&EPA
             United States
             Environmental Protection
             Agency
                          EPA-600/7-86-013a
                          April 1986
Research and
Development
            ENVIRONMENTAL ASSESSMENT OF AN
            ENHANCED OIL RECOVERY STEAM
            GENERATOR EQUIPPED WITH AN EPA
            HEAVY OIL LOW-NCx BURNER
            Volume I.  Technical Results
             Prepared for
            Office of Air Quality Planning and Standards
             Prepared by
            Air and Energy Engineering Research
            Laboratory
            Research Triangle Park NC 27711

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                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application  of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related  fields.
The nine series are:

    1.  Environmental Health Effects Research

    2.  Environmental Protection Technology

    3.  Ecological Research

    4.  Environmental Monitoring

    5.  Socioeconomic Environmental Studies

    6.  Scientific and Technical Assessment Reports (STAR)

    7.  Interagency Energy-Environment Research and Development

    8.  "Special" Reports

    9.  Miscellaneous Reports

This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort  funded  under the  17-agency  Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the  public
health and welfare from adverse effects of pollutants associated with energy sys-
tems.  The goal of the Program is to assure the  rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include  analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments  of,  and development of, control technologies  for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
                        EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for  publication. Approval does  not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation  for use.

This document is available to the public through the National Technical Informa-
tion Service, Springfield. Virginia 22161.

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                                      EPA-600/7-86-013a
                                      April 1986
        ENVIRONMENTAL ASSESSMENT OF AN
     ENHANCED OIL RECOVERY STEAM GENERATOR
 EQUIPPED WITH AN EPA HEAVY OIL LOW-NOX BURNER
                   Volume I
               Technical Results
                      by

C. Castaldini, L. R. Waterland, and R. DeRosier
              Acurex Corporation
        Energy & Environmental Division
               485 Clyde Avenue
                 P.O. Box 7044
        Mountain View, California 94039
            EPA Contract 68-02-3188
     EPA Project Officer:  0. A. McSorley
Air and Energy Engineering Research Laboratory
 Research Triangle Park, North Carolina 27711
                      for
     U.S. ENVIRONMENTAL PROTECTION AGENCY
      Office of Research and Development
             Washington, DC 20460

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                        ABSTRACT

    Comprehensive emission measurements and 30-day flue gas moni-
toring were performed on a 16-MW (55 million Btu/hr) enhanced oil re-
covery steam generator equipped with the EPA low-NOx burner firing
high-nitrogen crude. The 1-day comprehensive measurements included
quantification of semivolatile organics and 73 trace elements; volatile
organic sampling train (VOST) quantitation of volatile organic priority
pollutants; EPA Method 5/8 for particulate and SOX; controlled conden-
sation for SOX; Andersen impactors for particle  size distribution; grab
samples for NgO; and continuous flue gas monitoring. NOX emissions
during the comprehensive tests averaged 70  ppm at 3 percent O£, well
below the target level  of 85 ppm.  CO emissions were below 30 ppm, and
SO2 averaged about 550  ppm. Solid particulates were emitted at about
27 ng/J (96 mg/dscm); condensible particulates were about half that
level. Volatile organics (benzene, toluene, and ethylbenzene) were mea-
sured in the 0.4 to 20 ppb range.  Semivolatile organics (naphthalene
and phenol) were detected in the 0.3 ppb range. Subsequent continuous
monitoring of flue gas criteria emissions showed NOX below 80 ppm at
3 percent O2 with an average of 70 ppm. CO emissions were generally
less than 30 ppm.
                              11

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                              CONTENTS
     Figures	    iv
     Tables  	    v
     Acknowledgment  	    vii

1    Introduction  	    1-1
2    Source Description and Operation  	    2-1
3    Emission Results  	    3-1

     3.1  Sampling Protocol  	    3-1
     3.2  Criteria Pollutant and Other Gas Phase Species
          Emissions	    3-3
     3.3  Trace Element Analysis Results 	    3-12
     3.4  Organic Emission Results 	    3-16

          3.4.1  Volatile Organic Emissions  	    3-17
          3.4.2  TCO, GRAV, GC/MS, and IRS Analyses of Sample
                 Total Extracts	    3-21

     3.5  Extended Continuous Emissions Monitoring 	    3-21

4    Test Quality Assurance and Quality Control  	    4-1

     4.1  NOX Monitor Certification Test Results	    4-1
     4.2  Duplicate Analyses 	    4-5

          4.2.1  Trace Element Analyses  	    4-5
          4.2.2  Organic Analyses  	    4-5
          4.2.3  Particulate, S02, and $03 Emission
                 Measurements  	    4-7

     4.3  Analytical Recovery of Blind Spikes  	    4-9
     4.4  Reference Method Audit Samples 	    4-9
5    Summary	i	    5-1
     Appendix A  ..... 	    A-l
     Appendix B	    B-l

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                                  FIGURES

Number                                                               Page
 2-1    EPA low-NOx burner	    2-2
 2-2    Low-N0x burner retrofit arrangement 	    2-5
 3-1    Test activity schedule  	    3-4
 3-2    Particle size distribution  ..... 	    3-11
 3-3    Flue gas Q£ and C02 for the extended test period  ....    3-25
 3-4    Flue gas NOX and CO for the extended test period  ....    3-26
 3-5    Flue gas S02 for the extended test period	    3-27
 A-l    Schematic for continuous extractive sampling system .  .  .    A-2
 A-2    Source assessment sampling train schematic	    A-5
 A-3    Flue gas analysis protocol for SASS samples    	    A-6
 A-4    Flue gas sample analysis protocol	    A-7
 A-5    Organic analysis methodology  	    A-9
 A-6    Schematic of volatile organic sampling train (YOST) .  .  .    A-10
 A-7    Particulate and SOX sampling train (EPA Method 5 and 8)  .    A-12
 A-8    Controlled condensation system	    A-14
 A-9    M20 sampling system	    A-15
                                      iv

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TABLES
Number
1-1
2-1
2-2

3-1
3-2

3-3
3-4
3-5
3-6
3-7
3-8
3-9
3-10

3-11
3-12

3-13
4-1
4-2

Completed Tests during the Current Program 	
EPA Low-N0x Burner Design Characteristics 	
Steamer/ Burner Operation 	
V
Sampling Analysis Test Matrix3 	
Criteria Pollutant and Other Gas Species Emissions --
Comprehensive Tests 	
Flue Gas Parti culate Measurement Results 	
Sulfur Species Emissions By EPA Method 5/8a 	
Sulfur Species Emissions by Controlled Condensation3 . .
Particle Size Distribution Results3 	
Summary of Parti culate Loading Measurements 	
Trace Element Flowrates 	
Volatile Organic Compounds Sought in GC/MS Analysis . . .
Compounds Sought in the EPA Method 625 GC/MS Analysis
and their Detection Limits3 	
Volatile Organic Species Emissions 	
Total Organic and Sertii volatile Organic Priority
Pollutant Emissions 	
IR Spectra Summary 	
Method 7 Certification Results: January 24, 1984 ....
Method 7 Certification Results: February 8, 1984 ....
Page
1-4
2-3
2-7

3-2

3-5
3-7
3-9
3-10
3-10
3-13
3-14
3-18

3-19
3-20

3-22
3-23
4-2
4-3

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TABLES (concluded)
Number
4-3
4-4
4-5
4-6
4-7
4-8
4-9
A-l

Method 7 Certification Results: February 24, 1984. . . .
Duplicate SSMS Analyses of Test Fuela, ppm 	
Results of Duplicate GC/MS Analyses of the SASS Organic
Sorbent Module Extract3 	
Results of Duplicate Particulate, $03, and 503
Measurements . 	
Duplicate Method 5 Condensible Particulate Analysis
Results 	
Spike XAD-2 Resin Analysis Results 	
EMSL Audit Sample Analysis Results 	
Continuous Monitoring Equipment in the Mobile Laboratory
Page
4-4
4-6
4-8
4-8
4-10
4-10
4-11
A-3
        vi

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                               ACKNOWLEDGEMENTS

     This test was performed 1n cooperation with Chevron U.S.A.,  Inc. and  the
Energy and Environmental Research Corporation  (EERC).  Appreciation  is
greatly extended to Rich Podgers of Chevron U.S.A.,  and Glenn  England and
Yul Kwan of EERC.  Special recognition  and thanks  are  extended to the Acurex
field test crew of Curtis Beeman, Regan Best,  Bruce  DaRos,  Pete Kaufmann,
Gary Milburn, and Martha Murray.
                                  vu.

