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

-------
                                   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

-------
                                          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

-------
                                          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.

-------
                                          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

-------
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

-------
                           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

-------
                   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

-------
                                       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

-------
                           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

-------
                               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

-------
                                   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

-------
                                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

-------
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

-------
                                  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

-------
                          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

-------
                          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

-------
                                    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

-------
                             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

-------
                                  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

-------
      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

-------
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

-------
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

-------
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

-------
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

-------
                                        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

-------
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

-------
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

-------
       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

-------
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

-------
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

-------
                                       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

-------
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

-------
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.
                                            2-3

-------
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
                                            2-4

-------
              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.
                                              2-5

-------
                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

-------
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

-------
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

-------
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

-------
                                       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

-------
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

-------
                                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

-------
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

-------
                            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

-------
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

-------
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
on :
ou
E yn
TO I U
ti! fin
w ou _
w
0 50
ou
+->
0A.(\
*rU
e :
a) in
CL :
90
fM
1fl
I v»
n :


/
/
/
x
X
^



^-^
^^
^ r
/
/
X
X
,x
X
^—^— Orim
• •,-,«,,
™~ ~~ 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 :
o
•8 in
re 1U
O
n

4





S
«^





^

• Hea\
- Orirr



*• '
y Fuel (
ulsion '




DM
00

                                   0.5      1       1.5

                                        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
^00
LJ_
0 290
•5
tS 9RO
o :
Q.
£ 97O
o A»U
i- :
9RO
9KO


•
•



•

•



•

•



•

•



•

•



•

•


•





•






•


•


•

•
s
l\
M

•

•
tac
DIC

•
•

k



•


JW
•

•


po

•
•

nt
Ml

•
•



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

-------
        E
        Q.
        Q.
        O
        o
©
E
Q.
Q.
lf.\l
100
RO
60
40
90
o






A

.


•
k
A


<


L


>









^


•





»
100
               50
                                                               •  Heavy Fuel Oil

                                                               •  Orimulsion 100

                                                               A  Orinoco Bitumen
^v>UU
E :
S" 1500

0)
0"
0





0 0
•


u

5 1
^




0 1





5 2





0 2
A
1




5 3.
                               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
*>00
o :
E 400 "

E :
5" 9f)0
Q. :
100
0^









f



j

<





»
B









4







•

~s« Ann '-
E -i^n :
C~ 'inn '-
O «}UU :
•P 2*50
M 200
"O -icn :
fl) IOU
£100 :
o *>0 :
^ o:














••



^

A











fc
















A


„








•










• Heavy Fuel Oil

UMIIIUI&IUII IUU
A Orinoco Bitumen





            E
            Q.
            Q.
             W
            O
            (0
RO "

40

20 "
10 "
0









•



•

<

^
A



»












<

A


H

                        0.5
    1.5    2
Stack 02, %
2.5
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

-------
                     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

-------
(< 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

-------
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

-------
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

-------
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

-------
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

-------
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

-------
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.
                                             3-35

-------
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

-------
                                        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

-------
            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

-------
                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

-------
                                        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
                 T3
0
£
0
N
£
0
GO
                                        0
                                        £
                                        0
0
£
0
N
£
0
.Q
tfl
0
                                                                         0
                                                                                     0
                                                                          X
                                                                          6
                                                  LU
                 W          CO         i-         j»          X
                 b                                §,4
                 £
                 O

                 re
                 O
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
   o
   B

   15
   c
   o
   (A
   £
   m
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.
                   25





                 m 20
                 £ 15

                 oT

                 15
                 o

                 '
                 


                 LU
                             IVo. 6Fu«ION
rimulsion 100
                                                                          Pk
a
c
5
s
^
^
o
                                 a-
                                 «
                                 c
                                 •
   Ol



   e7
          o
          *i
          fi
          "
          <
                                               _
                                               >,
                                               N
                                                             o
                                                             O
                                                             •
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

-------
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

-------
Figure 5-17.  Scanning electron micrograph of untreated filter loaded with PM from Orimulsion 400 at 700 x
              magnification.
                                                  5-24

-------
                                       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

-------
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

-------
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

-------
      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

-------
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

-------
                                         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

-------
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

-------
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

-------
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

-------
                                      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

-------
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;


                                             7-6

-------
    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.
                                             7-7

-------
                                       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.

-------
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


                                             8-2

-------
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


                                             8-3

-------
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


                                              8-4

-------
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


                                             8-5

-------
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


                                             8-6

-------
(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

-------
                                        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^^
*///////<• /\
t^J^lx^H
^^m
t^^^H
Y/////1
•^m
nm
rjy/>M
tt
JM
^ZA
r^M
m
m
m
m
m
m
a
]
i
i




























•























































































>KK ^^
SM ^o

fffifl I--!
\y//A ' ' "-1

J$JS nj|
^^
^•zutr









































nmercial

i • i
jstnal

("".nmnanw


tv













































































                               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

-------
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

-------
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

-------

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

-------
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

-------
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

-------
                                       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

-------
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

-------
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

-------
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

-------
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

-------
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

-------
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

-------
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.
                                             10-17

-------
                                        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


                                            11-1

-------
   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.
                                         11-2

-------
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


                                             11-3

-------
    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.
                                             11-4

-------
                                       Chapter 12
                                       References

Allen, J.W., and Beal, P.R. (1996).  "The evaluation and application of Orimulsion by International
    Combustion Ltd.," in Proceedings of the 21st International Technical Conference on Coal
    Utilization and Fuel Systems, Clearwater, FL, March 18-21, 1996, pp. 723-732.
Allen, J.W., and Beal, P.R. (1997).  "The environmental impact of Orimulsion combustion in large
    utility boilers," in Proceedings of the 22nd International Technical Conference on Coal
    Utilization and Fuel Systems, Clearwater, FL, March 16-19, 1997, pp. 443-450.

