 1999).
Bitumen particles pose a threat in more ways than just "smothering." Many freshwater benthic
inhabitants are at risk by being exposed to the fine particles of bitumen during feeding and tube
building activities. Some benthic invertebrates produce membranous nets that capture the fine
detrital materials that are passing by in the current. Bitumen, even dispersed bitumen, is likely to be
entrapped and consumed by this type of feeding.
Reported Orimulsion Spill Studies
The NRC report cited four studies on Orimulsion spill behavior which were used to form the basis of
the NRC report. These studies were largely funded by Bitor or other interested parties. The U.S.
Coast Guard recently published a report (conducted by Battelle and funded by the U.S. Coast Guard
Research and Development Center, and Bitor) on the behavior of Orimulsion spills (Battelle 1999).
This report cites a number of studies that have been done on characterizing Orimulsion behavior in
spill situations. There have also been two recent documents prepared by Environment Canada
regarding Orimulsion spills in marine environments. One is a spill field guide, and the other
discusses options for disposing of bitumen recovered from a spill (Owens and Sergy 1999, Guenette
and Sergy 1999). The reports cited by the NRC, the U.S. Coast Guard, and Environment Canada that
are specific to Orimulsion behavior are listed in Appendix F.
Increased spreading
overtime/distance
Deposition of
bitumen/sediment
Current flow
I
Figure 7-3. Spill of nonfloating oil in high-current fresh water (adapted from National
Research Council 1999).
7-4
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Floating "tar"
Zone of high
nates of particle
contact and coalescence
into slicks
Current flow
Increased spreading
to the point that
recoalescence will not occur
Figure 7-4. Spill of nonfloating oil in high-current salt water (adapted from National
Research Council 1999).
Saltwater Spills
A number of studies of Orimulsion spills have been conducted, including containment and recovery
and fate and effects studies. Most, if not all, of these studies have been funded by Bitor, and have
been conducted by a range of organizations, including the University of Massachusetts, the University
of Miami, Environment Canada, and the U.S. Coast Guard. To date, nearly all of this work has
focused on marine (saltwater) spills. Research in the area of Orimulsion spills has largely been
guided over the past several years by the International Orimulsion Working Group (IOWG). The
IOWG includes members from Bitor, the U.S. Coast Guard, the Canadian Coast Guard, and
Environment Canada.* These studies include investigations of spill behavior, identification of spill
plume tracking technologies, evaluation of spill containment and recovery equipment and techniques,
and toxicological studies of the impact to marine life of exposure to Orimulsion.
Bitor has developed methods for spill containment and recovery (Bitor America 1999), and has
conducted limited open water testing of these techniques. No "real-world" test of the methods has
been conducted, as there have been no spills of Orimulsion reported to date.
Special spill containment equipment designed to handle Orimulsion is on site at terminals in Canada
and Denmark (Irvine and Eagles 1998, Miller and Shores 1999), as well as at other sites where
Orimulsion is off-loaded.
Freshwater Spills
There is little technical information available on what happens when Orimulsion is spilled into fresh
water. As noted above, Orimulsion is a heavy oil, meaning that it has high specific gravity and is
likely to sink once spilled into fresh water.
Contamination of fresh water can occur during activities other than transport. Storage and handling
activities at sites near bodies of fresh water such as lakes, ponds, or rivers have the potential to release
*In the U.S., the responsibility for responding to oil spills in marine environments generally
rests with the U.S. Coast Guard, with spills occurring in freshwater environments generally being the
responsibility of the U.S. EPA. EPA has not participated in the IOWG.
7-5
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a fuel into those bodies. Even in instances where a spill occurs at a site not located immediately next
to a body of fresh water, storm drains or other means can result in indirect contamination.
Laboratory tests in fresh water conducted by Environment Canada and Battelle indicate that the
bitumen particles in Orimulsion accumulate on the bottom of the test vessels with very little material
remaining on the surface.
The ramifications of this behavior are many:
(a) If Orimulsion behaves in a freshwater body as it does in the laboratory, then the bitumen
particles can sink through the water column and be deposited on the bottom, downstream
from the spill location. Orimulsion is not a liquid but a heavier-than-water suspension which
dissipates once spilled. The impact from this behavior would likely be the smothering of
benthic organisms living on or in the sediments. The Battelle study indicated that the
bitumen fraction of Orimulsion would sink to the bottom under calm water situations, and
that in low energy situations, dilute Orimulsion remained in suspension. The new data
suggest that pelagic (open-sea) species may also be vulnerable if low energy levels keep
Orimulsion in suspension (Battelle 1999).
(b) Oil spill cleanup technology is based upon removing the spilled product from the water
surface and contaminated surfaces. Subsurface removal of a sunken product is limited to
accumulations in distinct pockets, indentations, or depressions. The lighter-than-water spilled
product sometimes is entrained and adheres to bottom substrates, e.g., cobble, algae and
aquatic vegetation. This product will often float to the surface if disrupted and dislodged
where conventional equipment can remove the product from the surface. Orimulsion does not
have the same physical properties and will not resurface in fresh water.
Castle et al. (1995) characterized fate and transport mechanisms and removal techniques for
sunken oils. The assessment procedures mentioned in their paper are more applicable for
marine waters but have some application for the freshwater environment. They stressed the
importance of field observations made from aircraft and predictive models to ascertain the
probable fate and transport of a spill of heavier-than-water petroleum product. Accessing
expertise in local resource and navigation offices can be helpful in determining sinks and
collection spots on the bottom of a receiving water body. An assortment of geophysical
instruments and techniques have been shown to be valuable in locating and mapping
submerged product.
Physical removal of bitumen is currently limited to a subsurface operation using divers and
vacuum hoses. Limited success for containing bitumen using fish netting was observed in
tests performed in a wave tank in Canada (Brown and Goodman 1989). In these tests, bitumen
leaked through the netting being towed at 0.3 m/s (0.77 miles/hour), indicating that in
currents carrying spilled bitumen at greater than 0.3 m/s, bitumen would not be completely
trapped and contained. A spill of fresh Orimulsion would even be harder to trap and contain
due to the smaller particle size of the bitumen/surfactant.
Many conventional oil booms will begin to leak under the boom (i.e., entrain) at about 0.75
knot. In higher currents, the booms can be placed at an angle to the current (i.e., deflection
booming) so that the normal current to the boom is below 0.75 knot. This prevents the boom
from leaking and allows the operator to divert the oil to a quieter area where it can be
removed from the surface with conventional skimming equipment. These techniques may
possibly be employed with an Orimulsion spill by deploying booms below the surface to
collect and then recover the bitumen using vacuum pumps. However, no tests of this
approach have been documented.
Several technologies for recovery of Orimulsion and Orimulsion bitumen in fresh- and
saltwater environments are in various stages of development (Bitor America 1997, 1999;
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Lorenzo 1996). However, one of the areas of concern for these experimental recovery
systems is their "scalability." As the Orimulsion becomes more dispersed, more water must be
pumped through the system with the Orimulsion. While these approaches may be reasonably
effective in the lab, the question remains as to how effective they will be when pumping large
quantities of water through them in an actual spill. Further, none of these techniques have
been demonstrated in riverine environments, which require different approaches and in some
cases different technologies compared to open water spill recovery methods.
The lack of case histories of Orimulsion spilled into fresh water leaves speculation and
assumptions as to the fate and transport of this product. Considering the state of the
knowledge and practices for oil spill cleanup, which is geared primarily toward removing
surface oil, the degree of success for removing subsurface deposits of spilled Orimulsion
remains an open question. In the absence of more information, a conservative assumption is
that an Orimulsion spill will defy cleanup by conventional means and the material will
therefore remain intact in the environment.
(c) Orimulsion is composed mostly of bitumen, which is a complex mixture of hydrocarbons and
is similar in handling and content to liquefied asphalt (Deis et al., 1997). Some of the
hydrocarbon compounds associated with this fraction are known carcinogens; e.g.,
benzopyrenes (Jokuty 1999). One of the dangers of a spill of Orimulsion into a major
freshwater body would be the threat presented to public water supplies. Most public water
supply intakes are submerged. A submerged plume of spilled Orimulsion moving
downstream could intercept an intake pipe and be drawn into the supply, especially if the
plant operators had not been warned beforehand to cease pumping. A slug of Orimulsion
could potentially overwhelm a water supply treatment capacity for removing organics
including some of the carcinogenic compounds mentioned above. Most plants are set up to
remove settlable solids and low concentrations of organics but not heavier-than-water liquids
or suspensions; e.g., heavy oils, Orimulsion.
Data Gaps
As the above sections show, a number of data gaps exist with respect to understanding the behavior
and fate of Orimulsion spilled in fresh water. Because of the significant increase in cost associated
with transfer of the fuel from ocean-going tankers to barges or other means of transport, Bitor's
current plans are to develop U.S. customers only at sites accessible by ocean-going tankers.
Nevertheless, understanding the behavior and fate or Orimulsion in fresh water is important due to the
presence of streams, wetlands, and other bodies of fresh water near a site that receives Orimulsion by
ocean, and because of the potential for Orimulsion to enter bodies of fresh water through indirect
routes such as storm drains. Any freshwater bodies near a site using Orimulsion may be impacted by
a spill that occurs during fuel handling or other activities not associated with marine shipment.
As noted in the Orimulsion Technology Assessment Plan (EPA 1999a), if Bitor does begin to develop
U.S. customers at sites accessible only by fresh water, at a site near bodies of fresh water, or at sites
where freshwater contamination may occur (even if indirectly), Bitor should fund the research to
address the data gaps as they have done for marine environments. Such research does not fall under
the Congressional directive for this report, and should not be considered to be EPA's responsibility
under that directive. However, since EPA is responsible for responding to spills in certain situations,
the Agency should continue to investigate Orimulsion spill behavior and response as appropriate.
EPA and the Coast Guard have initiated a study on Orimulsion by the National Academy of Sciences
to evaluate the information needed to develop an effective Orimulsion spill response. EPA will use
this guidance to determine what additional research may be required to support their regulatory
requirements with regard to spill response. Other work on Orimulsion is being carried out within
EPA's Office of Research and Development to more fully characterize specific chemical and physical
properties of Orimulsion and to evaluate a spill behavior model and extend the model to cover
Orimulsion.
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Chapter 8
Environmental Risk Assessment
This chapter contains two major sections. The first was prepared by EPA's National Center for
Environmental Assessment (NCEA), and is an evaluation of a previous study on risk and
environmental impacts associated with marine spills of Orimulsion. The second section was prepared
by EPA's National Risk Management Research Laboratory (NRMRL), and compares Orimulsion to a
heavy fuel oil in the context of a health risk assessment of exposure to hazardous air pollutants
generated by electric utility steam generating units.
Comparative Ecological Risk Assessment Evaluation
As part of the Orimulsion Technology Assessment Plan, an evaluation of the primary environmental
studies on the risk and environmental impacts of marine spills associated with Orimulsion was
identified as a topic to be included in the Assessment Plan. NRMRL requested that the EPA National
Center for Environmental Assessment (NCEA) lead this task. NCEA scientists decided that an
evaluation of the major ecological risk assessment conducted on Orimulsion, by external reviewers
and EPA scientists, would provide the most information on the environmental impacts of a marine
spill of Orimulsion. The primary ecological risk assessment on Orimulsion 100 was led by the
University of Miami to compare the risks associated with a spill of Orimulsion 100 to those of a spill
of No. 6 fuel oil to the Tampa Bay, Florida, ecosystem. The results of this effort are contained in
Harwell et al. (1995) and Ault et al. (1995). Further, the University of Miami team conducted
additional studies to expand the ecological risk assessment in support of the licensing process
followed by a Florida utility seeking to use Orimulsion in the Tampa Bay, Florida area. These
additional studies are listed in Appendix G. In support of the Orimulsion Technology Assessment
Program, NCEA scientists identified key assessment issues, developed a charge to the reviewers of the
Harwell study, and selected three reviewers to address these issues in their evaluation of the
documents.
The Harwell assessment evaluated by NCEA did not examine in detail the potential physical effects of
spilled Orimulsion, which have the potential to be as serious as toxicological effects. The NCEA
evaluation examined only a single study and not the larger body of literature on Orimulsion spills,
and did not discuss factors outside the scope of the Harwell study that may have additional significant
ecological and health impacts.
This evaluation contains three sections: an introduction of the topic and NCEA's role in the effort; a
summary of the approach for the comparative ecological risk assessment conducted by Harwell et al.
(1995) and their conclusions as to the comparative ecological risk between the use of Orimulsion 100
versus No. 6 fuel oil; and a scientific evaluation, by the external reviewers and EPA scientists, of the
comparative ecological risk assessment. The reviewers' comments address assessment methodologies,
portability of the assessment, fate and transport methods, toxicity methods, and research needs.
Introduction
Orimulsion is a new compound in the environment and it has unique aspects to consider. For
example, the density of Orimulsion is important when determining the transport and fate of the
material in marine, brackish and freshwater systems. Also, organisms or ecological resources most at
risk from releases of Orimulsion may be different from biota at risk from oil spills. In addition, the
delivery of the material in toxicity studies to assess effects of this compound on aquatic life requires
special attention to ensure the exposure is similar to what could occur in marine systems.
The comparative assessment conducted by Harwell et al. (1995) was funded by Florida Power &
Light. Florida Power & Light applied for a permit to burn Orimulsion 100 at their Manatee Parrish
power plant located on Tampa Bay, Florida. The power plant currently burns No. 6 fuel oil, and a
comparative assessment was one of several studies funded by the utility. Florida Power & Light's
request for a permit to burn Orimulsion 100 at their Manatee Parrish power plant was denied for
policy reasons on June 24, 1998.
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Summary of Comparative Ecological Risk Assessment Reports
The comparative ecological risk assessment conducted by Harwell et al. (1995) and the related
technical support document (Ault et al. 1995) on environmental impacts of spills associated with
Orimulsion 100 versus No. 6 fuel oil in the Tampa Bay ecosystem were determined to be of sufficient
depth and quality to appropriately describe the ecological risks to marine systems and to the Tampa
Bay ecological system in particular. This determination was made by the external panel and was
reviewed by NCEA. The comparative ecological risk assessment incorporated much of the pertinent
environmental fate and effects studies available on Orimulsion 100. The accompanying technical
support document (Ault et al. 1995) generated or reviewed much of the aquatic and terrestrial
toxicity data, the environmental fate and transport data, geographical information systems (GIS)
techniques, and the modeling data. The assessment utilized state-of-the-art methods, presented new
approaches and scientific advancements, and applied appropriate ecological risk assessment
techniques, following the ecological risk assessment framework (Rodier and Norton 1992), to
compare the environmental impacts from various spill scenarios of Orimulsion 100 and No. 6 fuel
oil.
Scope of Harwell Work
The project (Harwell et al. 1995) consisted of:
1. developing sophisticated modeling tools to simulate dynamically the physical environment of
Tampa Bay;
2. establishing geographical information and scientific data visualization systems to collate an
extensive database on the ecology of Tampa Bay and its biological resources into a spatially
distributed, graphically appealing system;
3. conducting experiments to test toxicological responses of biological resources to No. 6 fuel oil
and Orimulsion 100 in addition to the survey of existing toxicological data;
4. applying stochastic models of population-level toxicological effects;
5. developing scenarios of hypothetical conditions that might occur at the time of a spill of No. 6
fuel oil or Orimulsion 100;
6. applying models to develop maps of estimated concentrations and exposures of
lexicologically important constituents of each fuel type;
7. analyzing the co-occurrence of exposures with distributional data of selected fish and
invertebrate species of Tampa Bay;
8. analyzing the fate and shoreline impacts of the slick that would ensue from a spill of No. 6
fuel oil;
9. calculating the risk of ecological effect from the water and shoreline exposures to the two fuel
types; and
10. synthesizing analyses into an overall judgment of the comparative ecological risks of No. 6
fuel oil and Orimulsion 100 spill in Tampa Bay.
Approach of Harwell Work
The approach chosen by Harwell et al. (1995):
1. was conservatively protective by choosing parameters that were plausibly conservative for the
scenarios used;
2. studied species and life stages that were sensitive to the stress and important to society;
3. examined potential effects on populations and critical habitats;
4. emphasized cumulative exposures on ecotoxicological endpoints using plausibly conservative
assumptions; and
5. utilized sensitivity analysis to evaluate changes in key factors on the magnitude of the
ecological effects.
Conclusions of Harwell Work
The conclusions reported by the authors of the comparative ecological risk assessment of the two
materials (Harwell et al. 1995) determined that the ecological risks from No. 6 fuel oil and
Orimulsion 100 to the Tampa Bay ecological system are essentially similar. Their assessment
demonstrated that, while the materials have the likelihood to impact individual ecological endpoints
differently (e.g., spotted sea trout versus coastal systems), the overall risks were judged, by the
authors, to be comparable. If No. 6 fuel oil risks are assumed to be socially acceptable, since a power
plant is currently utilizing No. 6 fuel oil, then the overall ecological risks from Orimulsion 100 would
not be significantly greater. There is greater uncertainty about some of the effects on aquatic systems
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from Orimulsion 100 because it does not have an extensive data base. A synopsis of the comparative
risk methodology is presented in Appendix H.
Orimulsion 100 and No. 6 fuel oil impact ecological endpoints differently. In the comparative risk
assessment conducted by Harwell et al. (1995), the risks of the two materials to biota in the water
column, coastal systems, and avian species were evaluated. Water column risks from Orimulsion 100
exceed those from No. 6 fuel oil. The lower amount of No. 6 fuel oil that enters the water column,
combined with a shorter residence time, results in a lower cumulative exposure. After a spill,
Orimulsion 100 will be dispersed into the seawater column and it will therefore have a longer
cumulative exposure. However, fuel oil contains much higher levels of dissolved aromatics than
Orimulsion 100. These dissolved aromatics cause much of the toxicity to aquatic life. Therefore when
ecological effects in the water column are compared, Orimulsion 100 has only a slightly higher
toxicity. The ecological impacts from the fuel oil slick on coastal systems and avian species will be
significant for some spill scenarios of No. 6 fuel oil. Orimulsion 100 spills will have limited effects on
these endpoints (Harwell et al. 1995).
Scientific Evaluation of the Comparative Ecological Risk Assessment of Spills from
No. 6 Fuel Oil and Orimulsion 100
The comparative ecological risk assessment (Harwell et al. 1995) and the related technical support
documents (Ault et al. 1995) were evaluated by EPA and external scientists for technical adequacy,
technical approach, and research needs. Their comments are summarized in the following categories:
assessment methodologies, portability of the assessment to other sites, fate and transport methods,
toxicity test methods, and research needs.
Overview of Harwell Assessment
Overall, this comparative ecological risk assessment (ERA) was impressive in its scope, level of
research effort, and use of innovative approaches for estimating and understanding risks. The
approach taken by the investigators was also well-conceived and well-documented in its prediction of
the environmental distribution and consequences of compounds resulting from a spill of each fuel in
Tampa Bay. Use of dynamic fate and transport models, geographic information systems, extensive
toxicity testing, and other tools in this assessment puts it ahead of most assessments that have been
reviewed in the past. Reviewers agreed with the authors' major conclusion that a spill of Orimulsion
100 likely poses a similar or lower risk to Tampa Bay biota than does an equivalent spill volume of
No. 6 fuel oil. However, parts of the assessment, such as risk characterization, population modeling,
and impacts to benthic (sea-, lake-, or river-bottom) communities, were identified by reviewers as
assessment topics that could be improved. These improvements would enhance the present report,
however they do not impact the conclusions put forward by the authors. The research needs section
identifies research and modeling studies to address these issues.
Assessment Methodologies
Questions 1, 2, and 3, in this section come from the NCEA charge to the reviewers.
Question 1. How well does the Harwell et al. (1995) document present models, techniques (GIS,
sensitivity analyses, population models, etc.), and experimentation to assess the
ecological risks associated with marine spills of Orimulsion 100?
The document generally describes appropriately applied models, techniques, and experimentation.
Overall, they are consistent with the current state-of-the-art methods and, more importantly, generally
apply appropriate technology to address the relative risk of Orimulsion 100 and No. 6 fuel oil. As a
model of what can be done with ecosystem assessment and toxicological information, the state-of-the-
art-modeling procedures and the combination of GIS and data visualization approaches are an
exceptional management tool. The use of GIS to illustrate the outputs of the hydrodynamic and fate
modeling, levels of hydrocarbons and aromatics following spills of Orimulsion 100 and No. 6 fuel
oil, abundances of different fish species, etc., is an excellent means of helping readers visualize spatial
patterns. However, the GIS tool could have been used more effectively and the results better presented
by providing more text to support the graphics.
Although consistent with current methods, standard toxicity test results are mathematically limited
information with which to imply population effects and to convert toxicity metrics to population
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model parameters. The toxicity data are mathematically limited for use in the matrix-based
demographic and metapopulation-based models. Approximations were attempted (e.g., applying a
logistic model with assumptions of a probabilistic process for lethality or exponential death through
time due to toxicant action [Ault et al. 1995; pp. 8-24 and 8-42]) that are not generally valid for
many situations. It would have been preferred if the test results had been used to generate survival
time information based on exposure concentration and duration of exposure.
Joint distribution analysis can also be considered a state-of-the-art tool because it can be used to
estimate probabilities of effects of differing magnitudes (referred to as risk curves). Risk curves
present a great deal of information to risk managers and stakeholders, much more so than risk
quotients. In this assessment, however, the joint distribution approach was used to generate risk
quotient distributions. The same information is required to generate probabilistic quotients and risk
curves (an exposure distribution, a concentration-response relationship), yet the latter is much more
informative than the former. Generation of risk curves is a research need that would improve the
assessment. This research need is not limited to risk assessments for Orimulsion, but, rather, is a
general need for the field of ecotoxicology.
Satisfying all the assumptions to determine risk to ecological communities is very difficult. Although
it also carries some dubious assumptions, a species sensitivity distribution approach producing a HC5
and associated 95% confidence interval could have been used. Although imperfect evidence, it could
have been helpful in evaluating this assessment. The present assessment used a Monte Carlo-
generated "joint" distribution of hazard quotients that is reasonable and similar to the suggested
approach. However, neither approach satisfies all assumptions needed to determine risk to an
ecological community.
The rationale for the decision that "the exposure and effects data were treated as log-normal
distributions in the analyses" (Harwell et al. 1995; p. 133) is unclear. There are good theoretical
reasons for treating exposure as a log-normal distribution (see Ott 1995), but probably none for
treating the effects data as such. Generally, the appropriate underlying distribution for effects data is
the binomial distribution for quantal endpoints (e.g., mortality), the Poisson distribution for count
endpoints (e.g., number of young), and the normal or Gaussian distribution for continuous endpoints
(e.g., growth rate, biomass) (Bailer and Oris 1997).
Sensitivity analysis is a very important tool for risk assessment, particularly in probabilistic risk
assessments, and it appeared to be used effectively. It would have been useful to see figures of model
sensitivity results that allowed easy comprehension of the relative level of influence of the major
variables on model prediction outcome. The authors made extensive use of sensitivity analysis in this
assessment to investigate, for example, the influence of location, timing, season, climate (e.g., wet
season, dry season), and other variables on the resulting spatial distribution of plumes from spills of
Orimulsion 100 and No. 6 fuel oil. Size of spill was also briefly considered (i.e., comparison of spills
of 10,000 and 25,000 barrels). Some parameters expected to be important in estimating spill risks
(e.g., spill duration in the 3-D hydrodynamic model; dispersion coefficients, degradation rates and
physicochemical properties in the SIMAP fate and transport model) were held constant, so their
influence on outputs could not be investigated through the use of sensitivity analysis. Although the
use of the stochastic RAMAS population model should have been amenable to sensitivity analysis to
determine important input parameters, reviewers could not find any such analysis in any of the
supporting documentation.
The linkage to population risk is central to a meaningful ecological risk assessment. The authors
recognized this and spent considerable effort trying to do this. In this context, the present assessment
is much better than most assessments. While population-level modeling was done to assess potential
effects on population abundance for sea trout and other species, population modeling could have
used the available information effectively through linkage to stock management models, better
utilization of lethality data, and providing better rationales for assumptions and equations. It would
have been interesting to compare estimated population losses from a spill versus recreational and
commercial fishing. The production of survival functions would have been relatively straightforward
from the generated data and would have utilized the mortality data more effectively. The
extrapolation from lethal concentration to 50% of exposed population (LCso) to dose response curves
with dubious relationships to predict effects at different exposure durations on mortality, could have
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been improved through the use of the generation of survival functions with time (i.e., time to event).
More discussion on the use of assumptions and equations (e.g., exponential mortality with time due
to toxicant effect; focus on lethal effects in demographic analyses; operationally assuming that the
most sensitive stage of an individual's life is the most important to consider in population viability
analysis) would have been beneficial.
Question 2. Are assessment endpoints and measures of effect appropriate for this site? Are they
linked in the risk characterization section?
The document did a good job developing selection criteria for the assessment endpoints and linking
them to appropriate metrics (measurement endpoints). While population-level impacts were modeled,
it would have been helpful for risk communication and translation among resource managers if the
document could have provided estimates of yield reduction in the context developed by fisheries
stock assessors. Given the selection of sea trout as the focal species for the risk assessment, due to its
status as the most sensitive species, but also with important commercial and recreational value, it
would have helped to incorporate the "take" from a spill into terms of a fisheries stock management
model. Placing spill "take" into the same context as takes from recreational and commercial fishing
would have been helpful in assessing the relative magnitudes of these demands on the population.
Information on the sea trout stock remaining well above the level of sustainable harvest after a spill
scenario would be useful. However, this is not a major flaw and its omission did not detract from the
generally insightful and thorough job done here.
The general focus in this assessment was on estimating risks of spills to spotted sea trout, although
considerable effort was also directed at estimating risks to other biota such as sea grasses, mangroves,
aquatic invertebrates, and other fish species. The general arguments presented in the problem
formulation for selecting these species seem well supported. However, key pieces of the problem
formulation thought process are scattered throughout Volume I of the assessment (Harwell et al.
1995). For example, the rationale for key species selection was presented at the end of the analysis
section (Ault et al. 1995; pp. 98-99) and the details of what actually was selected were not provided.
The assessment endpoints and measures of effect chosen for this site seem appropriate (e.g., meet the
criteria of potentially exposed, sensitive, and of ecological, social and economic value), and the
assessment endpoints were appropriately considered in the risk characterization phase. The risks of
spills posed to endangered species could have been more directly addressed, although clearly no
toxicity tests can be done on endangered species or on marine mammals. As the authors correctly
note, many populations can recover quickly from acute toxic effects because of source refugia
outside the spill area. However, with endangered species, particularly those that would recover very
slowly from a spill impact (e.g., manatees), acute toxic effects to individuals within the spill area could
be devastating at the population level. It would be useful for the authors to identify which endangered
species are at risk in and near Tampa Bay and to at least qualitatively consider the risks spills would
pose to these species.
The statement is made about developing a metric assuming that "The contribution that a given
species makes to the total abundance of Tampa Bay's fish and invertebrate fauna provides insight
into its ecological position and function in the ecosystem. From this perspective, the relative
abundance or density of a given species represents a simple index of its importance." (Ault et al.
1995; pp. 8-34). Given numerous examples to the contrary (e.g., keystone species) and the different
ways that abundance is measured (e.g., number of individuals, biomass, coverage), this section could
be rephrased.
Question 3. Does the risk characterization appropriately present the risk estimate and discuss the
comparative risk fully? Are the conclusions of the comparative assessment supported
by the risk characterization presentation?
The breadth of methods employed to characterize risks of Orimulsion 100 and No. 6 fuel oil spills
was truly impressive. Given the data and analyses developed, the conclusions were supported.
Reviewers supported the conclusions that Orimulsion 100 presents slightly greater water column risks
than does No. 6 fuel oil, but that the risks of a fuel oil slick to shoreline and tidal communities likely
exceed the water column risks posed by Orimulsion 100. However, the presentation of the risk
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characterization section could have been improved. Often key details were missing and assumptions
were not justified.
The analysis is very ambitious and provides a comprehensive assessment of the behavior and toxicity
of the two fuel types. The conclusion from the analysis is that the ecological risks associated with
spills of either No. 6 fuel oil or Orimulsion 100 are comparable. This is based on the lack of
demonstrated phytotoxicity to mangroves and sea grasses; the normalized exposure fields for each
fuel type; and the model predictions of physical transport. Orimulsion 100 is considered to behave
like "pre-dispersed" oil and much of the interpretation of physical fate and toxicity is based on the
assumptions that the exposure field (toxic concentrations and time) of the two fuel types will be
comparable. This is due primarily to the relatively high toxicity but short duration of the aromatic
fraction of No. 6 fuel oil and lesser toxicity but longer duration of the total hydrocarbon fraction of
Orimulsion 100. The authors then conclude that the longer term effects associated with spills of No. 6
fuel oil reported in the literature would not likely occur with Orimulsion 100 due to the lack of
sediment accumulation of hydrocarbons from Orimulsion 100. This latter statement was addressed in
subsequent studies listed in Appendix H.
Several statements in the risk characterization section make expert judgments without enough
explanation for the decision presented to the reader. For example, in the documents (Harwell et al.
1995; pp. 110 and 114) it is stated that selection of sea trout and silversides as focal species
effectively bounds the range of expected effects to aquatic biota in Tampa Bay. Further information
is needed to explain how the figure (Harwell et al. 1995; p. 124, Figure V7) provides evidence that
"some population impacts would be experienced over a significant area." The figure merely shows
what proportion of the Bay would be exposed to Orimulsion 100 or No. 6 fuel oil following
hypothetical spills at four locations. How this translates to population level effects is never explained.
The comparative risk was based on identical scenarios (Harwell et al. 1995). A reviewer did not
accept the "common conditions" characteristic of the comparison process. It may be a useful
comparison if the selected scenario is benign for one fuel and negative for the other; yet, with another
scenario, the relative impacts were reversed. Alternatively, one could pick "the most probable"
scenario and use that for comparison; this would also require an estimation of the variation expected
from the associated predictions. In a comparative risk assessment, relative risks, odds ratios, or risk
ratios could have been applied very effectively for the No. 6 fuel oil versus Orimulsion 100.
However, the report (Harwell et al. 1995) strongly argued and the administrative law judge agreed
that a comparative ecological risk assessment, examining the relative risks of two different fuels, must
have identical scenarios in all regards except for the fuels themselves in order for a valid comparison
to be made.
The joint distribution analyses did not take into account some significant sources of uncertainty. For
example, a point estimate of 0.02807 is used to convert nominal concentrations of No. 6 fuel oil to
benzene, toluene, ethylene, and xylenes (BTEX). This estimate is presumably a measure of centrality
(the authors do not tell) derived from limited samples of a single fuel preparation made by a single
laboratory. The authors do not indicate the possible bounds on this conversion factor. A second
conversion factor was used to normalize the BTEX toxicity data to the AR2 fraction described in the
transport model. The factor used was 3, but the document states (Harwell et al. 1995; p. 108) that the
factor could range from 2 to 5. Further, benzene and toluene were not included in the AR2 fraction,
despite the significant contribution toluene makes to total BTEX in bulk fuel (25%) and the fact that
it is quite soluble in water (535 mg/L). The exclusion of toluene from the exposure estimation biases
the analysis to underestimate risk but it is uncertain by how much. Finally, the model analyses
assumed that 48% of No. 6 fuel oil is aromatics, yet the authors state that the percent aromatics have
been shown to vary from 7 to 65%. Including this source of uncertainty in the joint distribution
analysis could have a profound effect on the resulting distribution of quotients (this topic is listed as a
research need).
In many places in the risk characterization section interesting and useful analyses were being done,
but key details were often missing that made it difficult for reviewers to judge the quality of the
analyses and the validity of the conclusions. Missing details were often in the supporting
documentation, other times not. For example, the logistic regression analyses on the toxicity data
represent a considerable improvement over derivation of no observable effects concentrations
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(NOECs) and lowest observable effects concentrations (LOECs), but unfortunately goodness-of-fit
statistics, confidence intervals about the mean, and prediction intervals were not provided. Without this
information, it is hard to decide how confident one should be about the estimated effects and lethality
concentrations.
One of the approaches used to estimate community level risks was to combine "model key species"
into a "complex that represents a 'holistic' picture of the distribution and abundance of 13 key
ecological resource species .... " (Harwell et al. 1995; p. 114). This complex is stated to "be a good
gauge of interaction and co-occurrence." Information is needed to explain how this "complex" was
calculated and how it could possibly take into account species interactions and co-occurrence.
Information is not provided as to whether the exposure distributions are probability density functions
or reverse cumulative distributions. Finally, discussions in Harwell et al. (1995; p. 128) indicate that
expected mortalities from co-occurrence of sea trout of the recruit age class with either fuel type are
expected to be very small (<0.6%). Figure V 8, however, shows that a considerable portion of the
exposure distribution exceeds levels that would cause greater than 10 to 20% mortality (depending
on fuel type). In the text evaluating how oil slicks in the past have affected the environment
(Section V.4.5), no information is provided to determine if past spills of bunker C, light diesel have
any relevance to the kinds of damage that might be expected from spills of No. 6 fuel oil.
It appears that the effects concentrations (e.g., LCi0- LC95-) were "multiplied by 50 to represent the
associated exposure of a two-day period (comparable to the 48-hr tests)" (Harwell et al. 1995; p.
104). It is unclear why this was done. A more appropriate approach to incorporate exposure duration
in the toxicity estimates would be to explicitly model the concentration-duration-response
relationship or use one of the time-to-death methods discussed in chapter 4 of Newman (1995).
Portability of this Assessment to Other Sites
This charge to the reviewers evaluated the major issues to consider and applicability of this ecological
risk assessment to assess impacts on ecological resources from a spill at other coastal sites.
The approach seems appropriate for application to other sites. The many issues tackled in the
assessment would all need to be considered in assessments of other sites. These include identifying
selected locations, spill sizes, climatological and hydrological conditions, at-risk biota, and a
modification of scenario characteristics. Also, the inclusion of population models could draw more
on survival time models and/or fisheries stock assessment models, etc., that together can be used to
construct risk scenarios that are internally consistent and represent the range of risks posed by a
future spill. Other issues to consider would be data availability, budgets for new research (e.g.,
toxicity studies on native biota, collection and entering of data into a GIS database), and availability
of local expertise to conduct fate modeling, toxicity testing, etc.
To some extent, the assessment endpoints and measures of effect for Orimulsion 100 are
transportable to assessments of other marine and estuarine sites. For example, any assessment of risks
posed by an Orimulsion 100 spill in saline waters would likely focus on sensitive, pelagic biota
because the bitumen particles for the most part end up in the water column. Thus, sea trout is an
appropriate assessment endpoint for marine sites throughout its range. Farther north, one might
choose early life stages of sea bass. Another species that could be considered for risk assessments of
spills on the west coast would be salmon because juveniles have to pass through estuaries on their way
out to sea. Similarly, adult salmon pass through estuaries on their way to spawning grounds. Spills in
west coast estuaries during these critical times could have a significant impact on salmon populations.
As with the Tampa Bay assessment, assessments at other estuarine and marine sites would not likely
need to focus on emergent vegetation and other high shoreline communities because Orimulsion 100
is not deposited to this area in significant quantities.
The approach of using spatially explicit methods and sophisticated hydrodynamic fate and transport
models to estimate exposures resulting from hypothetical spills is a useful one and could be used at
other sites. Population modeling, toxicity testing with native species, and distributional analyses to
account for uncertainties are also highly recommended for other sites. Details of how the methods are
applied need to be put forward.
-------
Fate and Transport Methods
This charge to the reviewers evaluated Orimulsion 100 density issues; exposure assumptions, transport
models, and impacts of spills; and the ability of models to predict the release rate, weathering, and
transport of Orimulsion 100. In addition, the scenario factors and conditions were evaluated for
appropriateness.
The reports (Harwell et al. 1995, Ault et al. 1995) give excellent overviews and analyses of the
buoyancy of Orimulsion 100 in different salinity waters and following weathering. The use of
spatially explicit and dynamic models that account for local conditions is a state-of-the-art approach.
Further, there appears to have been an extensive effort to gather the information required to
parameterize these models.
An assumption is implied that only the instantaneous concentration to which an organism is exposed
determines the toxic effect at any moment, "...the impact of the spill can be measured by the integral
of the concentration time series of the total hydrocarbons in the water at the given critical-habitat
location ...." However, there could easily be a cumulative dose effect that results in death. In that
case, exposure to one concentration at time tx could be influenced by the concentration experienced
at time tx_i , tx_2 , etc. Or, after exposure ends (time x), latent mortality could still occur at times longer
than x.
The decision to focus on four locations for hypothetical spill sites and three seasonal conditions
seems logical and follows from extensive consultations and early modeling efforts. The transport
models chosen (and further developed) seem to be state-of-the-art and their use to investigate
sensitivity of outputs to factors such as location, season, climatic conditions, wind direction, and spill
size was very informative.
Preliminary studies on weathering of both fuel types (Brown et al. 1995, Chapter 4) suggest that
further analysis of the persistence of medium-to-high molecular weight compounds in both fuel
types would be warranted. More information is certainly needed on a larger scale (e.g., mesocosms)
to better understand the weathering processes, physical and chemical fate of oil in water dispersions
of the two fuel types, and the long-term fate of the two fuels.
Toxicity Test Methods
This topic evaluated whether the toxicity studies conducted were adequate to assess effects of this
compound on aquatic life. Toxicity tests were evaluated for appropriate endpoints and scenarios of
relevant target organisms or ecological resources most at risk from releases of Orimulsion and oil
spills.
The scenarios seem to focus on the appropriate ecological entities. The toxicity studies were generally
acceptable for the assessment. It might have been useful to have a bottom fish, such as the southern
flounder, which was valued in the area. With the exception of benthic biota (identified as a research
need), the risk scenarios addressed for waterborne exposures of Orimulsion 100 and No. 6 fuel oil
were appropriate (i.e., juvenile species of fish, pelagic invertebrates). Further, the focus on risks to
mangroves, sea grasses and other shoreline biota was appropriate for estimating risks of No. 6 fuel oil
slicks. The Orimulsion 100 toxicity tests involving mangrove propagules and seedlings convincingly
demonstrated that Orimulsion 100 poses little risk to these organisms. Perhaps the risks of Orimulsion
100 tar balls to shoreline biota should have been considered. More effort on effects on reproduction
and growth would have been useful but would have been expensive and time consuming to produce.
The subsequent toxicity tests did include a number of indigenous benthic species.