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                                   SECTION  1
                                 INTRODUCTION

     This report describes  and  presents  results  for  a  set  of  environmental
assessment tests performed  for  the Environmental  Protection Agency's
Air and Energy  Engineering  Research Laboratory/Research  Triangle  Park
(EPA-AEERL/RTP) under the Combustion  Modification Environmental Assessment
(CMEA) program, EPA  Contract  No.  68-02-3188.   The CMEA started  in  1976 with  a
3-year study, the  NOX Control Technology Environmental Assessment  (NOX EA,
EPA Contract No. 68-02-2160), having  the following objectives:
     o   Identify  potential multimedia environmental effects  of stationary
         combustion  sources and combustion modification  technology
     e   Develop and document control application guidelines  to minimize
         these  effects
     o   Identify  stationary  source and  combustion modification R&D
         priorities
     «   Disseminate program  results  to  intended  users
     During the first year  of the  NOX EA, data for the environmental
                              I
assessment were compiled and methodologies were developed.  Furthermore,
priorities for the schedule and level of effort to be devoted to evaluating
the various source/fuel/control combinations were identified.   This effort
revealed major data gaps, particularly for noncriteria pollutants  (organic
emissions and trace elements) for  virtually all combinations of stationary
                                      1-1

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combustion sources and combustion modification  techniques.  Consequently,  a
series of seven environmental field test programs was undertaken  to  fill
these data gaps.  The results of these  tests are documented in  seven
individual reports (References 1-1 through 1-7} and in the NOX  EA final
report summarizing the entire 3-year effort  (Reference 1-8).
     The current CMEA program has as major objectives the continuation of
multimedia environmental field tests initiated  in the original  NOX EA
program.
     Table 1-1 lists all the tests performed in the CMEA program,  outlining
the source tested, fuel used, combustion modifications implemented and the
level of sampling and analysis performed in each case.  Results of these test
programs are discussed in spearate reports. These new tests, using
standardized Level 1 sampling and analytical procedures (Reference 1-9) are
aimed at filling the remaining data gaps and addressing the following
priority needs:
     •   Advanced NOX controls
     •   Alternate fuels
     •   Secondary sources
     •   EPA program data needs
         —  Residential oil combustion
         —  Wood firing in residential, commercial, and industrial  sources
         —  High interest emissions determination  (e.g., listed  and
             candidate hazardous air pollutant  species)
     •   Nonsteady-state operation
Within these priority needs, enhanced oil recovery  (EOR) steamers were
                                      1-2

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accorded high ranking because of their emerging  importance as an emission
source in California.
     The petroleum reserves which can be recovered  through primary production
methods have been essentially exhausted in  the oil  fields in Kern County,
California.  These fields still contain significant reserves, although  the
remaining crude is too heavy  (viscous) to be  produced  by normal means.  This
crude is currently being produced using what  has been  termed enhanced oil
recovery (EOR).  In  this process, near saturated (80 to  90 percent quality)
crude is currently being produced using what  has been  termed enhanced oil
recovery (EOR).  In  this process, near saturated (80 to  90 percent quality)
steam is injected into a field.  This steam heats the  oil, thereby decreasing
its viscosity and allowing  it to be  pumped.
     The steam for injection  is raised by crude-oil-fired steam generators
(often termed steamers) which have  uncontrolled  NOX emissions of 300 ppm and
greater.  Since Kern County is only  in borderline attainment of the N0£
ambient air quality  standard, EOR steamers  have  received close regulatory
attention with respect to reducing  NOX emissions.
     One approach to reducing NOX emissions from these steamers incorporates
a low-NOx emission burner design.  One such burner was developed by the
Energy and Environmental Research Corporation (EERC) under EPA sponsorship.
The EERC development program,'which  spanned a period of  6 years, called for
the field demonstration of  the low-NOx burner having the capability of
meeting the program goal of 85 ppm NOX, 45  ppm CO (at  3  percent 02), and
acceptable smoke and particulate emissions  while burning high nitrogen  fuel
oil.
                                      1-3

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    The EOR steamer equipped with  the  EPA  low-NOx  burner  was  tested in  the
current CMEA program.  These tests, described  in this  report,  were  conducted
to augment the emissions measurements  by EERC  required under  their  field
                                                 ^
demonstration program.
     In addition to the tests described in  this report, another  EOR steamer,
this one equipped with a Mitsubishi Heavy  Industries  (MHI)  low-NOx  burner
marketed by CE-Natco (a steamer manufacturer), was also tested.   Results from
these tests are documented in Reference 1-10.
                                      1-4

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                                    TABLE  1-1.   COMPLETED  TESTS  DURING  THE  CURRENT  PROGRAM
             Source
       Description
      Test points
     unit operation
       Sampling  protocol
                                                                                                                     Test collaborator
  Spark-ignited, natural -
j  gas-fueled reciprocating
j  internal combustion
I  engine
                                 Large-bore. 6-cy Under.
                                 opposed piston, 186 kW
                                 (250  Bhp)/cy1, 900 rpm.
                                 Model 38TDS8-1/8
                               Baseline  (pre-NSPS)
                               Increased  air-fuel
                               ratio  aimed  at
                               meeting proposed
                               NSPS of 700  ppm
                               corrected  to 15
                               percent 02 and
                               standard atmospheric
                               conditions
                            Engine exhaust:
                              ~ SASS
                              ~ Method 5
                              — Gas sample
                              — Continuous   .   X
                              ' •  C02, 02, CH4, TUHC
                            Fuel
                            Lube oil
                     g HC)
   —  Continuous NO. NOX, CO,
                                 Fairbanks Morse
                                 Division of Colt
                                 Industries
Ul
    i  Compression-Ignition,
    1  diesel-fueled
      reciprocating  Internal
      combustion engine
Large-bore,  6-cylinder
opposed piston,  261-kW
(350 Bhp)/cyl, 900-rpm.
Model 38TDD8-1/8
   Baseline (pre-NSPS)
   Fuel injection retard
   aimed at meeting pro-
   posed NSPS of 600 ppm
   corrected to 15 per-
   cent 0? and standard
   atmospheric conditions
Engine exhaust:
  ~ SASS
  ~ Method 8
  — Method 5
  — Gas sample
                                                                                                               HC)
                                                                            s
                                                         — Continuous NO, NOX, CO,
                                                            C02, 02, CH4, TUHC
                                                       Fuel
                                                       Lube oil
                                                                                                                    Fairbanks Morse
                                                                                                                    Division of Colt
                                                                                                                    Industries
      Low-N0x residential
      condensing heating
      system furnished  by
      Karl sons Blueburner
      Systems Ltd.  of Canada
Residential  hot water
heater equipped with
M.A.N. low-NOx burner,
0.55 ml/s (0.5 gal/hr)
firing capacity, con-
densing flue gas
Low-N0x burner design
by M.A.N.
Furnace exhaust:
  ~ SASS
  ~ Method 8
  — Method 5
  — Gas sample (Ci-Cg HC)
  -- Continuous NO,  NOX,  CO,
     C02, 02, CH4,  TUHC
Fuel
Waste water
                                                            New test
      Rocketdyne/EPA
      low-NOx residential
      forced warm air  furnace
Residential  warm air
furnace with modified
high-pressure burner and
firebox, 0.83 ml/s
(0.75 gal/hr) firing
capacity
Low-N0x burner design
and integrated furnace
system
Furnace exhaust:
  — SASS
  — Method 8
  — Controlled condensation
  ~ Method 5
  — Gas sample (CI-CK HC)
  ~ Continuous NO,  NOX,  CO,
     C02, 02. CH4, TUHC
Fuel
                                                                                       New test