American Society of Mechanical Engineers (1991)."Power Test Code PTC 4.1 - Steam Generating
    Units," ASME, New York, NY.
Ault, J., M. Harwell, and V. Myers (eds) (1995). Comparative Ecological  Risk Assessment. Volume
    2.  Technical Support Document for the  Comparison of the Ecological Risks to the Tampa Bay
    Ecosystem from Spills of Fuel Oil No. 6 and Orimulsion.  Center for  Marine and  Environmental
    Analyses, Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL.

Babcock & Wilcox (1972). Steam: Its Generation and Use. 38th edition, Babcock & Wilcox, New
    York, NY.
Bailer, A.J., and Oris, J.T. (1997). "Estimating inhibition concentrations  for different response scales
    using generalized linear models," Environmental Toxicology and Chemistry, 16,  pp. 1554-1559.

Barta, L.E., Szederkenyi, S., Horvath, G., Allen, J.W., Darar, J.S., and Wright, J.A. (1996).
    "Comparison of the combustion behavior  of Orimulsion and heavy fuel oil in 70 MW flames,"
    in Proceedings of the 21st International Technical Conference  on  Coal Utilization and Fuel
    Systems, Clearwater, FL, March 18-21, 1996, pp. 607-618.
Battelle (1999). "Predicting the behavior of Orimulsion spilled on water,"  USCG R&D Report No.
    CG-D-24-99, U.S. Coast Guard Research and Development Center, Groton, CT, July 1999.

Bertacchi, S., Del Romi, G., De Santis, R., Ligasacchi, S., Mainini, G., Monanni, T., Pasini, S.,
    Saponaro, A.,  and Sorrenti, R. (1997). "Orimulsion firing in low-NOx combustion systems," in
    Proceedings of the 1997 Joint Power Generation Conference, Volume  1,  pp. 623-632.
Biede,  O., Lund, J.S., Hansen, S.L., and Berg, M. (1997). "Measurement of irradiation of a 640 MW
    Orimulsion-fired utility furnace under part load  conditions," in Proceedings of the 22nd
    International Technical Conference on Coal Utilization and Fuel Systems,  Clearwater, FL, March
    16-19,  1997, pp. 451-460.

Bitor America (1996). Orimulsion containment and  recovery test carried  out in  Puerto La Cruz.
    Anzoatgui  State. Venezuela.  Bitor America report, Bitor America, Boca Raton, FL, October 1996.
Bitor America (1997). Physical and chemical characterization of Orimulsion-100 fuel, its constituents
    and byproducts of combustion. Bitor America, Boca Raton, FL, August 1997.

Bitor America (1999). Orimulsion spill response manual. Bitor America,  Boca Raton, FL,  February
    1999.
Bitor America (2000).  "Orimulsion®: Clean Power for the Future," Web site,
    http://www.orimulsionfuel.com/index.html, April 6, 2000.

Bitor Europe (1994). Orimulsion: A natural bitumen-in-water emulsion.  Design and  operations
    manual. Version 4.0. Bitor Europe, Brentford, Middlesex, England, August 1994.
Bitor Europe (1998).  "Orimulsion in Germany," Bitor Energy News, Issue 6, Spring 1998.

Blum, J., Halpin, M., Morgan, D., and Alcantara, J. (1998). "Conversion  of an 800 MW oil fired
    generating unit to burn Orimulsion," in Proceedings of the 23rd International Technical
    Conference on  Coal  Utilization and Fuel Systems, Clearwater, FL, March 9-13, 1998, pp. 641-
    651.
                                            12-1

-------
Bowman, C.T. (1992).  "Control of combustion-generated nitrogen oxide emissions: Technology
    driven by regulation," pp. 859-878, 24th Symposium (International) on Combustion. The
    Combustion Institute, Pittsburgh, PA.

Brooks, G.  (1989). "Estimating Air Toxics Emissions from Coal and Oil Combustion Sources,"
    EPA-450/2-89-001 (NTIS PB89-194229), U.S. Environmental Protection Agency, Office  of Air
    Quality Planning and Standards, Research Triangle Park, NC, April 1989.

Brown, H.M., and Goodman, R.H. (1989).  "The recovery of spilled heavy oil with fish netting," in
    Proceedings of the 1989 Oil Spill Conference, February 13-16, 1989, San Antonio, TX,
    Americal Petroleum Institute, Washington, B.C.,  pp.  123-126.
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. Volume II (Ault et al. 1995),
    Center for Marine and Environmental Analyses, Rosenstiel School of Marine and Atmospheric
    Science, University of Miami, Miami, FL.

CARB (1990). "CARB Method 501- Determination of size distribution of particulate matter
    emissions from stationary sources," in State of California Air Resources Board Stationary Source
    Test Methods: Volume 1 - Methods for Determining Compliance with District Nonvehicular
    (Stationary Source) Emission Standards, adopted March 23, 1988; amended September 12,
    1990.

Castle, R.W., Wehrenberg, F., Bartlett, J., and Nuckols, J. (1995).  "Heavy oil spills: out of sight, out of
    mind," in Proceedings  of the 1995 International Oil Spill Conference, February 27-March 2,
    1995, Long Beach, CA., Americal Petroleum Institute, Washington, B.C., pp. 565-571.

Caswell, H. (1989). Matrix population models. Sinauer Associates, Sunderland, MA.
Clean Air Act (1990).  Public Law 101-549, Clean Air Act Amendments of 1990, November 15,
    1990.

Costa, D.L., Lehmann, J.R, Winsett, D.W., Richards, J., and Dreher, K.L. (1998). "Pulmonary Toxicity
    of Residual Oil Fly Ash In The Rat: Inhalation Versus Intratracheal Instillation," Toxicological
    Sciences, The  Toxicologist, 42, No.  1-S, p. 405.
DB-Riley (1998). DB-Riley Web page, http://www.dbriley.com/orimul.htm#orimulsion, October 28,
    1998.