The toxicity studies conducted as part of this project contributed valuable information to the
assessment. For example, the tests involving mangrove propagules and seedlings helped convince one
reviewer that No. 6 fuel oil slick poses more of a risk to these species than does Orimulsion 100. The
comparative study of toxicities of No. 6 fuel oil and Orimulsion 100 to early life stages of sea trout
was particularly important given that this species was the major assessment endpoint in this project.
Results are presented in the documents (e.g., growth and production on page 5-14; page 5-20,
paragraph 1 in 5.4.1. of Harwell et al. 1995) with no expression of power or minimum significant
-------
difference. Discussions on the effects of the materials on growth and uncertainty in hypothesis tests
without a statement of power or minimum significant differences are of limited use.
The analysis of the data and endpoints was inadequate for fitting the demographic models. Use of
basic demographic methods (Caswell 1989, as cited in the report) or survival models (e.g., Newman
1995) would have eliminated this problem. If the LC50 dose response curves were used later by the
modelers in a logistic model, the data should have been analyzed with logit methods. The rationale
for using 48 hr LC50 data in a logistic model to predict an LC10 and then using this as a threshold of
detectable/significant toxicity in simulations (which was based on acceptable criteria for control
mortality in the toxicity tests, Harwell et al. 1995; p. 106) needs to be stated as a science policy
decision rather than one based on ecology.
The assumption is made throughout the report that the major concern with a spill of either fuel will
be the acute effects associated with water column concentrations of hydrocarbons. Given the
relatively high concentrations of low molecular weight aromatic compounds associated with No. 6
fuel oil, this is a relatively sound assumption to make in a first approximation of spill conditions. The
toxicity of No. 6 fuel oil is normalized to benzene, toluene, and xylene concentrations that are indeed
the most toxic and the most short-lived compounds in an oil slick following a spill. Little analysis is
given to the longer-term effects associated with the accumulation of higher molecular weight
compounds from No. 6 fuel oil, especially in sedimentary environments, although it is acknowledged
that this could occur.
Another assumption made throughout the analysis is that Orimulsion 100 will not have long-term
effects on ecosystems because it does not adhere to sediment particles and is not likely to accumulate
in benthic habitats. This is largely unsubstantiated by the data presented in the supporting documents.
In fact the Orimulsion 100 showed a greater adhesion to sediments than No. 6 fuel oil and could
under certain hydrographic conditions accumulate in benthic habitats. However, the authors of the
comparative risk assessment report and subsequent studies make the case that the vertical velocities of
water movement in Tampa Bay greatly exceed settling velocities of Orimulsion, including when
particulate-bound, suggesting that there would not be significant settling onto the bottom or
significant exposures to the benthic organisms of the Bay.
Suggested Improvements for the Tampa Bay Risk Assessment
To further address the relative risks associated with a spill of Orimulsion in Tampa Bay, there are
several technical issues that could be addressed to better understand the ultimate fate and effects of
Orimulsion in Tampa Bay and other coastal environments. These research needs are considered to be
the responsibility of Bitor and/or users of Orimulsion (EPA 1999a).
Toxicology
Further research could verify the differences in toxicity and persistence of major hydrocarbons of
concern (lower-to-higher molecular aromatic compounds, alkyl-substituted aromatics, and
compounds unique to Orimulsion) between the two fuel types.
The toxicity database is not large for Orimulsion 400, especially for oil-in-water preparations. To
determine the species sensitivity distribution for pelagic biota, it would be useful to test additional
early life stages of marine fish species other than spotted sea trout, and invertebrates and macroalgae.
The additional data would be useful in determining whether spotted sea trout is a very sensitive
species.
Several of the factors used to convert the No. 6 fuel oil toxicity data so that the results were
comparable to the exposure data were based on very limited information. Studies involving multiple
fuel preparations and laboratories should be conducted to establish the BTEX conversion factor and
the distribution around it. The appropriate distribution and parameterization for normalizing the
BTEX to the AR2 fraction also need to be established. Clearly, studies need to be done to establish
the percent fraction of aromatics in No. 6 fuel oil. If this fraction is highly variable, then this
information needs to be incorporated in future exposure analyses.
8-9
-------
Research on how aquatic species respond to the types of exposure expected after a spill (e.g.,
declining concentrations over time) rather than the constant exposures used in typical toxicity tests
would provide useful information.
Benthic Community
A more in-depth analysis of the fate and effects of Orimulsion on benthic communities including
more effects on invertebrates and key fish species would be of interest. This would include:
weathering processes, bacterial associations, and ultimate deposition.
The potential effects, from the formation of Orimulsion tar balls at the surface of marine waters, on
shoreline and tidal communities should be further evaluated in the risk characterization section.
Modeling
Use of basic demographic methods (Caswell 1989, as cited in the report) or survival models (e.g.,
Newman 1995) should be utilized for toxicity data. The generation of survival functions with time
could then be applied to population models.
Improved prediction methods are needed for the exposure fields for both fuel types, including
estimates of the exposure concentrations and persistence of medium to higher molecular weight
aromatics, and alkyl-substituted aromatics of both fuel types and the surfactant components of
Orimulsion.
Modeling comparisons of chemically dispersed oil, naturally dispersed oil and Orimulsion, with
specific evaluation of short-term and near-field exposure regimes and long-term and far-field
exposure regimes should be conducted.
The joint distribution analyses could further address significant sources of uncertainty. Including
these sources of uncertainty in the joint distribution analysis could have a profound effect on the
resulting distribution of quotients.
Mitigation
Although deliberately not addressed in the review, the mitigation procedures that could be used
following a spill of either fuel type need to be explored in more detail to fully evaluate Orimulsion as
a fuel alternative.
Assessment of Risk from Air Emissions
It was not possible in this study to conduct a complete assessment of risks associated with exposure to
air pollutants from the emissions of Orimulsion combustion. However, it is possible to examine a very
complete risk assessment for a similar fuel. In 1996, EPA completed a major study (referred to here
as the Utility Study) of the risks to human health from emissions by electric utility steam generating
units (EPA 1998). In that study, a complete inhalation exposure study was done to evaluate cancer
risks associated with exposure to hazardous air pollutants (HAPs).
One of the HAPs evaluated in detail was Ni emitted from both coal- and oil-fired power plants. The
study calculated the risk of cancer to a maximally exposed individual due to inhalation exposure to
Ni, the number of people that would be at different levels of risk, the number of plants for which the
additional cancer risk was greater than 1 in 106 , and the total number of additional cancer cases that
could be attributed to Ni exposure from power plant emissions.
The study assumed that 100% of Ni emissions were in subsulfide form, which is the most
carcinogenic form of Ni; however, the dominant forms of nickel are typically the soluble salts and
oxides (EPA 1998). The study notes that this is a very conservative assumption, since it is likely that
other forms of Ni are also present, which would reduce the total carcinogenicity of the pollutants.
For coal-fired plants, a maximally exposed individual would face a cancer risk due to exposure to Ni
from utility combustion of IxlO-7, and for the U.S. as a whole, an increase of 0.02 case of cancer
could be expected to be caused by exposure to utility-generated Ni emissions. This analysis does not
consider long-range transport of emissions, nor does it account for exposure pathways other than
8-10
-------
inhalation. Both of these factors would act to increase the calculated cancer risk, by a factor of up to
7 (EPA 1998). These factors may be somewhat offset by the assumption that all Ni emitted is in the
subsulfide form, but in any case, Ni emissions from coal-fired power plants do not appear to form a
substantial cancer risk for the U.S. population as a whole.
The situation is somewhat different for Ni emissions from oil-fired power plants. Because of the
higher Ni content of heavy fuel oils and the fact that more oil-fired plants are closer to population
centers than are coal-fired plants, a maximally exposed individual would face a 9xlO-5 risk of cancer
due to exposure to Ni emissions from oil-fired utility plants, roughly 2 orders of magnitude greater
risk than for coal. The Utility Study estimated that 1.65 million people faced a cancer risk greater
than IxlO-6, and that nationwide, inhalation exposure to Ni emissions from oil-fired power plants
would result in an additional 0.4 cancer cases. Similar analyses were also conducted in the Utility
Study for As and Cr. Similar to Ni, speciation of Cr compounds is an important factor in the toxicity
of Cr compounds. The Utility Study assumed that the only risk of cancer from inhalation of Cr was
due to hexavalent chromium (Cr VI) species, and that trivalent chromium (Cr III) species did not
contribute to cancer risk.
The Utility Study also noted differences in reported Inhalation Unit Risk Estimate (IURE) values for
As. IURE values ranged from 1.4xlO-3 to 6xlO-3 per (ig/m3, with the higher value representing higher
risk per unit As concentration. In the Utility Study's quantification of risk, an IURE value of
4.3xlO-3 per (jg/m3 was used.
Table 8-1 presents a summary of cancer risk data for exposure to HAPs reported in the Utility Study.
These results indicate that the total additional cancer cases attributed to emissions from oil-fired
utility boilers is 0.5. These results do not account for indirect exposure or exposure to emissions
transported over long range, but do account for the conservative assumptions of 100% subsulfide
forms of Ni and the mid-range value for As IURE.
One can use these results as a basis for understanding the potential risks that may result from
widespread use of Orimulsion. If Orimulsion were to replace all heavy fuel oil in utility boilers, a
reasonable initial estimate of cancer risk due to Ni emissions from those boilers would be to assume
similar results as for heavy fuel oil, since Ni content of heavy fuel oil and Orimulsion are often very
similar. In general, the Ni content of Orimulsion is likely to be slightly higher than that of heavy fuel
oil. However, the majority of oil-fired plants are installed with minimum abatement equipment and
therefore relative emissions of nickel from a commercially operating Orimulsion plant installed with
ESPs and FGD would be orders of magnitude lower. A complete risk assessment would have to be
conducted for a quantitative estimate to be made.
Since Orimulsion will be introduced incrementally and in small quantities compared to the total use
of heavy fuel oil,1 it is reasonable to consider the maximum risk calculated for exposure to heavy fuel
oil HAP emissions. There were 0.4 additional incidences of cancer estimated to be caused by
exposure to Ni emissions from all 137 oil-fired plants in the U.S. A reasonable initial estimate of the
cancer risk associated with exposure to emissions of Ni from Orimulsion combustion would be less
than the 0.4 incidences noted above. For all HAPs emitted from heavy fuel oil, the total additional
incidences of cancer were estimated to be 0.5. Again, the additional incidences of cancer associated
with Orimulsion combustion would be expected to be less than this.
This comparison assumes that Orimulsion is introduced incrementally over a period of years, and that
the total use of Orimulsion is not a significant percentage (say more than 10%) of heavy fuel oil use.
Significant increases in Orimulsion use, in terms of both number of plants and total consumption,
would require a dedicated analysis to accurately estimate the risks associated with its use.
The risk assessment results presented in Table 8-1 do not include long-range transport or indirect
exposure. Including either of these factors will increase the total cancer risk (EPA 1998). In addition,
there are risks other than cancer that may play a role in determining the total risk to health. Exposure
1 Total U.S. fuel oil use is discussed in Chapter 9.
8-11
-------
Table 8-1. Summary of risk estimates from inhalation exposure to priority HAPs for 137 oil fired utility boilers in the
U.S. (EPA 1998).
Pollutant
As
Be
Cd
Cr
Dioxin/Furans
HCI
Pb
Mn
Hg
Ni
Carcinogens
Highest MElO)
Cancer Risk
1x10-5
7x1 0-7
2x1 0-6
5x1 0-6
1x1 0-7
NA
NA
NA
NA
9x1 0-5
Population with
Risk> 10-6
2,400
0
45
2,300
0
0
0
0
0
1,650,000
No. of Plants
with MIR(2)> 10-6
2
0
1
1
0
0
0
0
0
20
Cancer
Incidence
(cases/year)
0.04
0.002
0.005
0.02
0.0007
NA
NA
NA
NA
0.4
Noncarcinogen
Maximum HQ(3)
NA<4>
NA
NA
NA
NA
0.06
0.004
0.04
-
NA
1. Maximum exposed individual
2. Maximum individual risk
3. Health quotient
4. Not applicable
to PM2 5, for instance, has been linked to increases in cardio-pulmonary disease (EPA 1996), and that
issue is not addressed here.
Conclusions
Reviewers of a risk assessment of Orimulsion use in the Tampa Bay, Florida area (Harwell et al. 1995)
agreed with that report's major conclusion that a spill of Orimulsion 100 likely poses a similar or
lower risk to Tampa Bay biota than does an equivalent spill volume of No. 6 fuel oil. However, the
reviewers noted that parts of the assessment, such as risk characterization, population modeling, and
impacts to benthic communities, were identified as assessment topics that could be improved. The
reviewers recommended that these improvements would enhance the Tampa Bay report, but their
judgment was that the improvements would not impact the conclusions put forward by the original
report. The review of the original report (Harwell et al. 1995) did not examine factors outside the
scope of the Harwell study, which may have additional significant ecological or health impacts.
Emissions of Ni from the combustion of Orimulsion were compared to those from heavy fuel oil in
the context of an assessment of risk associated with HAP emissions from electric utility power boilers.
This comparison estimated that the cancer risk associated with exposure to emissions of Ni from
Orimulsion combustion would be less than the 0.4 incidences estimated to be similar to those
associated with heavy fuel oil combustion in utility steam generating units.
8-12
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Chapter 9
Comparison of Orimulsion
with Other Fossil Fuels
One of the key questions regarding the environmental impact of Orimulsion use is, "How will
emissions change if Orimulsion is used instead of other fossil fuels?" From the perspective of fuel
reserves, Orimulsion has the potential to contribute a significant portion of U.S. energy consumption.
Total recoverable Orinoco bitumen reserves have been estimated at approximately 267x109 bbls (oil
equivalent) (U.S. Department of Energy 1998a), compared to 22.5xl09 bbls of U.S. recoverable
crude oil reserves and an energy equivalent of 995xl09 bbls of crude oil in U.S. recoverable coal
reserves (U.S. Department of Energy 1998b). The actual degree to which Orimulsion is used in the
U.S. will depend upon many factors, such as relative delivered prices of different fuels and the cost of
using those fuels, including environmental and other operating costs.
The most significant potential use of Orimulsion is in utility and industrial fuel combustion, where
currently the most heavily used fuel is coal, followed, in order, by natural gas and fuel oil. Coal
comprises approximately 83% of the fuel consumed for electricity production in the U.S. and
approximately 47% of the combined utility and industrial fuel use. Natural gas is used for less than
14% of the U.S. electricity production and for just over 30% of the combined utility and industrial
fuel consumption. Less than 4% of electricity is generated from the combustion of fuel oil, and just
under 23% of combined utility and industrial fuel consumption is fuel oil (U.S. Department of
Energy 1998b). While the most attractive opportunity for Orimulsion in the U.S. may currently be as
a replacement for fuel oil due to the relative prices and the ability to use much of the existing fuel
handling and storage equipment at an oil-fired facility, Orimulsion can also be used in place of coal
or natural gas, as illustrated in Chapter 3 by the number of (originally) coal-fired units converted to
Orimulsion.
Because nearly any use of Orimulsion would replace coal, oil, or natural gas, it is important to
compare the air emissions of these fuels with Orimulsion to understand the impact Orimulsion use
would have from an environmental perspective. The different properties of these fuels and the
manner in which they are used are responsible for differences in pollution emissions, and the contents
of impurities in these fuels play the strongest role in emissions of air pollutants.
Previous chapters have presented properties, use, and emissions of Orimulsion in considerable detail.
The following discussions provide less detailed information on properties, use, and emissions
associated with other fossil fuels.
Fuel Properties
Coal
There is a broad body of literature devoted to studies of the properties and characteristics of coal.
While much of this work is focused on energy conversion, a significant portion of the literature
addresses issues associated with air pollution from the combustion of coal. Coal contains relatively
high levels of sulfur (S) compared with many other fuels. In the U.S., the sulfur content of coal
ranges from less than 0.4% to greater than 2.5% (see Figure 9-1). Nearly all of the S in coal is
transformed to SO 2 during combustion, resulting in a substantial level of SO2 emissions from coal
combustion. In 1995, coal combustion by utility and industrial users accounted for 13.7 million tons
of the U.S. total of 18.3 million tons of SO2 emissions (Fitz-Simons et al. 1995). The S content of
coal is therefore an important factor in determining what fuel to use in a particular application.
In addition to the S content of coal, trace metal concentrations in the fuel are also of concern. Of
primary concern are arsenic (As), chromium (Cr), mercury (Hg), and Ni (see Table 9-1). Swaine
(1994) reports As concentrations in world coals range from 0.5 to 80 ppm, Cr from 0.5 to 50 ppm,
Hg from 0.02 to 1 ppm, and Ni from 0.5 to 50 ppm. In addition, he notes that V contents range
from 2 to 100 ppm and Zn from 5 to 300 ppm. Measured values of trace elements in U.S. coals
9-1
-------
70000-
60000-
50000-
w
o 40000-
i 30000-
20000-
10000-
xxxxx
< 0.40%
0.41 - 0.60%
0.61 - 0.83%
0.84- 1.67%
1.68- 2.50%
> 2.50%
Figure 9-1. Estimated recoverable reserves of coal in the U.S. by sulfur content (U.S. Department of Energy
1997).
indicate similarly broad ranges, but average values tend to be toward the lower end of the ranges.
Table 9-2 shows average values and ranges of As, Cr, Hg, and Ni contents of coals from different
regions in the U.S.
Coal cleaning can reduce the amount of metals fed into a boiler or furnace. The effectiveness of
cleaning processes depends strongly upon how an element is bound chemically within a coal and how
the element is physically distributed throughout the coal. As much as 95% of some metals can be
removed during cleaning, but in many cases, wide ranges of metal removals are reported, making it
difficult to predict the effectiveness of coal cleaning (Finkelman 1994).
Elemental carbon (C) contents of U.S. coals range from just over 70% to as high as 94%, with
elemental hydrogen (H) contents ranging from 4 to 11%. These values result in molar H:C ratios
ranging from 0.5 to 1.7 (Babcock & Wilcox 1972).
Fuel Oil
Trace metal and S contents of fuel oils are dependent upon both the source of the crude oil and the
Table 9-1. Ranges of trace element concentrations in coals, ppm (Swaine1994).
Element
As
Be
Cd
Cr
Cu
Hg
Mn
Range
0.5-80
0.1-15
0.1-3
0.5-60
0.5-50
0.02-1
5-300
Element
Ni
Pb
Sb
Se
V
Zn
Range
0.5-50
2-80
0.05-10
0.2-10
2-100
5-300
9-2
-------
Table 9-2. Range of selected average trace element concentrations for U.S. coals from different regions of the
country, and maximum and minimum concentrations from individual samples (Brooks 1989).
Element
As
Cr
Hg
Ni
Range (ppm)
2-27
5-27
0.06-4.4
3-27
Minimum (ppm)
0.5
<0.5
<0.01
<0.5
Maximum (ppm)
357
400
63
580
extent to which refining and blending processes remove, dilute, or concentrate the elements. Crude
oils contain substantially lower inorganic matter than do coals, and also significantly lower
concentrations of most impurities. Due to the refining process, residual oils usually have different
trace element contents than the crude oils from which they are formed, although crude oils that have
high trace element content will produce residual oils that are also high in the same trace element
concentrations. In addition to S, the most common trace elements in residual oils are Ni and V.
Sulfur contents of selected residual oils have been reported as ranging between 0.22 and 2.44%.
Residual oils from California, Indonesia, Malaysia, Pennsylvania, and Venezuela contain greater than
50 ppm of V, and the California, Pennsylvania, and Venezuela residual oils also contain greater than
50 ppm of Ni. Trace metal and S contents are not necessarily correlated. The highest S content of
the reported residual oils was found in a Mexican oil, which had less than 50 ppm Ni and V, while the
residual oil with the lowest reported S content (0.22%) was the Indonesian/Malaysian oil, which had
101 ppm V. Table 9-3 presents trace element concentrations of residual fuel oils used in the U.S.
Residual fuel oils contain 85-87% C and 10-12% H by weight, resulting in molar H:C ratios of 1.4-
1.7 (Reed 1998a).
Natural Gas
Natural gas is composed primarily of methane (CH4), with some heavier hydrocarbons and typically
small amounts of CO2 and N2. When extracted, natural gas may contain sulfur compounds such as
hydrogen sulfide (H2S), but these compounds are normally removed before distribution. Natural gas
does not contain substantial quantities of HAPs. EPA's study of HAP emissions from electric power
generating units estimated 1990 emissions of As, Cd, Cr, Pb, Hg, and Ni to total less than 4.2 tons/year
from all 267 natural gas fired units in operation at the time the report was prepared (EPA 1998). Of
these HAPs, the majority was estimated to be of Ni at 2.3 tons/year of total industry emissions,
followed by Cr at 1.2 tons/year. Molar C:H ratios for natural gas range approximate 4 (equal to the
C:H ratio for CH4), but are in practice somewhat less due to the presence of heavier hydrocarbons
such as ethane (C2H6) (Reed 1998b).
Table 9-3. Range of averages and reported typical values of trace element concentrations
in residual fuel oils from different sources (Brooks 1989, Reed 1998a).
Element
As
Cr
Hg
Ni
V
Range (ppm)
0.011-0.8
0.001 9 -<5<1>
0.007-10
6-73
>50 - 226
Typical Values (ppm)
0.36
0.40
0.06
24
Not reported
1. The upper bound of measured Cr concentrations was reported as 5
ppm, with 2 ppm as the highest reported specific value.
9-3
-------
Fuel Use
In evaluating the potential impact of Orimulsion use in the U.S., it is important to understand the
current energy use patterns that may be affected by the introduction of Orimulsion, particularly for
utilities, since nearly all Orimulsion use has been as a utility fuel. In 1997, U.S. utilities generated
2.15xl012 kW-hrs of electricity from fossil fuels. As illustrated in Figure 9-2, the majority (83%) of
this was generated from coal, with 13% from natural gas and the remaining 4% from petroleum (fuel
oil). The 1997 price of these fuels ranged from an average of $1.27/106 Btu for coal to $2.88/106
Btu for petroleum, with natural gas slightly less costly at $2.76/106 Btu (U.S. Department of Energy
1998c).
Note that, based on the capacities of plants currently burning Orimulsion, the maximum level of
power generation (full load for 24 hr/day, 365 days/yr) would result in just under 34,000 million kW-
hr of electricity generation. This figure, representing world-wide generating capacity, is less than half
the 1997 U.S. generation from petroleum, and approximately 1.5% of the total U.S. generation in
1997. No figures for fuel cost have been reported for Orimulsion.
The combination of high price and technical similarity to fuel oil makes Orimulsion more likely to
replace fuel oil than either coal or natural gas in the U.S. However, there is a potential for Orimulsion
to be considered as a replacement for any of these fuels. As a liquid fuel, Orimulsion is limited in its
means of cost-effective transportation modes, and is most likely to be used in situations where the
end-user is near a seaport or where suitable existing pipelines are available, given the expense and
time required to install a pipeline. Although Orimulsion can be transferred to river barge or railroad
tank cars for transport, this transfer would raise the cost of the fuel substantially compared to direct
transport from ocean tanker to end-user fuel tanks. Sites with the most cost-effective potential as
Orimulsion users would then most likely be situated on or very near major seaports and currently use
fuel oil as their primary fuel.
Location and current fuel type are only two factors that influence the cost of conversion to
Orimulsion. Other factors may include additional or upgraded pollution control equipment and/or
283,625(13%)
77,753 (4%)
Coal
Petroleum
Natural Gas
1,787,806(83%)
Million kW-hrs (percent of total)
Figure 9-2. U.S. electricity generation in 1997 by fossil fuel (U.S. Department of Energy 1998c).
9-4
-------
improvements to the plant control system. Over the long term, the largest impact on cost
effectiveness will most likely be the differential cost of the two fuels. Even though conversion of oil-
fired plants near seaports may be the most likely scenario in the near term, it is worthwhile to examine
the pattern of fuel consumption for all three fossil fuels.
Coal
Coal is the primary fuel for utilities, with a much smaller amount directly burned for industrial
energy (this section is concerned only with "steam coal" and not with metallurgical coal). In 1997,
Texas used more coal than any other state, at just over 100 million tons. Roughly 95 million tons of
this was used for power generation by utilities. The next 9 highest coal consumers in 1997 were
Indiana, Ohio, Pennsylvania, Illinois, Kentucky, Missouri, West Virginia, Michigan, and Alabama
(U.S. Department of Energy 1997). These top 10 coal consumers account for over 50% of the total
U.S. consumption by utility and industrial users (see Figure 9-3). While Indiana, Ohio, Illinois, and
Michigan have access to seaports on the Great Lakes and Pennsylvania has a major seaport at
Philadelphia, for the most part the coal use is located away from these areas and along the Ohio River.
Kentucky, Missouri, and West Virginia have water transport only via river. Alabama does have ocean
access at Mobile, but again, the majority of coal use is farther inland and would require an additional
form of transport if Orimulsion were to be used at an existing utility plant in the state.
Substantial replacement of coal by Orimulsion does not appear likely, based on the low price of coal
relative to fuel oil and natural gas and the location of utility and industrial plants away from major
seaports. That is not to say that Orimulsion cannot displace coal in individual situations. Florida, for
instance, used over 20 million tons of coal in utility and industrial applications in 1997, and has
several plants located at or near seaports where Orimulsion transport would be economically feasible.
Fuel Oil
U.S. fuel oil consumption by utility, industrial (including use by oil companies), and commercial
sectors is shown in Figure 9-4.* Fuel oil consumption for electric power generation is substantially
lower than was the case for coal, as illustrated in Figure 9-2, and is geographically distributed
differently than coal. Approximately 50% of fuel oil use occurs in only 3 states: Florida, New York,
and Massachusetts. A total of 75% of U.S. fuel oil consumption occurs in only 8 states - the top 3
plus Connecticut, Hawaii, Maine, North Carolina, and Pennsylvania. The majority of this
consumption is for utility power generation, although little or no fuel oil is used by utilities in Maine,
North Carolina, or Pennsylvania. In contrast with coal, all of the top 15 fuel oil-consuming states
have access to seaports. Pennsylvania is the only state in the top 10 consumers of both coal and fuel
oil, and is a producer of both fuels. Also in contrast to coal, the top 7 fuel oil-consuming states
produce little or no oil, where the top coal consuming states are also coal producers (U.S. Department
of Energy 1998d).
Orimulsion may have significantly greater potential to replace fuel oil than coal or natural gas due to
two factors (not associated with plant configuration or hardware). First, the cost of fuel oil is higher
than coal (U.S. Department of Energy 1998c). Second, the location of the major oil-consuming
states along coast lines makes transport of Orimulsion less expensive. Finally, since Orimulsion
handles and burns similarly to fuel oil, the technical issues surrounding conversion from fuel oil to
Orimulsion are less difficult to overcome than similar conversions from coal or natural gas.
The greatest potential for Orimulsion use appears to be in areas where there is significant fuel oil
usage, since these areas (in the U.S.) tend to have good access to seaports. Florida, Massachusetts,
Connecticut, and Hawaii appear to have the largest potential for Orimulsion use (New York is not
included here as most of the power-generating capacity is located away from direct access to
seaports).
*Residential fuel oil consumption is not considered here as it is not likely to be targeted as a
potential Orimulsion market in the short term.
9-5
-------
Texas"
Indiana"
Ohio"
Pennsylvania"
Illinois"
Kentucky"
Misspuri"
West Virginia"
Michigan"
Alabama"
Georgia"
North Carolina"
Florida"
Tennessee"
Wyoming"
Wsconsin"
North Dakota"
Iowa"
Oklahoma"
Minnesota"
Arizona"
Colorado"
Kansas"
New Mexico"
Utah"
South Carolina"
Virginia"
Arkansas"
Louisiana"
Maryland"
Nebraska"
New York"
Montana"
Nevada"
Mississippi"
Washington"
Massachusetts"
New Jersey"
South Dakota"
California"
ew Hampshire"
Delaware"
Connecticut"
Oregon"
Alaska"
Hawaii"
Idaho"
Maine"
Rhode Island"
Vermont"
0 20000 40000 60000 80000 100000 120000
1997 Coal Use, Thousand Tons
Figure 9-3. U.S. utility and industrial coal consumption in 1997 by state (U.S. Department of Energy 1997).
9-6
-------
Honaa-
Maccaphi icpttc~
Connecticut
Hawaii
Maine
North Carolina
Pennsylvania"
Mississippi"
Virginia
Georgia
Maryland"
Delaware"
New Jersey
South Carolina
New Hampshire
Texas
Louisiana
Michigan
Illinois"
Ohio
Indiana
Wisconsin
Rhode Island
Minnesota
Alabama
Kansas
Missouri
Washington
Vermont
Oklahoma
West Virginia
Oregon
Nevada
North Dakota
Kentucky
Montana
New Mexico
Tennessee
Utah
Alaska
Nebraska
California
Arkansas
Iowa
South Dakota
District of Columbia
Arizona
Wyoming
Colorado
Idaho
•#////// / / //;/J^^
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400000 800000 1200000 1600000
1997 Fuel Oil Use, Thousand Gallons
2000000
Figure 9-4. U.S. fuel oil consumption by the commercial, industrial, oil company, and utility sectors in 1997 by
state (U.S. Department of Energy 1998d).
9-7
-------
However, it should be noted that, in many conversions, Orimulsion has replaced coal as the primary
fuel. Table 3-2 shows that, of the 13 boilers converted to Orimulsion, 4 were converted from
pulverized coal and 3 more from a combination of pulverized coal and heavy fuel oil. The
remaining six conversions were from heavy fuel oil to Orimulsion. Plants burning pulverized coal
almost always have the equipment necessary to control both SO2 and PM, potentially making the
conversion from coal to Orimulsion more cost-effective than from heavy fuel oil to Orimulsion.
However, the presence of existing pollution control equipment must be balanced with the potential
need to install fuel storage tanks and handling systems and the possible need to upgrade or modify
the pollution control equipment. In some cases, modifications to boiler components may also be
needed.
Natural Gas
Natural gas consumption in the U.S. commercial, industrial, and utility sectors was highest in Texas in
1997, followed by California, Louisiana, and New York (see Figure 9-5). Texas and Louisiana are
also major natural gas producers. Unlike either coal or fuel oil, natural gas is used primarily in non-
utility sectors.* Natural gas consumption is distributed more evenly among coastal and inland states
than is the case for either coal (largely inland) or fuel oil (mostly coastal) (U.S. Department of
Energy 1998e). The ability to handle and burn natural gas without heating or pumping, or the need
for compressed air or steam for atomizing the fuel, make natural gas more attractive as a combustion
fuel compared to either fuel oil or Orimulsion. Even given the high cost of natural gas, its ease of use
makes it a preferred fuel for industrial applications. There have been no reported conversions of
utility plants from natural gas to Orimulsion.
Air Pollutant Emissions and Control
Emissions of air pollutants vary significantly with fuel and with combustion system design. Even for
a given type of fuel, there may be substantial variation in air pollutant emissions from a single plant,
due to changes in fuel properties. Both coal and heavy fuel oils vary widely in sulfur and trace
element content, resulting in differences in emissions of SO2 and metals. Differences in the amount
of volatile matter in coal can impact emissions of CO, NOX, and unburned carbon, since such
differences affect the ease of fuel burnout. The design of the furnace and burners and the
combustion conditions used also affect emissions of CO, NOX, and unburned carbon, but have less
influence on total emissions of PM, SO2, and trace metals, although PM mass emissions can be
strongly influenced by the amount of unburned carbon, particularly for heavy oils.
CO Emissions and Control
CO emissions from the combustion of fossil fuels can vary widely, since they are largely the result of
the conditions under which combustion occurs. The major factor in determining CO emissions is the
level of excess air in the boiler or furnace. CO emissions are often less than 10 ppm for natural gas
combustion systems, but may be higher than 1000 ppm under low excess air conditions. Nearly all
combustion systems exhibit a rapid and substantial increase in CO below a certain O2 level. This
point is often termed the "CO knee," and will vary from one unit to another. CO emissions can also
increase during transient changes in load or fuel feed, as the airfuel ratio in a single burner drops
below a critical point. Smaller units and units burning less volatile fuels tend to have higher CO
emissions than do larger units and units burning volatile fuels. Thus, a large natural-gas-fired boiler
will be expected to emit lower concentrations of CO than a small boiler burning either coal or heavy
fuel oil.
The values of CO emission rates from the combustion of bituminous coal, fuel oil, and natural gas in
boilers from EPA's AP-42 are given in Table 9-4 (EPA 1995) for purposes of comparison. These
values compare to emission factors from EPA's pilot-scale tests of 0.008 lb/106 Btu for Orimulsion
100 and No. 6 fuel oil and 0.010 lb/106 Btu for Orimulsion 400, all below the values given for other
* As was the case for fuel oil, there is a significant residential consumption of natural gas, but
the residential sector is not likely to be targeted as a potential Orimulsion market.
9-8
-------
fossil fuels in Table 9-4.
Combustion air control is the most common method used to control CO. As combustion air levels
(measured by the O2 level in the stack or furnace combustion gases) increase, CO decreases.
Alternatively, decreasing O2 results in increased CO. This behavior holds for coal, oil, natural gas,
and Orimulsion. Field tests of Orimulsion indicated CO would either decrease or stay relatively
steady (see Table 3-9), and pilot-scale tests conducted prior to EPA's study also indicated either
minor decreases or modest increases in CO emissions compared to the baseline fuel (usually heavy
fuel oil). The results of the EPA pilot-scale tests indicate that CO emissions increased slightly when
using Orimulsion 100 and Orimulsion 400 compared to those from a No. 6 fuel oil. However,
optimization of the pilot-scale unit was not done, which would have likely reduced CO emissions
from Orimulsion compared to the reported values.
In general, there is no evidence that would indicate that CO emissions from Orimulsion are
substantially different than those from heavy fuel oil. CO emissions from coal are likely to be
slightly higher, and those from natural gas slightly lower than CO emissions from the combustion of
Orimulsion. For all fuels, CO emissions can be minimized by proper maintenance and operation of
the combustion system to ensure steady and accurately controlled fuel and air flows through each
burner.
NOX Emissions and Control
NOX emissions, like CO emissions, depend upon a number of factors including fuel and combustion
system type, operating conditions, and the amount of nitrogen in the fuel. Advances in combustion
system design (particularly burners) have resulted in significant decreases in NOX emissions per unit
heat input. NOX emissions vary significantly with combustion conditions and burner and boiler
design due to the strong influence of temperature and air/fuel mixing on NOX formation.
For coal, NOX emissions depend upon both the boiler and burner designs as well as the type of coal
fired. For bituminous coals, uncontrolled NOX emission rates range from 0.25 lb/106 Btu for arch -
fired boilers to greater than 2.0 lb/106 Btu for wall-fired wet bottom boilers. The majority of boilers
in the U.S. are either wall- or tangentially-fired designs. Tangentially-fired boilers have uncontrolled
emission rates between 0.4 and 0.7 lb/106 Btu, while wall-fired dry bottom boilers typically have
uncontrolled NOX emission rates between 0.7 and 1.0 lb/106 Btu (Muzio and Quartucy 1997).
Application of low NOX combustion technology (typically burners) can reduce these emissions by
50% or more.
Uncontrolled NOX concentrations from wall-fired dry bottom boilers firing coal are on the order of
600 ppm, while emissions from heavy fuel oil firing are roughly 250-300 ppm, and about 150 ppm
for natural-gas-fired units, all corrected to 3% O2 (Bowman 1992). These values compare to
emissions from Orimulsion 100 ranging between 150 and 400 ppm and from Orimulsion 400
ranging from 80 to 160 ppm, as reported in Chapter 3.
Table 9-4. CO emission factors for coal, fuel oil, and natural gas (EPA 1995).
Fuel
Bituminous coal (pulverized
Fuel oil (except for No. 2 or
coal and cyclone boilers)
distillate fuel oil)
Natural gas
Emission Factor (lb/106 Btu)
0.019
0.033
0.082
9-9
-------
Texas
California
Louisiana-
New York-
Illinois
Michigan
Ohi
Florid
New Jersey
Pennsylvani
Oklahoma
Indiana-
Massachusetts-
Wisconsin-
Alabama
Georgia
Minnesota-
Arkansas
Tennessee
Kansas-
Mississippi
Iowa-
Washington
Virginia
North Carolina-
Missouri-
Colorado-
Kentucky
Alasks
Marylanc
Oregon-
South CaroNna-
New Mexico"
Nevada-
Connecticut"
West Virginia-
Arizona"
Nebraska"
Utah-
Rhode Islancr"
Wyoming-
ldaho~
Delaware"
Montana"
North Dakota-
South Dakota"
D.C.-
ew Hampshire-
Vermpnt"
Maine"
HawaiT
0 1000000 2000000 3000000 4000000
1997 Natural Gas Consumption, Million Cubic Feet
Figure 9-5. U.S. natural gas consumption by the commercial, industrial, and utility sectors in 1997 by state (U.S.
Department of Energy 1998e).
9-10
-------
Emission factors for bituminous coal range between 0.20 lb/106 Btu when fired in NSPS*
tangentially-fired boilers to 0.92 lb/106 Btu for cyclone furnaces. For No. 6 fuel oil, AP-42 lists NOX
emission factors between a low of 0.28 lb/106 Btu for tangentially-fired boiler to a high of 0.45 lb/106
Btu for utility boilers under "normal firing." Uncontrolled NOX emission rates for natural gas are
listed as between a low of 0.17 lb/106 Btu for tangentially-fired boilers to a high of 0.28 lb/106 Btu
for pre-NSPS wall-fired boilers. Controlled NOX emissions when firing natural gas range between
0.075 lb/106 Btu for tangentially-fired boilers with flue gas recirculation to 0.98 lb/106 Btu for wall-
fired boilers using low NOX burners (LNBs) (EPA 1995). These values compare to NOX emission
factors measured during EPA's pilot-scale tests of 0.46 lb/106 Btu for Orimulsion 100, 0.468 lb/106
Btu for Orimulsion 400, and 0.542 lb/106 Btu for No. 6 fuel oil.
Uncontrolled NOX emissions from Orimulsion combustion appear to be slightly lower than those
reported for heavy fuel oil, although there are instances where NOX emissions have increased when
burning Orimulsion compared to heavy fuel oil (Osaka No. 4, for instance, in Table 3-10). NOX
emissions from Orimulsion are in general lower than those from coal and higher than those from
natural gas.
Like CO, NOX formation depends upon the combustion conditions, and can be minimized through
optimization of the combustion system and parameters. The pilot-scale work of de Santis et al.
(1996) in particular demonstrates that NOX from Orimulsion combustion can be controlled using the
conventional methods of controlled air/fuel mixing that are the basis of current LNB designs (Muzio
and Quartucy 1997). Results of full-scale tests also show that staged combustion principles
developed for use in reducing NOX from coal, fuel oil, and natural gas can be effectively applied to
NOX reductions when burning Orimulsion.