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                                                        TABLE 1-1.   (continued)
            Source
       Description
      Test points
     unit operation
      Sampling protocol
                                Test collaborator
     Pulverized-eoal-fired
     utility boiler.
     Conesville station
400-MW tangential 1y
fired; new NSPS
design aimed at
meeting 301 ng/J
N0y limit
ESP inlet and outlet,
one test
ESP Inlet and outlet:
  -- SASS
  ~ Method 5
  ~ Controlled condensation
  — Gas sample (C^-Cg HC)
  — Continuous NO, NOX, CO,
     C02. 02
Coal
Bottom ash
ESP ash
                                Exxon Research and
                                Engineering (ER&E)
                                conducting cor-
                                rosion tests
     Nova Scotia Technical
     College industrial
     boiler
•jl
en
1.14 kg/s steam
(9.000 Ib/hr) firetube
fired with a mixture
of coal-oil-water (COW)
— Baseline (COW)
— Controlled SO?
   emissions with
   limestone injection
Boiler outlet:
  --SASS
  — Method 5
  — Method 8
  — Controlled condensation
  ~ Gas sample (Cj-Cg HC)
  — Continuous 0?, CO?,
     CO, NOX
Fuel
                                Envirocon per-
                                formed parti culate
                                and sulfur
                                emission tests
     Adelphi  University
     industrial  boiler
1.89 kg/s steam
(15,000 Ib/hr)
hot water
firetube fired with a
mixture of coal-oil-
water (COW)
   Baseline (COW)
   Controlled SO?
   emissions with
          injection
Boiler outlet:
  ~ SASS
  ~ Method 5
  — Method 8
  — Controlled condensation
  — Gas Sample (C^Cg HC)
  -- Continuous 0?, CO?, NO*,
     CO
Fuel
                                Adelphi University
     Pittsburgh Energy
     Technology Center (PETC)
     Industrial boiler
3.03 kg/s steam
(24,000 Ib/hr) watertube
fired with a mixture of
coal-oil (COM)
   Baseline  test only
   with  COM
Boiler outlet:
  — SASS
  — Method 5
  -- Controlled condensation
  ~ Continuous 0?, CO?, NOX,
     TUHC, CO
  — N?0 grab sample
Fuel
                                PETC and General
                                Electric (GE)

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                                                     TABLE  1-1.   (continued)
Source
Description
Test points
unit operation
Sampling protocol
Test collaborator
TOSCO Refinery vertical
crude oil heater
2.54 Ml/day
(16,000 bbl/day) natural
draft process heater
burning oil/refinery gas
   Baseline
   Staged combustion
   using air injection
   lances
 Heater  outlet:
   --  SASS
   ~  Method  5
   —  Controlled  condensation
      Gas sample  (Ci-Ce  HC)
      '   "       '    "
                                                                                    — Continuous 02,
                                                                                       C02, HC
                                                                                    — N20, grab sample
                                                                                  Fuel oil
                                                                                  Refinery gas
                                                                                CO,
 KVB coordinated
 the staged com-
 bustion operation
 and continuous
 emission
 monitoring
Mohawk-Getty Oil
industrial boiler
8.21 kg/s steam
(65,000 Ib/hr)
watertube burning
mixture of refinery gas
and residual oil
   Baseline
   Ammonia injection
   using the noncatalytic
   thermal deNOx
   process
Economizer outlet:
  — SASS
  — Method 5, 17
  — Controlled condensation
  — Gas sample (Ci-Cs HC)
  — Ammonia emissions
  -- N20 grab sample
  — Continuous 0?, NOX,
     CO, C02
Fuels  (refinery gas and
  residual oil)
 Mohawk-Getty Oil
Industrial boiler
2.52 kg/s steam
(20,000 Ib/hr) watertube
burning woodwaste
   Baseline (dry wood)
   Green wood
Boiler outlet:
  ~ SASS
  ~ Method 5
  — Controlled condensation
  — Gas sample (Cj-Cs HC)
  ~ Continuous 02, NOX, CO
Fuel
Flyash                     ,
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
Industrial boiler
3.16 kg/s steam
(29,000 Ib/hr)
firetube with refractory
firebox burning woodwaste
— Baseline (dry wood)
Outlet of cyclone particulate
collector:
  ~ SASS
  ~ Method 5
  — Controlled condensation
  — Gas sample (Cj-Cg HC)
  — Continuous 02,  NOX.  CO
Fuel
Bottom ash
North Carolina
Department of
Natural Resources,
EPA IERL-RTP

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                                                                    TABLE  1-1.    (continued)
Source
Enhanced oil recovery
steam generator
Pittsburgh Energy
Technology Center
(PETC) Industrial
boiler
Description
15-MH (50 million Btu/hr)
steam generator burning
crude oil equipped with
MHI low-NOx burner
3.03 kg/s steam
(24,000 Ib/hr) watertube
fired with a coal-
water-slurry (CHS)
Test points
unit operation
— Performance mapping
— Low-N0x operation
~ Baseline test only
with CHS
Sampling protocol Test collaborator
Steamer outlet Getty Oil Company,
— SASS CE-Hatco
— Method 5
— Method 8
-- Gas sample (Cj-C6 HO
— Continuous Oy, NO.. CO,
CO;
— NjO grab sample
Fuel
Boiler outlet PETC
« SASS
-- Method 5
— Method 8
-- Gas sample (Cj-C* HC)
-- Continuous 03, NOX, CO,
GO
                                                                                                       to,, TUHC
                                                                                                    — N2D grab sample
                                                                                                  Fuel
                                                                                                  Bottom ash
                                                                                                  Collector hopper ash
                    Spark-Ignited,  natural-
                    gas-fueled reciprocating
                    Internal  combustion
                    engine — nonselectlve
                    NOX reduction catalyst
610-kH (818-hp)  Haukesha
rich-burn engine
equipped with DuPont
NSCR system
Low-N0x (with catalyst)  Catalyst Inlet and outlet
15-day emissions          ~ SASS
monitoring                -- NHj

                          — NjO grab sample
                          -- Continuous 0?, CO?.  NO.
                            TUHC
                        Lube oil
                               Southern California
                               Gas Company
                    Industrial boiler
180 kg/hr steam
(400 Ib/hr)  stoker fired
with a mixture of coal
and plastic  waste
Baseline (coal)
Coal and plastic
waste
Boiler outlet
  — SASS
  — VOST
  — Method  5
  ~ Method  8
  — HC1
  — Continuous  0?, NO.,
     CO,, TUHC
  — N?0  grab sample
Fuel
Bottom ash
Cyclone ash
Vermont Agency  of
Environmental
Conservation
                                                                                                                          CO.
                                                                                                                                         (continued)