Deis, Donald R., et al.  (1997).  "Orimulsion®: research and testing and open water containment and
    recovery trials," in Proceedings  of the  1997 International Oil Spill Conference, April 7-10,
    1997, Fort Lauderdale, FL.  Americal Petroleum Institute, Washington, D.C., pp. 459-467.
De  Santis, R., Pasini, S., and Giovanni, D.V. (1996).  "Combustion trials of Orimulsion for low-NOx
    utility applications," presented at the 21st International Technical Conference on Coal Utilization
    and Fuel Systems, Clearwater, FL, March 18-21, 1996.

DeVito, M.S., and Smith, D.L. (1991).  "Controlled condensation method: New option  for SO3
    sampling,'Tower Magazine, pp. 41-43, February 1991.
Dreher, K., Costa, D., Hoffman,  A., Bonner, J., and  Osornio-Vargas, A. (1996a). "Pulmonary toxicity
    of urban air particulate matter (PM),"  Air & Waste Management Association Meeting on
    Measurement of Toxic and Related Air  Pollutants, Research Triangle Park, NC, May 1996.

Dreher, K.,  Jaskot, R., Richards, J.H., Lehmann, J.R, Winsett, D., Hoffman, A., and Costa, D. (1996b).
    "Acute  pulmonary toxicity of size-fractionated ambient air particulate matter," American
    Journal of Respiratory and Critical Care Medicine, 153, No. 4 p. A15.
Dreher, K.,  Jaskot, R, Lehmann,  J.R., Richards, J.H., McGee, J.K., Ohio, A.J., and Costa, D.L. (1997).
    "Soluble transition metals mediate residual oil fly ash induced lung injury," Journal of
    Toxicology and Environmental Health, 50, pp. 285-305.

Dryer, F.L. (1976).  "Water addition to practical combustion systems - Concepts and applications,"


                                            12-2

-------
    16th Symposium (International) on Combustion. The Combustion Institute, Pittsburgh, PA, pp.
    279-295.
Dryer, F.L., Rambach, G.D., and Glassman, I. (1976).  "Some preliminary observations on the
    combustion of heavy fuels and water-in-fuel emulsions," presented at the Central Section
    Meeting of the Combustion Institute, Columbus, OH, April 1976.

ENEL (1999). "Preliminary results concerning metal  emissions during Orimulsion firing," ENEL
    Technical Report 512FO44119, Fiume Santo, Italy, April 13, 1999.
EER/Intevep (undated). "Orimulsion Feasibility Study," Energy and Environmental Research
    Corporation/Intevep report, Caracas, Venezuela.

Entropy (1991).  "Stationary source sampling report: Florida Power and Light Sanford Plant,"
    Entropy Environmentalists Inc. report to Florida Power and Light, Entropy Environmentalists
    Inc. reference No.  8165A, Research Triangle Park,  NC, May 13, 1991.
EPA (1986a).  Test Method 0030 "Volatile Organic Sampling Train" in Test Methods for
    Evaluating Solid Waste. Volume II. SW-846 (NTIS PB88-239223). Environmental Protection
    Agency, Office of  Solid Waste and Emergency Response, Washington, B.C., September 1986.

EPA (1986b).  Test Method 0010 "Modified Method 5 Sampling Train" in Test Methods for
    Evaluating Solid Waste. Volume II. SW-846 (NTIS PB88-239223). Environmental Protection
    Agency,  Office of Solid Waste and Emergency Response, Washington, B.C., September  1986.
EPA (1994).  "EPA Test Method 5 - Betermination of Particulate Emissions from Stationary
    Sources," in 40 CFR Part 60 Appendix A, Government Institutes Inc, Rockville, MB,  July 1994.

EPA (1995).  "Compilation Of Air Pollutant Emission  Factors, Volume I: Stationary Point And Area
    Sources," Fifth Edition, AP-42, U.  S.  Environmental Protection Agency, Research Triangle Park,
    NC, January  1995.  Bituminous and sub-bituminous coal and fuel oil data updated in Supplment
    E, September 1998, anthracite data updated in Supplment B, October  1996, and natural gas data
    updated in Supplment B, July 1998.
EPA (1996).  "Air quality criteria for particulate matter," U.S. Environmental Protection Agency
    report EPA-600/P-95/001 (NTIS PB96-168224), National Center for Environmental Assessment,
    Research Triangle  Park, NC, April  1996.

EPA (1997). Test Method 1311 "Toxicity Characteristic Leaching Procedure" in Test Methods for
    Evaluating Solid Waste. Final Update III. SW-846  (NTIS PB97-156137). Environmental
    Protection Agency, Office of Solid Waste, Washington, B.C., February 1997.

EPA (1998). "Study of hazardous air pollutant emissions from electric utility  steam generating units
    ~ Final report, Volume 1," U.S. Environmental Protection Agency report EPA-453/R-98-049,
    Office of Air Quality Planning and Standards, Research Triangle Park, NC, 1998.

EPA (1999a). Orimulsion Technology Assessment Plan, U.S. Environmental Protection Agency,
    National Risk Management Research Laboratory, Research Triangle Park, NC, January 1999.
EPA (1999b).  "Physicochemical and Toxicological Properties of Fugitive Orimulsion Ash,"
    Research Protocol  IRP-NHEERL-RTP/ETB/PTB/Breher/99-03-00, National Health and
    Environmental Effects Research Laboratory, Research Triangle Park, NC, August 30,  1999.

Federal Register  (1996). "Response Plans for Marine Transportation-Related Facilities; Final Rule,"
    Federal Register, 61, p. 7889, February 29, 1996.
Finkelman, R.B.  (1994). "Modes of occurrence of potentially hazardous elements in coal: levels of
    confidence,"  Fuel  Processing Technology, 39,  pp. 21-34.