Reburning technology developed for NOX reduction at plants burning coal and fuel oil has been
demonstrated as also reducing NOX emissions when burning Orimulsion. Although much of the
previously reported work centers on the use of Orimulsion as the reburning fuel, the fact that
conventional combustion modification techniques can be applied to Orimulsion and its success as a
reburning fuel demonstrate that plants burning Orimulsion can expect to achieve NOX reductions with
appropriately designed reburning systems in the same manner, and at approximately the same
reduction level, as plants firing other fossil fuels as a primary fuel.
The experience at Osaka Unit 4 demonstrates that selective catalytic reduction (SCR) can also be used
to reduce NOX emissions from Orimulsion-fired plants. There are issues associated with other flue
gas constituents, primarily SO3, that complicate the use of SCR. The injection of NH3 or urea can
result in high levels of bisulfate particles being formed, which will substantially increase the
particulate loading of the particle control equipment. Nevertheless, if adequate capacity is designed
into the particle control equipment, SCR is effective in reducing NOX emissions to a degree similar to
reductions when other fossil fuels are used.
There has not been any reported use of selective noncatalytic reduction (SNCR) when using
Orimulsion. Similar increases in particle loading from the formation of sulfates as noted when
applying SCR would be expected when using SNCR, since both technologies rely on injection of
NH3-based compounds. Fundamentally, one would expect that SNCR would reduce NOX to a level
similar to other fossil fuels if adequate reagent is used.
SOX Emissions and Control
SO2 emissions are almost entirely dependent upon the amount of sulfur in the fuel. Thus, for fuels
such as Orimulsion that contain relatively high sulfur, one would expect high uncontrolled SO2
*New Source Performance Standards (NSPS) were implemented for NOX control through
design of boilers in 1977. Because these standards resulted in significant changes to boiler designs,
boilers built before 1977 are referred to as "pre-NSPS" and those built after 1977 as "NSPS" or
"post-NSPS."
9-11
-------
emissions. As discussed in the above section on fuel properties (and as seen in Figure 9-1), there is a
broad range of sulfur contents in coal and fuel oil, making it difficult to make general statements
comparing SO2 emissions from Orimulsion to those from other fossil fuels. However, since the sulfur
content of Orimulsion is similar to the upper range of sulfur contents for coal and oil, uncontrolled
SO2 emissions from Orimulsion would be expected to be in the upper range of those from fossil fuels
in general.
AP-42 emission factors for SO2 are given in terms of sulfur content for coal and fuel oils, and are
noted as being in trace quantities in natural gas (EPA 1995). Table 9-5 presents emission factors for
bituminous, sub-bituminous, and anthracite coal and for No. 6 fuel oil as listed in AP-42, and
assuming a 2% sulfur content for each of the listed fuels. These values compare to those measured in
EPA's pilot-scale tests of 0.85 lb/106 Btu for Orimulsion 100, 0.93 lb/106 Btu for Orimulsion 400,
and 1.02 lb/106 Btu for No. 6 fuel oil.
SO3 emissions depend upon the sulfur content as well as upon presence of other elements, notably V
or Mg, that can impact the rate of SO3 formation from SO2 at the temperature and flue gas
composition of the system. Since fuel oil tends to contain substantially more V than coal, SO3 is
typically considered to be more likely to be emitted from fuel oil combustion than from the
combustion of coal. As for SO2, SO3 emission factors are based upon the sulfur content of the fuel
oil. For No. 6 fuel oil, the listed SO3 emission factor (in lb/106 Btu) is 0.038S, where S is the percent
sulfur in the fuel* (EPA 1995). Full-scale experience reported for Orimulsion 100 firing lists a range
of SO3 emissions from 1 to 68 ppm, with 3 of 4 test programs reporting emissions less than 15 ppm
(see Table 3-11), and recent results for Orimulsion 400 are reported as 1 ppm SO3 at between 2 and
2.5% O2 in the stack (Gibb 1999).
Control of SO2 is the same for Orimulsion as for other fossil fuels, since there are no characteristics of
Orimulsion combustion gases that would substantially interfere with the chemistry of conventional
post-combustion SO2 control technologies. Reductions in SO2 emissions of 95% using a
conventional limestone scrubber have been reported for full-scale operations during Orimulsion
firing (SK Energy undated). SO3 emissions control is somewhat more difficult, and may require
installation of specialized equipment such as a wet ESP to adequately reduce emissions. A more
common approach is that taken by several plants to minimize stack O2 levels. This may result in
problems maintaining CO levels at adequately low levels, but will help in minimizing NOX .
In general, control of SO2 emissions from the combustion of Orimulsion does not appear to present
any significant technical difficulties beyond those normally associated with SO2 removal for other
fossil fuels. Likewise, controlling SO3 emissions from Orimulsion combustion has been shown to be
a problem that can be addressed using conventional techniques developed for other fossil fuels.
Table 9-5. SO2 emission factors (uncontrolled) for three coal types and for No. 6 fuel oil (EPA 1995).
Fuel
Bituminous coal
Sub-bituminous coal
Anthracite coal
No. 6 fuel oil
Emission Factor, lb/106 Btu
1.46S<1)
1.35S
1.50S
1.047S
Emission Factor for 2% S Fuel, lb/106 Btu
2.92
2.70
3.00
2.09
1. S = % sulfur content of the fuel (for a 2% sulfur fuel, multiply by 2).
*For a 1.5% sulfur oil, the emission factor would be calculated as 5.7 x 1.5 to give the
estimated SO3 emissions in lb/106 Btu.
9-12
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PM Emissions and Control
PM emissions from the combustion of fossil fuels depend upon the amount of inorganic material in
the fuel and on the effectiveness of the combustion system to fully convert the available carbon to
CC>2. For coal, the primary factor in determining PM emission rates is the amount of ash in the coal.
Likewise for oil, the level of inorganic matter in the fuel plays a major role in the rate of PM
emissions, although the rate of PM emissions from fuel oil is more strongly influenced by the level of
carbon burnout than is the case for coal, primarily because the inorganic material in fuel oils are
significantly lower than in coals.
Ash levels in U.S. coals range from about 6% to as much as 30% by as-found mass (Keppler 1998),
while residual oils have significantly lower ash contents, ranging from ash-free (<0.001% ) to 0.2%
by weight (Reed 1998a). Natural gas has no mineral matter of consequence (Reed 1998b). PM
emission levels are determined by both the ash content and the level of carbon that is not consumed
in the combustion process. The unburned carbon is usually a consequence of low temperatures
and/or inadequate combustion O2, and can make up a majority of the PM emitted from certain
combustion system designs. Poor carbon burnout can increase PM emissions by a factor of 10 or
more when burning a heavy fuel oil, compared to calculated values based on the fuel ash content.
PM from natural gas combustion is usually considered to be the consequence of soot formation in
high temperature, low Q^ regions of the combustor. The presence of sulfur can also contribute to PM
emissions, particularly for heavy fuel oil or natural gas through formation of sulfate compounds or
SOs droplets, making the PM emissions also dependent upon the sulfur content of the fuel.
PM emission factors for coal are given by AP-42 in terms of the coal ash content and combustion
system design. Dry bottom boilers will tend to emit more PM than wet bottom and cyclone boilers,
since a portion of the mineral matter is drawn off as liquid slag in the latter two types of units. Table
9-6 presents uncontrolled emission factors for different coal types and coal combustion systems, for
the fuel types listed in general and for the same fuels assumed to contain 10% ash (for coals) and
1.5% sulfur (for fuel oils).
Three emission factors have been reported for previous tests of Orimulsion, two for full-scale tests
and one for a pilot-scale test. The full-scale tests (during testing at Dalhousie and at the Florida
Table 9-6. Filterable PM emission factors (no controls) for different fuels and different combustion system
designs (EPA 1995).
Fuel/Boiler Type
Bituminous, sub-bituminous, or
anthracite coal/Dry bottom PCO)
boilers
Bituminous, sub-bituminous, or
anthracite coal/Wet bottom PC
boilers
Bituminous coal/Cyclone furnaces
No. 6 Fuel oil/All boiler types
Natural gas/All boiler types
Emission Factor, lb/106 Btu
0.385A<2)
0.269A
0.077A
0.061 (S)+0.021<3)
0.002<4)
Emission Factor, lb/106 Btu
(10% ash in coal
or 1.5%S in fuel oil)
3.85
2.69
0.77
0.11
0.002
1. Pulverized coal
2. Percent ash in coal (A = 10 for 10% ash in coal)
3. Percent sulfur in oil (S = 1.5 for 1.5% sulfur in coal)
4. Filterable PM. Condensable PM = 0.006 lb/106 Btu
9-13
-------
Power & Light Sanford Plant) reported PM emission factors of 0.22 and 0.17 lb/106 Btu, respectively
(Janati 1997, Entropy 1991). The pilot-scale test (at PowerGen) reported a PM emission factor of
0.30-0.35 for No. 6 fuel oil, but less than those for pulverized bituminous coal. Emission factors
measured lb/106 Btu (Allen and Beal 1996). Both these emission factors are higher than those given
in Table 9-6 during EPA's pilot-scale testing: 0.69 lb/106 Btu for Orimulsion 100 and 0.75 lb/106
Btu for Orimulsion 400. These values compare to 0.82 lb/106 Btu for No. 6 fuel oil, which is
substantially higher than the emission factor reported in AP-42.
Particle size distributions are an area where there does appear to be significant differences between
different fossil fuels. PM generated by the combustion of pulverized coal is dominated by particles
larger than 1 (jm in diameter (the coarse fraction). As much as 95% of the total PM mass may be in
the coarse fraction, with the remainder in the fine fraction (less than 1 (am in diameter) (Linak and
Wendt 1994). On the other hand, PM generated by the combustion of heavy fuel oil tends to be
almost entirely (80% or more) in the fine fraction (Hersh et al. 1979, Piper and Nazimowitz 1985,
Walsh et al. 1991), although there may be some larger particles that are the consequence of
incomplete oil droplet burnout (Miller et al. 1998a). Natural gas does not contain significant
amounts of inorganic or solid matter, resulting in very low (and often undetectable) levels of PM
emissions.
Recent editions of AP-42 (EPA 1995) have included emission rates of particles 10 (jm in diameter
and smaller (PM10) and particles 2.5 (am in diameter and smaller (PM2 5). For bituminous, sub-
bituminous, and anthracite coal, AP-42 reports uncontrolled emissions of PM2 5 as being 6% of the
total mass, with only 2% of the total mass being smaller than 1 (jm in diameter. For residual fuel oil,
AP-42 lists PM2.s as being 52% of the total uncontrolled PM mass emitted, and 39% being smaller
than 1 (jm in diameter.
Full-scale tests of Orimulsion combustion reported 80 to 97% of the total PM mass as being smaller
than 1 (jm in diameter, and 98 to 100% of the total PM mass as PM10 (see Table 3-13). PM from fuel
oil combustion in one of the units reporting Orimulsion results reported PM smaller than 1 (jm in
diameter as being 45% of the total mass, and 75% of the total mass being PM10.
These values compare to approximately 90% of the total mass of PM from Orimulsion combustion
being PM2 5 and 80% smaller than 1 (jm in diameter in the EPA pilot-scale tests. PM2 5 from fuel oil
combustion in these tests accounted for just over 40% of the total mass, with about 30% of the total
PM mass being smaller than 1 (am in diameter. Note that a coal with 10% ash and 6% of the PM mass
as PM2 5 will have an uncontrolled PM2 5 emission factor of 0.23 lb/106 Btu, comparable to the total
PM emission factors for Orimulsion measured at Dalhousie and Sanford (0.22 and 0.17 lb/106 Btu,
respectively).
Electrostatic precipitators (ESPs) are the most common form of PM control for utility applications.
For industrial applications, other PM control equipment may be used, including fabric filters, wet
scrubbers, or multiple cyclones. Each of these systems have collection efficiencies that are affected
by particle size. Markowski et al. (1980) compared size distributions of PM from the combustion of
pulverized coal, and showed that the mass of particles smaller than 1 (am was approximately equal to
the mass of particles larger than 1 (am downstream of an ESP (i.e., each fraction accounts for
approximately 50% of the total mass - see Figure 9-6). This is in contrast to the uncontrolled size
distribution, in which as much as 95% of the total mass is in particles larger than 1 (am in diameter.
This means that the collection efficiency of the smaller particles is significantly less than that of the
larger particles. Note that the data shown in Figure 9-6 indicate that the total mass of particles smaller
than 1 (im is substantially reduced, but not to the same degree as those of larger size.
Data for ESP control of residual oil PM included in AP-42 indicate that although PM2 5 is controlled
to a higher degree than larger particles, the difference is slight. In general, one would expect particles
in the size range 0.1-1 (am in diameter to have lower collection efficiencies than either smaller or
larger particles, based on aerosol behavior mechanisms. The lower collection efficiency for smaller
9-14
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ro
E
"
3000
2500 -
2000 -
1500 -
1000 -
500-
a.
-a
0) °
§, 30
25-
20-
15 •
10 •
5-
(a) electrostatic precipitator inlet
(b) electrostatic precipitator outlet
0.01 0.1 1 10 100
Particle Diameter (|jm)
Figure 9-6. Comparison of particle size distributions from the combustion of pulverized coal before and after an
ESP, with data from Markowski et al. (1980) (Linak and Wendt 1994).
particles is also evident in the AP-42 emission factor data for residual fuel oil controlled by wet
scrubbers. In this case, PM2 5 accounts for 52% of uncontrolled mass emissions, but 97% of
controlled mass emissions. While the scrubber removes 94% of the total mass, it removes 89% of
PM2 5 and 99.8% of the mass larger than 2.5 um in diameter.
Recent data for Orimulsion 400 do not agree with the above comments that small particles are
removed at a lower efficiency than the larger particles. Data from Gibb (1999) show removal
efficiencies of 98.4% for PM2 5 and 91.2% for particles larger than 2.5 um in diameter. However, the
author notes that there was likely to be some re-entrainment of larger particles during rapping
operations in the ESP, which may account for the lower apparent collection efficiency for the larger
particles.
In general, ESPs appear to be able to adequately reduce PM emissions from the firing of Orimulsion.
As discussed in Chapter 3, the ESP at Asnaes Unit 5 collected an average of 96.7% of the PM
entering the ESP, although the overall drop in PM concentration (ESP inlet to stack) was just over
96%, probably due to the entrainment of droplets as the flue gas passed through the wet scrubber.
ESP designs must account for the change in flue gas volumetric flow rate for such levels of particle
removal to be consistently attained. The high level of water in Orimulsion significantly increases the
total volumetric gas flow, which will result in increased gas velocities through the ESP. In addition,
9-15
-------
there have been reports of increased furnace exit gas temperatures when using Orimulsion, which can
also lead to higher flue gas volumes, even at steady mass flow rates (Biede et al. 1997, Meisingset et
al. 1997). A further consideration is the use of NH3-based NOX removal technologies, which can
significantly increase the particle loading upstream of PM removal equipment. Modifications such as
those described in Chapter 3 at the Kashima-Kita plant may be required to address these issues, but
have been shown to result in stack emissions of 20 mg/Nm3, compared to inlet concentrations of 550-
600 mg/Nm3. Although there is limited data for capture of PM from Orimulsion using fabric filter
systems, the characteristics of the particles do not appear to make use of such systems unable to
adequately capture PM from Orimulsion. The pilot-scale tests of a fabric filter system did, however,
note that use of a sorbent material may be required to ensure adequate filter life due to the higher
levels of SO3 present in the gas. Nevertheless, conventional technologies are able to adequately
control PM from the combustion of Orimulsion, with proper design and operation.
The particle size distribution for Orimulsion PM may be more closely compared to that for a water-
in-oil emulsion. Tests were conducted at EPA in 1995 on an emulsified No. 6 fuel oil to evaluate the
emissions of HAPs from a No. 6 fuel oil and from the same No. 6 fuel oil emulsified with
approximately 10% water (Miller 1996). Particle size distributions were also measured during those
tests, and can be compared to the size distributions measured during Orimulsion firing. The 1995
tests were conducted in a Scotch marine type firetube boiler, which has much more cold surface area
that tends to quench combustion reactions and produce higher levels of unburned carbon than the
pilot-scale unit used in EPA's combustion tests of Orimulsion. Figure 9-7 shows the particle size
distributions measured by an Andersen impactor for the No. 6 fuel oil and the emulsified No. 6 fuel
oil tested in the firetube boiler in the 1995 tests. Over 70% of the particle mass from the emulsified
No. 6 fuel oil are smaller than 2.5 (am in diameter, compared to less than 40% of the particle mass
from the non-emulsified No. 6 fuel oil.
These results can be directly compared to those presented earlier in Figure 5-7. The No. 6 fuel oil
tested during the Orimulsion pilot-scale tests showed approximately 45% of particle mass smaller
than 0.3 (jm in diameter, compared to only 6% of particle mass smaller than 0.4 (jm in the 1995 tests
conducted in the firetube boiler. This is most likely due to the higher level of unburned carbon in
the firetube boiler samples compared to the pilot-scale combustor used in the Orimulsion tests (Miller
et al. 1998a). Even with the greater percentage of larger particles, the emulsification of the No. 6 fuel
oil results in a significant shift of the particle size distribution toward smaller particles. Figure 9-7
shows that the emulsified No. 6 fuel oil has over 25% of particle mass in particles smaller than 0.4 (jm
in diameter. Using the emulsified No. 6 fuel oil clearly results in smaller particle sizes. This shift is
also seen when comparing the No. 6 fuel oil used in the Orimulsion pilot-scale tests with the particle
size distributions from both Orimulsion formulations, although not to the same degree as seen in the
1995 tests.
Hazardous Air Pollutants Emissions and Control
HAPs from the combustion of fossil fuels are generally low as measured by stack gas concentration,
and, with a few exceptions, low in terms of total mass emissions. The threshold level of regulatory
concern for HAPs is 10 tons/year of any single HAP and 25 tons/year of any combination of HAPs
from a single source. For utility boilers firing coal, only HC1 and HF are found to be above these
annual mass emission levels with any significant frequency. The other HAPs of concern in utility
emissions, such as mercury, are of concern because of the total mass emissions of the industry rather
than of a single source. Mercury is of most concern because of its persistence in the environment
and its bioaccumulative behavior. Organic HAPs are typically found in very low trace concentrations,
if at all, in utility stack gases. The Utility Study did not find the health risks from organic HAPs,
including dioxins and furans, to be significantly increased due to utility emissions (EPA 1998).
Organic emissions from Orimulsion have been measured as being of roughly the same level as those
from coal and heavy fuel oil combustion. In general, organic HAPs from the combustion of
Orimulsion are very low, and the results to date indicate that such compounds are not likely to be
emitted at significantly higher levels than are found in coal and heavy fuel oil stack gases. Because
9-16
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PWn
9D%
1 'Wn
1 n%
>
>
(0 K0/n
(0
o n%
^^^^^
Emulsified No. 6 Fuel Oil
^^^^
H
9^%
90%
1 'Wn
1 n%
CO/
-
^^^^^
^^^M
^^^^
^^
h
^^H
Jc
•
). 6
^^^H
Fuel Oil
0.1
1 10
Particle size,
100
Figure 9-7. Particle size distributions for a No. 6 fuel oil and the same fuel oil in a 90% oil/10% water emulsion.
of the very low concentrations and the low annual mass emissions, there have not been any
demonstrations of organics controls implemented for utility boilers, and such controls have not been
proposed. The conventional view of controlling organics emissions is to maintain adequate
combustion O2 and adequate temperature, which are also operating practices that are desirable for
optimum efficiency and are routinely followed.
Metal HAPs are strongly influenced by the concentration of the metals in the fuel. As noted earlier
in this section, coal typically contains arsenic, chromium, mercury, and nickel. Heavy fuel oil often
contains significant levels of nickel. Natural gas is normally considered to have few impurities,
although trace levels of sulfur are usually present. Nickel is the only metal found in Orimulsion in
9-17
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significant quantities that is also listed as a HAP under Title III of the 1990 CAAAs (Clean Air Act
1990). The levels of Ni found in Orimulsion are similar to those in heavy fuel oil, on the order of 50
ppm. Ni is controlled primarily through control of solid particles, using an ESP or fabric filter. As
noted above, conventional PM control equipment can be used on an Orimulsion-fired unit, if
adequate allowance is made for the higher flue gas volumetric flow and the potential corrosion due to
SO3 condensation.
Pulverized coal tends to have higher levels of metals listed as HAPs under Title III, and the plants
burning coal are on average larger than oil-fired plants, resulting in higher total emissions of metal
HAPs. The 1996 study of HAP emissions from utility boilers indicated that the metal having the
most potential for concern was mercury (EPA 1998). Coal-fired utility boilers account for a
substantial percentage of anthropogenic mercury emissions into the atmosphere (EPA 1998).
However, Orimulsion does not contain measurable amounts of Hg, and is not expected to be a
significant source of Hg emissions.
Transition Metals Emissions and Control
Transition metals are those metals that lie between groups 2 and 13 on the periodic chart. Of most
concern relative to fossil fuel combustion are Cu, Fe, Ni, Zn, and V, due to their abundance in fossil
fuels. Of these metals, only Ni is also listed as a HAP. Fossil fuels may also contain cobalt (Co), Cr,
Mn, or Cd. The primary reason for concern regarding emissions of transition metals is their potential
role in causing acute pulmonary damage upon inhalation (Dreher et al. 1996a, 1996b, 1997).
Orimulsion contains high levels of Ni and V compared to many other fossil fuels, although there are
residual fuel oils that are also high in these elements (see Table 9-3). In addition, refined fuel oils
may contain Zn introduced during the refining process. This was seen in the higher Zn level of the
No. 6 fuel oil used in the EPA pilot-scale tests discussed in Chapter 5. Coals tend to have higher
levels of Cu, Fe, and Zn than Orimulsion or residual fuel oils, but the total amount of coal burned in
the U.S. is much higher than that of fuel oil, resulting in higher total mass emissions of these
compounds compared to those originating from residual fuel oil use.
As was the case for metal HAPs, control of transition metals is most often achieved by conventional
PM control equipment such as ESPs or fabric filters. Proper design and operation is required for
these systems to be used in Orimulsion applications, but the full-scale results reported in Chapter 3
indicate that these systems can be successfully used to control transition metals from Orimulsion
combustion.
CO2 Emissions
CO2 emissions are not currently regulated in the U.S., but are of considerable interest due to the role
CO2 is suspected to play in global climate change. CO2 is produced by the combination of fuel-
bound carbon and atmospheric O2, and is dependent upon the amount of carbon per unit energy in
the fuel. Of the three major fossil fuels (coal, fuel oil, and natural gas), coal has the highest amount
of carbon per unit energy, followed by fuel oil and natural gas. Natural gas is primarily methane,
CH4, and therefore has significantly lower CO2 emissions than either fuel oil or coal, which have
much higher ratios of carbon to hydrogen. On a molar basis, natural gas has a carbon to hydrogen
ratio of roughly 1 to 4, which translates to a mass ratio of roughly 3 to 1 due to carbon's higher
molecular weight. Coal, on the other hand, has carbon to hydrogen mass ratios near 15 to 1 and will
release between 60 and 75 Ibs carbon per 106 Btu (Keppeler 1998). Fuel oil has carbon to hydrogen
mass ratios ranging roughly between 6 and 9 to 1, with carbon release rates near 47 Ibs carbon per
106 Btu (Reed 1998a). Orimulsion falls into the range of the fuel oils, with a carbon to hydrogen
mass ratio of roughly 8 to 1 and a carbon release rate of about 46 Ibs carbon per 106 Btu (see Table
5-1).
Thus, Orimulsion will generate less CO2 per unit energy input (and per unit production) than will
coal. This advantage of Orimulsion over coal is being exploited in Denmark, where the conversion
from coal to Orimulsion at the Asnaes Power Station is credited with reducing CO2 emissions by 16%.
9-18
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This reduction is 5% of Denmark's total national target reduction of 20% (Miller and Shores 1999).
Orimulsion will generate roughly the same CC>2 per unit energy as fuel oil, and more than natural gas.
Summary of Air Pollutant Emissions
The preceding sections have pointed out the fact that air pollutants are generated by all fossil fuels.
Orimulsion must be evaluated in comparison to these other fuels and not in isolation. The issues of
concern with regard to Orimulsion are also of concern with respect to heavy fuel oil and coal in
particular. Developing issues such as PM2 5 require that several characteristics of pollutant formation
and emission be considered as possibly resulting in adverse environmental impacts, regardless of the
fuel being used. While formation and emission of submicron particles, SO2, and transition metals are
of concern with respect to Orimulsion, these characteristics are also of concern with respect to other
fuels.
9-19
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Chapter 10
Quality Assurance
Quality assurance (QA) is the process of documenting the steps taken to ensure that measured data
are adequate to support the conclusions drawn from them. Measurements of data uncertainty,
variability, and error can provide an understanding of how closely a reported measurement represents
the actual variable of interest.
Data Reported in Literature
Most of the reports in the literature do not address QA issues. CEM calibration, measurements of
variability (such as maximum, minimum, and standard deviation) are often not reported, even if they
have been measured. For this reason, one must evaluate the reliability of such data through other
means. In the case of Orimulsion, several reports documented QA measures to some degree. These
reports were the Carnot, Inc. report on emissions testing at the Dalhousie plant in Canada (Janati
1997), the Entropy report on the Orimulsion trials at the Sanford Plant in Florida (Entropy 1991),
and the SK Power report on emissions testing at the Asnses Power Station in Denmark (SK Power
undated). In each case, the reports provided substantial background on the measurements taken.
The background information included discussion of sampling methods, identification of any
problems during sampling, and reporting of all results, including average and standard deviations.
In addition to these reports, several site visits were made by EPA to plants operating with Orimulsion
to observe operation and gather information. During the visit to the Asnaes plant, discussions were
held with plant personnel regarding steps taken to ensure CEM data quality. The staff at the Asnaes
plant followed procedures that were similar to those used in the U.S. The Asnaes QA procedures will
be discussed following a discussion of in-house QA activities.
In-House Combustion Testing
The testing described in Chapters 4 and 5 was conducted under an approved APPCD Level II Quality
Assurance Project Plan (QAPP) titled QAPP for Characterization of Orimulsion Emissions dated
March 1999 and the Addendum dated April 9, 1999. The plan set forth the operating, sampling, and
analysis procedures to be used during the testing, as well as the data quality indicator (DQI) goals for
the project.
Data Quality Indicator Goals
The DQI goals established in the QAPP for all critical measurements are shown in Table 10-1. The
following sections summarize calculated DQIs in terms of accuracy, precision, and completeness.
Sampling critical measurements included continuous emission monitor measurements and combustor
parameters such as temperature, pressure, and air flows. Table 10-2 is a summary of the CEM quality
control (QC) checks. CEM calibration was verified by performing mid-point and span checks daily,
before and after testing. The table shows average values taken from 17 days' worth of testing. The
percent bias is calculated using Eq. 10-1 from the average of pre- and post-test checks.
Percent bias = measured concentration-known concentration x joO% 10-1
known concentration
Precision is expressed as percent relative standard deviation (RSD) and is calculated from
££) _ standard deviation oj"replicate measurements x joO% 10-2
average of replicate measurements
by determining the standard deviation between the pre- and post- test values of the 34 replicates.
Completeness is expressed as a percentage of the number of valid measurements (i.e., meeting their
10-1
-------
specified DQI goal) compared to the total number of measurements taken, and is given by:
Completeness = amount of ^iddata collected x 100o/o 10_3
total amount of data collected
Numbers shown in italic print in Table 10-2 did not meet the DQI goals established in the QAPP.
System bias checks were not done until after an internal technical systems audit was performed by
EPA's on-site contractor on May 25, 1999. Immediately following the internal audit, system bias
checks were performed with an available gas standard. Additional system bias checks were
performed at the start of each test day. Results are tabulated by date in Table 10-3. The DQI goal
for system bias checks was ±5%. As can be seen in the table, the mid-level standard for a ppm level
of CO did not pass. O2 and NOX values also fell slightly out of range on the system bias check
conducted May 28, 1999 and the NOX value also failed on the system bias check conducted June 8,
1999.
Table 10-1. Data quality indicator goals for critical measurements.
Parameter
Particulate
Weights
Volume Sampled
Semivolatile organic
compounds
Volatile organic
compounds
CO
NOX
°2
SO2
THC
Temperatures
Fuel Flow
Fuel Analysis
Pressure
Fuel Lower Heating
Value
TCLP
Loss on Ignition
Method
Gravimetric
Dry Gas Meter
Method 0010
SW846 8270
Method 0030
SW846 8260
CEM
CEM
CEM
CEM
CEM
Thermocouple
Volume Totalizer
Ultimate and
Proximate
Manometer
ASTM<2> D240
SW846
Thermogravimetric
Accuracy
(% Bias)
±0.1 mg
based on weight
±5
±2
10-140 % recovery
±2
50% recovery
calibration ±2
drift ±3
system bias ±5
±2
±10
±5
±10
Not Available
±10
±10
Precision
(% Difference)
<±0.5 mg agreement
between
successive weights
±2
NA<1>
30%
NA
30%
±7
±5
±7
±5
±5
±5
±15
±5
±10
0.5 kJ/kg
±10
±5
Completeness
(%)
>70
>70
>90
>90
>90
>90
>90
>90
>90
>90
>90
>90
1. Not applicable
2. American Society for Testing and Materials
10-2
-------
Calculation ofDQI Values
The quality controls checks in place to determine whether or not DQI goals were met for sampling
and analytical activities are summarized in the following sections. Results of specific DQI goals in
terms of accuracy, precision, and completeness are tabulated.
Sampling Goals
Assessment of CEM DQI goals for span checks is summarized in Table 10-2. Accuracy for CEM
measurements is expressed as percent bias and was calculated using the averaged value of replicate
measurements. Precision, in terms of percent relative standard deviation (RSD), was calculated for
replicate analyses. Values that did not fall within DQI goals are in italic text.
System bias checks were performed by running known concentrations of span gases through the
entire system and measuring concentrations using the same methods used to measure sample gas
concentrations. Table 10-3 summarizes the results of the system bias checks that were performed
between May 25 and June 7, 1999. Checks that did not meet DQI goals are indicated by italic text.
Analytical Data Quality Indicators
Samples were submitted for analysis of volatile and semivolatile organic compounds. Criteria were
established for recovery, precision, and completeness. Assessment of DQI goals is discussed in the
following subsections.
Volatile Organic Compounds
VOCs were analyzed using Method 5041. Calibrations ranged between 10 ng and 250 ng on each
column. Internal standards were injected into the sidearm of the sparging vessel during each
calibration and analysis. All target analytes had a relative standard deviation less than 30% for this
initial calibration.
A 6-point method detection limit (MDL) study was done by the Organic Support Laboratory prior to
Table 10-2. CEM full-range and mid-range span check results. Values in italics did not meet DQI goals.
CEM
CO
(ppm)
CO2
(%)
NOX
(ppm)
02
(%)
THC
(ppm)
SO2
(ppm)
Span range
Full
Mid
Full
Mid
Full
Mid
Full
Mid
Full
Mid
Full
Full
Mid
Actual
850
309
15.1
7.98
762
210
14.8
8.06
92
11
2190
4,000
1,010
Measured
(average)
855
347
14.9
7.23
771
216
14.88
8.12
89
8.4
2180
3865
1021
% Bias
0.6
10.1
1.3
9.4
1.2
2.6
0.5
0.7
3.3
1.3
0.5
3.4
1.1
Precision
(%RSD)
3.9
5.4
4.3
2.3
4.6
6.5
2.3
2.7
6.5
36.2
2.3
7
6.7
Completeness
(%)
92
12.5
85
3
76
53
94
91
68
24
100
78
44
10-3
-------
analyzing project samples by spiking and analyzing a clean VOST pair spiked with 10 ng of each
target VOC and surrogate VOC in accordance with SW-846 methodology for determining MDLs.
The target list of analytes along with the established MDLs for each analyte are shown in Table 10-4.
A mid-level standard was analyzed daily prior to sample analysis. Relative percent deviations less
than 30% when compared to the average response factors calculated using the initial calibration were
found for all target analytes of interest.
Sample VOST tubes were spiked prior to field sampling with surrogate compounds specified by the
method. Surrogate recoveries are summarized in Table 10-5. Samples that did not meet established
recovery criteria are shown in italic text.
Replicated matrix spikes of a separate benzene, toluene, ethyl benzene, and xylenes (BTEX) standard
were performed using flash evaporation. Matrix spike and matrix spike duplicate (MS/MSD) results
are summarized in Table 10-6. All recoveries and percent difference values fell within the established
acceptable limits.
The VOC field blank demonstrated that all compounds were below the calculated detection limits
except for dichloromethane, which fell directly on the detection limit of 3.7 ng.
Semivolatile Organic Compounds
Semivolatile organic compound (SVOC) analysis was performed according to Method 8270. A
rigorous method detection limit study was not performed prior to sample analysis. Past SVOC
analysis allowed insight for establishing an arbitrary 1 ug/mL for the instrumental detection limit.
Sample concentrations near this value were scrutinized carefully to ensure retention time matching
and adequate confirmation ion ratios.
Table 10-3. CEM system bias check results. Values in italics did not meet DQI goals.
Full-range Bias Check
Actual
Measured
% Bias
Mid-range Bias Check
Actual
Measured
% Bias
5/25/99 bias check results
02 (%)
CO2 (%)
CO (ppm)
14.8
15.1
850
14.98
15.6
841
1.2
3.3
1.1
8.06
7.98
309
8.45
7.7
361
4.8
3.6
16.8
5/28/99 bias check results
NOX (ppm)
02 (%)
762
14.8
708
15.43
7.1
4.3
210
8.06
207
8.77
1.4
8.8
6/3/99 bias check results
02 (%)
8.06
8.16
1.2
NC<1)
NC
NC
6/7/99 bias check results
02 (%)
CO2 (%)
NOX (ppm)
15.2
15.2
762
15.6
14.9
635
2.6
2
16.7
NC
NC
NC
NC
NC
NC
NC
NC
NC
1. Not conducted.
10-4
-------
Daily QC measures included an initial passing of the decafluorotriphenylphosphine (DFTPP) tuning
criteria. The presence of benzidine in the DFTPP tuning solution was tested and the monitoring of
dichlorodiphenyltrichloroethane (DDT) for lack of degradation was done daily prior to sample
analysis. After the DFTPP tune phase, a mid-point calibration standard was analyzed. The mid-level
standard was compared to the response factors obtained during the initial calibration curve. Relative
standard deviations of all constituents of interest were less than 30%.
Three samples were run outside the method specified limit of 12 hours from the time of running a
standard. The samples in question were the XAD and filter portions of the field blank and the XAD
extract from the June 3, 1999, No. 6 fuel oil run. There does not appear to be any adverse effect on
data quality due to this oversight.
The 40 day hold time from extraction to analysis was exceeded by 4 days for the first set of No. 6
fuel oil samples. The runs at these conditions were repeated and the initial samples were not used.
Table 10-7 summarizes the results from the analysis of the matrix spike/matrix spike duplicate in
terms of recovery and percent difference and completeness. All values were within the established
DQI goals with the exception of di-n-butylphthalate, which had a recovery of only 10%.
Table 10-4. VOC target analytes and method detection limits.
Analyte
1,1-Dichloroethene
lodomethane
Carbon disulfide
Dichloromethane
t-1,2-Dichloroethene
1,1-Dichloroethane
c-1,2-Dichloroethene
Bromochloromethane
Chloroform
1,1,1 -Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
MDL(ng)
1.6
3.5
1.7
3.7
1.3
1.6
1.5
2.6
1.7
1.2
1.1
2.4
2.9
3.3
3.7
3.4
Analyte
Bromodichloromethane
c-1 ,3-Dichloropropene
Toluene
t-1 ,3-Dichloropropene
1,1,2-Trichloroethane
Tetrachloroethene
Dibromochloromethane
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
m,p-Xylenes
o-Xylene
Styrene
Bromobenzene
1,4-Dichlorobenzene
1 ,3-Dichlorobenzene
1,2-Dichlorobenzene
MDL(ng)
3.3
3.5
2.3
4.4
4.5
5.2
6.1
6.2
4
3.7
7.1
4.5
4.6
4.4
4.2
4.3
4
10-5
-------
Table 10-5. VOC surrogate recovery results. Values in italics did not meet DQI goals for recovery.
Sample ID
905031354
905041257
904301255
905181405
905194058
905211256
905441337
905251243
905261102
906031301
906011340
906071305
904301 23/FB<2)
MS
MSD
Average
Completeness
d4<1) 1,2-Dichloroethane
94.2
94.1
92.9
86.1
84.1
85.5
65.8
100.9
73.1
64.7
57.3
64.5
91.6
86.6
87.5
81.9
11/15=73.3%
d8<1> Toluene
92.2
102.1
98.4
100.4
97.3
32.2
94.1
71
96.3
90.7
95.5
82
101.6
103.9
89.4
89.8
14/15=93.3%
4-Bromofluorobenzene
93.6
79.8
117.1
119.7
107.6
109.1
115
119.8
117
123.9
134.1
157
120.6
112.7
112.5
116
13/15=86.7%
1. Deuterated compound
2. Field blank.
Table 10-6. VOC matrix spike and matrix spike duplicate results.
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Spiked
(M9)
150
150
150
150
150
MS
(pg)
135
145.3
161.4
173.8
168.8
% Recovery
90
96.9
107.6
115.9
112.5
MSD
(M9)
130.4
139.9
169
172
172.9
% Recovery
86.9
93.3
112.7
114.7
115.3
% Difference
3.5
3.8
4.6
1
2.4
10-6
-------
Table 10-7. SVOC matrix spike and matrix spike duplicate results. Values in italics did not meet DQI goals for
recovery or percent difference.