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                                                 TABLE 1-1.   (continued)
        Source
      Description
      Test points
     unit operation
       Sampling protocol
  Test collaborator
Industrial boiler
7.6 kg/s steam
(60,000 Ib/hr watertube
retrofit for coal water
slurry firing
   Baseline test
   with CWS
   30-day emissions
   monitoring
Boiler outlet
   ~ SASS
   ~ VOST
   ~ Method 5
   — Method 8
   — Gas sample (Ci-Cs HC)
     N20 grab sample
 EPRI,  DuPont
                                                                                  —  Continuous  NOX, CO, C02,
                                                                                Fuel
                                                                                     02,  TUHC,  S02
Enhanced oil  recovery
steam generator
15-MW (50 million Btu/hr)
steam generator burning
crude oil, equipped with
the EPA/EER low-NOx
burner
— Low-N0x burner
~ 30-day emissions
   monitoring
Steamer outlet
  -- SASS
  — VOST
  -- Method 5
  — Method 8
  — Controlled condensation
  — Andersen impactors
  — Gas sample (Ci-Cg HC)
  — N20 grab sample
  — Continuous NOX, CO,  C02,
     02, S02
Fuel
Chevron
EERC
U.S.A.,
Spark-ignited,
natural-gas-fueled
reciprocating
internal  combustion
engine — selective
NOX reduction catalyst
1,500-kW (2,000-hp)
Ingersoil-Rand engine
equipped with Engelhard
SCR system
— Low-N0x (with catalyst)  Catalyst inlet and  outlet
   15-Day emissions
   monitoring
~ SASS
— NH3
~ HCN
— N20 grab sample
~ Continuous 02, C02,  NOX
   TUHC
Lube oil
Southern California
Gas Company

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                          REFERENCES FOR SECTION 1
1-1.   Larkin, R. and E. B. Higginbotham, "Combustion Modification Controls
       for Stationary Gas Turbines:  Volume II.  Utility Unit Field Test,"
       EPA-600/7-81-122b, NTIS PB82-226473, July 1981.

1-2.   Higginbotham, E. B., "Combustion Modification Controls for Residential
       and Commercial Heating Systems:  Volume II.  Oil-fired Residential
       Furnace Field Test," EPA-600/7-81-123b, NTIS P882-231176, July 1981.

1-3.   Higginbotham, E. B. and P. M. Goldberg, "Combustion Modification NOX
       Controls for Utility Boilers:  Volume I.  Tangential Coal-fired Unit
       Field Test," EPA-600/7-81-124a, NTIS PB82-227265, July 1981.

1-4.   Sawyer, J. W. and E. B. Higginbotham, "Combustion Modification NOX
       Controls for Utility Boilers:  Volume II.  Pulverized-coal Wall-fired
       Unit Field Test," EPA-600/7-81-124b, NTIS PB82-227273, July 1981.

1-5.   Sawyer, J. W. and E. B. Higginbotham, "Combustion Modification NOX
       Controls for Utility Boilers:  Volume III.  Residual-oil Wall-fired
       Unit Field Test," EPA-600/7-81-124c, NTIS PB82-227281, July 1981.

1-6.   Goldberg, P. M. and E. B. Higginbotham, "Industrial Boiler Combustion
       Modification NOX Controls:  Volume II.  Stoker Coal-fired Boiler Field
       Test — Site A,* EPA-600/7-81-126b, NTIS PB82-231085, July 1981.

1-7.   Lips, H. I. and E. B. Higginbotham, "Industrial Boiler Combustion
       Modification NOX Control:  Volume III.  Stoker Coal-fired Boiler Field
       Test — Site B,* EPA-600/7-81-126c, NTIS PB82-231093, July 1981.

1-8.   Waterland, L. R., et a!., "Environmental Assessment of Stationary
       Source NOX Control Technologies — Final Report," EPA-600/7-82-034,
       NTIS PB82-249350, May 1982.

1-9.   Lentzen, D. E., et al., "IERL-RTP Procedures Manual:  Level 1
       Environmental Assessment (Second Edition)," EPA-600/7-78-201,
       NTIS PB293795, October 1978.

1-10.  Castaldini, C., L. R. Waterland, and H. I. Lips, "Environmental
       Assessment of an Enhanced Oil Recovery Steam Generator Equipped with
       a Low-N0x Burner," EPA 600/7-86-003 a/b, February 1986.
                                     1-10

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                                   SECTION  2
                       SOURCE  DESCRIPTION AND  OPERATION

     The tests were  performed on  an  enhanced  oil  recovery  steam generator
(EOR steamer) owned  and  operated  by  Chevron U.S.A.   The  steamer,  located in
the Kern Front oil field near Bakersfield, California, was retrofitted  in
1984 with  the EPA  low-NOx burner.  The  retrofit was  part of the field
verification of  the  commercial  prototype 16 MW  (55 million Btu/hr)  low-NOx
burner developed and fabricated by the  Energy and Environmental  Research
Corporation  (EERC) under EPA-sponsored  programs (References 2-1 and 2-2).
The goal of  the  field demonstration  was to validate  the  low-NOx capability
and thermal  performance  of the  burner firing  high nitrogen (X).7  percent)
Kern County  crude.
     Figure  2-1  illustrates the low-NOx burner  design.   The burner  utilizes
the staged air combustion concept in which a  primary fuel-rich  zone is
separated  from a fuel-lean zone where secondary combustion air  is injected.
The fuel-rich zone is established in a  large  refractory  lined combustor.
                               i
Primary combustion air is preheated  using  a regenerative combustor  shell
design.  Secondary (unpreheated)  combustion air is injected radially and
axially in the transition zone  connecting  the combustor  to the  steamer.
     Table 2-1 summarizes the design and operating characteristics  of the EPA
commercial prototype  burner.  The  important operating parameters  for the
advanced low-NOx burner  are a low  first-stage stoichiometric ratio  (SR) in
                                     2-1

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ro
               Ceramic Fiber
               (external
               insulation)
               Tile Support
                 King
                  Primary
                  Register
                         Insulating
                         Firebrick
                                                                                                     90* Aluuliw
                                                                                                     Brick (Greenal 90)
                                                      Figure  2-1.   EPA low-NOx burner.

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          TABLE 2-1.  EPA LOW-NOX BURNER DESIGN CHARACTERISTICS
e
e
Capaci ty
Overall combustor length
Combustor L/D
Combustor volume
Combustor lining
Temperature in the combustor
at full load
Gas residence time in the
combustor at full load
Design burner stoichiometry
Primary air temperature
Secondary air injection

Performance goals:
—  Fuel/oil nitrogen content
—  NOX at 3 percent Og
—  CO at 3 percent 02
~  Smoke
—  Sound mechanical and
    thermal performance
—  16 MW (55 MBtu/hr) heat input
--  5.5m (18 ft)
—  2.6
—  13m3 (460 ft3)
~  alumina refractory
—  about 1,430°C (2,600°F)

—  about 0.6 sec

—  0.60 to 0.65
—  preheated up to 250°C (480°F)
—  combination of radial and axial
    injection ports

—  >0.7 percent
—  85 ppm maximum
—  45 ppm maximum
—  Bacharach number 4 maximum
                                   2-3