Fitz-Simons, T., Freas,  W., Guinnup, B., Hemby, J., Mintz, B., Sansevero, C., Schmidt, M., Thompson,
    R., Wayland, M., and  Bamberg, R. (1995).  "National Air Quality and Emissions Trends Report,
    1995," U.S. Environmental Protection Agency report, EPA 454/R-96-005,  Office of Air Quality
    Planning and Standards, Research Triangle  Park, NC, Becember 1995.
                                            12-3

-------
Folsom, B.A. (1995)."Three gas reburning field evaluations:  Final results and long term
    performance," presented at the 1995 EPA/EPRI Joint Symposium on Stationary Combustion
    NOX Control, Kansas City, MO, May 16-19, 1995.

Freedman, S.I., Bitting, K., French, N., and Lester, T. (1998).  "Report of the Peer Review Panel of
    the Orimulsion R&D Plan (Revised Draft 7/15/98)," report submitted to the National Risk
    Management Research Laboratory, Research Triangle Park, NC, September 11, 1998.

Garcia Tavel, N.  (1999). Private communcation, Bitor American letter to R.E. Hall, U.S.
    Environmental  Protection Agency, National Risk Management Research Laboratory, Research
    Triangle Park, NC, March 31, 1999.
Garcia Tavel, N.  (2000). Private communication, Bitor America letter to C.A. Miller, U.S.
    Environmental  Protection Agency, National Risk Management Research Laboratory, Research
    Triangle Park, NC, January 19, 2000.

Garg, S. (1990).  "EPA Method 0060  - Methodology for the determination  of metals emissions in
    exhaust gases from hazardous waste incineration and similar combustion processes," in Methods
    Manual for Compliance with the BIF Regulations: Burning Hazardous Waste in Boilers and
    Industrial Furnaces. EPA/530-SW-91-010 (NTIS PB91-120006), pp. 3-1 through 3-48, Office of
    Solid Waste, Washington, D.C., December 1990.
Gibb, W.H. (1999). "Asnaes PS - Dust characterisation tests firing Orimulsion-400, March 1999,"
    PowerGen report PT/99/RA650/M, PowerGen UK pic, Nottingham, UK, May  1999.

Guenette, C., and Sergy, G. (1999).  "Disposal options for recovered bitumen," Environment Canada
    report, Emergencies Science Division, Environment Canada, Ottawa, Ontario,  Canada (98 pp.),
    May  1999.
Hall, R.E. (1976).  "The effect of water/residual oil emulsions on air pollutant emissions and
    efficiency of commercial boilers," Journal of Engineering for Power, 98, pp. 425-434.

Hall, R.E. (1975). " The effect of water/distillate oil emulsions  on pollutants and efficiency of
    residential and  commercial heating systems," presented at the 68th Annual Meeting of the Air
    Polution Control Association, Boston, MA, June 15-20, 1975.
Hall, R.E., and Lee, C.W.  (1998).  Private communication, report on EPA visit to Kansai Electric
    Osaka Unit No. 4, November  12, 1998.

Hall, K. (1998).  Memo to F. Marruffo, Bitor SA from  K. Hall,  Bitor Europe, April 17,  1998.
Hampartsoumian, E., Hannud, B., and Williams, A. (1993).  "An investigation of the burning rate of
    Orimulsion chars," Journal of the Institute of Energy, 66, pp.  13-16.

Harwell, M., and Golder, I.C. (2000).   "Appendix H. Comparative ecological risk assessment of
    Orimulsion spills in Tampa Bay: Supplemental information,"  submitted to EPA, National Center
    for Environmental Assessment via private communication to R. Wentsel from Mark Harwell,
    February 2000.
Harwell, M., Ault, J., and Gentile, J. (1995).  Comparative Ecological Risk Assessment. Volume I.
    Comparison of the Ecological Risks to the Tampa Bay Ecosystem from  Spills of Fuel Oil No. 6
    and Orimulsion. Center for Marine and Environmental Analyses, Rosenstiel School of Marine
    and Atmospheric Science, University of Miami, Miami, FL.

Hersh, S., Piper, B.F., Mormile, D.J., Stegman, G., Alfonsin, E.G., and Rovesti, W.C. (1979).
    "Combustion demonstration of SCR II fuel oil in a utility boiler," presented at the ASME Winter
    Annual Meeting, 79-WA/Fu-7, New York, NY, December 2-7, 1979.

Hidalgo, R., Jimeniz, E., Rodriguez, D., Alcantara, J., Carizzo, R., Nava, N., England, G.C., and
    Kennedy, B.A.  (1989). "Orimulsion demonstration tests at New Brunswick, Canada: A new
    technological step towards bitumen commercialization," in Proceedings of the 14th International
    Technical Conference  on Coal Utilization and Fuel Systems, Clearwater, FL, April 24-27, 1989.

Inumaru, J., et al. (1993). "Study on multi-fuel gasification of coal and extra-heavy oil: Investigation


                                            12-4

-------
    of adaptability in an air-blown two stage entrained gasifier," Sekitan Kagaku Kaigi Happyo
    Ronbunshu, 30, 71-74.

Irons, R.M.A., and Jones, A.R. (1996). "The effectiveness of Orimulsion as a reburn fuel for
    reduction of NOX in a pilot-scale pulverized fuel flame," Journal of the Institute of Energy, 69,
    pp.  163-166.

Irvine, B. and Eagles, R. (1998).  Private communication to C.A. Miller, U.S. Environmental
    Protection Agency,  National Risk Management Research Laboratory, Research Triangle Park, NC,
    during EPA visit to NB Power Dalhousie Generating Station, December 4, 1998.
Ivanov,  V.M., and Nefedov, P.I. (1962).  Trudy Instituta Goryachikh Iskopayemykh, 19 (in Russian).
    Translation  "Experimental investigation of the combustion process of natural and emulsified
    liquid fuels," NASA TTF-258, January 1965.