Compound
Naphthalene
Acenaphthylene
Acenaphthene (CCC)
Fluorene
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene (CCC)
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,9)perylene
Completeness
Spiked (ug)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Matrix spike
recovery (%)
55
62
59
69
72
73
10
75
75
75
75
72
76
77
73
73
73
Matrix spike
duplicate
recovery (%)
50
53
52
61
66
67
5
71
69
69
69
67
72
72
67
67
67
Average
Recovery
(%)
52.5
57.5
55.5
65
69
70
7.5
73
72
72
72
69.5
74
74.5
70
70
70
Percent
difference
9.5
15.7
12.6
12.3
8.7
8.6
66.7
5.5
8.3
8.3
8.3
7.2
5.4
6.7
8.6
8.6
8.6
16 of 17 compounds met DQI goals for recovery and percent difference, for
completeness of 94%
Table 10-8 summarizes recovery values of pre-extraction surrogates. The following compounds were
added to each sample prior to extraction:
• 2-fluorophenol (surrogate IE)
• d5-phenol (surrogate 2E)
• 2,4,6-tribenzophenol (surrogate 3E)
• d5-nitrobenzene (surrogate 4E)
• 2-fluorobiphenol (surrogate 5E)
• d!4-terphenyl (surrogate 6E)
Filter samples are indicated with an "F" in the sample ID, XAD samples are followed by an "X,"
and condensate samples are followed by a "C." Acceptable recovery limits varied slightly for each
compound but ranged from 19 to 135%. Compounds that did not meet DQI goals for recovery are
shown in italic text. Out of a total of 39 samples, only 3 samples did not meet DQI goals for one or
more compounds.
Table 10-9 summarizes pre-sampling surrogate recovery values. Pre-sampling surrogates were only
10-7
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Table 10-8. SVOC pre-extraction surrogate recovery levels.
Sample ID
904301209F
(1)
904301 209X
(2)
904301209C
(3)
905041 052C
905031315C
905031 31 5X
905051 149C
905031315F
905041 052F
905041 052X
905051 149F
905051 149X
905181131F
905181131X
905191016F
905191016C
905191016X
90521 1135F
90521 1135X
90521 1135C
905241202F
90524 1202X
905241202C
905251 144F
905251 144X
905251 144C
905261 054F
90526 1054X
Surrogate 1E
46
42
34
43
30
67
50
56
55
48
35
41
59
80
51
39
60
44
56
34
51
54
36
50
55
39
49
41
Surrogate 2E
54
48
32
40
29
56
47
51
52
46
44
48
71
66
61
34
61
53
57
25
60
59
31
62
60
35
62
53
Surrogate 3E
77
75
60
73
50
95
72
95
75
72
56
51
87
101
78
87
89
80
84
79
78
78
78
75
90
77
83
94
Surrogate 4E
51
53
46
59
39
83
62
75
69
56
41
45
70
89
58
64
68
52
63
59
59
63
56
59
61
61
56
56
Surrogate 5E
53
63
49
57
39
87
61
78
70
61
47
46
72
92
62
67
72
57
67
55
62
64
55
61
65
59
62
67
Surrogate 6E
100
91
83
98
72
115
101
108
82
89
69
74
93
128
105
113
119
101
115
112
106
98
118
106
114
127
117
120
(continued)
10-8
-------
Table 10-8. SVOC pre-extraction surrogate recovery levels (continued).
Sample ID
905261 054C
906031216F
906031 21 6X
906031216C
906041 304F
90604 1304X
906041 304C
906071229C
906071229F
606071 229X
Resin Blank
Complete-
ness
Surrogate 1E
42
42
48
30
42
48
51
58
56
72
67
Surrogate 2E
34
56
58
25
57
62
46
50
68
85
83
Surrogate 3E
77
85
85
57
75
91
98
105
95
-144
113
Surrogate 4E
62
56
60
45
59
65
74
80
73
87
82
Surrogate 5E
60
68
66
42
65
71
74
80
75
91
85
Surrogate 6E
108
116
108
83
105
123
131
-138
118
-144
-154
36 samples out of 39 met DQI goals for recovery = 92%
1. "F" denotes filter.
2. "X" denotes XAD.
3. "C" denotes condensate.
spiked on XAD samples and contained the following compounds:
• 13C6 1,2-dichlorobenzene (Surrogate IS)
• 13C6 naphthalene (Surrogate 2S)
• D10-anthracene (Surrogate 3S)
• 13C6 2,5-DCP (Surrogate 4S)
• 13C6 2,5-PA (Surrogate 5S)
Pre-sampling surrogates were considered experimental and no acceptance criteria for recovery were
established. However, in general, recoveries were qualitatively very good.
Metals Analyses
Metals were analyzed by Prism Laboratories, Inc. using EPA Method 29, Determination of Metals
Emissions from Stationary Sources. Laboratory data sheets are included in Appendix E. A report
was received from Prism Laboratories that contained analytical results, chain-of-custody records, and
QA/QC data. Table 10-10 is a tabulated summary of the internal matrix spike analysis to assess
method accuracy, and duplicate sample analysis for precision assessment. The acceptance criterion
for recoveries established by the method as passing is 75-125%. Values shown in italics did not pass
recovery acceptance criteria. The acceptance criterion established for percent relative standard
deviation (RSD) between duplicates was 20%. All duplicate analyses passed this criterion.
Table 10-11 shows recovery results from two spiked samples sent to the laboratory. A mixture
containing 100 (ig of each target metal (metals listed in Table 10-11) was spiked onto clean filters
and submitted to the laboratory for analysis. These data could be considered an internal
performance evaluation audit. Recoveries for all spiked materials fell within acceptable DQI goals for
recovery of 75-125%.
Laboratory blanks were generally below detection limits. A reported value for arsenic of 30.6 (jg
exceeded blank acceptance limits for samples analyzed on July 12, 1999. This will be taken into
10-9
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consideration when evaluating arsenic sample data analyzed with the same batch.
Audits
This project was performed under a QA Category II assignment. A Category II assignment requires
that internal and EPA audits be performed during the project. An internal systems audit was
performed by the EPA on-site contractor QA Officer on May 25-26, 1999. A checklist was prepared
by the EPA on-site contractor QA Officer using the QAPP for Characterization of Orimulsion
Emissions (dated March 1999) and the Addendum to the QAPP (dated April 9, 1999). Calibration,
start-up, and sampling (CEMs, VOCs, SVOCs, and particulate) activities were observed. Project
documentation was also reviewed for completeness and adequacy. An internal audit report detailing
findings and observations was submitted to the EPA on-site contractor work assignment leader on
June 2, 1999.
In addition to the internal audit, a performance evaluation and technical systems audit were also
performed by the EPA QA Representative.
Audit Summary
It was noted in both the internal and EPA audits that project documentation by the staff of EPA's on-
site contractor (ARCADIS Geraghty & Miller, hereafter referred to as ARCADIS) could be improved.
Several changes to the fuel feed system and modifications to CEMs that were made during the course
of the project had not been adequately documented in the project notebook. Findings from both
audits noted that CEM quality control checks as specified in the QAPP were not being performed.
Sampling and operation personnel demonstrated that they were familiar with methods used to
perform their assigned task and it was evident that personnel were familiar with the approved QAPP,
even though there were some deviations from the document. It was noted that, at the time of the
audit, deviations had not been formally documented by project personnel.
Table 10-9. Pre-sampling surrogate recovery/XAD samples.
Sample ID
904301 209X
905031 31 5X
905041 052X
905051 149X
905181131X
905191016X
90521 1135X
905241 202X
905251 144X
905261 054X
906031 21 6X
906041 304X
906071 229X
Surrogate 1S
48
83
54
46
86
66
66
64
61
46
49
53
59
Surrogate 2S
57
88
57
46
87
67
67
66
64
55
54
61
63
Surrogate 3S
76
98
73
61
100
86
82
72
86
75
73
73
78
Surrogate 4S
65
89
61
45
92
70
68
71
64
61
58
63
64
Surrogate 5S
96
161
126
9
142
70
57
116
97
218
165
45
29
10-10
-------
Table 10-10. Internal laboratory QC summary.
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Iron
Fraction
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
Accuracy
Spiked
(M9)
384
384
288
288
384
384
288
288
384
384
288
288
384
384
288
288
384
384
288
288
384
384
288
288
3840
3840
2880
2880
Measured
(M9)
294
350
231
252
314
338
348
278
316
347
259
243
307
335
225
249
332
358
246
264
360
381
249
261
3150
3100
2400
2415
Recov-
ery (%)
77
91
80
88
82
88
121
97
82
90
90
84
80
87
78
86
86
93
85
92
94
99
86
91
82
81
83
84
Precision
1st
Analysis
<2
32
<1.5
<1.5
10
9.3
1.5
<1.5
23
20
<1.5
1.8
6.8
9
1.5
3
8.2
30
2.4
1.6
17
70
4.8
3
69
69
101
30
Duplicate
Analysis
<2
32
<1.5
<1.5
8.5
8.6
1.5
<1.5
23
20
<1.5
1.8
6.8
8.5
1.5
3
8.2
30
2.4
1.6
16
70
4.9
2.9
70
68
102
30
RSD (%)
0
0
0
0
16
7.8
0
0
0
0
0
0
0
5.7
0
0
0
0
0
0
6
0
2.1
3.4
1.4
1.5
1
0
(continued)
10-11
-------
Table 10-10. Internal laboratory QC summary (continued).
Metal
Magnesium
Manganese
Nickel
Vanadium
Zinc
Fraction
0.0416667
0.0416667
0.0833333
0.0833333
0.0416667
0.0416667
0.0833333
0.0833333
0.0833333
0.0833333
0.0833333
0.0833333
0.0416667
0.0833333
0.0833333
Accuracy
Spiked
(M9)
3840
3840
2880
2880
384
384
288
288
288
288
288
288
384
288
288
Measured
(M9)
3010
3390
2130
2340
320
351
236
248
213
256
120
260
238
236
243
Recov-
ery (%)
78
88
-74
81
83
91
82
86
-74
89
-43
90
-62
82
84
Precision
1st
Analysis
1510
69
3045
<15
19
42
2.2
<1.5
695
<1.5
3420
21
<2
11
9.7
Duplicate
Analysis
1508
70
3060
<15
19
43
2.3
<1.5
700
1.6
3435
21
<2
12
9.6
RSD (%)
1.3
1.4
0.5
0
0
2.3
4.4
0
0.7
6.4
0.4
0
0
8.6
1
Completeness 39 samples pass/43 total samples = 90.7%
Findings and Observations
Findings were reported by both the EPA QA Representative and the ARCADIS QA Officer as a result
of their respective audits. Specific findings and observations are listed in the following sections.
These items are discussed in detail in the respective audit reports that were submitted by QA to the
EPA and ARCADIS project managers.
EPA Performance Evaluation and Systems Audits
A performance evaluation audit (PEA) of several project measurements was conducted by EPA QA
staff from NRMRL's Technical Services Branch. The PEA report focused on three findings: flue gas
flow, fuel feed rate, and CEMs. Comments by EPA's QA auditor are summarized below for each
finding.
Flue Gas Flow
For ducts smaller than 0.3 m (12 in.), EPA Method 1A should be used to determine stack flue gas
flow rates. In Method 1A, a standard pitot tube is specified, but in these tests, an "S"-type pitot tube
was used.
To determine flue gas flow rates, velocity measurements are taken at specified locations across the
duct (traverse points). The traverse locations listed in the data sheet for June 7, 1999, were not
correct, although the marks on the ruler used to determine probe location were correct. The reason
for this difference was unclear, but was not believed to have altered the resulting measurements. This
is primarily due to the fact that the flue gas exhibited a very "flat" velocity profile across the duct,
and slight changes to the traverse points would not have changed the measurements in any substantial
10-12
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way. Data used to determine sampling isokineticity were consistent with the actual measurements
taken, and no adjustment of the isokineticity results was required.
Fuel Input Flow
Measurements of fuel feed rate changed from approximately 0.984 gpm to 1.05 gpm during the
period of examination on June 7, 1999. This drift contributed to the fluctuations in O2 level
measured during testing on this date, and possibly during earlier tests.
CEM Calibrations
There were 12 test runs conducted during the test program. During each test run, four calibration
measurements were made (not including the zero point) for each CEM. These four measurements
were pre-test checks of mid- and high-span values and post-test checks at the same two points. Of the
48 measurements for each of the 5 gases (240 total measurements), 47.5% (114) did not meet DQI
goals. Of the 114 measurements that did not meet DQI goals, 85 were mid-span measurements, 28
were post-test high-span measurements, and 1 was a pre-test high-span measurement. A discussion of
the impact of these measurement problems is presented in the Data Limitations section below.
Other Discrepancies
Several other discrepancies between standard sampling methods and methods used during the test
program were noted during the EPA audit. For Method 29, these included using 125 mL of solvent
rather than 100 mL as called for by the method, recording weights instead of volumes when
measuring impinger contents, and spiking solutions rather than filters for QA samples. For
measurements taken using the dilution sampler, the QAPP called for a 4-hour sampling time, while in
actuality the measurements were taken until the pressure drop across the filter became excessive (at
approximately 2 hr of sampling time). For the VOST samples, 2 pairs of cartridges were used rather
than 6 pairs as called for in the method, but 3 runs (each using 2 cartridge pairs) were conducted for
each test condition.
Of these "other" discrepancies, the most serious was that the technique used to determine CEM
system bias did not follow the proper procedure, by connecting the calibration gas directly to the
Table 10-11. Spiked metal sample recoveries.
Target
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Magnesium
Manganese
Nickel
Vanadium
Zinc
Recovery (%)
Sample ID #90701 0942
93
97
95
99
104
121
99
90
93
96
90
Sample ID #90701 0943
94
91
99
101
104
124
100
95
95
98
92
Completeness 100%
10-13
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sample line rather than extracting the calibration sample at the same sampling pressure as the stack
flue gases. This change may have impacted the ability of the bias check to identify leaks into the
sample line.
ARCADIS Technical Systems Audit
The following specific findings and observations were included in the ARCADIS internal technical
systems audit (TSA) report:
• Finding 1: No CEM bias checks or independent calibration checks were performed on the
CEMs.
• Finding 2: Adequate leak checks around CEM system were not performed prior to testing.
• Observation 1: All required QC samples had not yet been prepared and submitted as of the date
of the TSA (May 25 and 26, 1999).
• Observation 2: There was no indication/documentation that the balance used to weigh filters had
been calibrated.
• Observations: Sample labels were not prepared with permanent ink.
• Observation 4: PBS operation notebook was not being routinely signed and dated by operator.
• Observation 5: There were minor deviations from the standard recovery methods. Example
deviations include:
• amber or tinted jars were not used
• filter dishes were not sealed with Teflon tape
• impinger weights were recorded instead of volume
• 100 mL rinse solution was not used, rather jars were filled to a known mark
after rinsing
The auditor did not feel sample integrity had been compromised by these deviations.
As a result of audit findings, a series of system bias checks were performed immediately following the
ARCADIS internal systems audit and then done on at least a weekly basis until testing was completed.
Other Discrepancies
Several other problems that arose during testing are not believed to have adversely impacted data
quality, but should be documented in this section. There were two main problems that required
modification of procedures and test configurations. The first is the fuel system design, which was
discussed briefly in Chapter 4. Initial short-term operation of the PBS with Orimulsion 400 indicated
that no modification of the fuel system (shown in Figure 4-2) would be required to conduct testing of
Orimulsion 100 or 400. However, during the first full day of testing with Orimulsion 400, the fuel
system was found to have substantial amounts of "sludge" that did not flow reliably into the
combustor. After discussing the situation with experts who had previously tested Orimulsion in pilot-
scale facilities, the fuel feed system was redesigned to that shown in Figure 4-3. Following this
modification, difficulties in maintaining O2 levels were encountered, leading to installation of
additional fuel regulators. The final design of the fuel feed system is that shown in Figure 4-3. The
final configuration resulted in relatively steady operation, although the O2 levels (and subsequently
the CO levels) still tended to vary to a greater degree than desired.
The second problem encountered was that both Orimulsion 100 and Orimulsion 400 tended to settle
to a slight degree in the drums. A gentle mixing was used to reduce the settling prior to feeding the
fuel into the PBS, and subsequent operation did not indicate significant changes in fuel characteristics
during testing.
Data Limitations
Of the discrepancies noted above, the most serious is the failure of the CEMs to meet the DQI goals
for accuracy as measured by the calibration results. Of these, the majority (nearly 75%) were mid-
span checks. The calibration procedure is to set the monitor zero point, followed by setting the high-
10-14
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span point, then repeating the checks until the two are as close as possible to their respective setpoints.
The mid-span calibration point will be met if the monitor has a linear relationship between actual and
measured values at each point between the zero and the high-span calibration point. If, after the zero
and high-span values have been set, the mid-span check does not agree with the calibration gas, then
one concludes that the monitor is not linear between zero and the high-span value. Monitor linearity
is important when the gas being measured is not near the zero or high-span points.
For these tests, mid-span checks showed the greatest deviation for CO and SO2. For CO, the CEMs
measured concentrations at the mid-span approximately 12-15% higher than the calibration gas
concentration (309 ppm). The high-span calibration gas concentration was 850 ppm. Because the
CO concentrations reported in Chapter 5 were below 100 ppm, the difference between actual and
measured concentrations is likely to be lower than 12-15%. The reported CO concentrations are also
likely to be slightly higher than the actual concentrations, but it is not possible to accurately estimate
the difference other than by comparison to the mid-span differences. For SO2, no mid-span
calibrations were made, making it impossible to evaluate CEM linearity for SO2. While nonlinear
CEM performance may have contributed to the discrepancies between measurement methods and
calculated concentrations (see Table 5-4), it is not believed that CEM nonlinearity was the major
factor in the measurement differences.
In general, the discrepancies noted here are not believed to have a significant impact on the
conclusions drawn from this study. This study is more concerned with measuring differences
between the different fuels than with absolute concentrations. Since measurements for all three fuels
were made using the same equipment, and since the measured deviations were consistent for all three
fuels, the relative changes are believed to be primarily due to differences in fuels. As with any pilot-
scale study, the absolute concentrations should be considered as indications of full-scale performance
and not directly transferable to full scale.
QA Review of Sampling and Measurement Activities at Asnaes
NRMRL technical staff members conducted a site visit to the Asnaes Power Station in Kalundborg,
Denmark to observe stack sampling activities and to gain an understanding of the procedures and
methods used during the sampling. One of the major goals of this visit was to determine the degree
of QA used by Asnaes during data collection and reduction, to allow an evaluation of the data quality
for results published in several reports on Orimulsion pollutant emissions.
Flue Gas Concentration Measurements
Gas measurements made in Denmark follow international standards. International standards specify
that all steps from sampling to recording and storage maintain performance characteristics to ensure
that the measurement system is reliable and gives satisfactory results. Because this is in fact the same
objective of the Environmental Protection Agency (EPA) methods, much of the sampling activities
are similar, but not the same. ISO procedure number 7935:1992(E), titled "Stationary source
emissions - Determination of the mass concentration of sulfur dioxide - Performance characteristics
of automated measuring methods" was provided by the Asnaes Power Station personnel.
Three different organizations were responsible for data collection during the test campaign being
conducted at Unit 5 during the site visit. The Asnaes power station personnel operate permanently
mounted continuous emission monitors (CEM) at the inlet of the electrostatic precipitator (ESP) and
at the stack. The Technical University of Denmark (DTU) operated particulate samplers and gaseous
CEMs at the ESP inlet, outlet and at the stack. FLS Milj0s (a supplier of ESP and FGD equipment)
operated particulate samplers at the ESP exit.
The Asnaes power station collected data for O2, CO, CO2, NOX, SO2, PM using CEMs, moisture, and
stack gas and ambient temperatures. These data are collected continuously, not just for the short-
term sampling effort. Instruments are calibrated using either compressed gases, certified by gas
manufacturers using gravimetric standards, or by comparison to other measurement method
techniques. Instrument response is evaluated on a daily to monthly basis, depending upon the
scheduled operations. The instrument operations are evaluated every morning and corrective action
10-15
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is taken as needed. The CEM data are collected every 10 seconds, averaged to 1/2 hour values and
every 24-hour period are stored on a power plant computer. Spreadsheets are used to calculate
monthly emissions rates and various other parameters reported by the plant. The spreadsheet has
links to the 1/2 hour averages and a summary spreadsheet is stored for each month. The August
1999 summary was reviewed while discussing the formulas and values calculated for the month.
Material collected includes calibration gas analysis certificates, data sheets used for QC activities and a
printout of spreadsheet formulas. Documentation observed includes calibration log books and gas
analysis certificates (kept in a locked cabinet) and various forms used for CEM operation.
Calibrations, operations and data calculations are considered satisfactory to generate data that are
representative of the process being evaluated and comparable to data collected in the United States.
PM Sampling Program
A PM sampling program was being conducted at Asnaes Unit 5 during the week of the site visit
primarily to measure particle size distributions. Sampling points were at (1) the air preheater outlet
upstream of the ESP; (2) the ESP outlet upstream of the FGD system; and (3) the FGD outlet (stack).
The test program was designed by researchers at DTU to evaluate particle size distributions (PSDs) at
different locations along the process. PSD measurements were being made using Berner cascade
impactors and scanning mobility particle sizing (SMPS) systems at locations 1 and 2, and with
impactors only in the stack.
DTU collected data for particle size distribution using eight stage impactors, sold by Hauge (located
in Austria), and a scanning mobility particle sizer (SMPS) sold by TSI, and total particulate samples
using in-stack filter holders. Impactor flow rate was provided using a German-made pump and
regulated with a critical orifice, calibrated in the DTU laboratory. These samples were collected
before the ESP, after the ESP and at the stack. The sampling location prior to the ESP contained too
much particulate to operate the SMPS and a dilution probe was used to provide an appropriate
concentration. The dilution probe also cooled the sample gas and lowered the dewpoint to parameter
ranges acceptable to the SMPS. The dilution ratio was determined by continuously monitoring the
carbon dioxide concentration of the raw gas within the duct and the concentration of the gas being
analyzed. Because of the extended range of concentrations required for a 50:1 dilution ratio, two
CEMs were operated.
The calibration gases used for calibration were certified by the specialty gas manufacturer using
gravimetric standards. Because of low particulate concentrations, the sampling location after the ESP
was not diluted. Cooling and moisture removal were conducted using permeable drying tubes,
constructed of stainless steel. Sample gas flowed through a permeable SS tube surrounded by a
drying agent. The stack gas flow rate and temperature were measured periodically using a standard
pitot tube attached to an electronic manometer that calculated the stack gas velocity. These
measurements were made 5-6 times a day. This frequency was considered acceptable because of the
operating stability of the boiler and the stack gas concentrations. Impactor filters were collected
using both aluminum and Teflon foils and various speciation analyses were conducted in the DTU
laboratories.
Conversations with both the Asnaes personnel and the DTU researchers demonstrated a thorough
understanding of sampling procedures and appropriate precautions to ensure acceptable data.
Observed documentation included sampling forms, log books, and sample labels (impactor samples).
The gaseous standards used for calibration had been certified by the specialty gas manufacturers
using gravimetric standards. As described previously, the DTU sampling requirements are to adhere
to ISO standards. Calibrations, operations and data calculations are considered satisfactory to
generate data that are representative of the process being evaluated and comparable to data collected
in the United States.
Personnel at Asnaes are in the process of formalizing their QA procedures in preparation for
expected competition within the utility sector in Europe.
10-16
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Toxicity Testing
Toxicity testing was conducted as a Category 2 project as defined in the 1996 NHEERL Quality
Management Plan, and required preparation and approval of a Research Protocol that described the
purpose, design, and analyses proposed for the testing (EPA 1999b). Reviews of the test plan and the
results were required, as were several QC requirements during testing. The QC requirements were:
Maintenance of equipment service and audits;
Monitoring recovery of particles from filters;
Monitoring recovery of extracted particles;
Monitoring alterations to the physicochemical properties of extracted particles;
Using caged control animals to monitor pulmonary health status of animals;
Using saline-exposed animals to monitor effect of intratracheal instillation;
Providing duplicate exposure design for each dose employed; and
Including sentinel animals to monitor general health status of animals maintained in EPA facilities.
No discrepancies in the test procedures were noted.
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Chapter 11
Conclusions and Recommendations
The purpose of this report was to respond to the request Congress made of EPA, "to provide better
scientific data on the qualities and characteristics of this product and the potential environmental
impact of its introduction" (U.S. House of Representatives 1997). It is not the objective of this
report to address possible regulatory requirements or to estimate the costs associated with meeting
such requirements. There are many site-specific factors that are determined by regulatory
requirements that can significantly impact the cost of converting to Orimulsion. The data and the
conclusions presented in this report should not be considered as endorsing or discouraging the use of
Orimulsion, and the conclusions of this report cannot be considered as identifying specific
approaches for meeting regulatory requirements. The conclusions presented here are technical and
not regulatory in nature.
In response to the Congressional directive, NRMRL convened a panel of technical experts to evaluate
EPA's proposed assessment plan. The peer review panel posed four questions at the beginning of the
program (EPA 1999a). These questions are addressed below, based on the results of this study.
After these specific questions have been addressed, further conclusions and recommendations are
presented.
Responses to Questions of the Peer Panel
1. Are the emissions from the combustion of Orimulsion significantly different from those from
other fossil fuels, and if so, how?
Emissions of air pollutants from Orimulsion are not fundamentally different from those from
other fossil fuels. From the perspective of air pollutant emissions, Orimulsion fundamentally
behaves like a heavy fuel oil, and the air pollution control technologies applicable to heavy fuel
oil are applicable to Orimulsion. The most significant difference in emissions characteristics is
that PM emissions appear to be in a slightly smaller size range than those from heavy fuel oil, and
are significantly smaller than those produced by pulverized coal combustion. Emissions of sulfur
trioxide from Orimulsion also appear to be somewhat higher than for other fossil fuels, largely
due to the high levels of sulfur and vanadium. Emissions of metals such as nickel and vanadium
may also be higher than for other fossil fuels due to the higher level of these elements in the fuel.
Pulmonary toxicity testing of captured PM from the two Orimulsion formulations and the No. 6
fuel oil used in the EPA in-house tests found PM derived from the combustion of Orimulsion
100 and Orimulsion 400 to be very similar to that from the No. 6 fuel oil in their ability to
induce acute pulmonary toxicity.
2. Can the emissions from the combustion of Orimulsion be adequately controlled using existing
air pollution control technologies? If not, are there modifications to existing technologies that
can be made to adequately control emissions, or are new control technologies required?
Results from both full- and pilot-scale tests indicate that emissions from the combustion of
Orimulsion can be adequately controlled using commercially available air pollution control
technologies. As with any application, proper design, operation, and maintenance are necessary
to ensure adequate performance, but there is no indication that new technologies must be
developed specifically for controlling air pollutant emissions from the combustion of Orimulsion
or that major modifications to commercially available control technologies are required to
adequately control emissions. However, significant modifications to fuel handling and storage
systems, installation of air pollution controls, and/or modifications to boiler internal components
may be required for successful conversion to Orimulsion from other fuels.
3. Is the behavior of Orimulsion during a spill significantly different than the behavior of other
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fossil fuels, and if so, how?
The behavior of Orimulsion in a spill is significantly different than that of most other fossil fuels.
The National Research Council (NRC) notes that emulsified fuels (of which Orimulsion is one)
will behave very differently than non-emulsified fuels due to the presence of a surfactant. The
surfactant will act to prevent coalescence of the particles into larger fuel particles or pools,
making containment and recovery more difficult. Secondly, Orimulsion falls into the category of
non-floating oils as defined by the NRC study. This characteristic of Orimulsion results in a
likelihood of its sinking or remaining below the surface in a spill scenario, making it difficult (at
best) to track any spill plume or recover the fuel, and which may increase its potential for
contaminating public drinking water supplies. While tests have been conducted of Orimulsion
spill containment and recovery systems in marine environments, there has been little work
conducted on spills of Orimulsion in freshwater environments. While this issue should be
addressed by Bitor as the need for such information arises, EPA should evaluate spill effects,
behavior and response as appropriate in support of their legislated responsibility for spill
prevention, preparedness, and response.
4. What gaps in understanding the behavior of Orimulsion exist, based on the behavior of other
fossil fuels and the known properties of Orimulsion? Are these gaps serious with respect to
understanding the potential environmental impacts, and if so, what research should be
conducted to address these gaps?
The major gaps in understanding Orimulsion behavior are in the areas of health effects of
inhaling fine particles and transition metals, and freshwater spill response and effects. There are
indications that inhalation exposure to fine particles (particles smaller than 2.5 (am in diameter)
and transition metals may contribute to adverse health effects. However, these problems are also
present for other fossil fuels, and EPA is conducting numerous studies into the mechanisms
associated with these health effects under their fine PM research program. Given the relatively
low levels of Orimulsion that are likely to be used in the U.S. in the near term, the contribution of
Orimulsion to ambient levels of fine PM is not likely to be significant on a national basis. Even
on a local basis, appropriate pollution controls should be able to adequately control emissions of
PM, transition metals, and fine PM precursors (such as SOX).
Little is known about the behavior of Orimulsion in a freshwater spill, and subsequently little is
known about how to respond to such a spill. The responsibility for addressing this issue should
rest primarily with Bitor and/or the utility using Orimulsion, although EPA should stay abreast of
such studies. This should not be construed to imply that EPA should not conduct research as
appropriate to ensure that they are able to meet their responsibilities to respond to spills. A study
by the National Academy of Sciences on information needs associated with Orimulsion effects,
behavior, and response is being funded by EPA and the Coast Guard, and EPA is conducting
research to determine characteristics of Orimulsion and to better model its behavior in spills.
A review of an ecological risk assessment of a potential spill in the Tampa Bay, Florida marine
environment agreed with the assessment's conclusion that a spill of Orimulsion 100 likely poses a
similar or lower risk to Tampa Bay biota than does an equivalent spill volume of No. 6 fuel oil.
Although the reviewers of the assessment felt a number of improvements could be made to the
assessment, they concluded that none of the improvements would be likely to change the
assessment's conclusions. However, the review was limited to the scope of the original assessment,
and did not examine other factors that may have significant adverse ecological and health
impacts. Nevertheless, as of the writing of this document, there has not been an equally
comprehensive assessment of a possible spill of Orimulsion 400 into either marine or freshwater
environments.
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Further Conclusions
Orimulsion Properties
Orimulsion is physically and chemically an emulsified hydrocarbon fuel oil with high sulfur,
vanadium, and nickel content.
Air Pollutant Emissions
• In comparison to other fossil fuels, Orimulsion will in general emit more pollutants than natural
gas, about the same as heavy fuel oil, and less than pulverized coal. These comparisons do not
hold for all cases, and are based on emission levels without air pollution control systems.
• Orimulsion contains higher levels of Ni, S, and V than most other fuels, including coal, resulting
in higher uncontrolled emissions of SO2, SOs, Ni, and V compared to other fossil fuels.
• Uncontrolled PM emissions from Orimulsion are significantly lower than those from pulverized
coal, similar to those from heavy fuel oils, and significantly higher than those from natural gas.
• Particles from Orimulsion combustion are generally smaller than those from heavy fuel oil, and
significantly smaller than those from pulverized coal combustion.
• NOX emissions from the combustion of Orimulsion are approximately the same as those from
heavy fuel oil, lower than those from pulverized coal combustion, and higher than those from
natural gas combustion. NOX emissions from Orimulsion, like those from other fossil fuels, are
sensitive to combustion conditions and design of the combustion system.
• Emissions of organic compounds from the combustion of Orimulsion are very low, similar to
those from the combustion of pulverized coal, heavy fuel oil, and natural gas.
Air Pollution Control Technologies
• Commercially available control technologies that are appropriately designed and operated are
capable of controlling air pollutant emissions from the combustion of Orimulsion.
• Previous experience with Orimulsion indicates that conversion to the fuel may require significant
changes to existing equipment, including air pollution control systems, fuel supply and handing
systems, and boiler internal components.
Solid Waste Disposal
Recovery of Ni and V from Orimulsion ash is currently being conducted. Although untreated
Orimulsion ash is less dense than ash from coal or heavy fuel oil, ash handling can be improved
through modification of ash hoppers and the addition of water to improve ash agglomeration.
Toxicity
In general, both formulations of Orimulsion generated PM emissions that were capable of
producing significant adverse acute pulmonary toxicity, very similar to the No. 6 fuel oil tested.
In all cases, PM from both Orimulsion formulations and the No. 6 fuel oil showed measures of
toxicity greater than or equal to either Arizona road dust or saline solution.
• Acute pulmonary toxicity as measured using 5 toxicity markers found the relative toxicity
ranking of PM from Orimulsion to be less than or equal to PM from No. 6 fuel oil, except for
pulmonary injury as indicated by lactate dehydrogenase (LDH), where Orimulsion 400 showed
higher indications of toxicity at lower doses (0.125 and 0.25 mg/ml).
Spills
• Orimulsion is likely to behave much differently in a spill than most other fossil fuels, leading to
significant difficulties in cleanup and recovery of spilled fuel, particularly in fresh water. The
presence of the surfactant and the density of the fuel are likely to result in spills that do not float
and that are not easily contained.
Ecological Risk
A review by an EPA-chosen expert panel of a utility-funded ecological risk assessment of a
potential spill in the Tampa Bay, Florida marine environment agreed with the assessment's
conclusion that a spill of Orimulsion 100 likely poses a similar or lower risk to Tampa Bay biota
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than does an equivalent spill volume of No. 6 fuel oil. However, the review was limited to the
scope of the original assessment, and did not examine other factors that may have significant
adverse ecological and health impacts. The reviewers' conclusion may differ for different
conditions associated with other combinations of variables such as location, weather conditions,
level of fuel use, and diversity and number of biota in the locality. Although the reviewers of the
assessment felt a number of improvements could be made to the assessment, they concluded that
none of the improvements would be likely to change the assessment's conclusions. While
additional factors could also have been included in the assessment, as of the writing of this
document, there has not been an equally comprehensive assessment of a possible spill of
Orimulsion 400 into either marine or freshwater environments.
Potential for Orimulsion Use
The most likely use of Orimulsion in the U.S. is as a replacement for heavy fuel oil, due to
similarity in handling and combustion properties, the price differential between the two fuels, and
the readiness of plants using heavy fuel oil to accept tanker shipments of Orimulsion. These
factors would indicate that Orimulsion is most likely to be used along the Atlantic and Gulf coasts
in the U.S.
• Orimulsion is designed to be a base load fuel, due to its pricing structure. Utilities may find
Orimulsion most attractive as a fuel for increasing utilization of older plants as electricity
demands increase.
As fuel oil prices increase, Orimulsion may become a more attractive alternative fuel.
Data Reported in the Literature
• The full-scale air emissions and pollution control data reported in the literature are consistent with
expected results, based on the properties of the fuel, and with EPA's pilot test results. Although
these studies have been largely supported by Bitor and/or other interested parties, there is no
indication that the data from these studies are any less valid than the results of the pilot-scale
study conducted by EPA for this report.
Recommendations
The following recommendations are made with regard to Orimulsion behavior and its potential
environmental impacts, and EPA's role in further studies:
1. Based on the these results of Phase I of the Orimulsion Technology Assessment Plan, it is not
necessary for EPA to proceed with Phases II and III.
2. From the perspective of air pollutant formation and control, Orimulsion should be considered to
be a heavy fuel oil, albeit with some properties that require special attention.
3. Studies of Orimulsion behavior in freshwater spills are needed in the event that Orimulsion is
transported along fresh waterways or used in situations where spills can reach fresh water, even
indirectly. This research should evaluate the effects and behavior of Orimulsion under different
conditions (water density, presence of silt or other solids, energy level of waves) and should
evaluate means of containing and responding to spills. Bitor or the end user should be responsible
for the cost of any such work that directly supports efforts to market Orimulsion in the U.S. EPA
should continue to follow any work conducted by others on the behavior and fate of Orimulsion
spills, and should conduct the research necessary to support their legislated responsibility for spill
response, outside the scope of the Congressional directive to provide improved scientific
information on the environmental impacts of Orimulsion use.
4. Research recommended in a review by an EPA-chosen panel for improvements to a utility-funded
ecological risk assessment of a potential spill in the Tampa Bay, Florida marine environment is
considered to be the responsibility of Bitor.
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Chapter 12
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12-9
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Appendix A
Conversion of English System to SI System Units
bbl (U.S., petroleum) x 158.987 = L
Btu/hrx 2.93x10-4 = kW
(°F - 32) x 0.556 = °C
ft3 X 0.028316 = m3
fWmin x 0.028316 = nvVmin
gallon x 3.7853 = L
gpm x 3.7853 = L/min
in. x 2.54 = cm
lb/106 Btu x 0.43021= g/MJ
lb/1012 Btu x 0.43021 = (ig/MJ
ppm of NO x 1.230 = mg/Nm3
ppm of SO2 x 2.620 = mg/Nm3
ppm of CO x 1.145 = mg/Nm3
tons x 0.9072 = tonnes
A-l
-------
Appendix B
Continuous Emission Monitoring Data for EPA Pilot-Scale Tests
CEM data collected from each of the 12 test runs are presented below. Figures B-l through B-12
present CO, NO, O2, and SO2 concentrations (uncorrected) for each of the four test runs conducted
for each of the three fuels. The top plot in each case shows O2 concentration, and the bottom plot
shows CO, NO, and SO2. The sampling personnel attempted to collect samples when O2 and CO
fluctuations were minimal, and did not sample during periods when there were large fluctuations in
conditions.
The plots are presented in chronological order, with Figures B-l through B-4 showing results from
tests of Orimulsion 400, Figures B5 through B-8 showing results from Orimulsion 100, and Figures
B-9 through B-12 showing results from No. 6 fuel oil.
B-l
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of Orimulsion 400.
B-2
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Figure B-2. CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 19, 1999 during EPA's pilot-scale testing
of Orimulsion 400.
B-3
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20-
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Figure B-4. CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 21, 1999 during EPA's pilot-scale testing
of Orimulsion 400.
B-5
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Figure B-5. CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 24, 1999 during EPA's pilot-scale testing
of Orimulsion 100.
B-6
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of Orimulsion 100.
B-7
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of Orimulsion 100.
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Figure B-8. CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 27, 1999 during EPA's pilot-scale testing
of Orimulsion 100.
B-9
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Figure B-10. CEM data for O2 (top), CO, NO, and SO2 (bottom) taken June 4, 1999 during EPA's pilot-scale testing
of No. 6 fuel oil.
B-ll
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APPENDIX C
Volatile Organic Compound Analysis Laboratory Reports
Concentrations of volatile organic compounds (VOCs) were measured in EPA's Organics Support
Laboratory, located in the Environmental Research Center in Research Triangle Park, NC. Analyses
were conducted by chemists from ARCADIS Geraghty & Miller, the contractor for EPA's Air
Pollution Prevention and Control Division.
The analyses were conducted to specifically determine levels of benzene, ethylene, toluene, and
xylenes (BTEX), which were the criteria compounds for the analyses. The laboratory report stated
that other compounds detected may have been outside the criteria used for BTEX, and the data
should be evaluated using the case narrative supporting the data.
The following pages are the detailed case narrative and laboratory reports for each of the three
samples collected from each of the three fuels. Also included are the matrix spike and matrix spike
dupicate results and the results from the field blank used to evaluate laboratory contamination of the
samples.