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the range of 0.60 to 0.65,  high combustor  temperature  of ^1,430°C (2,600°F),
near the adiabatic  flame temperature, and  a  long  first-stage  residence  time
of about 0.6 sec.  This combination of  long  gas residence  time  and high gas
temperature promotes the decay of  total  fixed  nitrogen (TFN)  species  {HCN  and
NH3) to Ng formed early in  the ignition  zone from fuel  nitrogen under very
fuel-rich conditions.  Low  TFN concentrations  at  the first-stage  exit result
in low-fuel NOX conversion.  In the second stage,  temperature and fuel/air
mixing are important to minimize thermal NOX while  keeping  CO,  smoke, and
particulate in check.  Efficient fuel/oil  atomization  and  fuel/air mixing  in
the ignition zone of the combustor are also  beneficial  to  the decay of  TFN in
the combustor.
     The goals of the low-NOx burner development  were  to achieve  NOX levels
at or below 85 ppm at 3 percent 03, with low CO,  smoke, and particulate when
burning Kern County crude with a typical nitrogen  content  of  0.7  percent or
greater.  Subscale burner prototypes tested  by EERC had shown that NOX  levels
as low as 45 ppm could be achieved using this  design approach almost
independently of the nitrogen content of the fuel  oil.  Figure  2-2
illustrates the overall layout of  the low-NOx  burner retrofit.   Preliminary
tests by EERC of the full-scale retrofit had demonstrated  that  the burner  was
capable of meeting the EPA  program goals.
     The objective of the CMEA tests were  to augment emission tests performed
by EERC as part of  the field verification  program.  The CMEA  tests consisted
of 30-day continuous monitoring of steamer flue gas emissions {03  C02, CO,
NOX, and $03) during typical unattended  steamer operation.  In  addition, a
comprehensive emission test program was  performed over a 1-day  period,  during
which burner operation was  adjusted to  achieve emission goals set by  the EPA
                                     2-4

-------
ro
en
                                               RETROFITTED  STEAMER
                                                   -92'-10" —
                                              ORIGINAL STEAMER
                                                               79'-9"
                              Figure 2-2.  Low-N0x burner  retrofit arrangement.

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for the field verification program.  Table 2-2 summarizes  the burner/steamer
operation during this 1-day comprehensive testing period.  The  burner fired
Kern County crude with a nitrogen and sulfur content of 1.04 and
1.06 percent, respectively.  Total firing rate during this test period
averaged approximately 24 1/min (215 bbl/day), corresponding to a heat  input
rate of nearly 17 MW (57 x 106 Btu/hr).  Measurement of primary and secondary
airflow indicated a first-stage combustor stoichiometry in the  range of 0.61
to 0.65, with an estimated gas residence time of 0.65 sec.
                                      2-6

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                       TABLE 2-2.  STEAMER/BURNER  OPERATION
                                                  Range
                                                                        Average
Fuel flow, 1/min  (bbl/day)
Heat input, MW (10^ Btu/hr)
Fuel temperature,  °C  (°F)
                                      23.4  to  24.1  (212  to  218)
                                      16.4  to  16.8  (55.8 to 57.4)
                                      129 to 132    (264  to  269)
                     23.8  (215)
                     16.6  (56.6)
                     130   (267)
Feedwater flow, 1/min  (10^ bbl/day)   380  to  400    (3.4 to  3.6)       390    (3.5)
                MPa  (psig)            7.03 to 9.10  (1,020  to 1,320)   8.41   (1,220)
Steam pressurej
Steam temperature, °C  (°F)
Stack temperature, °C  (°F)

Burner primary airflow, m^/s  (scfm)
Secondary airflow, m3/s (scfm)
First stage stoichiometry
First stage residence  time,'5  sec
                                      279  to  >300
                                      232  to  254
   (535 to >570)
   (450 to 490)
                                      2.71  to 2.87  (5,740 to 6,080)
                                      2.38  to 2.95  (5,040 to 6,260)
                                      0.61  to 0.65
Fuel oil analysis, percent weight (dry  basis,  unless  noted)
Carbon
Hydrogen
Sulfurc
Nitrogen0
Ash
Moisture^
Oxygen6
Gross heating value, MJ/kg  (Btu/lb)
Specific gravity  (degrees API)
    at 60°F
                                      1.00 to 1.
                                      1.00 to 1,
10
09
242   (468)

2.80  (5,940)
2.65  (5,630)
0.64
0.65
86.2
11.3
1.06
1.04
0.03
0.57
0.4
42.78 (18,430)
12.6
aSpans the entire 1-day period  of  comprehensive testing
bAssumes a combustor temperature of  1,430°C (2,600°F)
cAnalyses of  sulfur and nitrogen were  performed in triplicate
dAs fired
eBy difference
                                        2-7

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                          REFERENCES FOR SECTION 2


2-1.  England, 6. C., et al., "Evaluation and Demonstration of Low-N0x Burner
      Systems for TEOR Steam Generators; Test Report:  Preliminary Evaluation
      of Commercial  Prototype Burner," EPA-600/7-83-061, NTIS PB84-128727,
      December 1983.

2-2.  England, G. C., et al., "Evaluation and Demonstration of Low-N0x Burner
      Systems for TEOR Steam Generators — Design Phase Report,"
      EPA-600/7-84-076, NTIS PB84-224393, July 1984.
                                     2-8

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                                  SECTION  3
                              EMISSION  RESULTS

     The objectives of  this  test  program were:   (1)  to  measure  steamer  flue
gas emissions during a  30-day test  period  to  evaluate  the  continuous
performance of the EPA  low-NOx  burner and  (2) to  perform comprehensive  tests
over a 1-day period to  measure  inorganic and  organic pollutant  emissions.
Emission measurements were performed in cooperation  with EERC personnel who
assisted the test crew  in the operation of the  low-NOx  burner.
3.1  SAMPLING PROTOCOL
     Table 3-1 summarizes the sampling  and analytical  test matrix employed
during the comprehensive test program.  Fuel  samples of the crude oil were
collected for proximate, ultimate,  and  selected trace element analyses.  All
flue gas emissions were measured  at the stack,  downstream  of the steamer
economizer section.  Continuous monitors for  03,  C02> CO,  NOX,  and S0£  were
operated during the comprehensive tests as well as throughout the 30-day
continuous emission testing  period.  Volatile organic species emissions were
                               \
measured with the volatile organic  sampling train (YOST) according to EPA
protocol (Reference 3-1).  Trace element and  less volatile  organic compounds
were measured using the source assessment  sampling system  (SASS) per an
extended EPA level 1 protocol (Reference 3-2).  Particulate  and sulfur  oxide
compounds were measured using combined  EPA Methods 5 and 8 and a controlled
condensation system (CCS).  The size distribution of emitted particulate

                                     3-1

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             TABLE 3-1.  SAMPLING ANALYSIS TEST MATRIX*
Sample/
location  Sampling protocol             Analysis protocol
  Fuel    Grab sample        Proximate, ultimate, and selected trace
                              elements

 Stack    Continuous         NOX, CO, 0)3, 02, SOg
          emission monitors

          Volatile organic   Volatile organic priority pollutant
          sampling train     species by GC/MS (EPA Method 624)
          (VOST)

          Source assessment  Selected trace elements, total semi- and
          sampling system    nonvolatile organics, semivolatile
          (SASS)             organic priority pollutant species by
                             GC/MS (EPA Method 625)
          EPA Method 5/8     Particulate emissions by EPA Method 5,
          train              S02, and $03 emissions by EPA Method 8
          Controlled         S02 and $03 by titration
          condensation
          system (CCS)

          Andersen impactor  Gravimetry of nine-stage impactor for
          sampling system    particle size distribution
          Grab sample —     N20 by laboratory GC/ECD
          multiple sample
          bombs

          Grab sample —     NOX by EPA Method 7
          multiple sample
          flasks
Measurement and analysis techniques used are discussed in detail in
 Appendix A.
                                 3-2