Janati, K.D. (1997). "Program results for a comprehensive assessment of chemical emissions from
    New Brunswick Power's Dalhousie Station," Carnot, Inc. report, Tustin, CA, January 1997.

Jokuty, P. (1999). Personal communication with R. Wentsel, U.S.  Environmental Protection Agency,
    Office of Solid Waste and Emergency Response, Washington, D.C.

Kamiura, T., Funasaka, K., Tajima, Y., Kawaraya, T., and Kuroda, K. (1996)."Pretreatment by yeast
    for determination of nickel and vanadium  in bitumen-in-water emulsion by inductively coupled
    plasma  atomic emission spectrometry," Analytica Chemica Ada, 327, pp. 61-64.
Kan, S.W.,  Wilson, J.W., Dharman, T., and Aksoy, B.S. (1998). "A study of a solvent/binder
    combination for viscosity reduction of Orimulsion in fine  coal dewatering," in Proceedings of
    the 23rd International Technical Conference on Coal Utilization and Fuel Systems, Clearwater,
    FL,  March 9-13, 1998, 731-739.

Kaneko, S., Iwanaga, A., and Hishida, M. (1996).  "Experience of Orimulsion fired power plant in
    Japan," presented at Power-Gen International '96, Orlando, FL, December 4-6,  1996.
Kennedy, B.A., and Sainz, F.A. (1992). "Conversion of NB Power's Dalhousie  Generating Station to
    Orimulsion  fuel," American Society of Mechanical Engineers  paper 92-JPGC-FACT-12, pp. 1-9.

Keppler, J.G. (1998). "Coals, Lignite, Peat," Ch. 48, p. 1535, Mechanical Engineers' Handbook. M.
    Kutz, ed., Wiley, New York, NY.
Khan, S. (1996).  "Orimulsion - Viability as a repowering fuel," in Proceedings of the 21st
    International Technical Conference on Coal Utilization and Fuel Systems, Clearwater, FL, March
    18-21,  1996, pp. 619-629.

Kuchibotla, S., Kalajian, E.H., Shieh, C.-S., and Olen, K.R. (1998). "The stabilization of Orimulsion
    spray dryer waste for landfill disposal," Florida Institute of Technology report, Melbourne, FL.
Lentjes  Bischoff (1997). "Salem Harbor conversion - Engineering study," report by Lentjes
    Bischoff Ltd. for Bitor America, Lentjes Bischoff Ltd., Cambridge, Ontario,  Canada,  July 23,
    1997.

Linak. W.P., McSorley,  J.A., Hall, RE., Srivastava, R.K., Ryan, J.V., Mulholland, J.A., Nishioka, M.G.,
    Lewtas, J., and DeMarini, D.M. (1991). "Application of staged combustion and  reburning to the
    co-firing of nitrogen-containing wastes," Hazardous Waste & Hazardous Materials, 8:1, pp. 1-
    15.
Linak W.P., and Wendt, J.O.L. (1994).  "Trace metal transformation mechanisms during coal
    combustion," Fuel  Processing Technology, 39, pp. 173-198.

Linak, W.P., Srivastava, R.K., and Wendt, J.O.L., (1994).  "Metal aerosol formation in a laboratory
    swirl flame  incinerator," Combustion Science and Technology, 101,  pp. 7-27.

Linak, W.P., Miller, C.A., and Wendt, J.O.L. (1999).  "Fine particle emissions from residual fuel oil
    combustion: characterization and mechanisms of formation," presented at Clean Air 99, Lisbon,
    Portugal, July 1999.
                                            12-5

-------
Lorenzo, T. (1996). "Orimulsion containment and recovery tests, October 1996, Puerto La Cruz,
    Venezuela," Trip report, BED Report Series No. 96, Emergencies Engineering Division,
    Environment Canada, Ottawa, Ontario, Canada.
Maki, T., and Miura, K. (1997). "A simulation model for the pyrolysis of Orimulsion," Energy &
    Fuels, 11, pp. 819-824.

Marcano, N., Pourkashanian, M., and Williams, A. (1991). "The combustion of bitumen-in-water
    emulsions," Fuel, 70, pp. 917-923.
Markowski, G.R., Ensor, D.S., Hooper, R.G., and Carr, R.C. (1980).  "A submicron aerosol mode in
    flue gas from a pulverized coal utility boiler," Environmental Science and Technology, 14(11),
    pp.  1400-1402.

Marruffo, F., and Sarmiento, W. (1997).  "Orimulsion - an alternative source of energy," in
    Proceedings of the 22nd International Technical  Conference on Coal Utilization and Fuel
    Systems, Clearwater, FL, March 16-19, 1997, 13-24.

Meadows, M.L., Kuo,  B.P., Roberts, A., and Puski, S.M. (1996). "Control of NOX emissions by
    reburning," U.S. Environmental Protection Agency report EPA-625/R-96/001 (NTIS PB97-
    208201), Office of Research and Development, Cincinnati,  OH, February  1996.

Meisingset, L., M011er, W., and Pedersen, P.H. (1997). "Experience from conversion of a 640 MW
    coal- and oil-fired unit into Orimulsion," in Proceedings of the 22nd International Technical
    Conference on Coal  Utilization and Fuel Systems,  Clearwater, FL, March  16-19, 1997, pp. 461-
    472.

Miles, J. (1999).  Private communcation, letter to C.A. Miller, U.S. Environmental Protection Agency,
    National Risk Management Research Laboratory,  Research Triangle Park,  NC, October 5, 1999.