C-l
-------
Case Narrative for Orimulsion VOST Analysis by GC/MS
A 5-point initial calibration was performed on April 28th and 29th, 1999. Each
calibration level and the method detection limit study was performed by flash evaporation at
235°C of methanolic aliquots of standard VOC's. Each VOST pair was allowed to stand for 5
minutes (after flash evaporation) at a flow of lOmL/min, transferred to the GC/MS clamshell
heater and thermally desorbed onto the GC/MS system. In an effort to ensure proper thermal
transfer for all of the target compounds, each VOST tube pair was positioned to bias the Tenax
portion fully into the heated zone. The calibration ranged between 10 ng and 250 ng on column.
Internal standards were injected into the sidearm of the sparging vessel during each calibration
and analysis. All target analytes had a relative standard deviation less than 30 % for this initial
calibration.
Next, a 6 point method detection limit study was performed by spiking and analyzing a
clean, VOST pair with the low level standard of 10 nanograms for each target VOC and
surrogate VOC in accordance with SW-846 methodology for determination of detection limits.
All target analytes had method detection limit values at least a factor of 2 less than the lowest
calibration (PQL) except for two brominated compounds and tetrachloroethylene which were
both below the PQL of 10 ng. Replicated matrix spikes of a separate BTEX standard was
peformed using flash evaporation. Spike recoveries ranged from 87 % to 116 % (values not
composited into a table but submitted in the regular report format). Two composited tables
inclusive of the calibration response factor data and the method detection limit study are
attached.
C-2
-------
A mid-level standard was performed prior to daily sample analysis. Relative percent
deviations less than 30 % when compared to the average response factors formed from the initial
calibration were found for all target analytes of interest. The 4-bromofluorobenzene peak
chosen from this standard passed method tuning criteria on each day. Prior to sample analysis,
the system's inherent background for target components was determined. Sample VOST tubes
were spiked prior to field sampling with surrogate compounds specified by the method. Samples
were tagged on the data spreadsheets to reflect the target VOC background determined from the
most recent matrix blank (other qualifiers were also attached). Values lower than the calculated
MDL for a few compounds such as dichloromethane, toluene, 1,2-dibromoethane, m,p xylenes,
bromobenzene and the dichlorobenzenes were noticed. The field blank demonstrated that all
compounds were below the calculated detection limit except for dichloromethane (which was
directly on the detection limit of 3.7 ng). All samples had similar results with low to mid-range
values of benzene, toluene, xylenes and styrene present. Carbon disulfide and dichloromethane
were present at varying levels. If you have any questions, please give Dennis (ext...2686) a call.
Bill Preston
Arcadis Geraghty & Miller Chemist
C-3
-------
Orimulsion YOST Method Detection Limit Study
Analyte
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethane
t-1,2-DichIoroethene
1,1-Dichloroethane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1 -Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
Bromodichloromethane
c- 1,3-Dichloropropene
Toluene
t-1,3-Dichloropropene
1,1,2-Trichloroethane
Tetrachloroethene
Dibromochloromethane
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
m,p-Xylenes
o-Xylene
Styrene
Bromobenzene
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
4/28/99 4/29/99 4/29/99 4/29/99 4/29/99 4/29/99
Run#l Run #2 Run #3 Run #4 Run #5 Run #6 StdDev MDL(ng)
8.90
10.45
8.37
14.04
9.52
9.55
9.97
10.10
9.79
9.57
9.45
10.59
13.14
10.15
9.83
10.54
9.64
9.90
11.91
11.22
10.64
10.18
9.06
10.39
10.11
9.99
17.44
10.13
10.57
9.95
9.74
9.70
9.80
7.99
9.40
7.60
13.74
8.84
8.73
9.27
8.48
9.13
9.64
9.57
9.21
12.06
9.52
9.53
8.91
9.18
8.84
12.16
9.41
8.64
10.23
8.85
8.39
9.33
9.36
15.83
9.05
8.93
9.37
9.21
8.53
8.81
7.62
8.47
7.15
13.55
8.61
8.33
8.80
8.15
8.68
9.06
9.02
8.80
11.94
11.40
11.86
10.76
9.97
10.27
11.13
8.25
7.91
9.63
9.43
9.72
8.55
8.81
15.16
8.67
8.78
8.40
8.33
8.11
8.25
7.86
7.99
7.21
13.88
8.65
8.51
9.15
8.44
9.31
9.44
9.20
9.74
10.72
9.99
9.94
9.87
9.69
9.84
12.00
10.07
9.89
12.82
12.01
12.34
10.66
10.93
19.40
11.41
11.31
10.87
10.72
10.57
10.30
7.93
8.07
7.31
16.23
8.64
8.90
9.05
8.94
8.54
8.77
8.79
8.94
11.69
8.72
8.93
8.39
7.54
7.72
10.56
8.07
7.47
8.63
6.96
7.57
7.65
8.08
14.00
8.03
8.05
7.48
7.52
7.36
7.37
8.02
7.69
7.47
17.06
8.60
9.35
8.56
9.78
9.61
9.40
9.24
10.06
12.43
9.04
9.89
9.45
7.51
8.70
11.17
8.38
7.59
9.46
6.90
8.25
7.98
8.13
13.58
7.47
7.22
7.06
6.89
6.53
6.49
0.49
1.04
0.50
1.10
0.38
0.47
0.44
0.77
0.50
0.37
0.32
0.73
0.87
0.98
1.10
1.02
0.97
1.04
0.68
1.31
1.33
1.55
1.81
1.85
1.20
1.09
2.10
1.33
1.36.
1.32
1.24
1.28
1.18
1.6
3.5
1.7
3.7
1.3
1.6
1.5
2.6
1.7
1.2
1.1
2.4
2.9
3.3
3.7
3.4
3.3
3.5
2.3
4.4
4.5
5.2
6.1
6.2
4.0
3.7
7.1
4.5
4.6
4.4
4.2
4.3
4.0
C-4
-------
Method
Title
Last Update
Response via
Response Factor Report Volatile
H:\HPCHEM\2\METHODS\V042899.M (Chemstation Integrator)
Orimulsion VOST analysis by Method 5041
Wed May 05 20:07:56 1999
Initial Calibration
Calibration Files
3
4
1) I
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13) S
14)
15)
16) I
17)
18)
19)
20)
21)
22) s
23)
24)
25)
26)
27)
28)
29) I
30)
31)
32)
33)
34)
35) S
36)
T7\
=VS34289A.D 2
=VS44289A.D 5
Compound
Pentafluorobenzene
ccc-1, 1-Dichloroethen
lodomethane
Carbon disulfide
Dichlorome thane
trans-1, 2-Dichloroeth
1, 1-Dichloroethane
cis-1 , 2-Dichloroethen
Bromochloromethane
ccc-Chloroform
1,1, 1-Trichloroethane
Carbon tetrachloride
d4-l,2 Dichloroethane
1, 2-Dichloroethane
Benzene
1, 4-Diflluorobenzene
Trichloroethene
ccc-1, 2-Oichloroprop
Dibromomethane
Bromodichloromethane
cis-1, 3-Dichloroprope
d8 -Toluene
ccc-Toluene
trans-1, 3-Dichloropro
1, 1, 2-Trichloroethane
Tet rachloroethene
Dibromochloromethane
1, 2-Dibromoethane
d5-Chlorobenzene
Chlorobenzene
ccc-Ethylbenzene
m,p-Xylenes
o-Xylene
Styrene
4 -Bromof luorobenzene
Bromobenzene
Hd — "\ d — Hi nh 1 riKrtHon-y^n
=VS24289A.D
=VS54299A.D
3 2
1
1
=VS14289B.D
4 5 Avg
%RSD
0.800
0.756
1.621
0.763
0.496
0.948
0.534
0.669
0.923
0.740
0.623
0.435
0.521
1.792
0.500
0.422
0.254
0.493
0.532
1.061
1.271
0.381
0.185
0.329
0.259
0.273
0.854
0.772
1.709
0.839
0.504
1.007
0.548
0.677
1.000
0.757
0.623
0.472
0.520
1.864
0.540
0.448
0.258
0.572
0.602
1.253
1.395
0.467
0.231
0.350
0.336
0.309
J.O
0.666
0.739
1.240
1.139
0.435
0.848
0.493
0.627
0.855
0.646
0.524
0.514
0.502
2.290
T <.
0.505
0.394
0.262
0.468
0.521
1.290
1.545
0.444
0.201
0.324
0.239
0.289
LU
0.722
0.625
1.424
0.663
0;425
0.821
0.449
0.584
0.789
0.626
0.524
0.444
0.461
1.511
irnr\
>1U
0.491
0.366
0.246
0.449
0.498
1.109
1.137
0.380
0.195
0.293
0.268
0.306
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
699
652
420
652
424
816
451
549
801
598
477
364
368
254
453
371
222
442
478
992
135
306
138
294
217
215
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
1.
1.
0.
0.
0.
0.
0.
748
709
483
811
457
888
495
621
874
673
554
446
475
742
498
400
248
485
526
141
296
395
190
318
264
278
10.
9.
12.
24.
8.
9.
9.
8.
10.
10.
11.
12.
13.
22.
6.
8.
6.
10.
9.
11.
13.
15.
17.
7.
17.
13.
32
30
47
45
70
60
23
88
11
49
86
38
53
40
29
66
28
89
00
10
56
92
76
71
04
75
ISTD
0.814
1.484
0.444
0.404
0.565
0.477
0.309
1.074
1.892
0.591
0.548
0.813
0.705
0.443
0.867
1.523
0.489
0.438
0.658
0.547
0.337
T
0.782
1.411
0.448
0.416
0.588
0.537
0.323
<3Tn
0.
1.
0.
0.
0.
0,
0.
,752
,324
,341
,357
,488
,352
.281
0.
1.
0.
0.
0.
0.
0,
858
527
462
,433
,623
,524
,338
14.
14.
19.
16.
19.
24.
18.
93
25
51
,38
69
,41
,37
(t) = Out of Range
V042899.M
Fri Jul 16 17:10:43 1999
Page 1
C-5
-------
Method
Title
Last Update
Response via
Response Factor Report Volatile
H:\HPCHEM\2\METHODS\V042899.M {Chemstation Integrator)
Orimulsion VOST analysis by Method 5041
Wed May 05 20:07:56 1999
Initial Calibration
Calibration Files
3 =VS34289A.D
4 =VS44289A.D
Compound
2
5
=VS24289A.D
=VS54299A.D
=VS14289B.D
Avg
%RSD
38) 1,3-Dichlorobenzene
39) 1,4-Dichlorobenzene
40) 1,2-dichlorobenzene
0.926 1.430 0.997 0.963 0.834 1.030 22.48
0.895 1.350 0.968 0.962 0.816 0.998 20.64
0.775 1.151 0.854 0.882 0.699 0.872 19.66
(#) = Out of Range
V042899.M
Fri Jul 16 17:10:44 1999
Page 2
C-6
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5181405
Lab Sample ID: 9905029
MS Data file: V995299A
Method: 5041A
Date Sampled: 05/18/99
Date Acquired: 05/24/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/905181405SV 10BL04-Clamshell temp controller failed to maintain at 233°c
and was noticed at 330°C after analysis/Benzene in blank at 2.9 ng
Surrogates
d4-l,2-dichloroethane(suiT)
d8-toluene (surr)
4-bromofluorobenzene(surr)
Compound
% Recovery
86.1 P
100.4 P
119.7 P
Compound
ng
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethanc
t-1,2-Dichlorocthcne
1,1-Dichlorocthane
c-1 ,2-Dichloroethanc
Bromochloromethanc
Chloroform
1,1,1-Trichloroethane
Carbon Tetrachloridc
1,2-Dichloroethanc
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
ND
ND
5.9 J
183.0
ND
ND
ND
ND
ND
ND
ND
ND
40.2 B
ND
ND
ND
Bromodichloromethane
c-13-Dichloropropenc
Toluene
t-1,3-Dichloropropene
1,1,2-Trichloroethane
Tetrachloroethene
Dibromochloromethane
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
m,p-Xylenes
o-Xylene
Styrene
Bromobenzene
13-Dfchlorobenzene
1,4-Dichlorobenzene
1,2-DichIorobenzene
ND
ND
19.3
ND
ND
ND
ND
ND
ND
3.9
11.9
ND
16.5
ND
ND
ND
ND
ND = ooc detected
Badetected in blank
E = Peak over calibration range
J = Peak below the calibration range
7/28/99
ARCADIS Geraghty Miller
C-7
5181405.xls
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5191058
Lab Sample ID: 9905030
MS Data file: V99S309A
Method: 5041A
Date Sampled: 05/19/99
Date Acquired: 05/24/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/903191058SV20BUM-CUmshdl decorber temp controller failed to maintain at 233°C
and was noticed at 330°C after analysis/Benzene in blank at 2.9 ng
Surrogates
d4-1,2-dichlorocthane(«urr)
d8-toluene (SUIT)
4-bromofluorobenzene(furr)
Compound
% Recovery
84.1
97.3
107.6
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfidc
Dichlorotnethane
t-1,2-Dichloroethene
1,1-Dichloroethane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1-Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
ND Bromodichloromethane
5.5 1 c-l,3-Dichloropropcne
59.9 Toluene
59.9 t-l,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylcnes
ND o-Xytene
102.9 B Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobenzene
1 ,2-Dichlorobenzene
ND
ND
28.5
ND
ND
ND
ND
ND
ND
ND
9.5
ND
20.6
ND
ND
ND
ND
ND = not detected
Badetected in blank
E = Peak over calibnlwa range
J = Pe*k below the calibration note
7/28/99
ARCADIS Geraghty Miller
C-8
519105il.xls
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5211256
Lab Sample ID: 9905041
MS Data file: V995419A
Method: 5041A
Date Sampled: 05/21/99
Date Acquired: 05/24/99
Analyst Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/905211256SV10BL04-CUmsheII temp controller failed to maintain at 233°c
and was noticed at 330°C after analysis/Benzene in blank at 2.9 ng.
Surrogates
d4-1,2-dicbloroedune(surr)
d8-toluene (surr)
4-bramofluorobenzene(surr)
Compound
% Recovery
85.5 P
32.2 F
109.1 P
ng
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethane
t-l,2-Dichloroethene
1,1 -Dichloroethane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1.1 -Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichlorocthene
1,2-Dichloropropane
Dibromomethane
ND Bromodichloromethane
6.1 J c-l,3-Dichloropropene
72.4 Toluene
64.3 t-l,3-Dichloropropene
ND 1.1.2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromethane
ND 1.2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylenes
ND o-Xylene
135.0 B Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1.4-Dichlorobenzene
1,2-Dichlorobenzcne
ND
ND
7.1
ND
ND
ND
ND
ND
ND
ND
9.2
ND
22.3
ND
ND
ND
ND
ND
not detected
in blank
E = Fak over calibration nnge
J = PoUc below die calibmion note
7/28/99
ARCADIS Geraghty Miller
C-9
521l256.xU
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5241337
Lab Sample ID: 9905042
MS Data file: V990542A
Method: 5041A
Date Sampled: 05/24/99
Date Acquired: 05/31/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/905241337SV10BL01
Surrogates
d4- l,2-dichloroethane(surr)
d8-toluene (surr)
4-bromofluoroben2cne(surr)
Compound
% Recovery
65.8 F
94.1 P
115.0 P
Compound
ng
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethane
t-l,2-Dichloroethene
1,1-Dichloroethanc
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1-Trichlorocthanc
Carbon Tetrachloride
1,2-Dichlorocthane
Benzene
Trichloroethene
1,2-Dichloropropanc
Dibromomethane
ND Bromodichloromethanc
ND c-13-Dichloropropene
7.6 J Toluene
36.6 t-l,3-Dichloropropene
ND 1,1.2-Trichloroethane
ND Tctrachloroethene
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylenes
ND o-Xylenc
20.6 Styrene
ND Bromobenzene
ND 1.3-Dichlorobenzene
ND 1,4-Dichlorobenzene
1,2-Dichlorobcnzene
ND
ND
12.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND = not detected
B=detecied in blank
E E= Peak over calibration range
J = Peak below the calibration range
7/8/99
ARCADIS Geraghly Miller
5241337.xls
C-10
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5251243
Lab Sample ID: 9905051
MS Data file: V990551A
Method: 5041A
Date Sampled: 05/25/99
Dale Acquired: 05/31/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/905251243S V1OBLO1
Surrogates
d4-1,2-dichloroethane(surr)
d8-tolucne (SUIT)
4-bromofluorobenzene(surr)
Compound
% Recovery
100.9
71.0
119.8
ng
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfidc
Dichloromethane
t-1,2-Dichloroethene
1,1 -Dichloroe thane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1 -Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
ND Bromodichloromethane
ND c-l,3-Dichloropropene
3.0 J Toluene
10.7 t-l,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethenc
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m.p-Xylenes
ND o-Xylene
55.2 Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzcne
ND 1,4-Dichlorobenzenc
1,2-DichIorobenzene
ND
ND
13.3
ND
ND
ND
ND
ND
ND
ND
7.5
ND
9.3
ND
ND
ND
ND
ND = not delected
B=detected in blank
E - Peak over calibration range
J = Peak below the calibration range
7/28/99
ARCADIS Geraghty Miller
5251243-Xls
C-ll
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 5261102
Lab Sample ID: 9905057
MS Data file: V990557A
Method: 5041A
Date Sampled: 05/26/99
Date Acquired: 05/31/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/905261102SV10BL01
Surrogates
d4-1,2-dichloroethanc(surr)
d8-toluenc (SUIT)
4-bromofluorobenzene(surr)
Compound
% Recovery
73.1 P
96.3 P
117.0 P
Kg
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethane
t-1,2-Dichloroethene
1,1-Dichloroethane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1-Trichloroethanc
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropanc
Dibromomethane
ND Bromodichloromethane
ND c-l,3-Dichloropropcne
5.0 J Toluene
55.0 t-l,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Bthylbenzene
ND m,p-Xylenes
ND o-Xylene
73.6 Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobenzenc
1,2-Dichlorobenzenc
ND
ND
19.1
ND
ND
ND
ND
ND
ND
3.7
10.0
ND
5.4
ND
ND
ND
ND
NDc not detected
B^dctected in blank
E = Peak over calibration range
J = Peak below the calibration range
7/8/99
ARCADIS Gcraghty Miller
C-12
5261102.xls
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 6031301
Lab Sample ID: 9906006
MS Data file: V996006A
Method: 5041A
Date Sampled: 06/04/99
Date Acquired: 06/17/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/906031301S V1OBLR6
Surrogates
d4-1,2-dichloroethane(surr)
d8-toluenc (SUIT)
4-bromofluorobenzcne(surr)
Compound
Recovery
64.7
90.7
123.9
ng
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfidc
Dichloromethane
t-1.2-Dichloroethene
1,1-Dichloroe thane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1.1 -Trichloroethane
Carbon Tetrachloridc
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomcthane
ND Bromodichloromethane
ND c-l,3-Dich!oropropcne
28.9 Toluene
ND t-1,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylenes
ND o-Xylene
23.6 Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobenzene
1,2-Dichlorobenzene
ND
ND
47.9
ND
ND
ND
ND
ND
ND
30.9
113.1
37.6
15.3
ND
ND
ND
ND
ND = not delected
B=deiected in blank
E = Peak over calibration range
J = Peak below the calibration range
7/28/99
ARCADIS Oeraghly Miller
603l301.xls
C-13
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
6041340
9906015
V996015A
5041A
Date Sampled: 06/04/99
Date Acquired: 06/17/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/906041340SV10BLR6
Surrogates
d4-1,2-dichloroethanc(surr)
d8-toluene (SUIT)
4-bromofluorobcnzenc(suir)
Compound
% Recovery
57.3 F
95.5 P
134.1 F
ng
Compound
ng
1,1 Dichlorocthcne
lodomethane
Carbon Disulfide
Dichloromethane
t-1,2-Dichloroelhcne
1,1 -Dichloroethane
c-1,2-Dichloroethane
Bromochloromethane
Chloroform
1,1,1-Trichloroethane
Carbon Tctrachloride
1,2-Dichloroethane
Benzene
Trichloroethcne
1,2-Dichloropropane
Dibromomcthane
ND Bromodichloromethanc
ND c-l,3-Dichloropropcnc
7.2 J Toluene
383.8 t-l,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroelhenc
ND Dibromochloromethane
ND 1,2-Dibromocthane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylenes
ND o-Xylene
20.0 Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobcnzene
1,2-Dichlorobenzene
ND
ND
13.7
ND
ND
ND
ND
ND
ND
5.2
23.9
6.4
10.0
ND
ND
ND
ND
ND = not detected
B=detecled in blink
E = Peak over calibration range
J = Peak below the calibration range
7/28/99
ARCADIS Geraghly Miller
C-14
604l340.xls
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
6071305
9906018
V990618A
5041A
Date Sampled: 06/07/99
Date Acquired: 06/16/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/906071305SV10BLR6
Benzene in matrix blank at 4.9 ng.
Surrogates % Recovery
d4-l,2-dichloroethane(surr) 64.5 F
d8-ioluene (surr) 82.0 P
4-bromofluorobenzene(surr) 157.0 F
Compound ng Compound
ng
1,1 Dichloroethene
lodomelhane
Carbon Disulfidc
Dichloromethanc
t-1,2-Dichloroethene
1,1-Dichlorocthane
c-1,2-Dichlorocthanc
Bromochloromethane
Chloroform
1,1,1 -Trichlorocthane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromome thane
ND Bromodichloromethane
ND c-l,3-Dichloropropene
22.3 Toluene
ND t-1,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromcthane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylcnes
ND o-Xylene
16.0 B Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobenzene
1,2-Dichlorobenzene
ND
ND
25.9
ND
ND
ND
ND
ND
ND
8.2
36.7
9.9
10.4
ND
ND
ND
ND
ND = not detected E = Peak over calibration range
Undetected in blank J = Peak below the calibration range
7/28/99
ARCAD1S Geraghty Miller
6071305.xls
C-15
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: 4301230/FB
Lab Sample ID: 9905001
MS Datafile: V995001A
Method: 5041A
Date Sampled: 04/30/99
Date Acquired: 04/30/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Sample/904301230SV10BLR6/Field Blank
3.7 ng of dichloromethane was in the matrix blank
Surrogates
d4-1,2-dichloroethane(surr)
d8-toluene (surr)
4-bromofluorobenzene(surr)
Compound
% Recovery
91.6 P
101.6 P
120.6 P
ng
Compound
ng
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromethane
t-1,2-Dichloroethene
1,1-Dichloroe thane
c-1,2-Dichtoroethane
Bromochlotomethanc
Chloroform
1,1,1-Trichloroethane
Carbon Tetrachloride
1,2-Dichlorocthanc
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
ND Bromodichloromethanc
ND c-l,3-Dichloropropene
ND Toluene
3.7 J,B t-l,3-Dichloropropene
ND 1,1,2-Trichloroethane
ND Tetrachloroethene
ND Dibromochloromethane
ND 1,2-Dibromoethane
ND Chlorobenzene
ND Ethylbenzene
ND m,p-Xylenes
ND o-Xylene
ND Styrene
ND Bromobenzene
ND 1,3-Dichlorobenzene
ND 1,4-Dichlorobcnzene
1,2-Dichlorobenzene
ND
ND
2.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND = not detected
B=detectcd in blank
E = Peak over calibration range
J = Peak below the calibration range
7/28/99
ARCADIS Geragluy Miller
4301230.xls
C-16
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project: Orimulsion
Sample Name: Matrix Spike
Lab Sample ID: 9905049
MS Data file: V990549a
Method: 5041A
Date Spiked: 05/25/99
Date Acquired: 05/25/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Tenax-B05689/T/C-B05695
Matrix Spike #1 at 150 ng each B.T.E.X component
Surrogates
d4-1,2-dichloroethanc(surr)
d8-loluene (surr)
4-bromofluorobenzene(surr)
Compound
% Recovery
86.6 P
103.9 P
112.7 P
ng
Compound
ng
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichlorotnethane
t-l,2-Dichloroethcne
1,1 -Dichloroethanc
c-1,2-Dichlorocthanc
Bromochloromethane
Chloroform
1,1,1-Trichloroethane
Carbon Tetrachloride
1,2-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
NS Bromodichloromethane
NS c-l,3-Dichloropropcne
NS Toluene
NS t-l,3-Dichloropropene
NS 1,1,2-Trichloroethane
NS Tetrachloroethene
NS Dibromochloromethane
NS 1,2-Dibromoethane
NS Chlorobenzene
NS Ethylbenzene
NS m,p-Xylenes
NS o-Xylene
135.0 Styrene
NS Bromobenzene
NS 1,3-Dichlorobenzene
NS 1,4-Dichlorobenzene
1,2-Dichlorobenzene
NS
NS
1453
NS
NS
NS
NS
NS
NS
161.4
173.8
168.8
NS
NS
NS
NS
NS
ND = not spiked
B=dctccied in blank
E = Peak over calibration range
J = Peak below the calibration range
7/8/99
ARCAD1S Geraghty Miller
C-17
orivolmsl.xls
-------
APPCD Organic Support Laboratory
Volatile Organic Sampling Tube Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Matrix Spike
9905050
V990550A
5041A
Date Spiked: 05/25/99
Date Acquired: 05/25/99
Analyst: Bill Preston
QC reviewer: Dennis Tabor
Sample Description/Narrative:
Tenax-B05689/T/C-B05695
Matrix Spike #2 at 150 ng each B.T.E.X component
Surrogates
d4-1,2-dichloroethane(surr)
d8-toluene (SUIT)
4-bromofluorobenzene(surr)
Compound
% Recovery
87.5 P
89.4 P
112.5 P
Compound
1,1 Dichloroethene
lodomethane
Carbon Disulfide
Dichloromcthane
t-1,2-Dichloroethene
1,1 -Dichloroethane
c-1,2-Dichlorocthane
Bromochloromcthane
Chloroform
1,1,1-Trichloroethane
Carbon Telrachloride
1 ^-Dichloroethane
Benzene
Trichloroethene
1,2-Dichloropropane
Dibromomethane
NS Bromodichloromethane
NS c-l,3-Dichloropropene
NS Toluene
NS t-1,3-Dichloropropene
NS 1,1,2-Trichloroethane
NS Tetrachloroethene
NS Dibromochloromethane
NS 1,2-Dibromoethane
NS Chlorobenzene
NS Ethylbenzene
NS m,p-Xylenes
NS o-Xylene
130.4 Styrene
NS Bromobcnzcne
NS 1,3-Dichlorobenzene
NS 1,4-Dichlorobcnzene
1,2-Dichlorobcnzene
NS
NS
1393
NS
NS
NS
NS
NS
NS
169.0
172.0
172.9
NS
NS
NS
NS
NS
ND = not ipiked
B detected in blank
E = Peak over calibration range
J = Peak below (he calibration range
7/8/99
ARCADIS Geraghty Miller
orivolmsd.xls
C-18
-------
APPENDIX D
Semivolatile Organic Compound Analysis Laboratory Reports
D-l
-------
Case Narrative for Orimulsion Semivolatile Analysis by Method 8270
A five-level calibration was performed on June 24 -25th, 1999. Levels 1 through 4
(10,30,60, and 90 ug/mL) were analyzed on June 24th and level 5 (100 ug/mL) was analyzed on
June 25th, 1999. The relative standard deviation of the average response factors throughout the
calibration range! was generally below 10 % with few exceptions. The relative standard deviation
for 13C6-2,5-phthalic anhydride was the only constituent greater than 30 % at 37.21%. A rigorous
method detection limit study was not performed prior to sample analysis. Past semivolatile analysis
allowed insight for establishing an arbitrary cutoff of 1 ug/mL (1 ng on column) for the instrumental
detection limit. Sample concentrations near this value were scrutinized carefully to ensure excellent
retention time matching and adequate confirmation ion ratios.
Method 8270 daily sample analysis consisted of initially passing the DFTPP tuning criteria.
The monitoring for the presence of benzidine in the DFTPP tuning solution (which was present hi
all cases) and the monitoring for DDT lack of degradation were done daily prior to sample analysis.
After the DFTPP passed all tuning criteria, a mid-point calibration standard was analyzed. The mid-
level standard was compared to the initial calibration curve. All constituents of interest were less
than 30 % relative deviation hi all cases.
Each sampling condition had three separate analyses: XAD, filter, and the condensate which
were analyzed bjetween July 25th and July 29th, 1999. Pre-extraction surrogates were spiked into
i
every sample arid pre-sampling surrogates (additional APPCD-OSL QC) were added to the XAD
portions only. Generally, the pre-extraction and pre-sampling surrogates passed pass/fail criteria (a
D-2
-------
table comprising the acceptance criteria for the pre-sampling and pre-extraction surrogates is
attached). Replicated matrix spikes of P AHs of interest determined recovery values between 50%
and 77% when compared to the initial calibration. This directly parallels the surrogates recovery
data. All samples had very low to non-detectable levels for most of the PAH targets and for the
additional analyte list with a few exceptions for phthalates. If you have any questions, please give
me a call at ext.. .2719.
Arcadis Geraghty & Miller Chemist,
Bill Preston
D-3
-------
Sheetl
Surrogates Recovery Limits Used for the Orimulsion Study
Description Recovery limits
2-Fluorophenol 24-113
d5-Phenol 25-121
2,4,6-Tribromophenol 19-122
dS-Nitrobenzene 23-120
2-Fluorobipheny 1 30-115
D-4
-------
Method
Title
Last Update
Response via
Response Factor Report Semi2
F:\ORIMUL~1\METHODS\S062499.M (RTE Integrator)
Orimulsion PAH Analysis by method 8270
Wed Jul 28 08:42:17 1999
Initial Calibration
Calibration Files
2
4
1) i
2)
3)
4) S
5)
6)
7)
8)
9) S
10) M
11)
12)
13) M
14) s
15)
16)
17)
18)
19)
20)
21)
22)
23) M
24) i
25) S
26)
27)
28)
29)
30)
31) s
32) M
33)
34) s
35)
36)
37)
38)
=SC26249A.D 1
=SC46249A.D 5
Compound
D4-1, 4-dichlorobenzen
n-Nitrosomethylethyla
Methyl Methanesulfona
2-Fluorophenol (surrll
n-Nitrosodiethylamine
Bis (2-chloroethyl) eth
Ethyl methanesulfonat
Aniline
D5-Phenol(surr#2)
Phenol (CCC)
2-Chlorophenol
1, 3-Dichlorobenzene
1, 4-Dichlorobenzene (C
13C6-1,2 dichlorobenz
1, 2-Dichlorobenzene
Benzyl Alcohol
Bis (2-chloroisopropyl
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
4-methylphenol
N-nitrosodi-n-propyla
08-Naphthalene (QS#2)
D5-Nitrobenzene (surr#
Nitrobenzene
1-Nitrosopiperidine
Isophorone
2, 4-Dimethylphenol
Bis (2-chloroethoxy)me
13C6-2,5 dichlorophen
2, 4-Dichlorophenol (CC
1,2, 4-Trichlorobenzen
13C6-Napthalene (pre
Naphthalene
2-Nitrophenol (CCC)
2, 6-Dichlorophenol
Hexachloropropene
=SC16249A.D 3
=SC56259A.D
213
=SC36249A.D
4 5 Avg
%RSD
T OT»I^
0.743
0.801
1.506
0.610
1.396
1.460
1.692
1.698
1.832
1.378
1.625
1.653
1.448
1.516
0.862
0.650
1.238
0.517
1.886
0.687
2.541
0.905
0.757
0.889
1.625
0.622
1.567
1.593
2.127
1.873
2.004
1.538
1.681
1.778
1.273
1.624
0.886
0.742
1.374
0.558
2.054
0.746
2.889
0.983
-L C
0.815
0.865
1.522
0.674
1.435
1.577
1.535
1.775
1.899
1.456
1.663
1.712
1.436
1.553
0.913
0.678
1.311
0.565
1.938
0.700
2.611
0.935
> j. u
0.817
0.827
1.446
0.671
1.358
1.488
1.594
1.662
1.797
1.382
1.632
1.647
1.391
1.491
0.815
0.653
1.175
0.533
1.736
0.668
2.275
0.889
0.
0.
1.
0.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
0.
0.
1.
0.
1.
0.
2.
0.
816
895
512
660
478
588
616
751
855
467
695
744
414
599
868
661
258
511
931
737
507
898
0
0
1
0
1
1
1
1
1
1
1
1
1
1
0
0
1
0
1
0
2
0
.790
.855
.522
.647
.447
.541
.713
.752
.878
.444
.659
.707
.392
.557
.869
.677
.271
.537
.909
.708
.565
.922
4
4
4
4
5
4
13
4
4
4
1
3
5
3
4
5
5
4
6
4
8
4
.64
.74
.25
.55
.58
.05
.91
.62
.26
.62
.84
.33
.06
.56
.17
.61
.92
.51
.03
.66
.61
.17
T CTH —
loiU
0.504
0.516
0.301
0.936
0.326
0.474
0.320
0.317
0.363
1.122
1.073
0.227
0.313
0.235
0.559
0.570
0.343
1.053
0.359
0.532
0.288
0.340
0.399
1.020
1.158
0.236
0.331
0.243
0.509
0.537
0.315
0.977
0.337
0.485
0.330
0.329
0.367
1.116
1.086
0.243
0.328
0.250
0.513
0.518
0.308
0.965
0.336
0.482
0.332
0.322
0.375
1.094
1.048
0.242
0.323
0.258
0.
0.
0.
1.
0.
0.
0.
0.
0.
1.
1.
0.
0.
0.
535
545
328
013
339
498
325
344
391
094
109
247
337
272
*
0
0
0
0
0
0
0
0
0
1
1
0
0
0
.524
.537
.319
.989
.339
.494
.319
.330
.379
.089
.095
.239
.327
.252
4
4
5
4
3
4
5
3
4
3
3
3
2
5
.36
.12
.28
.56
.64
.63
.53
.53
.07
.75
.81
.36
.71
.73
(#) = Out of Range
S062499.M
Fri Jul 30 14:47:33 1999
Page 1
D-5
-------
Method
Title
Last Update
Response via
Response Factor Report Semi2
F:\ORIMUL~1\METHODS\S062499.M (RTE Integrator)
Orimulsion PAH Analysis by method 8270
Wed Jul 28 08:42:17 1999
Initial Calibration
Calibration Files
2
4
39)
40) M
41)
42) M
43)
44) i
45)
46) s
47)
48) M
49) M
50)
51) S
52)
53)
54)
55)
56)
57)
58)
59)
60)
61) M
62)
63)
64)
65) M
66)
67)
68)
69)
70) M
71)
72)
73)
74)
75)
76)
77) $
=SC26249A.D 1
=SC46249A.D 5
Compound
4-Chloroaniline
Hexachlorobutadiene (C
n-Nitrosodi-n-butylam
4-Chloro-3-methyl-phe
2-Methylnaphthalene
DIO-Acenaphthene (QS#3
Isosaf role
13C6-Phthalic Anhydri
1,2,4, 5-Tetrachlorobe
Hexachlorocyclopentad
2,4, 6-Trichlorophenol
2,4, 5-Trichlorophenol
2-Fluorobiphenyl (surr
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1 , 4-Naphthoquinone
Dimethylphathalate
2, 6-Dinitrotoluene
Acenaphthene (CCC)
1 -Napthylamine
2-Napthylamine
4-Nitroaniline
2, 4-Dinitrophenol (SPC
Dibenzofuran
Pentachlorobenzene
2, 4-Dinitrotoluene
2, 3, 4, 6-Tetrachloroph
4-Nitrophenol (SPCC)
Fluorene
Diethyl phathalate
4-Chlorophenyl phenyl
2-Methyl-4, 6-dinitrop
5-Nitro-o-toluidine
Diphenylamine
2,4, 6-Tribromophenol (
=SC16249A.D 3
=SC56259A.D
213
0.378
0.214
0.225
0.312
0.651
0.434
0.219
0.236
0.353
0.716
0
0
0
0
0
.321
.219
.246
.330
.658
=SC36249A.D
4 5 Avg
0.215
0.227
0.241
0.321
0.647
0
0
0
0
0
.248
.238
.236
.340
.677
0.
0.
0.
0.
0.
319
223
237
331
670
%RSD
28.27
4.24
3.41
4.80
4.22
_ T cmr\
0.549
0.135
0.670
0.429
0.434
0.471
1.339
0.473
0.253
0.490
0.377
0.257
1.869
0.311
1.421
0.340
1.135
0.934
0.552
0.543
0.163
1.679
0.512
0.440
0.335
0.318
1.297
1.439
0.638
0.252
0.377
1.090
0.179
0.574
0.153
0.707
0.426
0.452
0.483
1.468
0.488
0.255
0.500
0.398
0.267
2.020
0.318
1.480
0.354
1.229
0.813
0.394
0.540
0.136
1.771
0.529
0.455
0.344
0.293
1.383
1.563
0.652
0.228
0.414
1.114
0.182
0
0
0
0
0
0
1
0
0
0
0
0
1
0
1
0
1
0
0
0
0
1
0
0
0
0
1
1
0
0
0
1
0
X v.
.588
.139
.709
.460
.464
.492
.406
.490
.270
.491
.383
.263
.955
.312
.431
.355
.181
.866
.482
.463
.187
.709
.539
.447
.335
.320
.291
.441
.654
.265
.350
.096
.183
3 J. LJ
0.578
0.083
0.709
0.462
0.463
0.484
1.367
0.478
0.269
0.475
0.371
0.261
1.922
0.301
1.408
0.351
1.168
0.760
0.371
0.463
0.196
1.666
0.535
0.449
0.336
0.319
1.267
1.422
0.644
0.274
0.351
1.072
0.185
0
0
0
0
0
0
1
0
0
0
0
0
1
0
1
0
1
0
0
0
0
1
0
0
0
0
1
1
0
0
0
1
0
.584
.236
.722
.465
.458
.489
.408
.481
.284
.502
.389
.269
.942
.276
.465
.365
.136
.833
.457
.518
.205
.746
.554
.487
.348
.333
.355
.530
.671
.293
.386
.130
.193
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
1.
0.
1.
0.
1.
0.
0.
0.
0.
1.
0.
0.
0.
0.
1.
1.
0.
0.
0.
1.
0.