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was determined using an Andersen cascade  impactor.  Flue gas  samples were
also collected for analyses of nitrous oxide  (N20), using gas  chromatography
with electron capture detection.  Certification  of  the  NOX analyzer readings
was performed three times during the  30-day  test period using  the  reference
EPA Method 7 protocol.  Figure 3-1  illustrates  the  actual test activity
schedule.
     The following sections summarize the emission  test results. Sections  3.2
through 3.4 present the emission results  obtained during the  comprehensive
tests that took place on February 1,  1984.   Section 3.5 summarizes results of
continuous emission measurements performed over  the extended  test  period from
                         i
January 21 to February 24, 1984.  Section 4  presents  results  of  Quality
Assurance (QA) activities performed,  including  results  of the EPA  Method 7
certification tests.  Details of the  sampling and analysis procedures  used
are discussed in  Appendix A.
3.2  CRITERIA POLLUTANT AND OTHER GAS PHASE  SPECIES EMISSIONS
     Table 3-2 summarizes gaseous and particulate emissions measured during
the 1-day comprehensive tests performed on February 1.  NOX emission levels
were maintained below 75 ppm as measured, averaging 69  ppm corrected to
3 percent 02, well below the target of 85 ppm set for the field  demonstration
program.  CO emissions averaged 24  ppm  (at 3  percent  02), again  within the
45 ppm program goal.  S02 emissions measured  by  continuous monitors were
relatively steady at about 565 ppm  as measured.   Conversion of all fuel
sulfur to S02 would result in an emission rate of 495 yg/J (643  ppm)
compared to the measured level of 435 ug/J (565  ppm).
     N20 levels in the flue gas, at 7 ppm corrected to  3 percent 02, were
about 10 percent  of the corresponding NOX emissions level.  This is at the
                                      3-3

-------
Test Activity
Continuous monitoring
Comprehensive tests
• SASS
t EPA Methods 5/8
• VOST
• Controlled condensation
• H20
• Andersen Impactor
Quality Assurance tests
* EPA Method 7
January 19B4 February 1984
21 22 23 24 25 26 27 28 29 30 31 1« 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24



A
A
A
A
A
A

A A A
"Comprehensive tests.
                                     Figure  3-1.   Test activity schedule.

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TABLE 3-2.  CRITERIA POLLUTANT AND OTHER GAS SPECIES
            EMISSIONS — COMPREHENSIVE TESTS
       Pollutant*
    Range
        Average
As measured by continuous
gas analyzers
Q£, percent dry
C02, percent dry
CO, ppm dry
NOX, ppm dry
S02, ppm dry
2.3 to 2.8
12.2 to 13.7
21 to 27
66 to 75
560 to 579
2.7
13.1
24
70
565
Corrected average
gaseous emissions

  CO
  N0xd
  S02
  N20e

Particulate mass emissions

  •   SASS solids
  •   Method 5/86
      —  Solids
      ~  Condensible
      —  Total
 ppmb

  24
  69
 556
   7

mg/dscm

  26

  96
  50


 146
ng/Jc    lb/MBtuc
 8.2
 39
435
 0.5
 7.3

26.7
13.8
40.5
 0.019
 0.09
 1.01
 0.001
0.017

0.062
0.032
0.094
aAppendix A discusses continuous monitor analyzers  used,
 the conditioning system,  particulate  sampling  equipment,
C0n a  heat input basis
dAs N02
eAverage of  two test measurements.  Condensible  particulate
 measured, since the Kern County Air  Pollution Control
 District continues to regulate this  fraction.
                          3-5

-------
low end of the range exhibited in recent data  from several  fossil-fuel-fired
external combustion sources  (Reference 3-3).   These other data  suggest  that
N£0 emissions are generally about 20 to 25 percent of  the corresponding  NOX
level.
     Particulate emissions were measured using SASS and the combined EPA
Methods 5 and 8 sampling trains.  Comparison of the solid particulate catch
indicates an emission rate of 7.3 ng/J (26 mg/dscm) based on the SASS
results, compared to about 27 ng/J  (96 mg/dscm) using  the EPA Methods 5  and
8 results.  This difference may be attributed  in part  to the higher sampling
temperature of the SASS (230°C) versus the Method 5 (120°C).  At higher
temperatures, condensible matter which might escape the SASS filter could  be
caught on the Method 5 filter, perhaps causing this disparity.  Impinger
solutions of the combined EPA Methods 5 and 8  were also analyzed for
condensible particulate matter.  The Kern County Air Pollution  Control
District still requires condensible particulate to be  included  in  the total
particulate emission result reported.  On the  average, the  condensed matter
accounted for about one-third of the total particulate catch of 40.5 ng/J
(146 mg/dscm).
     Table 3-3 summarizes the particulate emission results  of the  two EPA
Methods 5 and 8 sample runs and the corresponding burner/steamer conditions
during each test run.  As shown, total particulate emissions for both runs
were comparable (149 and 142 mg/dscm).  This is in the range typical for
uncontrolled EOR steamer emissions.  However,  the split between solid and
condensible particulate between the two runs changed significantly.  For
run 1, only about 43 percent of the Method 5 catch was solid particulate
                                      3-6

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          TABLE 3-3.  FLUE GAS PARTICULATE MEASUREMENT RESULTS
Method 5
Solid (front half)a
Condensible (back half)&
Total
Burner /steamer
operating data:
Fuel flow, 1/min (bbl/day)
Heat input, MW (106 Btu/hr)
Fuel temperature, °C (°F)
Steam pressure, MPa (psig)
Steam temperature, °C (°F)
Feedwater flow, 1/min
(103 bbl/day)
Burner primary air flow,
m3/s (scfm)
Secondary air flow,
m3/s (scfm)
Combustor stoichiometryc
Stack temperature, °C (°F)
Run 1

(mg/dscm) (gr/dscf)
64 0
85 0
149 0
Range
—
—
129 to 131
(264 to 268)
--
—
—
167 to 172
(5,900 to
6,080)
152 to 158
(5,360 to
5,590
0.62 to 0.64
232 to 241
(450 to 466)
.028
.037
.065
Average
24.1
(219)
16.9
(57.7)
130
(266)
7.03
(1,020)
279
(535)
400
(3.6)
170
(6,000)
155
(5,460)
0.63
236
(456)
Run 2

(mg/dscm) (gr/dscf)
128
14
142
Range
—
—
130 to 131
(266 to 268)
—
—
—
163 to 172
(5,740 to
6,080)
153 to 177
(5,390 to
6,260)
0.61 to 0.64
244 to 254
(472 to 490)
0.056
0.006
0.062
Average
24.1
(218)
16.8
(57.4)
131
(267)
9.10
(1,320)
>300
(>570)
375
(3.4)
167
(5,880)
170
(6,000)
0.62
248
(479)
*Solid particulate calculated from tne niter and prooe catcnes
bCondensible particulate calculated from the impinger solutions; duplicate
 analyses performed
cAssumes combustor temperature of 1,430°C (2,620°F)

                                   3-7

-------
 (57 percent condensibles); for run 2, 90 percent was  solid  participate
 (10 percent condensibles).
     The operating data in Table 3-3 show  that  two  operational  changes
occurred between the two runs.  Steam pressure  (thus  temperature)  was
increased in run 2, though fuel flow was held constant.   Feedwater flow  was,
therefore, reduced slightly to maintain steam quality.  The  net result of
this change was slightly higher stack temperature  (less heat absorption  in
the convection section of the steamer) for run  2.   In addition,  burner
primary air flow was slightly lower in run 2, and  secondary  air  flow higher.
Combustor stoichiometries, therefore, were slightly lower for run  2,
0.63 versus 0.62 on the average.  The slightly  lower  combustor  stoichiometry
may have contributed to an increase in emissions of carbonaceous particulate
matter and thus an increase in the solid catch  of  the Method 5  sampling
system.
     Table 3-4 shows results of the Method 8 analyses for the two  combined
Methods 5 and 8 runs.  For comparison, the average  $03 continuous  monitor
reading over each run is also noted.  The agreement between  the  reference
method and the $03 monitor was within 10 percent for  run  1 and  3 percent for
run 2.  The SOX (SOg + $03) levels measured  (600 to 632 ppm  dry at 3 percent
02) are as would be expected from total conversion  of the fuel  sulfur to SOX
(632 ppm at 3 percent 03, as noted above).   Interestingly,  the  ratio of  $03
to total SOX, at between 0.7 percent (run 2) and 2.0  percent (run  1), is much
lower than the range typical for oil-fired sources  (5 to  10  percent).  This
ratio is more in the range typical for coal-fired  sources (less  than
2 percent).
                                     3-8