Miller, C.A. (1996). "Hazardous air pollutants from the combustion of an emulsified heavy fuel oil
    in a firetube boiler," U.S. Environmental Protection Agency, National Risk Management
    Research Laboratory, Research Triangle Park, NC, EPA Report EPA-600/R-96-019 (NTIS PB96-
    168281), February 1996.
Miller, C.A. (1998). "Environmental Technology Verification:  Verification testing of emissions from
    the combustion of A-55® Clean Fuels in a firetube boiler," U.S.  Environmental Protection
    Agency, National Risk Management Research Laboratory, Research Triangle Park, NC, EPA
    Report EPA-600/R-98-035 (NTIS PB98-142169), April 1998.

Miller, C.A., and Shores, R.C. (1999). Report of visit to SK Power Asnaes Power Station, September
    20,  1999 to September 24, 1999, U.S. Environmental Protection Agency, National Risk
    Management Research Laboratory, Research Triangle Park, NC, September 28, 1999.
Miller, C.A., and Srivastava, R.K.  (2000). "The combustion of Orimulsion and its generation of air
    pollutants," Progress in Energy and Combustion  Science,  Vol. 26, pp. 131-160, 2000.

Miller, C.A., Linak, W.P., King, C., and Wendt, J.O.L. (1998a). "Fine particle emissions from heavy
    fuel oil combustion in a firetube  package boiler,"  Combustion Science and Technology,  134, p.
    477.
Miller, C.A., Touati, A.D., Becker, J., and Wendt, J.O.L. (1998b). "NOX abatement by fuel-lean
    reburning: laboratory combustor and  pilot-scale package boiler results," 27th Symposium
    (International)  on  Combustion. The Combustion Institute,  Pittsburgh, pp.  3189-3195.

Mulholland, B. (1996)."A two unit repowering project: Dalhousie Orimulsion conversion  & flue gas
    desulfurization project," Proceedings  of the 1996 American Power Conference, Volume 2, pp.
    864-874.
Muzio, L.J., and Quartucy, G.C. (1997).  "Implementing NOX control: Research to application,"
    Progress in Energy and Combustion Science, 23, pp. 233-266.

National Research Council (1999). Spills of Nonfloating Oils:  Risks and Response, Committee on
    Marine Transport of Heavy Oils, National Academy Press, Washington, D.C., 1999.


                                            12-6

-------
New Brunswick Power (1989). "Dalhousie Orimulsion demonstration technical report," NB Power
    report, August 1, 1989.
Newman, M.C. (1995). Quantitative Methods in Aquatic Ecotoxicology. Lewis, Boca Raton, FL.

Olen, K. (1998a).  "Environmental impacts of firing Orimulsion in utility boilers," International
    Directory of Power Generation, Turret RAI pic., Fourth Edition, pp. 38-42.
Olen, K. (1998b).  "Orimulsion," in Opportunity Fuels Guidebook, EPRI Technical Report TR-
    111487, Electric Power Research Institute, Palo Alto, CA.

Olen, K., and Alcantara, J. (1993).  "The development of Orimulsion into a viable fuel for the utility
    market," presented at Power-Gen Americas '93,  Dallas, TX, November 17-19,  1993.
Olen, K.R, Gushing, K.M., Fereday F.D., Grubb,W.T., and Chang, R.L. (1991). "Fabric filtration of
    Orimulsion fly ash," presented at the Ninth Symposium on the Transfer and Utilization of
    Particulate Control Technology, Williamsburg, VA, October 15-18, 1991.

Ott, W.R. (1995). Environmental Statistics and Data Analysis. Lewis, Ann Arbor, MI.
Owens, E.H., and Sergy, G.A. (1999).  "Orimulsion spill field guide for the protection and cleanup
    of marine shorelines," Environment Canada report, Emergency Sciences Division, Environment
    Canada, Edmonton, Alberta, Canada (194 pp.), March  1999.

Parsons (1997). "Carbon dioxide capture in oxygen-blown integrated gasification  combined cycle
    power and chemical plants fueled with Orimulsion," Parsons final report to the International
    Energy Agency Greenhouse Gas R&D Programme, May 1997.
Piper, B., and Nazimowitz, W. (1985).  "High viscosity oil evaluation, 59th street station - unit 110,"
    Vol.1, KVB report to Consolidated Edison  Co.,  21640-1 (March 1985).

Platteau, O., and Carrillo, M. (1995)."Determination of metallic elements in crude oil-water
    emulsions by flame AAS," Fuel, 75, pp. 761-767.
PowerGen (1998a).  PowerGen Web page, http://www.powergen.co.uk/company/
    index.html?releases/970522a.html, Oct 28,  1998.

PowerGen (1998b). PowerGen Web page, http://www.pgen.com/community/index.html?env_data.html,
    Oct 28, 1998.
Power Generation (1998). "Guatemala tries out Orimulsion," Power Gen. Tech. and Markets, 19(9)
    1-6, February 27,  1998

Quig, R.H. (1999). "Orimulsion ash processing alternatives," presented at the 24th International
    Technical Conference on Coal Utilization and Fuel Systems, Clearwater, FL, March 8-11, 1999.
Quig, R.H., and Woodworth, L. (1997). "Clean power generation resulting from Orimulsion
    utilization," in Proceedings of the 22nd International Technical Conference on Coal Utilization
    and Fuel Systems,  Clearwater, FL, March 16-19, 1997.

Quintana, M.E., and Davis, L.A. (1990). "Pilot plant evaluation of Orimulsion as a feedstock for the
    Texaco gasification process," Texaco Development Corporation, White Plains, NY.
Reed, R.J. (1998a). "Liquid fossil fuels from petroleum,"  Ch. 47, p. 1517, Mechanical  Engineers'
    Handbook. M. Kutz, ed., Wiley, New York, NY.