575
149
704
448
454
484
398
482
266
492
384
263
942
303
441
353
170
841
451
505
178
714
534
456
339
317
318
479
652
263
376
100
184
2.69
37.21
2.79
4.36
2.63
1.64
3.48
1.49
4.75
2.17
2.81
1.88
2.81
5.53
2.09
2.61
3.32
7.67
16.02
7.83
15.74
2.57
2.84
4.06
1.80
4.57
3.67
4.27
1.88
9.23
7.05
2.03
2.90
(#) = Out of Range
S062499.M
Fri Jul 30 14:47:41 1999
Page 2
D-6
-------
Response Factor Report Semi2
Method : F:\ORIMUL~1\METHODS\S062499.M (RTE Integrator)
Title : Orimulsion PAH Analysis by method 8270
Last Update : Wed Jul 28 08:42:17 1999
Response via : Initial Calibration
Calibration Files
2
4
78)
79)
80) i
81)
82)
83)
84)
85)
86) M
87)
88)
89) s
90)
91)
92)
93) M
94)
95) i
96)
97)
98) S
99)
100)
101)
102)
103)
104)
105) i
106) M
107)
108)
109)
110) M
111)
112)
113)
114)
=SC26249A.D 1
=SC46249A.D 5
Compound
Diallate
1,3, 5-Trinitrobenzene
DIO-Phenanthrene (QS#4
4-Bromophenyl phenyl
Phenacetin
Hexachlorobenzene
4-Aminobiphenyl
Dinoseb
Pentachlorophenol (CCC
Pentachloronitrobenze
Phenanthrene
dlO- Anthracene
Anthracene
Di-n-butyl phthalate
Isodrin
Fluoranthene (CCC)
3,3' -Dimethylbenzidin
D12-Chrysene (QS#5)
Pyrene
Chlorobenzilate
D14-Terphenyl (surr#6)
p-Dimethylaminoazoben
2-Acetylaminofluorene
Benzyl butyl phthalat
3,3' -Dichlorobenzidin
Benzo (a) anthracene
Chrysene
D12-Perylene(QS#6)
di-n-Octyl phthalate (
Benzo (b) f luoranthene
7, 12-Dimethylbenz (a) a
Benzo (k) f luoranthene
Benzo (a)pyrene (CCC)
3-Methylcholanthrene
Indeno (1,2, 3-cd)pyren
Dibenz (a, h) anthracene
Benzo (ghi) perylene
=SC16249A.D
=SC56259A.D
213
0.698
0.325
0.763
0.306
0.
0.
3
674
328
=SC36249A.D
4 5 Avg
0.656
0.335
0
0
.713
.385
0
0
.701
.336
%RSD
5.86
8.78
_ _. Tonnn
0.211
0.453
0.243
0.516
0.221
0.136
0.093
1.140
1.025
1.172
1.541
0.148
1.172
0.245
0.226
0.472
0.255
0.432
0.197
0.137
0.096
1.234
0.911
1.262
1.578
0.150
1.209
0.324
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
0.
1.
0.
233
457
264
526
250
135
098
193
054
223
533
142
181
256
) J. U
0.232
0.454
0.264
0.464
0.258
0.135
0.098
1.166
1.047
1.199
1.494
0.140
1.172
0.257
0
0
0
0
0
0
0
1
1
1
1
0
1
0
.241
.486
.268
.507
.267
.149
.104
.220
.032
.251
.622
.148
.255
.296
0
0
0
0
0
0
0
1
1
1
1
0
1
0
.228
.464
.259
.489
.239
.138
.098
.191
.014
.221
.553
.146
.198
.275
5.01
3.13
3.80
8.11
12.08
4.46
4.09
3.26
5.77
3.03
3.12
2.98
2.95
12.16
T CTr\
— ibi U ~ —
1.539
0.405
0.922
0.289
0.582
0.815
0.382
1.336
1.255
1.661
0.420
0.998
0.322
0.545
0.876
0.434
1.434
1.338
1.
0.
0.
0.
0.
0.
0.
1.
1.
612
424
974
292
651
831
427
423
346
1.585
0.416
0.974
0.276
0.651
0.809
0.412
1.401
1.345
1
0
0
0
0
0
0
1
1
.596
.438
.999
.281
.671
.854
.433
.443
.374
1
0
0
0
0
0
0
1
1
.598
.420
.973
.292
.620
.837
.417
.408
.332
2.77
2.90
3.19
6.16
8.65
3.31
5.24
3.07
3.36
T CTH —
— — — IbilJ — —
1.862
1.206
0.520
1.156
1.058
0.520
1.007
0.988
1.048
1.943
1.296
0.568
1.235
1.105
0.531
1.000
0.972
1.052
1.
1.
0.
1.
1.
0.
1.
1.
1.
935
282
565
222
130
558
095
093
139
1.904
1.266
0.562
1.195
1.126
0.549
1.066
1.065
1.101
2
1
0
1
1
0
1
1
1
.046
.344
.585
.265
.178
.561
.123
.100
.150
1
1
0
1
1
0
1
1
1
.938
.279
.560
.215
.119
.544
.058
.043
.098
3.52
3.93
4.27
3.41
3.91
3.26
5.11
5.74
4.33
(#) = Out of Range
S062499.M Fri Jul 30 14:47:48 1999 Page 3
D-7
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131F
9905026
S995026A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905181131SBFO- Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
Recovery % Recovery
59 P D5-Nitrobenzene(surr#3) 70 P
71 P 2-Fluorobiphenyl(surr#4) 72 P
87 P D14-Terphenyl(surr#6) 93 P
Recovery % Recovery
NS 13C6-2.5 Dichlorophenol NS
NS 13C6-2,5-Phthalate anhydride NS
NS
ug Compound ug
ND 4-Methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
1 J Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
D-8
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131F
9905026
S995026A
8270
HRGC/LRMS
Sample Description/Narrative:
905181131SBFO- Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachloijophenol
4-Nitrophenol(SPiCQ
Fluorene
Diethyl phathalat^
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound Mg
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 7
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
D-9
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131F
9905026
S995026A
8270
HRGC/LRMS
Sample Description/Narrative:
905181131SBFO- Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/18/99
6/1/99
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
7 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-10
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131X
9905027
S995027A
8270
HRGC/LRMS
Sample Description/Narrative:
905181131WSBXO-
Pre Extraction Surrogates
2-Ruorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10- Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene(CCC)
1 ,2-Dichlorobenzene
Benzyl Alcohol i
Bis(2-chloroisopropyl)ether
2-Methylphenol '
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Recovery
80 P
66 P
101 P
Recovery
86
87
100
Mg
ND
ND
ND
ND
ND
ND
2 J
ND
ND
ND
ND
ND
ND
ND
ND
8 J
ND
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1 ,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
% Recovery
89
92
128
% Recovery
92
142
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
9
ND
ND
ND
ND
ND
ND
ND
P
P
P
J
J = Peak below the calibration range NS= not spiked
D-ll
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131X
9905027
S995027A
8270
HRGC/LRMS
Sample Description/Narrative:
905181131WSBXO-XAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 15
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
2 J
J = Peak below the calibration range
NS= not spiked
D-12
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131X
9905027
S995027A
8270
HRGC/LRMS
Sample Description/Narrative:
905181131WSBXO-XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/18/99
6/1/99
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
3 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-13
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131C
9905028
S995028A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
NA
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905181131SBIO Condensate-Not spiked with pre-extraction surrogates
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(suir#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1,2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisoproiy l)ether
2-Methylphenol <
n-Nitrosospyrrolidijne
Acetophenone j
Hexachloroethane !
% Recovery % Recovery
NS D5-Nitrobenzene(surr#3) NS
NS 2-Fluorobiphenyl(surr#4) NS
NS D14-Terphenyl(surr#6) NS
% Recovery % Recovery
NS 13C6-2.5 Dichlorophenol NS
NS 13C6-2,5-Phthalate anhydride NS
NS
fig Compound fig
ND 4-Methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-14
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131C
9905028
S995028A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/18/99
NA
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905181131SBIO Condensate-Not spiked with pre-extraction surrogates
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
fig Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate 3
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-15
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905181131C
9905028
S995028A
8270
HRGC/LRMS
Sample Description/Narrative:
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
905181131SBIO Condensate-Not spiked with pre-extraction surrogates
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
B enzo(k)fluoranthene
5/18/99
NA
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
2 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-16
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016F
9905032
S995032A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905191016SBFO Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
Recovery
51 P
61 P
78 P
Recovery
NS
NS
NS
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D 14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-DichlorophenoI
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
% Recovery
58 P
62 P
105 P
% Recovery
NS
NS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
J = Peak below the calibration range
NS= not spiked
D-17
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016F
9905032
S995032A
8270
HRGC/LRMS
Sample Description/Narrative:
905191016SBFO Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzerje
2,4-Dinitrotoluenej
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 15
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate 3
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
1 J
J = Peak below the calibration range
NS= not spiked
D-18
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016F
9905032
S995032A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/19/99
6/1/99
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905191016SBFO Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
|iig Compound
ND Benzo(a)pyrene(CCC)
2 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib
> = not detected
J = Peak below the calibration range
NS= not spiked
D-19
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016C
9905034
S995034A
8270
HRGC/LRMS
Sample Description/Narrative:
905191016SBIO Condensate
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Recovery
39 P D5-Nitrobenzene(surr#3)
34 P 2-Fluorobiphenyl(surr#4)
87 P D14-Terphenyl(surr#6)
Recovery
NS
NS
NS
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
64 P
67 P
113 P
Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
ug Compound ug
ND 4-Methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
NS= not spiked
D-20
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016C
9905034
S995034A
8270
HRGC/LRMS
Sample Description/Narrative:
905191016SBIO Condensate
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluenei
2,3,4,6-Tetrachlon
)phenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-21
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016C
9905034
S995034A
8270
HkGC/LRMS
Sample Description/Narrative:
905191016SBIO Condensate
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/19/99
6/1/99
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluorantherie
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
fig Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib N£> = not detected
J = Peak below the calibration range
NS= not spiked
D-22
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
9Q5191016X
9905033
S995033A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905191016SBXO XAD
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
% Recovery
60 P
61 P
89 P
% Recovery
66
67
86
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
68 P
72 P
119 P
Recovery
70
70
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzen*(CCC)
1,2-Dichlorobenzeni:
Benzyl Alcohol
Bis(2-chloroisoprop yl)ether
2-Methylphenol
n-Nitrosospyrrolidir e
Acetophenone
Hexachloroethane
Hg Compound fig
ND 4-Methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
4 J Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
6 J n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCd) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-23
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016X
9905033
S995033A
8270
HRGC/LRMS
Sample Description/Narrative:
905191016SBXOXAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopeilitadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPGC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/19/99
06/01/99
06/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 13
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-24
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135F
9905043
S995043A
8270
K3C/LRMS
Hk(
Sample Description/ Narrative:
905211135SBFO Filter
Pre Extraction Surrogates
2-Fluorophenol(surr$ 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenoll(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene (CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisopropy l)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/21/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Recovery
44 P
53 P
80 P
Recovery
NS
NS
NS
MS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
i
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
1
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1 ,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
% Recovery
52 P
57 P
101 P
% Recovery
NS
NS
ug
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
J = Peak below the calibration range
NS= not spiked
D-25
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135F
9905043
S995043A
8270
HRGC/LRMS
Sample Description/Narrative:
905211135SBFO Filter
Compound
2-Methylnaphthaleme
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethylphathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1 -Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluenc
2,3,4,6-Tetrachlor aphenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
Mg
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
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/21/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 6
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak • below the calibration range NS= not spiked
D-26
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135F
9905043
S995043A
8270
FtRGC/LRMS
Sample Description/Narrative:
905211135SBFO Filter
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/21/99
6/4/99
6/27/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
fig Compound
ND Benzo(a)pyrene(CCC)
9 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-27
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135X
9905044
S995044A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/21/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905211135BXO Filter
Pre Extraction Surrogates
2-Fluorophenol(surr# I)
D5-Phenol(surr#2)
2,4,6-Tribromophenoi(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Recovery
56 P D5-Nitrobenzene(surr#3)
57 P 2-Fluorobiphenyl(surr#4)
84 P D14-Terphenyl(surr#6)
Recovery
66
67
82
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
63 P
67 P
115 P
Recovery
68
57
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135X
9905044
S995044A
8270
HRGC/LRMS
Sample Description/Narrative:
905211135BXO Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethylphathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
Mg
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
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/21/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 4
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-29
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135X
9905044
S995044A
8270
HRGC/LRMS
Sample Description/Narrative:
905211135BXO Filter
Compound
Chrysene
di-n-Octyl phthalate(tCCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/21/99
6/4/99
6/27/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
"g
ND
ND
ND
ND
ND
E = exceeded calib Nip = not detected J = Peak below the calibration range NS= not spiked
D-30
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135C
9905045
S995045A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/21/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905211135SBIO Condensate
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1,2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Recovery
34 P D5-Nitrobenzene(surr#3)
25 P 2-Fluorobiphenyl(surr#4)
79 P D14-Terphenyl(surr#6)
Recovery
NS
NS
NS
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
59 P
55 P
112 P
Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidin4
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
ug Compound ug
ND 4-Methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
NS= not spiked
D-31
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135C
9905045
S995045A
8270
HjlGC/LRMS
Sample Description/Narrative:
905211135SBIO Condensate
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethylphathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(; 5PCC)
Dibenzofuran
Pentachlorobenzen 5
2,4-Dinitrotoluene
2,3,4,6-Tetrachlordphenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled: 05/21/99
Date Extracted: 06/04/99
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-32
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905211135C
9905045
S995045A
8270
HRGC/LRMS
Sample Description/Narrative:
905211135SBIO Condensate
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/21/99
6/4/99
6/27/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib
= not detected J = Peak below the calibration range NS= not spikec
D-33
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202F
9905046
S995046A
8270
I^RGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905241202SBFOBLO1 Filter
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidijie
Acetophenone
Hexachloroethane
% Recovery
51 P
60 P
78 P
% Recovery
NS
NS
NS
"g
ND
ND
ND
ND
ND
ND
1 J
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D 14-Terphenyl(surr#6)
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
% Recovery
59 P
62 P
106 P
% Recovery
NS
NS
ug
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-34
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202F
9905046
S995046A
8^70
tilGC/LRMS
Sample Description/Narrative:
905241202SBFOBLGU Filter
Compound
2-Methylnaphthalei^e
Isosafrole
1,2,4,5-Tetrachloro jenzene
Hexachlorocyclope itadiene(SPCC)
2,4,6-Trichlorophemol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
l.SDinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethylphathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(|SPCC)
Dibenzofuran
Pentachlorobenzerie
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/04/99
06/27/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 8
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
5 J
J = Peak below the calibration range
NS= not spiked
D-35
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202F
9905046
S995046A
8270
HRGC/LRMS
Sample Description/Narrative:
905241202SBFOBLO1 Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/24/99
6/4/99
6/27/99
Bill Preston
Dennis Tabor
1 ml
1
Hg Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-36
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202X
9905047
S995047A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905241202SBW2BLO1-XAD
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene (CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropj[l)ether
2-Methylphenol
n-Nitrosospyrrolidin
Acetophenone
Hexachloroethane
Recovery
54 P
59 P
78 P
Recovery
64
66
72
Mg
ND
ND
ND
ND
ND
ND
ND
3 J
ND
ND
ND
ND
ND
ND
ND
ND
5 J
ND
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2,5 dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1 ,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
% Recovery
63
64
98
% Recovery
71
116
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
ND
ND
ND
ND
ND
ND
P
P
P
J
4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range NS= not spiked
D-37
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202X
9905047
S995047A
8270
HRGC/LRMS
Sample Description/Narrative:
905241202SB W2BLO1 -XAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophei iol(CCC)
2,4,5-Trichlorophejiol
2-Chloronaphthalene
l.SDinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(|SPCC)
Dibenzofuran
Pentachlorobenzer ie
2,4-Dinitrotoluene
2,3,4,6-Tetrachlon jphenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 9
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-38
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202X
9905047
S995047A
8270
HRGC/LRMS
Sample Description/Narrative:
905241202SBW2BLO1-XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethy lbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
"g
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-39
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202C
9905048
S995048A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905241202SBIOBLO1 Condensates
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
% Recovery
36 P
31 P
78 P
% Recovery
NS
NS
NS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
% Recovery
D5-Nitrobenzene(surr#3) 56 P
2-Fluorobiphenyl(surr#4) 55 P
D14-Terphenyl(surr#6) 118 P
% Recovery
13C6-2.5 dichlorophenol NS
13C6-2,5-Phthalate anhydride NS
Compound ug
4-methylphenol ND
N-nitrosodi-n-propylamine ND
Nitrobenzene ND
1-Nitrosopiperidine ND
Isophorone ND
2,4-Dimethylphenol ND
Bis(2-chloroethoxy)methane ND
2,4-Dichlorophenol(CCC) ND
1,2,4-Trichlorobenzene ND
Naphthalene ND
2-Nitrophenol(CCC) ND
2,6-Dichlorophenol ND
Hexachloropropene ND
4-Chloroaniline ND
Hexachlorobutadiene(CCC) ND
n-Nitrosodi-n-butylamine ND
4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range NS= not spiked
D-40
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
905241202C
9905048
S995048A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
905241202SBIOBLO1 Condensates
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine j
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenoi(SPCC)
Dibenzofuran \
Pentachlorobenzejne
2,4-Dinitrotoluen ;
2,3,4,6-Tetrachlo -ophenol
4-Nitrophenol(SP,CC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-41
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905241202C
9905048
S995048A
8270
HRGC/LRMS
Sample Description/Narrative:
905241202SBIOBLO1 Condensates
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethy lbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/24/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
jig Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib .^D = not detected J = Peak below the calibration range NS= not spiked
D-42
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905251144F
9905058
S9950£8A
8270
HRGC/LRMS
Sample Description/Narrative:
905251144SBFOBLO1 Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
% Recovery
50 P
62 P
75 P
% Recovery
NS
NS
NS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D 14-Terphenyl(surr#6)
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
% Recovery
59 P
61 P
106 P
% Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
ug Compound ug
ND
ND 4-methylphenol ND
ND N-nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-43
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
905251144F
9905058
S&95058A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
905251144SBFOBLO1 Filter
Compound
2-Methylnaphthalejne
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluenb
2,3,4,6-Tetrachlo|rophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 11
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
11
J = Peak below the calibration range
NS= not spiked
D-44
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orinfiulsion
905151144F
990! 1058
S99:i058A
8270
HRCBC/LRMS
Sample Description/Narrative:
905251144SBFOBLO1 Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
3 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND fc not detected
J = Peak below the calibration range
NS= not spiked
D-45
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905251144X
9905059
S995059A
82170
HRGC/LRMS
Sample Description/narrative:
905251144SBXOBl4l-XAD
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene:(CCC)
1,2-Dichlorobenzem;
Benzyl Alcohol
Bis(2-chloroisoprop /l)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Recovery
55 P D5-Nitrobenzene(surr#3)
60 P 2-Fluorobiphenyl(surr#4)
90 P D14-Terphenyl(surr#6)
Recovery
61
64
86
Mg
ND
ND
ND
ND
ND
ND
ND
3
ND
ND
ND
ND
ND
ND
ND
ND
5
ND
J
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
N-nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol(CCC)
1,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
Recovery
61 P
65 P
114 P
Recovery
64
97
"g
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
J = Peak below the calibration range
D-46
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905251144X
9^05059
SJ95059A
8270
HRGC/LRMS
Sample Description/Narrative:
905251144SBXOBL01-XAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachloijophenol
4-Nitrophenol(SP|CC)
Fluorene
Diethyl phathalati
Mg
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
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 3
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-47
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905251144X
9905059
S995059A
8270
HRGC/LRMS
Sample Description/Narrative:
905251144SBXOBL01-XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/04/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
1 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-48
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
90251144C
9905060
5995060A
^270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
90251144SBIOBL01 Condensate
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(sun#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopro0yl)ether
2-Methylphenol
n-Nitrosospyrrolidipe
Acetophenone
Hexachloroethane
Recovery
39 P D5-Nitrobenzene(surr#3)
35 P 2-Fluorobiphenyl(surr#4)
77 P D14-Terphenyl(surr#6)
Recovery
NS 13C6-2.5 Dichlorophenol
NS 13C6-2,5-Phthalate anhydride
NS
fig Compound
ND 4-Methylphenol
ND n-Nitrosodi-n-propylamine
ND Nitrobenzene
ND 1-Nitrosopiperidine
ND Isophorone
ND 2,4-Dimethylphenol
ND Bis(2-chloroethoxy)methane
ND 2,4-Dichlorophenol(CCC)
ND 1,2,4-Trichlorobenzene
ND Naphthalene
ND 2-Nitrophenol(CCC)
ND 2,6-Dichlorophenol
ND Hexachloropropene
ND 4-Chloroaniline
ND Hexachlorobutadiene(CCC)
ND n-Nitrosodi-n-butylamine
ND 4-Chloro-3-methyl-phenol(CCC)
% Recovery
61 P
59 P
127 P
% Recovery
NS
NS
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range NS= not spiked
D49
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905191016X
9905033
S095033A
8270
HRGC/LRMS
Sample Description/Narrative:
905191016SBXOXAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
5/19/99
6/1/99
6/26/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
3 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-50
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
90251144C
9905060
S995060A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
90251144SBIOBL01) Condensate
i
Compound j
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenze^ie
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
MS
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
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound pg
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate ND
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-51
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
90251144C
9905060
S995060A
8270
HRGC/LRMS
Sample Description/Narrative:
90251144SBIOBL01 Condensate
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/25/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Hg Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-52
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054F
9905061
S9;95061A
8^70
HkGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905261054SBFOBLul Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
% Recovery
49 P
62 P
83 P
% Recovery
NS
NS
NS
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D 14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
56 P
62 P
117 P
Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzend
Benzyl Alcohol i
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
ug Compound ug
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
2 J Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
NS= not spiked
D-53
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
905261054F
9905061
S995061A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
905261054SBFOBL01 Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlo|-ophenol
4-Nitrophenol(SpJCG)
Fluorene
Diethyl phathalat^
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound fig
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 8
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
3
J
J = Peak below the calibration range
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054F
9905Q61
S995061A
8270
HRGC/LRMS
Sample Description/Narrative:
905261054SBFOBL01 Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054X
9905062
S995062A
4270
HRGC/LRMS
Sample Description/Narrative:
905261054SBXOBL01 XAD
Pre Extraction Surrogates
2-Fluorophenol(surrw 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzenje
Benzyl Alcohol
Bis(2-chloroisopro{jyl)ether
2-Methylphenol |
n-Nitrosospyrrolidime
Acetophenone
Hexachloroethane
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Recovery
41 P D5-Nitrobenzene(surr#3)
53 P 2-Fluorobiphenyl(surr#4)
94 P D14-Terphenyl(surr#6)
Recovery
46
55
75
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
% Recovery
56 P
67 P
120 P
% Recovery
61
218
ug Compound fig
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine . ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
3 J Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
5 J n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-56
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
905261054X
9905062
S995062A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
905261054SBXOBL01 XAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate!
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 20
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate 1
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
D-57
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054X
9905062
S995062A
$270
HRGC/LRMS
Sample Description/Narrative:
905261054SBXOBioi XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-58
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054C
9(905063
3995063A
^270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
905261054SBIOBL01 Condensate
Pre Extraction Surrogates % Recovery
2-Fluorophenol(surr#l) 42 P
D5-Phenol(surr#2) 34 P
2,4,6-Tribromophenol(surr#5) 77 P
Pre Sampling Surrogates % Recovery
13C6-1,2 Dichlorobenzene NS
13C6-Napthalene NS
D10-Anthracene NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisoprobyl)ether
2-Methylphenol |
n-Nitrosospyrrolid|ne
Acetophenone
Hexachloroethane
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
62 P
60 P
108 P
Recovery
NS
NS
ug Compound fig
ND 4-methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-59
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
905261054C
9905063
S995063A
8270
HRGC/LRMS
Sample Description/Narrative:
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
905261054SBIOBL01 Condensate
L6l
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
l,3Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
Mg
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
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate ND
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-60
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
905261054C
9905063
3995063A
3270
HRGC/LRMS
Sample Description/Narrative:
905261054SBIOBL01 Condensate
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
05/26/99
06/07/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib
ND = not detected
J = Peak below the calibration range
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Glassware Blank
9906001
S996001A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/01/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
Glassware Blank
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
% Recovery
71 P
80 P
90 P
% Recovery
NS
NS
NS
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2,5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Compound
4-Methylphenol
n-Nitrosodi-n-propylamine
Nitrobenzene
1 -Nitrosopiperidine
Isophorone
2,4-Dimethylphenol
B is(2-chloroethoxy )methane
2,4-Dichlorophenol(CCC)
1,2,4-Trichlorobenzene
Naphthalene
2-Nitrophenol(CCC)
2,6-Dichlorophenol
Hexachloropropene
4-Chloroaniline
Hexachlorobutadiene(CCC)
n-Nitrosodi-n-butylamine
4-Chloro-3-methyl-phenol(CCC)
% Recovery
79 P
76 P
118 P
% Recovery
NS
NS
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
J = Peak below the calibration range
D-62
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Glassware Blank
9906001
S996001A
8270
HRGC/LRMS
Sample Description/Narrative:
Glassware Blank :
Compound ug
2-Methylnaphthalene ND
Isosafrole ND
1,2,4,5-Tetrachlorobenzene ND
Hexachlorocyclopentadiene(SPCC) ND
2,4,6-Trichlorophenol(CCC) ND
2,4,5-Trichlorophenol ND
2-Chloronaphthalene ND
1,3 Dinitrobenzene ND
2-Nitroaniline ND
3-Nitroaniline ND
Safrole ND
Acenaphthylene ND
1,4-Naphthoquinone ND
Dimethyl phathalate ND
2,6-Dinitrotoluene ND
Acenaphthene(CCC) ND
1-Napthylamine ND
2-Napthylamine ND
4-Nitroaniline ND
2,4-Dinitrophenol(SPCC) ND
Dibenzofuran ND
Pentachlorobenzene ND
2,4-Dinitrotoluene ND
2,3,4,6-Tetrachlorpphenol ND
4-Nitrophenol(SPCC) ND
Fluorene ND
Diethyl phathalate ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/01/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 11
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-63
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Glassware Blank
9906001
S996001A
8270
HRGG/LRMS
Sample Description/Narrative:
Glassware Blank
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/01/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = iJot detected
J = Peak below the calibration range
NS= not spiked
D-64
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216F
9006007
S$96007A
8^70
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906031216SBFOBLR6 Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Recovery
42 P
56 P
85 P
Recovery
NS
NS
NS
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
% Recovery
56 P
68 P
116 P
% Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzenej(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
fig Compound ug
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range NS= not spiked
D-65
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216F
9906007
S$96007A
8l?0
HRGC/LRMS
Sample Description/Narrative:
906031216SBFOBLR6 Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluen^
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Hg Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 10
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
D-66
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216F
9906007
S996007A
8270
HRGC/LRMS
Sample Description/Narrative:
906031216SBFOBLR6 Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
ND Benzo(a)pyrene(CCC)
2 J 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D67
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216X
9906008
S996008A
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906031216SBXOBLR6 - XAD
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenze|ne(CCC)
1,2-Dichlorobenzejne
Benzyl Alcohol
B is(2-chloroisopr0pyl)ether
2-Methylphenol ;
n-Nitrosospyrroli4ine
Acetophenone ''
Hexachloroethane
% Recovery
48 P
58 P
85 P
% Recovery
49
54
73
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
60 P
66 P
108 P
Recovery
58
185
jig Compound fig
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
4 J Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene 2
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
5 J n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-68
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216X
9906008
S996008A
^270
fclRGC/LRMS
Sample Description/Narrative:
906031216SBXOBLR6 - XAD
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(S|>CC)
Fluorene i
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 13
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
2
J
J = Peak below the calibration range
D-69
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Orimulsion
906031216X
9906008
S996008A
8270
Project:
Sample Name:
Lab Sample ED:
MS Data file:
Method:
Sample Description/Narrative:
906031216SBXOBI[R6 - XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/09/99
06/28/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-70
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216C
9906009
S996009B
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/07/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906031216SBFOBLR6-Condensate
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10- Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisopi|opyl)ether
2-Methylphenol |
n-Nitrosospyrroliliine
Acetophenone
Hexachloroethane
Recovery % Recovery
30 P D5-Nitrobenzene(sun#3) 45 P
25 P 2-Fluorobiphenyl(surr#4) 42 P
57 P Dl4-Terphenyl(surr#6) 83 P
i Recovery % Recovery
NS 13C6-2.5 Dichlorophenol NS
NS 13C6-2,5-Phthalate anhydride NS
NS
fig Compound fig
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
D-71
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216C
9906009
S996009B
8270
HRGC/LRMS
Sample Description/Narrative:
906031216SBFOBLR6-Condensate
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
l,3Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/07/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
jig Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-72
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906031216C
9906009
S996009B
8270
HRGC/LRMS
Sample Description/Narrative:
906031216SBFOBLR6-Condensate
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/03/99
06/07/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
1 J 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
M8
ND
ND
ND
ND
ND
E = exceeded calib I ND = not detected
J = Peak below the calibration range
NS= not spiked
D-73
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304F
9906019
S996019B
8270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906041304SBFOBLR6 Filter
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisopropy l)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
% Recovery
42 P
57 P
75 P
% Recovery
NS
NS
NS
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
% Recovery
59 P
65 P
105 P
% Recovery
NS
NS
fig Compound jig
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
NS= not spiked
D-74
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304F
9906019
S996019B
8270
HRGO/LRMS
Sample Description/Narrative:
906041304SBFOBLR6 Filter
Compound ;
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenz me
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate 40
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
2
J
J = Peak below the calibration range
NS= not spiked
D-75
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304F
9906019
S996019B
8270
HRGC/LRMS
Sample Description/Narrative:
906041304SBFOBLR6 Filter
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
9 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-76
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304X
9906020
S996020B
81270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
!
Sample Description/Narrative:
906041304SBXOBLR6 XAD
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenze
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304X
9906020
S996020B
8270
HRGC/LRMS
Sample Description/Narrative:
906041304SBXOBtR6 XAD
Compound ug
2-Methylnaphthalene ND
Isosafrole ND
1,2,4,5-Tetrachlorobenzene ND
Hexachlorocyclopentadiene(SPCC) ND
2,4,6-Trichlorophenol(CCC) ND
2,4,5-Trichlorophtnol ND
2-Chloronaphthalene ND
1,3 Dinitrobenzene ND
2-Nitroaniline ND
3-Nitroaniline ND
Safrole ND
Acenaphthylene ND
1,4-Naphthoquinone ND
Dimethyl phathalate ND
2,6-Dinitrotoluene ND
Acenaphthene(CCC) ND
1-Napthylamine ND
2-Napthylamine ND
4-Nitroaniline ND
2,4-Dinitrophenol(SPCC) ND
Dibenzofuran i ND
Pentachlorobenzene ND
2,4-Dinitrotoluene ND
2,3,4,6-Tetrachlorophenol ND
4-Nitrophenol(SPiCC) ND
Fluorene i ND
Diethyl phathalate ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 5
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-78
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ED:
MS Data file:
Method:
Orimulsion
906041304X
9906020
S996020B
8270
HRGC/LRMS
Sample Description/Narrative:
906041304SBXOBLR6 XAD
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/09/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
1 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-79
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906041304C
9906021
$9960216
$270
ilRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906041304SBIOBLR6 Condensate
Pre Extraction Surrogates % Recovery
2-Fluorophenol(surr#l) 51 P
D5-Phenol(surr#2) 46 P
2,4,6-Tribromophenol(surr#5) 98 P
Pre Sampling Surrogates % Recovery
13C6-1,2 Dichlorobenzene NS
13C6-Napthalene NS
DIO-Anthracene NS
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
74 P
74 P
131 P
Recovery
NS
NS
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfbnate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone !