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              TABLE 3-4.  SULFUR SPECIES EMISSIONS BY COMBINED
                          EPA METHODS 5 AND 8a

                                               Run 1  Run 2
                 Method 8
                   S02, ppm dry, 3  percent 03  619    593
                   $03, ppm dry, 3  percent 03    12.9    4.4
                 Continuous monitor
                   S02, ppm dry, 3  percent Og  557    574
                   03, percent  dry               2.7     2.7

                 aTests performed on  February  1,  1984

     Table 3-5 shows results of the controlled condensation  (CCS)  analysis
for two separate measurements made  on February 23.   By  this  method,  S02
emissions were about 600 and 610 ppm  as measured,  in fairly  good agreement
with the Method 8 results obtained  on February 6.  Agreement between the CCS
S0£ measurement and the continuous  monitor reading was  also  good,  within
7 percent.  However, flue gas $03 measured with  CCS,  at 47 and 51 ppm,  was
much higher than as measured on February  1 using Method 8.   The ratio of $03
to total SOX  for the CCS measurements was 7.2  to 7.7 percent.   This, as noted
above, is well within  the range typical for  oil-fired  sources.   The  authors
can not explain this disparity  between Method  8  and  CCS.
     Table 3-6 summarizes particle  size distribution data obtained in
two separate  Andersen  impactor  measurements.   Figure 3-2  indicates a
log-normal distribution (as evidenced by  the straight curve  fits).  Mean
particle size (D50) was 0.056 urn  (run 1)  to  0.14 ym  (run  2); 90 percent of
the total particulate  was less  than 1.4 ym  (run  1) to  11  vm  (run 2).
                                      3-9

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           TABLE 3-5.  SULFUR SPECIES EMISSIONS BY
                       CONTROLLED CONDENSATION3
                                         Run 1  Run 2
         Controlled condensation system
           S02, ppm dry, as measured      602    611
                (ppm dry, 3 percent 02)  (653)    —b
           $03, ppm dry, as measured       47     51
                (ppm dry, 3 percent 02)   (51)
        —b
         Continuous monitor

           S02, ppm dry, as measured
           02, percent dry
642
  4.4
—c
—c
         aTests performed on February 23, 1984
         bCannot be calculated, since flue gas 02 not known
         cMonitors inoperative
       TABLE 3-6.  PARTICLE SIZE DISTRIBUTION RESULTS3
                    Run 1
    Run 2
Impactor
stage
Cyclone
1
2
3
4
5
6
7
Filter
050 Cumulative weight 059 Cumulative weight
(pm) percent less (urn) percent less
than Dsn than Dgo
13.04
7.52
7.11
4.35
3.03
1.57
0.78
0.48
0.22
100
100
98.45
94.03
91.94
90.23
85.65
79.60
72.54
12.52
7.55
7.15
4.37
3.04
1.58
0.79
0.49
0.22
92.35
89.63
85.96
83.05
79.51
74.51
68.82
64.01
57.12
aTests performed on February 22, 1984.
                             3-10

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    lo1   :
E
o
£
    10
     10
      -1
                                                                                   RUN  1
                                                                                   RUN  2
                                          —i	1	1	1	1	1	i—
                                           2O  3Q  4O  SO  OO  7O BO
—I—
 BO
                                                                             T
.O.1   .09.1.2  .912    9   1O   2O  3O  4O  SO  BO  7O BO    BO   OS   OB  QOOe. 9   OB. 0

                    Cumulative wt  percent less than diameter of particle  (DP)
                                                                                               aa. oo
                             Figure  3-2.   Particle size distribution.

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     Table 3-7 summarizes the particulate loadings obtained  using  the
Andersen impactors, the SASS train, and EPA Method 5.   Interestingly,  the
Andersen results compare quite well with the SASS measurement.   However, both
are significantly less than the EPA Method 5 solid (front  half)  result.  The
solid particulate collection temperature for each method is  also noted  in
Table 3-7 (stack temperature for the in-stack Andersen  impactors and filter
oven temperature for SASS and Method 5).  The relatively good agreement
between SASS and Andersen particulate load is consistent with the  similar
high temperatures at which solid particulate is collected  in these methods.
The high Method 5 solid particulate results suggests that  significant
quantities of material condense in the temperature range from 120° to 230°C
(250° to 450°F), the difference between the Method 5 oven  temperature and  the
stack and SASS oven temperatures.
3.3  TRACE ELEMENT ANALYSIS RESULTS
     The Kern County crude oil  fuel samples and the SASS train samples  from the
steamer flue gas were analyzed for 73 trace elements using the spark source mass
spectrometry (SSMS), supplemented by atomic absorption  spectrometry  (AAS).
(Selective ion electrode, x-ray fluorescence spectrometry, and wet chemical
methods were employed for selected elements in some samples.)  Once  the trace
element concentrations were determined, trace element flowrates  for  fuel oil  and
flue gas vapor and condensed phases could be computed.  Trace element
concentrations and flowrates are presented in Appendix  B.
     Table 3-8 summarizes the calculated trace element  flowrates corresponding  to
the fuel oil and flue gas samples.  A mass balance closure measure based on the
                                      3-12

-------
         Table 3-7.  SUMMARY OF PARTICULATE LOADING MEASUREMENTS

Andersen
Run 1:
Run 2:
SASS
Solid
Method 5
Run 1:


Run 2:


Method
Impactor
Solid Parti cul ate
Solid Parti cul ate

Parti cul ate
Solid Parti cul ate
Condensible Particulate
Total
Solid Particulate
Condensible Particulate
Total
Particulate Collection
load, mg/dscm temperature, °C (°F)
30.8 290 (550)a
38.2 280 (530)a

26 230 (450)b
64 120 (250)b
85
149
128 120 (250 )b
14
142
aStack temperature  (in-stack  impactor  train)
bFilter oven nominal temperature
                                   3-13

-------
                    TABLE 3-8.  TRACE ELEMENT FLOWRATES
Element9
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmi urn
Calcium
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysprosium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Hoi mi urn
Iodine
Iron
Lanthanum
Lead
Lithium
Lutecium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Fuel oil
ConcentrationD
(ug/g)
5.0
— c
0.006
0.55
<0.0l
—
0.14
0.13
—
9.0
__
—
23
0.40
0.40
0.70
--
—
16
— —
0.20
<0.02
—
0.50
7.5
__
0.55
0.35
—
6.5
0.35
<0.4
1.2
—
13

Flowrate
(ug/s)
1900
—
2.3
210
<3.9
—
54
50
—
3500
_.
--
8900
160
160
270
—
—
6200
— —
78
<7.8
—
190
2900
«_
210
140
—
2500
140
<160
470
—
5000
Flue
Concentration
(ug/dscm)
79
0.69
2.0
6.9
0.0091
0.0046
3.3
4.8
<0.49
6.2
0.27
0.11
720
73
1.4
1700
0.091
0.0091
17
0.091
1.2
2.2
<4.9
1.8
310
0.36
2.4
2.1
0.0091
41
5.6
0.77
24
0.27
610
gas
Flowrate
(ug/s)
370
3.2
9.1
32
0.042
0.021
15
22
<2.2
290
1.3
0.49
3300
340
6.2
8100
0.42
0.042
77
0.42
5.4
10.3
<23
8.1
1400
1.7
11
9.6
0.042
190
26
3.5
110
1.3
2600
Mass balance
closure
flue gas flowrate/
fuel oil flowrate
(percent)
19