Reed, R.J. (1998b). "Gaseous fuels," Ch. 46, p. 1505, Mechanical Engineers' Handbook.  M. Kutz,
    ed., Wiley, New York, NY.
Rodier, D., and Norton, S. (1992).  Framework  for Ecological Risk Assessment. EPA/630/R-92/001
    (NTIS PB93-102192), Risk Assessment Forum. Washington, D.C.

Rostorfer, C.R., Krueger, S., and Payne, R. (1998). "Demonstration of Orimulsion  reburning on a
    coal-fired utility boiler," in Proceedings of the 23rd International Technical Conference on  Coal
    Utilization and Fuel Systems, Clearwater, FL, March 9-13, 1998.
                                            12-7

-------
Rostorfer, C.R., Krueger, S., Middleton, C., Morrison, O.K., Sommer, T.M., and Latham, C.E. (1997).
    "Demonstration of Orimulsion reburning on a coal-fired utility boiler," presented at Power-Gen
    International, Dallas, TX, December 9-11, 1997.
Schimmoller, B.K. (1998).  "Orimulsion rivals gas as reburn fuel," Power Engineering, February
    1998, pp. 32-36.

Scotto, M.A., Peterson, T.W., and Wendt, J.O.L. (1992).  "Hazardous waste incineration: the in-situ
    capture of lead by sorbents in a laboratory down-flow combustor," 24th  Symposium
    (International) on Combustion, pp. 1109-1118, The Combustion Institute, Pittsburgh, PA (1992).
Sharma, R.K., and Olson, E.S. (1995). Division of Fuel Chemistry,  1995, 40(3), 604.

SK Energy (undated).  "Environmental tests during firing of Orimulsion, block 5," SK Energy,
    Kalundborg, Denmark.
Steele, W.J., Williamson, A.D., and McCain, J.D. (1988). "Construction and operation of a 10 cfrn
    sampling system with a 10:1 dilution ratio for measuring condensable emissions," EPA/600-8-
    88-069 (NTIS PB88-198551), Air and Energy Engineering Research Laboratory, Research
    Triangle Park, NC, April 1988.

Swaine, D.J. (1994).  "Trace elements in coal and their dispersal during combustion," Fuel
    Processing  Technology, 39, pp. 121-137.
Tombs, R. (1996).  "PowerGen  PLC:  An experienced  user of Orimulsion," in Proceedings of the 21st
    International Technical Conference on Coal Utilization and Fuel Systems, Clearwater, FL, March
    18-21, 1996, pp.  824-839.

TUV Siidwest (1993). "Marbach III Power Plant trial operation with Orimulsion: Short report on the
    analysis  and evaluation of emission measurements," TUV Siidwest, Department of power
    engineering and environmental protection, TUV Siidwest report, Order No. 47571, Stuttgart
    Office, Stuttgart, Germany,  September 1, 1993.
U.S. Department of Energy (1997).  "Coal Industry  Annual 1997," DOE/EIA-0584(97), Energy
    Information Administration, U.S. Department of Energy, Washington, D.C.,  1997.

U.S. Department of Energy (1998a). "Country analysis briefs: Venezuela,"  Energy Information
    Administration, U.S. Department of Energy, Washington, D.C., December 1998.
U.S. Department of Energy (1998b). "Annual Energy Review 1997,"  DOE/EIA-0384(97), Energy
    Information Administration, U.S. Department of Energy, Washington, D.C., July 1998.

U.S. Department of Energy (1998c).  "Electric Power Annual 1997: Volume 1," DOE/EIA-
    0348(97)71, Energy Information Administration, U.S. Department of Energy, Washington, D.C.,
    July  1997.

U.S. Department of Energy (1998d).  "Fuel Oil and Kerosene Sales 1997,"  DOE/EIA-0535(97),
    Energy Information Administration,  U.S. Department of Energy, Washington, D.C.,  August 1998.

U.S. Department of Energy (1998e).  "Natural Gas Annual 1997," DOE/EIA-0131(97), Energy
    Information Administration, U.S. Department of Energy, Washington, D.C., October 1998.

U.S. House of Representatives (1997). Conference Report on H.R.  2158, Departments of Veterans
    Affairs and  Housing and Urban Development, and Independent Agencies Appropriations Act,
    1998, October 6,  1997.

Walsh, P.M., Wei, G., and Xie, J. (1991). "Metal oxide and coke particulates formed during
    combustion of residual fuel oil," presented at the  10th Annual  Meeting of the American
    Association for Aerosol Research, paper 7P.36, Traverse City, MI,  October 1991.
Wen, W.W., and Killmeyer, R.P. (1996). "Centrifugal dewatering and reconstitution of fine coal.  The
    Granuflow™ process," Coal Preparation, 17, 89-102.

Whaley, H.,  Wong, J.K.L., and  Banks, G.N. (1991). "Combustion and heat transfer characteristics of
    pipelineable water-bitumen emulsions," presented at the  1991  International Joint Power


                                           12-8

-------
    Generation Conference, San Diego, CA.
Williams, A., and Pourkashanian, M. (1987). "The combustion of bitumen-in-water mixtures,"
    Communication to the Journal of the Institute of Energy, 209, pp. 209-211.