Hexachloroethane
E = exceeded calib ND = not detected
ug Compound fig
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene ND
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
J = Peak below the calibration range
NS= not spiked
D-80
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
3rimulsion
)06041304C
>906021
S996021B
3270
HRGC/LRMS
Sample Description/Narrative:
906041304SBIOBLR6 Condensate
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
l,3Dinitrobenzeiiie
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(G
CC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotolueijie
2,3,4,6-Tetrachlqrophenol
4-Nitrophenol(SPCC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
NS= not spiked
D-81
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
rimulsion
6041304C
&96021B
3270
IGC/LRMS
Sample Description/Narrative:
906041304SBIOBLR6 Condensate
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/04/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
Chrysene
di-n-Octyl phthalaie(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
ug Compound
ND Benzo(a)pyrene(CCC)
1 J 3-Methylcholanthrene
ND Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
ND
ND
ND
ND
ND
E = exceeded calib
ND = not detected
J = Peak below the calibration range
NS= not spiked
D-82
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Qrimulsion
906071229C
9906024
J 996024B
S270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/08/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906071229BIOBLR6 Condensate/dl4-Terphenyl out of criteria
Pre Extraction Surrogates
2-Fluorophenol(sunf#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylarfline
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
Bis(2-chloroisoproJ3yl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
E = exceeded calib ND = not detected
% Recovery
58 P D5-Nitrobenzene(surr#3)
50 P 2-Fluorobiphenyl(surr#4)
105 P D14-Terphenyl(surr#6)
% Recovery
NS 13C6-2.5 Dichlorophenol
NS 13C6-2,5-Phthalate anhydride
NS
ug Compound
ND 4-Methylphenol
ND n-Nitrosodi-n-propylamine
ND Nitrobenzene
ND 1-Nitrosopiperidine
ND Isophorone
ND 2,4-Dimethylphenol
ND Bis(2-chloroethoxy)methane
ND 2,4-Dichlorophenol(CCC)
ND 1,2,4-Trichlorobenzene
ND Naphthalene
ND 2-Nitrophenol(CCC)
ND 2,6-Dichlorophenol
ND Hexachloropropene
ND 4-Chloroaniline
ND Hexachlorobutadiene(CCC)
ND n-Nitrosodi-n-butylamine
ND 4-Chloro-3-methyl-phenol(CCC)
I = Peak below the calibration range NS= not spiked
D-83
% Recovery
80 P
80 P
138 F
% Recovery
NS
NS
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906071229C
^906024
1996024B
270
HRGC/LRMS
i
Sample Description/Narrative:
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/08/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
906071229BIOBLB[6 Condensate/dl4-Terphenyl out of criteria
Compound <
2-Methylnaphthal^ne
Isosafrole '
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichloroph0nol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlo
4-Nitrophenol(SP|CC)
Fluorene
Diethyl phathalatje
E = exceeded calib ND = not delected
•ophenol
ug Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
ND Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene ND
ND Anthracene ND
ND Di-n-butyl phthalate ND
ND Isodrin ND
ND Fluoranthene(CCC) ND
ND 3,3'-Dimethylbenzidine ND
ND Pyrene ND
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
ND Benzo(a)anthracene ND
ND
J = Peak below the calibration range
D-84
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Ojrimulsion
)6071229C
J06024
S596024B
8 HO
FRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
Sample Description/Narrative:
906071229BIOBLR6 Condensate/dl4-Terphenyl out of criteria
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
06/08/99
06/15/99
06/29/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-85
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
906071229F
9906022
S996022A
!!270
1RGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
906071229SBFOBtR6 Filter
j
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromopheilol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Recovery
56 P D5-Nitrobenzene(surr#3)
68 P 2-Fluorobiphenyl(surr#4)
95 P D14-Terphenyl(surr#6)
Recovery
53
59
69
13C6-2.5 dichlorophenol
13C6-2,5-Phthalate anhydride
% Recovery
73 P
75 P
118 P
% Recovery
61
21
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylarfline
Bis (2-chloroethy
) ether
Ethyl methanesulfqnate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenze
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Oripmlsion
90(071229F
99(6022
S9%022A
82'
0
HPGC/LRMS
Sample Description Narrative:
906071229SBFOBLR6 Filter
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorob snzene
Hexachlorocyclopen adiene(SPCC)
2,4,6-Trichlorophen< >1(CCC)
2,4,5-Trichlorophend)l
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCQ
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(S PCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluene
2,3,4,6-Tetrachlorophenol
4-Nitrophenol(SPCC)
Fluorene |
Diethyl phathalate
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
2
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 6
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-87
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project: Orimulsion
Sample Name: 9Q6071229F
Lab Sample ID:
MS Data file:
Method:
906022
996022A
270
HRGC/LRMS
Sample Description/Narrative:
906071229SBFOBLR6 Filter
Compound
Chrysene
di-n-Octyl phthalatte(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
ND Benzo(a)pyrene(CCC)
34 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
O^imulsion
906071229X
9'K)6023
S J96023A
8170
ERGC/LRMS
Sample Description ^Narrative:
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
2,4,6-Tribromophejiol
Pre Extraction
2-Fluorophenol(surr|* 1)
D5-Phenol(surr#2)
906071229SBXOBtR6 XAD-dl4-Terphenyl out of criteria
1 out of criteria
% Recovery
72 P D5-Nitrobenzene(surr#3)
85 P 2-Fluorobiphenyl(surr#4)
144 F D14-Terphenyl(surr#6)
Sur -ogates
2,4,6-Tribromophenbl(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobfcnzene
13C6-Napthalene
D10-Acenapthalene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamfne
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzeii»e(CCC)
1,2-Dichlorobenzeffle
Benzyl Alcohol
B is(2-chloroisopro i>y l)ether
2-Methylphenol [
n-Nitrosospyrrolidjne
Acetophenone
Hexachloroethane
Recovery
59 13C6-2.5 Dichlorophenol
63 13C6-2,5-Phthalate anhydride
78
ug Compound
ND 4-Methylphenol
ND n-Nitrosodi-n-propylamine
ND Nitrobenzene
ND 1-Nitrosopiperidine
ND Isophorone
ND 2,4-Dimethylphenol
5 J Bis(2-chloroethoxy)methane
ND 2,4-Dichlorophenol(CCC)
ND 1,2,4-Trichlorobenzene
ND Naphthalene
ND 2-Nitrophenol(CCC)
ND 2,6-Dichlorophenol
ND Hexachloropropene
ND 4-Chloroaniline
ND Hexachlorobutadiene(CCC)
6 J n-Nitrosodi-n-butylamine
ND 4-Chloro-3-methyl-phenol(CCC)
% Recovery
87 P
91 P
144 F
% Recovery
64
29
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
ND
ND
ND
ND
ND
ND
ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-89
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project: Orimulsion
Sample Name: 906071229X
Lab Sample ID: ^906023
MS Data file:
Method:
996023A
5270
1RGC/LRMS
Sample Description/Narrative:
906071229SBXOB
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
,R6 XAD-dl4-Terphenyl out of criteria
Compound ng
2-Methylnaphthalene 1
Isosafrole ND
1,2,4,5-Tetrachloitobenzene ND
Hexachlorocyclopentadiene(SPCC) ND
2,4,6-Trichlorophenol(CCC) ND
2,4,5-Trichlorophenol ND
2-Chloronaphthalene ND
l,3Dinitrobenzene ND
2-Nitroaniline ND
3-Nitroaniline ND
Safrole ND
Acenaphthylene ND
1,4-Naphthoquin(j>ne ND
Dimethyl phathaljate ND
2,6-Dinitrotoluene ND
Acenaphthene(CCC) ND
1-Napthylamine ND
2-Napthylamine ND
4-Nitroaniline ND
2,4-DinitrophenoI(SPCC) ND
Dibenzofuran ND
Pentachlorobenzene ND
2,4-Dinitrotoluene ND
2,3,4,6-Tetrachlorophenol ND
4-Nitrophenol(SPCC) ND
Fluorene ND
Diethyl phathalate ND
Compound fig
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 9
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-90
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
OrimUlsion
90607J1229X
9906C23
S996Q23A
8270
HRGC/LRMS
Sample Description/Narrative:
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
906071229SBXOBLR6 2 AD-dl4-Terphenyl out of criteria
Compound
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)ahthracene
Benzo(k)fluoranthene
06/07/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
fig Compound
ND Benzo(a)pyrene(CCC)
8 J 3-Methylcholanthrene
ND Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
ND Benzo(ghi)perylene
"g
ND
ND
ND
ND
ND
E = exceeded calib ND = i lot detected
J = Peak below the calibration range
D-91
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Qrganics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Matrix Spike
9906048
I996048A
270
^RGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Description/Narrative:
Matrix Spike-100 ug of PAH components only
Pre Extraction Surrogates
2-Fluorophenol(surt#l)
D5-Phenol(surr#2)
2,4,6-Tribromophertol(surr#5)
Pre Sampling Surrogates
13C6-1,2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfanate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzeme
1,4-Dichlorobenze
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
OJrimulsion
atrix Spike
9^06048
S')96048A
8:170
HRGC/LRMS
Sample Descriptio n/Narrative:
Matrix Spike-100 ug
of PAH components only
Compound
2-Methylnaphthalene
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclop4ntadiene(SPCC)
2,4,6-Trichlorophehol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinotie
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline
2,4-Dinitrophenol(SPCC)
Dibenzofuran
Pentachlorobenzene
2,4-Dinitrotoluen§
2,3,4,6-Tetrachlorjophenol
4-Nitrophenol(SP<
tC)
Fluorene
Diethyl phathalate
E = exceeded calib ND = not detected
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
pg Compound ug
ND 4-Chlorophenyl phenyl ether ND
ND 2-Methyl-4,6-dinitrophenol ND
ND 5-Nitro-o-toluidine ND
ND Diphenylamine ND
ND Diallate ND
ND 1,3,5-Trinitrobenzene ND
ND 4-Bromophenyl phenyl ether ND
ND Phenacetin ND
ND Hexachlorobenzene ND
ND 4-Aminobiphenyl ND
ND Dinoseb ND
62 Pentachlorophenol(CCC) ND
ND Pentachloronitrobenzene ND
ND Phenanthrene 72
ND Anthracene 73
59 Di-n-butyl phthalate 10
ND Isodrin ND
ND Fluoranthene(CCC) 75
ND 3,3'-Dimethylbenzidine ND
ND Pyrene 75
ND Chlorobenzilate ND
ND p-Dimethylaminoazobenzene ND
ND 2-Acetylaminofluorene ND
ND Benzyl butyl phthalate ND
ND 3,3'-Dichlorobenzidine ND
69 Benzo(a)anthracene 75
ND
J = Peak below the calibration range
NS= not spiked
D-93
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project: Oitimulsion
Sample Name: M itrix Spike
Lab Sample ID: 9906048
MS Data file: S996048A
Method: 8270
HllGC/LRMS
Sample Description/Narrative:
Matrix Spike-100 ug Of PAH components only
Compound
Chrysene
di-n-Octyl phthalatd(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
ug Compound
75 Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
72 Indeno( 1,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
76 Benzo(ghi)perylene
Mg
77
ND
73
73
73
E = exceeded calib
i = not detected
J = Peak below the calibration range
NS= not spiked
D-94
-------
APPCD Organic Support Laboratory
Semi-Volatile Qrganics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Qrimulsion
Matrix Spike Dup
9906049
996049A
3270
HRGC/LRMS
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Sample Descriptioi /Narrative:
Matrix Spike Duplicate-100 ug of PAH components only
Pre Extraction Surrogates
2-Fluorophenol(surr#l)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Anthracene
Compound
n-Nitrosomethylethjylamine
Methyl Methanesutfonate
n-Nitrosodiethylam|ine
Bis (2-chloroethyi) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene(CCC)
1,2-Dichlorobenzene
Benzyl Alcohol
B is(2-chloroisopropy l)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
Recovery
NS
NS
NS
Recovery
47
53
78
D5-Nitrobenzene(surr#3)
2-Fluorobiphenyl(surr#4)
D 14-Terphenyl(surr#6)
13C6-2.5 Dichlorophenol
13C6-2,5-Phthalate anhydride
Recovery
NS
NS
NS
Recovery
49
89
fig Compound ug
ND 4-Methylphenol ND
ND n-Nitrosodi-n-propylamine ND
ND Nitrobenzene ND
ND 1-Nitrosopiperidine ND
ND Isophorone ND
ND 2,4-Dimethylphenol ND
ND Bis(2-chloroethoxy)methane ND
ND 2,4-Dichlorophenol(CCC) ND
ND 1,2,4-Trichlorobenzene ND
ND Naphthalene 50
ND 2-Nitrophenol(CCC) ND
ND 2,6-Dichlorophenol ND
ND Hexachloropropene ND
ND 4-Chloroaniline ND
ND Hexachlorobutadiene(CCC) ND
ND n-Nitrosodi-n-butylamine ND
ND 4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected
J = Peak below the calibration range
NS= not spiked
D-95
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
0rimulsion
latrix Spike Dup
506049
3996049A
170
IRGC/LRMS
Sample Description/Narrative:
Matrix Spike Duplicjate-100 ug of PAH components only
Compound
2-Methylnaphthale ne
Isosafrole
1,2,4,5-Tetrachlorobenzene
Hexachlorocyclopentadiene(SPCC)
2,4,6-Trichlorophenol(CCC)
2,4,5-Trichlorophenol
2-Chloronaphthalene
1,3 Dinitrobenzene
2-Nitroaniline
3-Nitroaniline
Safrole
Acenaphthylene
1,4-Naphthoquinone
Dimethyl phathalate
2,6-Dinitrotoluene
Acenaphthene(CCfC)
1-Napthylamine
2-Napthylamine
4-Nitroaniline |
2,4-Dinitrophenoj(SPCC)
Dibenzofuran I
Pentachlorobenze ne
2,4-Dinitrotoluens
2,3,4,6-Tetrachlo -ophenol
4-Nitrophenol(SFCC)
Fluorene
Diethyl phathalati
E = exceeded calib ND = not detected
"g
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
53
ND
ND
ND
52
ND
ND
ND
ND
ND
ND
ND
ND
ND
61
ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Compound ug
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Aminobiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene 66
Anthracene 67
Di-n-butyl phthalate 5
Isodrin ND
Fluoranthene(CCC) 71
3,3'-Dimethylbenzidine ND
Pyrene 69
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene 69
J = Peak below the calibration range
D-96
NS= not spiked
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project: Oiimulsion
Sample Name: M atrix Spike Dup
Lab Sample ID: 9906049
MS Data file: S<'96049 A
Method: 8170
HJIGC/LRMS
Sample Description/Narrative:
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
Matrix Spike Duplicate-100 ug of PAH components only
Compound ug Compound
NA
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Chrysene
di-n-Octyl phthalate(CCC)
Benzo(b)fluoranthene
7,12-Dimethylbenz(a)anthracene
Benzo(k)fluoranthene
69 Benzo(a)pyrene(CCC)
ND 3-Methylcholanthrene
67 Indeno(l,2,3-cd)pyrene
ND Dibenz(a,h)anthracene
72 Benzo(ghi)perylene
Mg
72
ND
67
67
67
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-97
-------
APPCD Organic Support Laboratory
Semi-Volatile Organics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Rtsin Blank
9906050
S«)96050A
8:170
HRGC/LRMS
Sample Description'Narrative:
Resin Blank-dl4-T« rphenyl is out of criteria
Pre Extraction Surrogates
2-Fluorophenol(surr# 1)
D5-Phenol(surr#2)
2,4,6-Tribromophenol(surr#5)
Pre Sampling Surrogates
13C6-1.2 Dichlorobenzene
13C6-Napthalene
D10-Acenapthalene
Compound
n-Nitrosomethylethylamine
Methyl Methanesulfonate
n-Nitrosodiethylamine
Bis (2-chloroethyl) ether
Ethyl methanesulfonate
Aniline
Phenol(CCC)
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzenje(CCC)
1,2-Dichlorobenzen e
Benzyl Alcohol
Bis(2-chloroisopropyl)ether
2-Methylphenol
n-Nitrosospyrrolidine
Acetophenone
Hexachloroethane
Recovery
67 P
83 P
113 P
i Recovery
58
61
87
Mg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/21/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
% Recovery
D5-Nitrobenzene(surr#3) 82 P
2-Fluorobiphenyl(surr#4) 85 P
D14-Terphenyl(surr#6) 154 F
% Recovery
13C6-2.5 Dichlorophenol 59
13C6-2,5-Phthalate anhydride 101
Compound ug
4-Methylphenol ND
n-Nitrosodi-n-propylamine ND
Nitrobenzene ND
1-Nitrosopiperidine ND
Isophorone ND
2,4-Dimethylphenol ND
Bis(2-chloroethoxy)methane ND
2,4-Dichlorophenol(CCC) ND
1,2,4-Trichlorobenzene ND
Naphthalene ND
2-Nitrophenol(CCC) ND
2,6-Dichlorophenol ND
Hexachloropropene ND
4-Chloroaniline ND
Hexachlorobutadiene(CCC) ND
n-Nitrosodi-n-butylamine ND
4-Chloro-3-methyl-phenol(CCC) ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-98
-------
APPCD Organic Support Laboratory
Semi-Volatile Orgahics Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
Orimulsion
Resin
Blank
9906050
S996Q50A
8270
HRG£/LRMS
i
Sample Description/Narrative:
Resin Blank-dl4-Terphenjyl is out of criteria
Compound ug
2-Methylnaphthalene ND
Isosafrole ND
1,2,4,5-Tetrachlorobenzene ND
Hexachlorocyclopentadiiene(SPCC) ND
2,4,6-Trichlorophenol(CCC) ND
2,4,5-Trichlorophenol ND
2-Chloronaphthalene ND
1,3 Dinitrobenzene ND
2-Nitroaniline ND
3-Nitroaniline ND
Safrole ND
Acenaphthylene ND
1,4-Naphthoquinone ND
Dimethyl phathalate ND
2,6-Dinitrotoluene ND
Acenaphthene(CCC) ND
1-Napthylamine ND
2-Napthylamine ND
4-Nitroaniline ND
2,4-Dinitrophenol(SPCC) ND
Dibenzofuran ND
Pentachlorobenzene ND
2,4-Dinitrotoluene j ND
2,3,4,6-Tetrachlorophe|nol ND
4-Nitrophenol(SPCC) ND
Fluorene ND
Diethyl phathalate ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/21/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Compound fig
4-Chlorophenyl phenyl ether ND
2-Methyl-4,6-dinitrophenol ND
5-Nitro-o-toluidine ND
Diphenylamine ND
Diallate ND
1,3,5-Trinitrobenzene ND
4-Bromophenyl phenyl ether ND
Phenacetin ND
Hexachlorobenzene ND
4-Amindbiphenyl ND
Dinoseb ND
Pentachlorophenol(CCC) ND
Pentachloronitrobenzene ND
Phenanthrene ND
Anthracene ND
Di-n-butyl phthalate 6
Isodrin ND
Fluoranthene(CCC) ND
3,3'-Dimethylbenzidine ND
Pyrene ND
Chlorobenzilate ND
p-Dimethylaminoazobenzene ND
2-Acetylaminofluorene ND
Benzyl butyl phthalate ND
3,3'-Dichlorobenzidine ND
Benzo(a)anthracene ND
E = exceeded calib ND = not detected J = Peak below the calibration range NS= not spiked
D-99
-------
APPCD Organic Support Laboratory
Semi-Volatile Of games Report
Project:
Sample Name:
Lab Sample ID:
MS Data file:
Method:
timulsion
Blank
•06050
•96050A
8270
IGC/LRMS
Sample Description/Narrative:
Resin Blank-dl4-Terphenyl is out of criteria
Compound ug
Chrysene ND
di-n-Octyl phthalate(CCC) ND
Benzo(b)fluoranthene ND
7,12-Dimethylbenz(a)anthracene ND
Benzo(k)fluoranthene ND
Date Sampled:
Date Extracted:
Date Acquired:
Analyst:
QC reviewer:
Extract Volume
Dilution Factor
06/21/99
06/21/99
06/30/99
Bill Preston
Dennis Tabor
1 ml
1
Compound
Benzo(a)pyrene(CCC)
3-Methylcholanthrene
Indeno( 1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Mg
ND
ND
ND
ND
ND
E = exceeded calib
D = not detected
J = Peak below the calibration range
NS= not spiked
D-100
-------
APPENDIX E
Metals Analysis Laboratory Reports
E-l
-------
PRISM
LABORATORIES, INC.
Full Service Analytical & Environmental Solutions
!
CLIENT:
PROJECT (D:
LAB GROUP ID:
SAMPLE ID:
CASE NARRATIVE
08/11/99
ARCADIS Geraghty & Miller
Orimulsion
8401E24
AB34730-AB34753
MATRIX:
NUMBER OF SOURCES:
DATE COLLECTED:
DATE RECEIVED.
Main Office:
449 Springbrook Road
P.O. Box 240543
Charlotte, NC 28224-0543
Phone: 704/529-6364
1/800/529-6364
Fax: 704/525-0409
AIR
12
06/18-7/1/99
07/2/99
Sample Disposition:
36 containers were received on 07/2/9911:00 in the laboratory. The samples were received in good
condition.
; '•" ; ^ ^T088 Reference^ Field Jr^ to i.aboratorVJD$ ; i
"•'."• ••.-• timpleneldTO'r-':^;:-;^
907010942 Train 1 sample 1
907010942 Train 1 sample 2
907010942 Train 1 sample 3
90701 0943 Train 1 sample 1
907010943 Train 1 sample 2
907010943 Train 1 sample 3
90603121 5SMFOBLR6
906031215SMNOBLR
906031215SMIOBLR6
906041303SMFOBLR6
90603121 5SMNOBLR
906031 21 5SMIOBLR6
906071228SMFOBLR6
906071228SMNOBLR
906071228SMIOBLR6
905171200SMFFBL01
905171200SMNFBL01
905171200SMIFBL01
905181 131SMFOBL04
905181 131SMNOBL04
905181 131SMIOBL04
905191016SMFOBL04
905191016SMNOBL04
905191016SMIOBL04
90521 1133SMFOBL04
90521 11 33SMNOBL04
905211 133SMIOBL04
^ • f*ffemi^oriiQrylD
AB34730
AB34731
AB34732
AB34733
AB34734
AB34735
AB34736
AB34737
AB34738
AB34739
AB34740
AB34741
AB34742
AB34743
AB34744
AB34745
AB34746
AB34747
E-2
-------
. Cross Reference of Field IDs to Laboratory IDs
Sample Field ID
905241201SMFOBL01
905241 201 SMNOBL01
905241201SMIOBL01
905251 142SMFOBL01
905251 142SMNOBL01
905251 142SM1OBL01
905261053SMFOBL01
905261053SMNOBL01
; 90526 1053SMIOBL01
Prism Laboratory ID
AB34748
AB34749
AB34750
AB34751
AB34752
AB34753
Sample Analysis:
The samples! were analyzed using approved USEPA methodology.
The following test method was utilized for the analysis of the samples:
AiialyWs
Metals
•. ^::;>t«*i ^,: "
'':'-MM^^
EPA Method 29
" "' - '^ ' ': :- ' ' " |^$afce«BrjptlQn ' v::;:: /
Determination of metals emissions from stationary sources.
Analytical Fraction 1A
Samples AB34748, AB34750, AB34752, AB34734, AB34736, AB34738, AB34744 and AB34746,
were analyzed for nickel at a 1:200 dilution due to the high concentration of nickel.
Samples AB34748, AB34750, AB34752, AB34734, AB34736, AB34738, AB34742, AB34744 and
AB34746, were analyzed for vanadium at a 1:200 dilution due to the high 'concentration of vanadium.
Zinc and antimony recoveries for sample AB34748 were outside specified limits, possible matrix
interference suspected.
Zinc recovery for sample AB37736 was outside specified limits, possible matrix interference suspected.
The %RSD ;»nd matrix spike recovery for nickel and vanadium on samples AB34748and AB34746 was
not calculated because of the high dilution needed.
The reporting limit standard in position 84 exhibited carry over from the previous samples. However, the
values of the associated samples were greater than 10 times the reporting limit.
Analytical Fraction 2A
The matrix Spike recovery for vanadium on sample AB34749 was outside laboratory control limits
because the spike true value was less than one fifth the sample concentration.
E-3
-------
Nickel and magnesium recoveries for sample AB34747 were outside specified limits, possible matrix
interference suspected.
If you have any questions concerning this narrative report, please call (704) 529-6364.
PRISM LABORATORIES, INC.
Helmuth M.B. Janssen
Quality Assurajnce Manager
E-A
-------
Lab Report
PRISM
H4 Swvict MitlyliCtl t EmirtiMttflM SnUiai
7/29/99
Mr. Dennis Tabor
ARCAOIS Oeraghty
2301 Rexwoods Dr.
Raleigh, NC 27607
& Miller
StelOO
Page 5 of 24
Customer Project Name: RN 992010-0024.00001
Customer Sample ID: M603121SFILTE
Priam Sample ID: AB34734
Login Group: 8401E24
Sample Collection DateHTme: 6/3/99
Lab Submtttai Date/Time: 7/2/99 11."00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 29
SAMPLE PREPARATION POR METHO
ARSENIC BY METHOD 28
ANTIMONY BYMETH0029
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD d>
COPPER BY METHOD X
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METH >0 29
ZINC BY METHOD 29
VANADIUM BY METHOD :>9
NICKEL BY METHOD 2fl
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Computed
Completed
Completed
9.1
20
11
7.0
63
It
3000
30
210
760
29000
MOO
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
UDL
2.0
2.0
2.0
2.0
2.0
2.0
20
2.0
20
2.0
400
400
METHOD
REFERENCE
Meted 29
Meted 29
Method 29
Mated 29
Meted 29
Mttxxl29
Meted 29
Meted 29
Meted 29
Meted 29
Meted 29
Meted 2s
Meted 29
DATE/TIME
STARTED
7/7/99 06:00
7/7/99 16:00
7/a«906AO
invnwM
7/12«908flO
T/12A9MOO
7/12«008«0
7/12m06.-00
7/12A908fiO
7/12/990*00
7M2«9 06^)0
7M2«908«)
7/12«90fl«)
7/12/99 03:00
7/12/99 06:00
ANALYST
DHJ
DHJ
OKI
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
. Overcash. V.P. Laboratory Services
E-5
-------
Lab Report
PRISM
LABORATORIES, INC.
Fill gftminl Amtylicil-1, Friv n.ui.i
7/29/99
Mr. Dennis Tabor
ARCADISGeraghty I taller
2301 Rexwoods Dr. Ste 100
Raleigh, NC 27607
Page 6 of 24
Customer Project Nime: RH 992010.0024.00001
Customer Sample ID: 806031215
Prism Sample ID: AB34735
Login Group: B401E24
Sample Collection Date/Time: 6/3/99
Lab Submlttal Data/Time: 7/2/99 11:00
The following analytical
results nave been obtained for the indicated sample which was submitted to this laboratory.
TEST
PARAMETER
SAMPLE PREPARATION F0« METHO
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 26
BERYLLIUM BY METHOD 2JB
CADMIUM BY METHOD 29
COPPER BY METHOD 28
CHROMIUM BY METHOD 39
IRON BY METHOD 29
MANGANESE BY METHOH 29
MAGNESIUM BY METHOI129
NICKEL BY METHOD 29
VANADIUM BY METHOD M
ZINC BY METHOD 29
Sample Comments:
RN 992010.0024
TEST
RESULT
Completed
Lenten
6.4
1.7
Leu then
16
3.8
400
6J5
110
650
3200
150
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MDL
1.6
14
\£
1.5
1.6
1.6
16
1.6
16
1.6
1.6
1.S
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 2B
Method 29
Method 29
Method 28
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/98 06:00
7/12/99 06:00
7/12/99 06:00
7/12/9906:00
7/12/99 06:00
7/1 2M 06:00
7/12*908:00
7/12/99 OBflO
7/12/9908:00
7/12/9908:00
7/12/9906:00
7/12/9908:00
7/12/9906:00
ANALYST
DHJ
DKJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
Angela D. Overcash. V.P. Laboratory Services
E-6
-------
Lab Report
PRISM
UWORATOfUEl, tkO.
KM StMM AfttyflCti» Ciwiiam
7/29/99
Mr. Dennis Tabor
ARCADIS Oeraghty & Miller
2301 Rexwoods Or. Ste 100
Raleigh. NO 27607
Page 7 of 24
Cuttomer Project Name: RN 992010.0024.00001
Cuatomer Sample ID: W604130JFILTE
Prfam Sample ID: AB347S6
Login Group: 8401E24
Sample Collection Dale/Time: 6/4/99
Lab Submlttal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the Indicated sample which was submitted to this laboratory:
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 20
SAMPLE PREPARATION FOR METH0
ARSENIC BV METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 2f
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
2INC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Completed
f^MIUllflhul
9.1
32
20
0.0
70
30
4600
42
•9
1000
48000
MOO
UNITS
ug
UQ
ug
UB
ug
ug
ug
ug
ug
ug
ug
ug
MDL
2.0
2.0
24
2.0
2.0
2.0
20
2.0
20
2.0
400
400
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method Z9
MaUiod29
Method 29
MMhed29
flwothod 29
Method 29
Method 29
Method 29
Method 29
Method 20
DATE/TIME
STARTED
7/7/99 16:00
7/7/99 08*0
7/8*9 08:00
7/12/9908:00
7/1 2»9 08:00
7/12/99 08:00
7/12/99 06:00
7/12/W 08:00
7/12/99 08:00
7/12/9908:00
7/12/99 08:00
7/12)9908:00
7/12/9908:00
7/12/9908:00
7/12/M 08:00
ANALYST
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
OHJ
OHJ
OHJ
DHJ
OHJ
DHJ
OHJ
OHJ
Angela D. Overcash. V.P. Laboratory Services
E-7
-------
Lab Report
PRISM
lA»QftATOMGC. IMC.
Ful S*Mo* ArJiyumtK fcnvnnnwtiui Sourion
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh, NC 27607
Page 8 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 806041303
Prism Sample ID: AB34737
Login Group: 8401E24
Sample Collection Date/Time: 6/4/99
Lab SubmHtal Date/Time. 7/2/99 11:00
The following analytical results have been obtained for the Indicated sample which was submitted to this laboratory:
TEST TEST
PARAMETER RESULT
ZINC BY METHOD 29 »-'
VANAWUK W METHODS* 21
NICKEL BY METHOD 29 Le«* <•»"
MAGNESIUM BY METHOD 29 Le«« than
MANGANESE BY METHOD 29 Lett than
IRON BY METHOD 29 30
CHROMIUM BY METHOD 29 3.0
COPPER BY METHOD 29 3.0
CADMIUM BY METHOD 211 3.0
BERYLLIUM BY METHOD 29 Lew man
ANTIMONY BY METHOD 29 Lew then
ARSENIC BY METHOD 29 Lew than
SAMPLE PREPARATION TORMfTHO Completed
UNITS
Ufl
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MOt
1JS
1.6
1.5
15
1.9
16
1.6
1.5
1.S
14
1.5
1.S
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/12/99 06:00
7/12/89 08:00
7/12/990*00
7/12/9908.00
7/28/99 14:47
7/12/9906:00
7/12/9906:00
7/26/99 14:47
7/26/99 14:47
7/28/09 14:47
7/28/99 14:47
7/26/99 14:47
7/7/990*00
ANALYST
DHJ
DHJ
DHJ
DHJ
OKI
DHJ
OHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
Sample Comments:
RN 992010.0024.00001
Angela 0. Overcash. V.P. Laboratory Services
E-8
-------
ab Report
PRISM
Fui £*tv«* Aralyuo*! 4 fcnwironmtna: Seiuiiodi
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh. NC 27607
Page 9 of 24
Customer Project Nam*: RN 992010.0024.00001
Customer Sample ID: 906071228FILTE
Prism Sample ID: AB34738
Login Group: 8401E24
Sample Collection Date/Time: 6/7/99
Lab Submittal Date/Time: 7/2/99 11:00
fhe following analytical results haveibeen obtained for the Indicated sample which was submitted to this laboratory:
resT
»ARAMETER
3OMB PREP. FOR METHOD 29
3OMB PREP. FOR METHOD 29
ZINC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESIUM BY METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 29
CADMIUM BY METHOD 29
BERYLUUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
SAMPLE PREPARATION FOR METHO
Sample Comments:
RN 982010.0024.00001
TE
RE
Ct
Ct
1C
3(
71
ST
SUIT
oipleted
mplolod
DO
000
IOO
no
40
4100
22
76
9.6
16
3D
7i.6
UNITS
ug
"fl
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MDL
2.0
400
400
20
2.0
20
2.0
2.0
2.0
2.0
2.0
2.0
Completed
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
M«thod29
Ma(hod20
Method 29
Method 29
Method 29
Mathod29
M«lhod29
Method 20
DATE/TIME
STARTED
7/7/99 16:00
7/7/99 08:00
7/12/99 08:00
7M 2/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/9906:00
7J12/99 06:00
7/12/99 08:00
7/12/99 08:00
7/12/9908:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7fB/B9 08:00
ANALYST
DHJ
OHJ
DHJ
DHJ
OHJ
DHJ
OHJ
DHJ
OHJ
DHJ
OHJ
DHJ
DHJ
DHJ
OHJ
Angela D. Overcash, V.P. Labor? tory Services
E-9
-------
Lab Report
PRISM
LABORATORIES. IMC.
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh, NC 27607
Page 10 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 906071228
Priwn Sample ID: AB34739
Login Group: 8401E24
Sample Collection Dale/Time: 6/7/99
Lab Submittal Date/Time: 7/2/99 11:00
The following analytical results have been obtained (or the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
ZINC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESIUM BY METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 29
CADMIUM BY METHOD 25-
BERYLLIUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
SAMPLE PREPARATION FOR Mf THO
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
9.4
6.7
Less than
Lets than
Lace than
20
Less than
2.4
Less than
Less than
1.7
Less than
3 CompUWd
UNITS
og
UQ
ug
ug
UQ
ug
ug
ug
ug
ug
ug
ug
MOI-
LS
1.5
1.5
t5
1.5
15
1.5
1.5
1.5
1.5
1.5
1.5
METHOD
REFERENCE
Method 29
Malhod29
Method 29
Method 2B
Method 29
Method 29
Method 2S
Method 25
Method 29
Method 29
Method 2S
Method 29
Method 26
DATE/TIME
STARTED
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/0908:00
7(12/99 14:47
7/12/99 08:00
7/12/99 08:00
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/7/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
Angela
/\
. OverealTi. V.P.
Laboratory Services
E-10
-------
Lab Report
PRISM
Fun StMC* Arjlytietl ( fcnwonratrui Sourjoni
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Or. Ste 100
Raleigh. NC 27607
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
Page 11 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 9052712QOFILTE
Prism Sample ID: AB34740
Login Group: 8401E24
Sample Collection Date/Time: 5/27/99
Lab Sutjmittal Date/Time: 7/2/99 11:00
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 29
ZINC BY METHOD 29
VANADIUM BY METHOD 20
NlCKEt BY METHOD 29
MAGNESIUM BY METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 25
CHROMIUM BY METHOD :>9
COPPER BY METHOD 29
CADMIUM BY METHOD 29
BERYLLIUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
SAMPLE PREPARATION FOR METHO
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Completed
7.5
12
Less than
Less than
2.0
33
Leas than
2.0
6.8
Less than
Less than
Less than
> Completed
UNITS
Ufl
ug
ug
"9
ug
ug
ug
ug
ug
ug
ug
ug
MDL
2.0
2.0
2.0
20
2.0
20
2.0
2.0
2.0
2.0
2.0
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Melhod29
Method 29
Method 29
DATE/TIME
STARTED
7/7/99 16.00
7/7/99 08:00
7/12/99 08:00
7M2/99 08:00
7/12/99 08:00
7/12/99 Ofi:00
7/12/99 08:00
7/12/99 08:00
7/12/9908:00
7/12/9908:00
7/12/99 06:00
7/12/99 08.00
7/12/890600
7/12/9908:00
7/8/9908:00
ANALYST
DHJ
DHJ
OHJ
DHJ
DHJ
UHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash, V.P. Lai
moratory Services
E-ll
-------
ab Report
PRISM
LMO*ATO*ttS.INC.
Ful Swvic* Analytical & Environmental
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh. NC 27607
Page 12 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 905271200
Pritm Sampl* ID. AB34741
Login Group: 8401E24
Sample Collection Date/Time: 5/27/99
Lab Submtttal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
ZINC BY METHOD 29
VANADIUM BY METHOD ?9
NICKEL BY METHOD 29
MAGNESIUM BY METHOO 29
MANGANESE BY METHOO 29
IRON BY METHOD 29
CHROMIUM BY METHOD 28
COPPER BY METHOD 29
CADMIUM BY METHOD 29
BERYLLIUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 26
SAMPLE PREPARATION *OR METHO
Sample Comments:
RN 992010.0024.00001
TBCT
RtSULT
1*
214
Less than
23
1.6
20
Less than
7.3
2.0
L*ts than
20
Less than
D Completed
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
«9
ug
Ufl
ug
MOL
1.8
1.5
1.5
15
1.6
15
1.5
1.5
1.5
1.5
1.5
1.5
METHOO
REFERENCE
Method 29
Method 20
Method 20
Method 29
Method 29
Method 28
Mathod 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/12/9908:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 U:<7
7/12/99 08:00
7/12/99 08:00
7/12/99 14:47
7/12/99 t<:47
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/7/9908.00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
Angela D. Overcast). V.P. Laboratory Services
E-12
-------
Lab Report
PRISM
L*BORATOWE«,|NC.
Ful Swvioa Aiuilytisil t EtMronmtnlai VMons
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoodt Or. Ste 100
Raleigh, NC 27607
Page 13 of 24
Customer Project Name RN 992010.0024.00001
Customer Sample ID: 905181131FILTE
Prtem Sample ID: AB34742
Login Group: 8401E24
Sample (Election Date/Time: 6718/99
Lab Submttiai Data/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
"BOMB PREP. FOR METHOD »
BOMB PREP. FOR METHOD 29
ZINC BY METHOD 28
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESIUM BY METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 29
CADMIUM BY METHOD 29
BERYLLIUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
TEST
RESULT
Completed
Compiled
Lest thin
WW9
13000
2100
20
43
12
8.5
63
24
Loss than
6.3
UNITS
Ufl
HO
Ufl
ug
ug
uo
ug
ug
ug
ug
ug
ug
MDL
2.0
400
400
20
2.0
20
2.0
2.0
2.0
2.0
2.0
2.0
SAMPLE PREPARATION FOR METHO Completed
METHOD
REFERENCE
Method 29
MfltlWlPA
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
717199 16:00
7/7/9906:00
7/12/9908:00
THWM (W 00
7/12/99 08:00
7M2/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/6/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DH.I
Sample Comments:
RN 992010.0024.00001
Angela D. Overcash, V.P. Laboratory Services
E-13
-------
Lab Report
PRISM
h* Runic* Anityteil 4 fcnwrfe
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Millef
2301 Rexwoods Dr. Ste 10J)
Raleigh. NC 27607
Page 14 of 24
Customer Project Name: RN 992010.0024.00001
Customer Samplt ID: 905181131
Priam Sample ID: AB34743
Login Group: 8401E24
Sample Collection Date/Time: 5/18/99
Lab Submittal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
T1ST
PARAMETER
SAMPLE PREPARATION FOR MfiTHO
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sample Comments.
RN 992010.0024.00001
TEST
RESULT
ITHO Completed
LMtthtn
LttSthtn
Less than
LMtlton
4.6
Less than
26
Less than
Lass than
Ltstihan
Less than
8.1
UNITS 1
Ug
ug
ug
ug
ug
ug
Ufl
"9
ug
ug
ug
"0
irfDL
.5
.5
.5
.5
.5
.5
IS
1.5
15
1.5
1.6
1.6
METHOD
REFERENCE
Method 29
M«thod29
Method 29
Method 29
M«lhod29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
MMhod29
Method 29
DATE/TIME
STARTED
7/7/99 08:00
7/12/99 14:47
7/12/99 14:47
7*12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/9906:00
7/12/990840
7/12/99 14:47
7/12/8008:00
7/12/9908:00
7/12/9908:00
7/12/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
OHJ
OHJ
OHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-1A
-------
Lab Report
PRISM
lABORATOWtl.lNC.
F.* Sow* Antiyocti « FmrfnxtnMUl Soiuifen,
Page 15 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 905191016RLTE
Prism Sample ID: AB34744
Login Group: 8401E24
Sample Goaection Date/1 mne: 5/19/99
Lab Submittal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
7/29/99
Mr. Dennis Tabor
ARCADIS Oeraghty & Miller
2301 Rexwoods Or. Ste 100
, NC
TEST
PARAMETER
BOMB PREP. FOR METHOD 20
BOMS PREP. FOR METHOD 29
SAMPLE PREPARATION FOR METHO
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 28
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sample Comments
RN 992010 0024.00001
TEST
RESULT
Completed
Completed
Completed
0.4
Lest than
29
8.2
17
22
26
22
4700
15000
67000
2.0
UNITS
"9
ug
ug
ug
ug
ug
ug
ug
ug
UQ
ug
ug
MOL
2.0
2.0
2.0
2.0
2.0
2.0
20
2.0
20
400
400
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/0908:00
7/7/99 18:00
7/8/9908:00
7/12/9908:00
7M2/99 08:00
7/12/99 08:00
7/12/98 08:00
7/12/9908:00
7/12/96 08:00
7/12/9908:00
7/12/99 08:00
7/12/99 08:00
7/12/9908:00
7/12/99 08:00
7M2/99 08:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
Angela D.
sh. V.P. Laboratory Services
E-15
-------
.ab Report
PRISM
LUOIUTORIIt. INO.
Fit ScraiM Anilyictt 4 Enm(..«i«iul Solutoiu
7/29/99
Mr. Dennis Tabor
ARCADIS Qeraghty ft Miller
2301 Rexwoods Or, Ste 100
Raleigh, NC 27607
Page 16 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: «OS1«1016
Prism Sample ID: ABJ4745
Login Group: 8401E24
Sample Collection Date/Time: 6/18/99
The following analytical results hav
TEST T
PARAMETER R
SAMPLE PREPARATION FOR METHO 1
ARSENIC BY METHOD K 1
ANTIMONY BY METHOD 2B ;
BERYLLIUM BY METHOD 29 1
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29 1
IRON BY METHOD 29 '
» been obtained for the indicated sample which was submitted to this laboratory.
BT METHOD DATE/TIME
ESULT UNITS MDL REFERENCE STARTED ANALYST
Completed Method 29 7/7/9908:00 DHJ
AM than ug 14 Method 29 7/12/99 14:47 DHJ
0 Ufl 1.6 Method 29 7/12/9914:47 DHJ
AM than ug 1-6 Method 29 7/12/9914:47 DHj
AM than ug 1.6 Method 29 7/12/9914:47 OHJ
•7 UQ 1.5 Method 29 7/12/9914:47 OHJ
.MS than ug 1.6 Method 29 7/12/9906:00 DHJ
M ug 15 Method 29 7/12/9906:00 DHJ
MANGANESE BY METHOD 29 Lett (Kan
MAGNESIUM BY METHOD 29 220
NICKEL BY METHOD 29 220
VANADIUM BY METHOD 29 1 100
ZINC BY METHOD 29 7.3
ug
Ufl
ug
ug
ug
1.6
15
1.5
1.5
1.5
Method 29
Method 29
Method 29
Method 29
Method 29
7/12/99 14:47
7/12/9906:00
7/12/99 06:00
7/12/990*00
7/12/99 06:00
DHJ
DHJ
OHJ
DHJ
OHJ
Sample Comments:
RN 992010
Z010.0024.0j|a)1 *»
Angela D. Overcaeh. V.P. Laboratory Services
E-16
-------
Lab Report
PRISM
LUOAATMIM. INC.
Fun Stiwra Analytical & tnvircnnuifUiil Soluhor*
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Or. Ste 100
Raleigh, NC 27607
Page 17 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 906211133FILTE
Prtwn Sample ID: AB34746
Login Group: 8401E24
Sample CotocttonDatemme: 5/21/9B
Lab SubmlttBl Datenime: 7/2/99 11:00
The following analytical results have bean obtained for the Indicated sample which was submitted to this laboratory.
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 29
SAMPLE PREPARATION FOR METHO
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 2<1
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 2«
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Completed
Completed
1?
LeMthan
'1
7.9
15
45
96
35
4900
16000
74000
89
UNITS
UQ
ug
ug
ug
ug
ug
ug
ug
ug
ug
m
ug
MDL
2.0
2.0
2.0
2.0
2.0
2.0
20
2.0
20
400
400
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 28
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/9908:00
7/7/99 16:00
7/6/99 06.-00
7/12/99 06:00
7M2/99 06:00
7/12/99 08.00
7/12/9906:00
7/12/9906:00
7/12/9906:00
7/12/9906:00
7/12/9908:00
7/12/9900:00
7/12/99 08AO
7/12/99 06:00
7/12/9906:00
ANALYST
DHJ
OKI
DNJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash. V.P. Laboratory Services
E-17
-------
Lab Report
PRISM
UUKmATOftlES.tNC.
f\M S*me* Aratywul & Eny.-or'BW.ilSslulk.na
7/29/99
Mr. Dennis Tabor
ARCAD1S Oeraghty & Miller
2301 Rexwoods Dr, Ste 100
Raleigh, NC 2760?