Wong, J.K., Banks, G.N., and Whaley, H. (1989) "Combustion evaluation of BP Transoil emulsion in
    CCRL pilot-scale flame tunnel furnace," Energy Research Laboratories report ERL-IV(CF),
    Energy, Mines and Resources Canada, CANMET, Ottawa, Canada, March 1989.
Zitron, Z., Harrison, C., and Akers, D.  (1998). "GranuFlow™ - A technology for reducing moisture
    and enhancing coal handleability,"  in Proceedings of the 23rd International Technical
    Conference on Coal Utilization and Fuel Systems, Clearwater, FL, March 9-13, 1998, 741-743.
                                            12-9

-------
                            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

-------
        o

19DD
E-
R~ mnn
Q_ I UUU
cf
0
*= RDD
CO OUU
-HJ
o ROD

O
o
WAr\r\
tuu
O -
9nn
£\j\j
-
c
£
<
c
u
c
T

*l
1 1 1
>^







JV
> 2
f. <
3 5
0 T
NJ ^
— T
1
'i'1 '
'





:
/

>
2
t







i
1


1
H
«
£
<
c
c
c
L.
T







f *.* •


--
1 	 1
> :
t c
o c
M C
0 U
0 t
C

i i
r «




*•••"• '.
'

1
> 2
L C
3 5
0 T
c
Nl C


• ., .




'"•


V 	
> :
L C
0 C
r c
c
0 "
M C


, - i
•







^A-
> :
L C.
O '
N C
0 L
3" C
Nl •<


V1







s.
L
5
0



1 1r

1






c.
c
T
T
c
T











> :
L C
O "
^- c
- C
Nl C
— T











> :
L C
t C
Nl C
0 u
O u
— T



• • , lr l\







> :
L C
O "
D ^
0 t
0 t
C



' «. »jt







> :
L C.
t C
3" C
- C
C
Nl C



" \
1
%




^
> ^
L C
O C
Nl C
0 U
Nl T
Nl C
rn

	 NO
_ _ S09







>
L
0
0
t
Sl
Figure B-1. CEM data forO2 (top), CO, NO, and SO2 (bottom) taken May 18, 1999 during EPA's pilot-scale testing
            of Orimulsion 400.
                                               B-2

-------
          CO
          o
                   CD
                   CNl

                   CD
                            CNl

                            CO
co
q
CD
o
<
CO

CD
CNl

CO
CO
                                                                 CO
Q_

CO


CD
O
o_

CO
CNl

CO
CNl
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

-------
    20-
    18-

    14-
2?  12-
OCVMO-
     8-
     6-

     2-
     0-
  1200-
  1000-
Orim  ils
                              t
                                           on
40
 c
 o
"ro
"c
 CD
 o
o
O
      0-
   -200-
          r/n
                                                                                      CO
                                                                                -  -  so
        <<<
-------
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

-------

                                      Oi
imulsion 1
                                        00
               *jwl,'ui
     0
                         >""
                             \A	M
                                                                 CO
                                                            — so
      <
      o
Q_
O
                  CNl
                  03
                  CNl
                       CNl
                       od
                            m
                            CO
                                  LO
          CNl
          CNl
          ob
                m
                CNl
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

-------
    1.0-


    0.5-


    0.0-

   1200-




   1000-
                                   £ 725/99

                                   t)rimuls
ion 10
E
Q.


^  800-

o

"03

•£  600-
CD
O
c

O  400-
 CD

O
    200-
      0-
          \ *  '
        CO
                       / \
                                                                                  CO


                                                                                  NO
                              - -  S0
                 Q_

                 CO
                           CN

                           CO
                           CN
                                    CO
                                    CD
        CN

        CO
                 o
                 CO
Figure B-6.  CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 25, 1999 during EPA's pilot-scale testing

           of Orimulsion 100.
                                        B-7

-------
          CO
<
CM
CD
O
                               CO
                               CN1
                               CO
                               CM
                                         CO
<
CO

CD
CM
CN1
CO
                                                              CM
8
CD
CO
                     CD
Figure B-7.  CEM data for O2 (top), CO, NO, and SO2 (bottom) taken May 26, 1999 during EPA's pilot-scale testing
             of Orimulsion 100.

-------
<
CO
CD
CN1
o
<
CM
m
0
<
CM
0
•5—
<
CO
CD
•5—
<
\J
\J
m
CO
•5—
<
CO
CM
CN1
in
•5—
Q_
O
CD
0
CN1
Q_
CO
CN1
CN1
Q_
CO
CM
CM
CN1
Q_
O
CD
CN1
Q_
CO
m
•5—
Q_
m
CM
CO
•5—
Q_
m
CD
•5—
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

-------
        0
          q
          cb
Q_
CO

CD
CM

-------
 Q.
 Q.
   1000-
 c
 CD
 O

 o  600-
 CO
       0-
                          fV-r-


                                                                                                CO
                                                                  SO,
          8
                    CD
                    CM
CM
CN1

r^
CO
8
CO
CN1
r^
csi
                                                                        CO
Q_

CO


CD
q

CO
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

-------
                   6/7/1)9

                   Fuel  Oil
        0
 c
 o

I
"c
 CD
 O

 O
O
 CO
 CO
O

19DD
mnn
I UUU
-
finn
/inn
4UU
-


,
V.,






^ ..


i y •»
' k ' i'f * \








•w,

' V







•l'
, , 1
11 >l 1 "
1

,


/A


;.-.
1 * W4


*"•. •***

At
.JH



i
"t\








f
/•.\,; J




-A




L * *f

^.







'l'1'
1
	







VS.'/
..



• - - 1^-




L
l,




rn

	 NO
- - S09
z






         8

         CD
         CN1

         
-------
•E  600-
-


CD
O


O

O
 CD

0  200-



    100-



       0-
                                                                           •„..—.-
          CO
               <

               CM
Q_

CO
                  Q_

                  CO
                       CO
                       m
                       o_

                       s
                       in
                                   co
                                   m
                       CO
                       CO
                       s    s
          m
          CO
CM
m
CD
o
      m
      CM
CM



-------
                                   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
ug
ug
ug
ug
ug
    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

-------
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

-------
                                    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
                                           F-l

-------
    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

-------
                                     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.
                                             G-l

-------
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
                                            G-2

-------
   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.
                                             G-3

-------
                                     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.
                                            H-l

-------
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

-------
       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.
                                             H-3

-------