Page 18 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: «05211133
Prism Sample 10: AB34747
Login Group: 8401E24
Sample Collection Date/Time: 5/21/99
Lab Submlttal Date/Time: 7/2/99
11KX)
The following analytical results Have been obtained for the Indicated sample which was submitted to this laboratory:
TEST
PARAMETER
SAMPLE PREPARATION FOR METHd
ARSEN 1C BY METHOD 29 '
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Last than
Less than
Lets than
Less than
tew than
Lesclhan
27
Less than
Let* than
2.0
3.2
19
UNITS
ug
Ufl
ug
Ufl
ug
ug
ug
ug
ug
ug
ug
Ufl
MDL
1.6
V5
1.5
t.6
1.5
1.5
15
1.5
15
1.5
1.8
.v»
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
M«thod 29
Metnod29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/99 06:00
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/99 14:47
7/12/9908:00
7/12/99 08:00
7/12799 14:47
7/12/99 06:00
7/12/99 08 :00
7/12/9908:00
7/12/9908:00
ANALYST
OHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
Angela D. Overcash. V.P. Laboratory Services
E-18
-------
Lab Report
PRISM
LMOHMOMEt, INC.
FuH Sf mo* AnHytital t Environmtnw Sotuuont
7/29/99
Mr. Dennis Tabor
ARCAOIS Garaghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh. NC 27607
Page 19 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 905241201 FILTE
Prism Sample ID: AB34748
Login Group: B401E24
Sample Collection Date/Time: 6/24/99
Lab Submittal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 29
SAMPLE PREPARATION FOR METHO
AKJENIC BY METHOD 29
ANTIMONY BY METHOD 28
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29'
ZINC BY METHOD 28
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Completed
Completed
10
Less than
23
6.6
17
8.2
69
19
1500
16000
60000
Lets than
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
Ufl
MOL
2.0
2.0
0.01
2.0
2.0
2.0
20
2.0
20
400
400
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/99 06:00
7/7/99 16:00
7/8/99 06:00
7/12/99 06:00
7/12/BO 08:00
7/12/99 06:00
7/12/99 06:00
7/12/99 08:00
7/12/99 08:00
7/12/99 06:00
7(12/9908:00
7/12/9908:00
7/12/99 06:00
7/12/99 06:00
7/12/9908:00
ANALYST
DHJ
OHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash. V.P. Laboratory Services
E-19
-------
Lab Report
PRISM
LABORATORIES, INC
Ful 6«viM Anilyik»l I Enwwjugnial &*,(<„
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh, NC 27607
Page 20 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 905241201
Prism Sample ID: AB34749
Login Group: 8401E24
Sample Collection Date/Time: 5/24/99
Lab Submittal Date/Time: 7/2/99 11:00
The following analytic*!! results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
SAMPLE PREPARATION FOR METHO
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYU.I" 'M BY METHOD 29
CADMIUM BY METHOD 2!)
COPPER BY METHOD 2«
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 26
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sarrple Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Lett than
Last than
1.8
Let»«ian
4.6
2.4
too
2.2
3000
700
3400
11
UNITS
UQ
ug
"9
ug
ug
Ufl
ug
ug
19
ug
ug
ug
MOL
1.5
V5
1.S
1.5
1.6
1.5
15
1.5
15
1.5
1-5
1.5
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 28
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7/9906:00
7/12/9908:00
7/12/9906:00
7/12/9908:00
7/12/99 08:00
7/12/99 08:00
7/12/9908:00
7/12/99 08:00
7/1249 08:00
7/12/99 06:00
7/12/99 08:00
7M2/99 08:00
7/12/M 08*0
ANALYST
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
Angela D. Overcash. V.P. Laboratory Services
E-20
-------
Lab Report
PRISM
LABORATORIES, INC.
fiM Scrvn* Analytical & Envjronmtntil Sokjuont
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Mller
2301 Rexwoods Or, Sle 100
Raleigh. NC 27607
Page 21 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: M5251142FILTE
Prism Sample 10: AB34750
Login Group: 8401E24
Sample Collection Date/Time: 6/25/99
Lab Submtttal Data/Time: 7/2/99
lyticat results h^ve been obtained for the Indicated sample which
The following analy
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
BOMB PREP. FOR METHOD 29
ZINC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESIUM BY METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 29
CADMIUM BY METHOD 29
BERYU-IUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
SAMPLE PREPARATION FOR METHO Completed
Sample Comments
RN 992010.0024
was submitted to this laboratory.
TEST
RESULT
/*«*fMrdAfA*4
^ompwwa
Completed
Lett than
62000
15000
2300
*%n
20
43
8.9
Lett than
7.1
23
LMilhan
6.8
in f-MitdalBri
UNITS
ug
ug
ug
ug
i M
uy
ug
ug
ug
ug
ug
ug
ug
MDL
2.0
400
400
20
2.0
20
2.0
2.0
2.0
0.01
2.0
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/7A99 16:00
7/7/8908:00
7M2»9 08:00
7/12/B9 08OO
7/12/99 06:00
7/12/99 08.00
7/12/9908:00
7/12/99 08:00
7/12/99 08.00
7/12/99 08:00
7/12A9 08.00
7/12^9908:00
7/12^908:00
7/12«9 08:00
7/6/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
Angela D. Overcash. V.P. Laboratory Services
E-21
-------
Lab Report
PRISM
LMWATOMES.me.
h» S«vc* AnslyKtl & Enwrormwiai SoUitont
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 RexwoodS Dr. Ste 100
Raleigh. NC 27607
Page 22 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 905251142
Prism Sample ID: AB34751
Login Group: S401E24
Sample Collecyon Date/Time: 5/25/99
Lab Submlttal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST TEST
PARAMETER RESULT
ZINC BY METHOD 29 15
VANADIUM BY MET* CO ?9 14
NICKEL BY METHOD 29 44
MAGNESIUM BY METHOD 29 27
MANGANESE BY METHOD 29 18
IRON BY METHOD 29 42
CHROMIUM BY METHOD 29 3.0
COPPER dY METHOD 29 2.9
CADMIUM BY METHOD 29 4.0
BERYLLIUM BY METHOD 29 Lett then
ANTIMONY BY METHOD 29 Let* then
ARSENIC BY METHOD 29 Lees than
SAMPLE PREPARATION FOR METHO Completed
Sampb Comments:
RN 992010.0024.00001
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MDL
1.6
1J5
1.5
15
1.S
15
1.6
1.8
1£
1.6
1.5
1.5
METHOD
REFERENCE
Mothod 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/12/90 08:00
7/1279908:00
7/12/99 08:00
7/12/9608:00
-7/12/9908:00
7/12/99 08:00
7/12/99 06:00
7/12/M 06:00
7/12/9B 06:00
7/12/99 06:00
7/12/9908:00
7/12/99 08:00
7/7/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-22
-------
Lab Report
^^k l>»ORATOme«, INC.
rat Stnat Aiulylic*! ft Eiwirenmnw Solution.-
PRISM
7/29/99
Mr Dennis Tabor
ARCADIS Geraghty & Millar
2301 Rexwoods Dr. Ste 100
Ra'eigh, NC 27607
Pane 23 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: §08261053FILTE
Prism Sample ID: AB34752
Login Group: 8401E24
Sampte Collection Dale/Time; 5/26/99
Lab Submlttal Date/Time: 7/2/99 11:00
The following analytical results Have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
BOMB PREP. FOR METHOD 28
BOMB PREP. POR METHOD 26
ZINC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESIUM BY METHOD 2ft
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 2B
CADMIUM BY METHOD 20
BERYdJUM BY METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 2ft
SAMPLE PREPARATION FOR METHO Completed
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
Completed
Completed
LiMlhan
72000
17000
1600
20
78
6.3
6.0
6.6
27
Lmthan
10
Completed
UNITS
"9
ug
"0
"0
ug
UQ
ug
up
"9
ug
ug
ug
MDL
2.0
400
400
20
2.0
20
2.0
2.0
2.0
0.01
?n
2.0
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
MMhnri ?fl
Method 29
Method 29
DATE/TIME
STARTED
7/7/99 06:00
7/7/99 16:00
7/12/99 08:00
7/12/9908:00
7/12/99 06:00
7/12/9906:00
7/12/9906:00
7/12/9908:00
7/12/99 08:00
7/12/99 08:00
7/12/99 08:00
7/12/99 0600
7/i?ma mon
7/1249 06.00
7/6/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DH.I
DHJ
DHJ
Angela D Overcash. V.P. La xjratory Services
E-23
-------
Lab Report
PRISM
Ft* S«cn* AitttytWd A Ertvuanffltr.iftl Sotufconi
7/29/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh. NC 27607
Page 24 of 24
Customer Project Name: RN 992010.0024.00001
Customer Sample ID: 805281053
Prism Sample ID: AB34753
Login Group: 8401E24
Sample Collection Date/Time: 6/26/99
Lab SubmHtal Date/Time: 7/2/99 11:00
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
ZINC BY METHOD 29
VANADIUM BY METHOD 29
NICKEL BY METHOD 29
MAGNESlUt 3Y METHOD 29
MANGANESE BY METHOD 29
IRON BY METHOD 29
CHROMIUM BY METHOD 29
COPPER BY METHOD 29
CADMIUM BY METHOD 26
BERYLLIUM BV METHOD 29
ANTIMONY BY METHOD 29
ARSENIC BY METHOD 29
SAMPLE PREPARATION FOR METHO
Sample Comments:
RN 992010.0024.00001
TEST
RESULT
14
3.4
1.S
20
Leiithan
22
LASS than
7.9
t.e
Lwthan
Lett man
Lsstthan
0 Complttod
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MDL
1.5
1J5
1.5
15
1.5
15
1.6
1.5
1.5
1.5
1.5
1.5
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 28
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
7/12/9906:00
7/12*906:00
7/12/9906:00
7/1 2/99 08:00
7/12/99 06:00
7/12/99 08:00
7/12/9908:00
7/12/8906:00
7/12/99 06:00
7/12/96 06:00
7/12/99 06:00
7/12/99 06:00
7/7/9908:00
ANALYST
OR)
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
OHJ
DHJ
DHJ
DHJ
Angela D. Overcash. V.P. laboratory Services
E-24
-------
Lab Report
UBORATOWES.IHC.
Ful Swvloa Analytical & Envi.onm.ntal Solution)
9/21/99
Mr. Dennis Tabor !
ARCADIS Geraghty & Miller
2301 Rexwoods Or, Ste 100
Raleigh, NC 27607
Page 2 of 7
Customer Project 10: Orimulsion/RN992010.0024
Customer Sample ID: FOBLR6#2
Prism Sample ID: AB37197
Login Group: 9151E7
Sample Collection Date/Time: 6/3/99
Lab Submittal DateTTime: 7/29/99 14:30
The following analytical res
ills have been obtained for the indicated sample which was submitted to this laboratory:
TEST TEST
PARAMETER , RESULT UNITS MDL
LOSS ON IGNITION 16 % 1
METHOD DATE/TIME
REFERENCE STARTED
6/5/99 08:00
ANALYST
DHJ
Sample Comments:
Angela D. O^rcasnTXTPTLaboraJory Services
E-25
-------
Lab Report
PRISM
LABOMATOMU.INC.
Fun ScrvlM Analytical & Environmental Solutions
9/21/99
Mr. Dennis Tabor \
ARCADIS Geraghty & Miller
2301 Rexwoods Dr, Ste 100
Raleigh, NC 27607
i
I resets
Page 3 of 7
Customer Project ID: Orimulslon/RN992010.0024
Customer Sample ID: COBLR6#1
Prism Sample ID: AB37198
Login Group: 9151E7
Sample Collection Date/Time: 6/3/99
Lab SubmKtal Date/Time: 7/29/99 14:30
The following analytical resets have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
LOSS ON IGNITION
TEST
RESULT
UNITS
MDL
METHOD
REFERENCE
DATE/TIME
STARTED
8/5/99 08:00
^ANALYST
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-26
-------
* Report
FRISM
UBOHATORIEIINC.
Ful Swvica Analytical t Environmental Salmons
9/21/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Or, Ste 100
Raleigh, NC 27607
The following analytical results hive
Page 4 of 7
Customer Project ID: Orimulslon/RN992010.0024
Customer Sample ID: FOBLC4#1
Prism Sample ID: AB37109
Login Group: 9151E7
Sample Collection Date/Time: 5/18/99
Lab SubmHtal Date/Time: 7/29/99 14:30
"TEST
PARAMETER^
BOMB PREP. FOR METHOD 29
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
Sample Comments:
mr^ tl_ —
Ive been obtained for the Indicated sample which was submitted to this laboratory.
TEST
peei it T
t\CDUL 1
Completed
16
3.8
17
41
35
130
3300
55
8100
1600
7800
56000
UNITS
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
ug
MDL
2.S
2.5
2.5
2.5
2.5
2.5
25
2.5
25
2.5
120
120
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
8/20/9917:00
9/14/99 08:00
9/14/9908:00
9/14/9908:00
9/14/99 08:00
9/14/9908:00
9/14/99 08:00
9/14/9906:00
9/14/99 08:00
8/14/99 06:00
9/14/99 08 :00
9/14/99 08:00
9/14/99 08:00
ANALYST
DHJ
DHJ
DHJ
DHJ
OHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-27
-------
ib Report
PRISM
UkBORMOWM,mC.
9/21/99
Mr. Dennis Tabor
ARCADIS Geraghty & Miller
2301 Rexwoods Or, Ste 100
Raleigh, NC 27607
Ful Service Analytical I Environnwnui Soiutiont
Page 5 of 7
Customer Project ID: Orlmulsion/RN992010.0024
Customer Sample ID: FOBLC4*2
Prism Sample ID: AB37200
Lpgln Group: 9151E7
Sample Collection Date/Time: 6/18/99
Lab Submhtal Datemme: 7/29/99 14:30
The following analytical results have been obtained for the indicated sample which was submitted to this laboratory:
TEST
PARAMETER
TEST
RESULT
UNITS MDL
METHOD
REFERENCE
DATE/TIME
STARTED
ANALYST
LOSS ON IGNITION
Sample Comments:
i
8/5/9908:00
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-28
-------
b Report
PRISM
UBOIUnOMES. INC.
Ful SMvtot Ant»ytlctl I Envlioramnlal Solutions
9/21/99
Mr. Dennis Tabor
ARCADIS Qeraghty & Miller
2301 Rexwoods Dr. Ste 100
Raleigh, NC 27607
The following analytical results
Page 6 of 7
Customer Project ID: Orimulsion/RN992010.0024
Customer Sample ID: FOBLCKM
Prism Samole ID: AB37201
Loain Group: 9151E7
Sample Collection Date/Time: 5/24/99
Lab Submlttal Date/Time: 7/29/99
14:30
have been obtained for the Indicated sample which was submitted to Ihis laboratory.
TEST
PARAMETER
BOMB PREP. FOR METHOD 29
ARSENIC BY METHOD 29
ANTIMONY BY METHOD 29
BERYLLIUM BY METHOD 29
CADMIUM BY METHOD 29
COPPER BY METHOD 29
CHROMIUM BY METHOD 29
IRON BY METHOD 29
MANGANESE BY METHOD 29
MAGNESIUM BY METHOD 29
NICKEL BY METHOD 29
VANADIUM BY METHOD 29
ZINC BY METHOD 29
TEST
.RESULT
Completed
42
12
49
35
59
130
2600
90
15000
17000
79000
63000
UNITS
ug
ug
ug
ug
ug
ug
ug
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ug
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Sample Comments:
MDL
^ nny w
2.5
2.5
2.5
2.5
2.5
2.5
25
2.5
25
120
120
120
METHOD
REFERENCE
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
Method 29
DATE/TIME
STARTED
6/20/9917:00
9/14/99 06:00
9/14/9908:00
9/14/9906:00
9/14/9908:00
0/14/99 08:00
9/14/9906:00
9/14/99 08:00
9/14/99 08:00
B/14/99 08:00
9/14/99 06:00
9/14/9906:00
9/14/9908:00
ANALYST
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
DHJ
Angela D. Overcash, V.P. Laboratory Services
E-29
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ab Report
PRISM
FuH SwvkM Analytical 1 EnvtronnwnUI Solutions
9/21/99 Page 7 of 7
Mr. Dennis Tabor Customer Project ID: Orimuts!on/RN992010.0024
ARCADIS Geraghty & Miller Customer Sample ID: FOBLC1«2
2301RexwoodsDr,Ste100 Prism Sample ID: AB37202
Raleigh NC 27607 Login Group: 9151E7
Sample Collection Daterrime: 5/24/99
| Lab Submtttal Datemme: 7/29/99 14:30
The following analytical resuttjs have been obtained for the Indicated sample which was submitted to this laboratory:
TEST " ****njra\ nATP/TIMP"
PARAMETER
LOSS ON IGNITION
TEST
RESULT
14
UNITS
%
JMDL
1
METHOD
REFERENCED
STARTED
ANALYST
8««9 08:00 OHJ
Sample Comments:
Angela D. Overcash, V.P. Uboratory Services
E-30
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APPENDIX F
Orimulsion Spill References Cited by the NRC, U.S. Coast Guard, and
Environment Canada Reports
Bitor (1999). "Orimulsion spill response manual," PdVSA and Bitor America Corp., Boca Raton,
FL.
Bitor America (1997). "Orimulsion containment and recovery test carried out in Puerto La Cruz,
Anzoatgui State, Venezuela," Bitor America, Boca Raton, FL, October 1996.
Brown, J.W., Fuentes, H.R., Jaffe, R., and Tsihrintzis, V.A. (1995). "Comparative evaluation of
physical and chemical fate processes of Orimulsion and fuel oil No. 6 in the Tampa Bay marine
environment," Chapter 4, Comparative Ecological Risk Assessment - Final Report, Center for
Marine and Environmental Analysis, University of Miami, Miami, FL, June 1995.
CEDRE (1996). "Orimulsion bitumen clean-up trials," Centre de Documentation de Recherche et
d'Experimentations, Brest, France, Report R.96.11.
Clement, F., Gunter, P., and Oland, D. (1997). "Trials of recovery and cleanup techniques on
bitumen derived from Orimulsion," Proceedings of the 1995 International Oil Spill Conference,
American Petroleum Institute, Washington, DC, pp. 89-93.
Deis, D.R., Tavel, N.G., Masciangioli, P., Villoria, C., Jones, M.A., Ortega, G.F., and Lee, G.R. (1997).
"Orimulsion: Research and testing and open water containment and recovery trials,"
Proceedings of the 1997 International Oil Spill Conference, American Petroleum Institute,
Washington, DC, pp. 459-467.
Febres, G.A., Goncalves, J.A., Masciangoli, P., and Vilas, J. (1996). "Fate and behavior of
Orimulsion spilt in sea water,"unpublished report, Comparative Oil-Orimulsion Spill Assessment
Program, Volume III, Florida Power and Light Company, Miami, FL.
Guenette, C., Sergy, G., and Fieldhouse, B. (1998). "Removal of stranded bitumen from intertidal
sediments using chemical agents, Phase I: Screening of chemical agents," Environment Canada
report, Emergency Sciences Division, Environment Canada, Edmonton, Alberta, Canada (18 pp.).
Gunter, P., and Sommerville, M. (1991). "Orimulsion spill trials - Nelson Dock, Liverpool,"
NETCEN, AEA Technology/BP Research, Oxfordshire, U.K., July/August 1991.
Harper, J.R., and Kory, M. (1997). "Orimulsion sediment interaction experiments," Report to
Emergency Sciences Division, Environment Canada, Ottawa, Ontario, Canada (34 pp.).
Jokuty, P., Fieldhouse, B., Fingas, M., Whiticar, S., and Latour, J. (1998). "Characterizing the
dynamics of Orimulsion spills in salt, fresh, and brackish water "Proceedings of the 21st Arctic
and Marine Oilspill Program, Technical Seminar, Environment Canada, Ottawa, Ontario, Canada,
pp. 33-50.
Jokuty, P., Whiticar, S., Fingas, M., Wang, Z., Doe, K., Kyle, D., Lambert, P., and Fieldhouse, B.
(1995). "Orimulsion: Physical properties, chemical composition, dispersability, and toxicity,"
Report EE-154, Environment Canada, Ottawa, Ontario, Canada.
Jokuty, P., Whiticar, S., Wang, Z., Doe, K., Fieldhouse, B., and Fingas, M. (1999). "Orimulsion-400;
A comparative study," Report EE-160, Environment Canada, Ottawa, Ontario, Canada.
Lorenzo, T. (1996). "Orimulsion containment and recovery tests, October 1996, Puerto La Cruz,
Venezuela," Trip report, EED Report Series No. 96, Emergencies Engineering Division,
Environment Canada, Ottawa, Ontario, Canada.
Ostazeski, S.A., Stout, S.A., and Uhler, A.D. (1998). "Testing and characterization of Orimulsion 400
- Volume I - Technical Report," Final report to Bitor America Corp., 44 pp., February 25, 1998.
Ostazeski, S.A., Macomber, S.C., Roberts, L.G., Uhler, A.D., Bitting, K.R., and Hiltabrand, R. (1997).
"The environmental behavior of Orimulsion spilled on water," Proceedings of the 1997
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International Oil Spill Conference, American Petroleum Institute, Washington, DC, pp. 469-477.
Potter, T.L. (1995). "Chemistry of fuel oil #6 and Orimulsion," Chapter 14, Comparative
Ecological Risk Assessment - Final Report, Center for Marine and Environmental Analysis,
University of Miami, Miami, FL, June 1995.
Potter, T.L., Wu, J., Simmons, K., Kostecki, P., and Calabrese, E. (1997). "Chemical characterization
of the water soluble fraction of Orimulsion-in-water dispersions," Department of Food Science
and School of Public Health, University of Massachusetts, Amherst, MA.
Sneddon, R. (1989). "A report on a study to determine treatment options following spillage of
Orimulsion into marine and freshwater environments," Oil Spill Service Centre, Southampton,
UK.
Sommerville, M., Lunel, T., Bailey, N., Oland, D., Miles, C., Gunter, P., and Waldhoff, T. (1997).
"Orimulsion," Proceedings of the 1997 International Oil Spill Conference, American Petroleum
Institute, Washington, DC, pp. 479-487.
Wood, P. (1996). "Investigations into landspills of Orimulsion," Report by AEA Technology for
Bitor Europe (18 pp.).
F-2
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APPENDIX G
Additional Ecological Risk Assessment Studies
The original risk assessment by Harwell et al. (1995) was conducted for Bitor as part of their original
permit application to the State of Florida, and the document was reviewed by an independent
technical panel (chosen by EPA) for this report. The conclusions of that panel were presented in
Chapter 8.
Following the original assessment, additional studies were conducted that were not reviewed by the
independent panel. The studies for the updated assessment included:
1. Additional toxicity data on benthic organisms - Several additional benthic species indigenous to
Tampa Bay were tested for acute toxicity to Orimulsion and to No. 6 fuel oil.
2. Additional toxicity data on the surfactant - Additional toxicological tests were conducted to
evaluate the potential ecological impacts expected from exposure to the surfactant in Orimulsion
100 in the event of a spill, specifically focused on chronic life-cycle tests for endocrine
disruption effects.
3. Additional ecorisk assessment on surfactant - Based on those new chronic life-cycle tests, a risk
assessment was conducted on the ecological effects from the surfactant associated with
Orimulsion 100 in the event of a large-scale spill into Tampa Bay.
4. Additional ecorisk assessment on shallow water and nursery areas - Similarly, based on the new
acute toxicity information as well as the previous toxicity data, and using a new set of fate-and-
transport calculations, a new comparative ecological risk assessment was conducted that focused
on the risks to the shallow water critical habitats and nursery areas of Tampa Bay from
Orimulsion 100 and No. 6 fuel oil.
5. Additional assessment of risk reductions in Tampa Bay and elsewhere - An assessment was
conducted to examine the overall ecological risk reductions from fuel spills in Tampa Bay and
other estuarine ecosystems within the State of Florida.
6. Aquatic toxicity studies were conducted on Orimulsion 400. Comparative studies indicated a
similar toxicity of the two formulations.
The results of these studies were incorporated into an updated environmental risk assessment
conducted for Bitor. The key conclusions of that assessment are listed below:
1. The risks to the shallow water, critical habitats of Tampa Bay were reported as being orders-of-
magnitude lower for a major spill of Orimulsion than for a comparable spill of No. 6 fuel oil.
2. Exposures to the surfactant of Orimulsion 100 in Tampa Bay were reported as being many
orders-of-magnitudes lower than the lowest observed effect level as measured through a partial
life-cycle test using a sensitive fish species. It was concluded that a spill of Orimulsion 100
would pose no risk whatsoever for endocrine disruption of biota in Tampa Bay.
3. The updated assessment also noted that conversion from No. 6 fuel oil to Orimulsion at the
Manatee plant would shift electricity production in the rest of the State of Florida, resulting in
significant reduction in the risk of spills of #6 fuel oil in other areas of the State, including at the
Biscayne National Park, Canaveral National Seashore, and other protected waters of Florida.
4. The toxicity of Orimulsion 400 (the current formulation) is comparable to Orimulsion 100.
Further, the reformulation of the surfactant in Orimulsion 400 removes the concern regarding
potential endocrine disruption.
These conclusions were cited in a document submitted in response to comments on this report by
Bitor America (Harwell and Golder 2000). The document was prepared by the lead author of the
initial environmental risk assessment reviewed for this report (Harwell et al. 1995) and by an associate
of a technical firm that has conducted work in support of Bitor's permitting efforts in the U.S. The
submitted document provides additional detail and data, but has not been independently reviewed and
is therefore not included in its entirety as part of this report.
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References cited in the updated environmental assessment but not in the original assessment are listed
below.
Battelle (1998). Testing and Characterization of Orimulsion-400: Volume I - Technical Report,
Battelle, Duxbury, MA.
Bergman, H., and H. Eckert (1990). "Effect of monoethanolamine on growth and biomass
formation of rye and barley," Plant Growth Regulation 9, pp. 1-8.
Bicknell R.J., A.E. Herbison, and J.P. Sumpter (1995). "Oestrogenic activity of an environmental
persistent alkylphenol in the reproductive tract but not in the brain of rodents," J. Steroid
Biochem. Molec. Biol., 54(1/2), pp. 7-9.
Bjornestad, E., A.R. Pedersen, and S. Bowadt (1998). "Ecotoxicological characterization of
Orimulsion 400: A summary report," VKI Project No. 11020, Bitor Europe Ltd., Brentford,
Middlesex, England, 16 pages, January 1998.
Davis, J.W., and C.L. Carpenter (1997). "Environmental assessments of the alkanolamine," in
Reviews of Environmental Contamination and Toxicology. Volume 149. Springer-Verlag, New
York, N.Y.
Environmental Health Research and Testing (1987). "Screening of priority chemicals for
reproductive hazards: Monoethanolamine, diethanolamine and triethanolamine," report ETOX-
85-1002, Environmental Health Research and Testing, Cincinnati, OH.
Environment Canada (1998). "Orimulsion-400™ - A comparative study," prepared by
Emergencies Science Division, Environment Canada, Environmental Technology Centre, Ontario,
Canada, 27 pages.
Esclapes, M.M., et al. (1998). Unpublished data using Orimulsion-400, PDVSA-INTEVEP, Caracas,
Venezuela.
Esclapes, M.M., I. Galindo, and Y. Higuerey (1997). "Evaluacion toxicologica de nuevas
formulaciones de Orimulsion empleando bioindicadores acuaticos," report INT-4171, PDVSA-
INTEVEP, Caracas, Venezuela.
Golder Associates Geoanalysis (1999). "Orimulsion-400 and fuel Oil #6: A comparative study of
aquatic ecotoxicology," report 992210/3683 prepared for Bitor Italia S.r.l., Rome, Golder
Associates Inc., Gainesville, FL.
Johnson I.C., G.S. Ward, and H.J. Liu (1998a). "Acute toxicity of Orimulsion-400 and Orimulsion
100 to two estuarine species," report 9937563 prepared for Bitor America Corporation, Golder
Associates Inc., Gainesville, FL.
Johnson, I.C. G.S. Ward, and H.J. Liu (1998b). "Acute toxicity of Orimulsion-100 to estuarine
species," COSAP research under the sponsorship of the University of Miami, (In: Ault et al.,
1995, Chapter 10) Golder Associates Inc., Gainesville, Florida.
Johnson, I.C., C. Metcalfe, Y. Kiparissis, G. Balch, G.S. Ward, J.Wheat, J. Liu, and T. Potter (1997).
"Final report: Partial life-cycle studies using the estuarine fish sheepshead minnow to evaluate
the potential reproductive and estrogenic effects of Intan-100," presented at the SETAC 18th
Annual Meeting, Special Symposium on Endocrie Disrupters, San Francisco, California.
Knaak, J.B., H.W. Leung, W.T. Scott, J. Busch, and J. Bilsky (1997). "Toxicology of mono-, di-, and
triethanolamine," in Reviews of Environmental Contamination and Toxicology. Volume 149. p.
1, Springer-Verlag, New York, N.Y.
Liberacki, A.B., T.L. Neeper-Bradley, W.J. Breslin, and G.J. Zielke (1996). "Evaluation of the
developmental toxicity of dermally applied monoethanolamine in rats and rabbits,"
Fundamental and Applied Toxicology (USA), 31(1), pp. 117-123.
Mankes, R.F. (1986). "Studies on the embryopathic effects of ethanolamine in Long-Evans rats:
preferential embryopathy in pups contiguous with male siblings in utero," Teratog Carcinog
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Mutagen 6, pp. 403-417.
Patty's Industrial Hygiene and Toxicology, (1982). Third Edition, Wiley and Sons, New York, NY.
Routledge, E.J., and J.P. Sumpter (1996). "Estrogenic activity of surfactants and some of their
degradation products assessed using a recombinant yeast screen," Environ. Toxicol. Chem. 15(3),
pp. 241-248.
Soto, A.M., H. Justicia, J.W. Wray, and C. Sonnenschein (1991). "p-Nonylphenol: an estrogenic
xenobiotic released from "modified" polystyrene," Environ. Health Perspectives, 92, pp. 167-
173.
Tennant, R.W., B.H. Margolin, M.D. Shelby, E. Zeiger, J.K. Haseman, J. Spalding, W. Caspary, M.
Resnick, S. Stasiewicz, B. Anderson, and R. Minor (1987). "Prediction of chemical
carcinogenicity in rodent from in vitro genetic toxicity assays," Science 236, pp. 933-941.
United States Coast Guard (1997). "Micro- and meso-scale methods for predicting the behavior of
low-API gravity oils (LAPIO) spilled in water," 1995 Oil Pollution Grants Program, Research and
Special Programs, U.S. Coast Guard, Region , 1st District, Boston, MA.
Wason, S., E. Seigel, L. Sigell, M. McElwee, and W. Pratt (1991). "Acute exposure to ethanolamine:
Lack of serious toxicity," Veterinary and Human Toxicology, 33(4), p. 371.
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APPENDIX H
Comparative Risk Methodology Synopsis of Harwell et al. (1995)
The NCEA review of the comparative risk assessment conducted by Harwell et al. (1995) included a
synopsis of the methodology used in the assessment. The synopsis is presented below.
1) Meteorological and tidal conditions during and following the hypothetical spill event were
input to a hydrodynamical model, based on actual records for Tampa Bay during January
1991 and August 1991. Hydrodynamical conditions during and following each scenario
spill were simulated using the NOS-based 3-D hydrodynamical model. This model provided
spatially explicit projections following a hypothetical spill scenario of the current vectors
through the Tampa bay system and the area near the mouth of the Bay.
2) These output current vectors were input to a transport model to define the current field
necessary to simulate the transport of the No. 6 fuel oil and Orimulsion. Also provided as
inputs to the Orimulsion model and the SIMAP oil spill model were parameters representing
the characteristics of the two fuel types as derived from chemical, physical, and weathering
characteristics studies, as well as from values in the literature.
3) Transport of the spilled No. 6 fuel oil as an oil slick on the surface of Tampa Bay was
simulated using the reparameterized SIMAP model analyses: the oil slick was modeled as a
set of "spillets" at variable scales of resolution.
4) A post-processing algorithm was developed to generate a map of the movement of the oil
slick over the duration of the simulation. The map of the movement of the oil slick was
transferred into the GIS facility to produce maps of the Tampa Bay region and the oil slick
coverage for each scenario analyzed.
5) Interception of the No. 6 fuel oil slick that came into contact with the shoreline was also
simulated using the SIMAP model. Scientists developed another algorithm to calculate the
amount of mass of oil slick intercepting each section of the shoreline.
6) The map of the interception of the oil slick was transferred into the GIS facility to produce
maps that superimpose the coastal areas contacted by the No. 6 fuel oil slick overlain onto the
coverage of the oil slick for each scenario analyzed.
7) The oil slick outputs could not be directly compared with the toxicological exposure-
response because there are no data to relate the amount of fuel slick present (or cumulative
value for each cell) to ecological effects. Consequently, exposure maps of a No. 6 fuel oil
slick are presented with a scalar, using shades of brown to represent the area covered during a
simulation by the oil slick. A qualitative examination of the potential effects of the oil slick
from a spill of No. 6 fuel oil was developed, considering areal extent of the slick, the area and
types of shoreline habitats intercepted by the oil slick, and historical experiences with No. 6
fuel oil spills contacting mangrove and seagrass ecosystems. Note that, since Orimulsion was
considered not to develop a significant oil slick, this analysis was not done for Orimulsion
scenarios.
8) A reformulated and reparameterized SIMAP model was used to simulate the movement of
dissolved and particulate fractions entrained into the water column following a spill of No. 6
fuel oil. For each cell in the SIMAP grid for each time step, each non-zero value of aromatic
concentration was noted. For each cell, the cumulative exposure (concentration x duration)
was calculated, based on the maximum concentration seen at any level within the 5-layer
water column during each time step. Units for the cumulative exposures are ppb-hr of
dissolved aromatics.
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9) Transport of spilled Orimulsion was simulated using the Orimulsion spill model. This model
simulated the 3-D movement over time throughout Tampa Bay and associated waters of the
Orimulsion particulates and dissolved fraction in the water column. The modeled fraction
used in the risk characterization was the total hydrocarbon content of the water column.
10) The output files from the Orimulsion transport model were sent for post-processing. As for
the aromatics in No. 6 fuel oil, the cumulative exposures of Orimulsion at each cell in the grid
were calculated. Units for the cumulative exposures are ppm-hr of hydrocarbons.
11) As for No. 6 fuel oil aromatics, total Orimulsion hydrocarbons were transferred to the much
higher resolution GIS and advanced visualization system for mapping and for calculations of
co-occurrence.
12) The toxicity studies on the potential effects of No. 6 fuel oil and Orimulsion on mangroves
and seagrasses were carefully examined. It was concluded that no ecologically significant
habitat alteration to the mangrove or seagrass plant communities of Tampa Bay would result
from a spill of either No. 6 fuel oil or Orimulsion. The focus then turned to an examination
of water-column effects from the two fuel types and the oil slick effects from No. 6 fuel oil.
13) The toxicological information provided by the survey, the INTEVEP project on Orimulsion,
and other literature reviews, plus the results of the toxicological experiments conducted on
seagrasses, seagrass community invertebrate inhabitants, spotted sea trout early life stages, and
mangroves, were examined to identify appropriate toxicological benchmarks for No. 6 fuel
oil and Orimulsion. The result was the selection of the spotted sea trout yolksac larvae
toxicological responses to represent the sensitive species present in the Tampa Bay ecosystem.
This selection represents a conservative but ecologically and societally important choice.
14) Data for toxicity tests on spotted sea trout yolksac larvae were analyzed to identify dose-
response and time-dependent exposure-response relationships. It was decided to use the 48-
hr toxicity test for the oil-water dispersion (OWD) fraction of both Orimulsion and No. 6 fuel
oil as most representative of conditions in Tampa Bay following a spill. In part, this decision
derived from a detailed look at the frequency distribution of cumulative time of exposures
and, in part, this decision related to the leveling off of toxicity at exposure periods exceeding
48 hours.
15) A series of steps was developed to convert from dosing to modeled conditions; for No. 6 fuel
oil, this entailed calculating from the oil-water dispersed fraction stock solution
concentrations and nominal concentrations through BTEX to aromatics concentrations
effectively seen by the test organisms; for Orimulsion, it involved going from the
concentration of Orimulsion in the dosing conditions to the total hydrocarbons simulated in
the Orimulsion transport model.
16) These conversion factors were applied to toxicity data to derive lethality rate-modeled
fraction exposure relationships. The concentrations were multiplied by 50 to represent the
associated exposure of a two-day period (comparable to 48-hr tests).
17) Using these normalized exposure data, LCio and LC95 values for aromatics for No. 6 fuel oil
and total hydrocarbons for Orimulsion were calculated using a logistic equation to fit the raw
data. The LCio level was chosen on the assumption that no ecological responses would be
ecologically significant at changes <10%. The LCgs level was chosen to represent a
reasonable upper bound on the asymptotic logistic equation.
18) These LCio and LCgs values were used to provide the scalars for the graphical representation
of the exposure levels for each scenario simulation. By making this scaling, the graphical
outputs for No. 6 fuel oil and for Orimulsion are directly comparable in terms of effects to
the sensitive species. This allows direct, visual comparative analysis of the risks from each
H-2
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fuel type for each scenario.
19) These simulations were completed for all 96 scenarios, and the resultant suites of graphical
outputs were visually inspected to identify patterns with respect to the key scenario factors
(location, seasonality, and wind/current conditions).
20) Based on these considerations, four individual scenarios were selected as representative of the
types of transport and exposure regimes realized for the scenario set for each location. These
four selected scenarios were then explored much more thoroughly for detailed
ecotoxicological analyses.
21) The extensive database was entered into the GIS facility; we have acquired more than 50
separate environmental databases containing all relevant biological, ecological, and physical
information from federal, state, and local agencies concerned with management of Tampa
Bay. This extensive, unique database provides a unique capability to converge considerable
distribution data with well-defined exposure regime projects.
22) A series of steps was developed to relate the exposure and co-occurrence data for the spotted
sea trout species to population-level effects and recovery times. We conducted similar
analyses for inland silversides (i.e., the less sensitive species).
23) A series of steps was developed to use the exposure and co-occurrence information to
calculate quantitative values for comparing the risks of the two fuels to selected species in
Tampa Bay. Three approaches for integrating exposure and effects information into an
estimate of risk, derived from the EPA framework for ecological risk assessment, were used;
single value comparisons (one-dimensional models of toxicant-organism interaction); joint
distribution analysis (comparing distributions associated with estimates of exposure and
effects); and population modeling.
24) Expert judgment was applied to all sets of the risk assessment analyses to develop the
synthesis of the comparative risks to the ecological systems of Tampa Bay from a spill of No.
6 fuel oil and a spill of Orimulsion.
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