390
15
>11

28
44

8.2


37
220
3.9
3000


1.3

7.9
>130

4.2
49

5.2
7.0

7.5
19
>2.3
24

56
(continued)
aErbium, gold, hafnium, iridium, osmium, palladium, rhenium, rhodium,
 and ruthenium were also analyzed for but not found above the detection
 limit in any sample.
^Average of duplicate analyses.
C0ashes indicate element not found above detection limit.  See Appendix B
 for detection limits.
                                     3-14

-------
               TABLE 3-8.  (continued)
Element*
Niobium
Phosphorus
Platinum
Potassium
Praesodymium
Rubidium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Tantalum
Tellurium
Terbi urn
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
Fuel oil
Concentration^
(ug/g)
0.06
3.0
1.0
4.0
—
0.02
—
0.06
0.45
14
«»•*
120
0.20
--
--
•_
—
--
—
~
0.35
—
—
0.40
—
0.050
2.0
0.13

Flowrate
(wg/s)
23
1200
390
1600
— •
7.8
—
23
170
5400
».-
46,000
78
—
—
__
—
—
—
—
140
—
~
160
--
19
780
,'50
Flue
Concentration
(ug/dscm)
<0.89
34
1.7
90
0.33
0.26
0.091
12
12
83
2.2
120,000
3.3
0.046
2.1
0.018
0.0091
0.18
0.0091
0.091
24
0.0091
150
23
0.023
0.77
740
1.2
M,
gas flue
Flowrate fuel
(wg/s)
2.1
160
8.0
420
1.5
1.2
0.42
56
56
380
10.2
560,000
15
0.21
9.7
0.084
.0.042
0.84
0.042
0.42
110
0.042
670
100
0.105
3.6
3400
5.6
ass balance
closure
gas flowrate/
oi 1 f 1 owra te
(percent)
<18
13
2.1
27

15

240
32
7.0

1200
19







81


67

18
440
11
aErbium, gold, hafnium, tridium, osmium, palladium, rhenium, rhodium,
 and rutherium were also analyzed for but not found above the detection
 limit in any sample.
bAverage of duplicate analyses.
cDashes indicate element not found above detection limit.  See Appendix B
 for detection limits.
                                     3-15

-------
ratio of flue gas output to fuel input flowrates for each element  is  also
presented.  Laboratory analysis results for fuel oil are based  on  the average  of
results obtained for two separate oil samples collected during  the  SASS  test.
     Trace elements found in the fuel oil at levels greater  than 10 ug/g
(corresponding to flowrates greater than about 4 mg/s) were  chlorine,  fluorine,
nickel, silicon, and sodium.  Sodium was measured at the highest level.  The
source of this sodium is most likely the salt water brine in  the produced  crude.
The residual moisture content of the fuel was 0.57 percent by proximate
analysis.
     Trace elements emitted at levels exceeding 100 ug/dscm  (corresponding to
flowrates greater than about 0.45 mg/s) in the exhaust were  chlorine  condensed
chlorides, copper, iron, nickel, sodium, and zinc.  Copper and  sodium were
present in the flue gas at much higher levels than could be accounted for  by
the fuel oil.  Additional sodium may have been introduced through  suspended
salts in the combustion air.  Reasonably good mass balance closure  for
                                          i
several metals was obtained, including iron, nickel, titanium,  and  vanadium.
However, in general, mass balance closure was poor, with less element in the
flue gas than introduced with the fuel.
3.4  ORGANIC EMISSION RESULTS
     Total organics and organic species emissions were measured using two
methods (see Appendix A for complete method description).  The  volatile
organic priority pollutant compounds (those having boiling points  generally
less than 110°C (230°F) were analyzed by thermal desorption,  purge  and trap,
gas chromatography mass spectrometry (GC/MS) of YOST traps in accordance with
                                     3-16

-------
the EPA VOST protocol (Reference 3-1).  The volatile organic compounds sought
in the analysis are listed in Table 3-9.
     Organic analyses of SASS train samples were performed according to an
extended EPA Level 1 protocol (Reference 3-2).  The SASS  train particulate
(filter), organic module sorbent (XAD-2), and organic module condensate (OMC)
samples were extracted with methylene chloride  in a Soxhlet apparatus.  The
extracts (the XAD-2 and OMC extracts were combined) were  then subjected to
total chromatographable organic (TCO) and gravimetric  (GRAV) analyses  to
determine the total concentration  of organics within the  100° to  300"C (212°
to 572'F) and greater than 300°C (572°F) boiling point  ranges, respectively.
Infrared (IR) spectra of the GRAV  residue of  the extracts were also
obtained.
     In addition, the SASS train organic sorbent module extract was analyzed
for the semivolatile organic priority pollutant compounds (a category  which
contains several polynuclear aromatic hydrocarbon  (PAH) species)  by GC/MS  in
accordance with EPA Method 625.  (Reference 3-4).   Semivolatile organic
compounds sought by GC/MS are listed in Table 3-10.  A  discussion of the
analytical results follows.
3.4.1 Volatile Organic Emissions
     Table 3-11 summarizes volatile organic species emissions detected in  the
VOST measurement (three trap pairs were sampled and analyzed, denoted  "run"
                                 i
in table).  Only three compounds were detected:  benzene, toluene, and
ethylbenzene.  Flue gas concentrations were 60  ug/dscm  (18 ppb) for benzene
and less than 4 pg/dscm (1 ppb) for toluene and ethylbenzene, on  the
average.
                                      3-17

-------
TABLE 3-9.  VOLATILE ORGANIC COMPOUNDS SOUGHT  IN  GC/MS  ANALYSIS
    Halogenated Aliphatics      Ethers

    Chioromethane               Ethylene oxide
    Dichloromethane             Propylene oxide
    Chloroform
    Tetrachloromethane          Chlorinated Ethers
    Chioroethane
    1,1-dichloroe thane          2-chloroethyl vinyl ether
    1,2-di chloroethane
    1,1,1-trichloroethane       Aldehydes
    1,1,2-trichloroethane
    1,1,2,2-tetrachloroethane   Acrolein
    1,2-dichloropropane
    Vinyl chloride              Amines and Nitriles
    1,1-dichloroethylene
    1,2-dichloroe thylene        Aeryloni trile
    Trichloroethylene
    Tetrachloroethylene         Aromatic Hydrocarbons
    Alkyl chloride
    1,3-dichloropropene         Benzene
    Bromomethane                Toluene
    Bromodichloromethane        Ethyl benzene
    Dibromochloromethane        Xylenes
    Bromoform
    Trichlorofluoromethane      Chlorinated Aromatics

                                Chlorobenzene
                              3-18

-------
             TABLE 3-10.
COMPOUNDS SOUGHT IN THE EPA METHOD 625
GC/MS ANALYSIS AND THEIR DETECTION LIMITS5
2,4,6-trichlorophenol
p-cnloro-m-creso!
2-chlorophenol
2,4-di chlorophenol
2,4-dimethylphenol
     Acid Compounds

        5      2-nitrophenol
        5      4-nitrophenol
        5      2,4-dinitrophenol
        5      4,6-dinitro-o-cresol
        5      Pentachlorophenol
               Phenol

 Base Neutral Compounds
1.2,4-tri chlorobenzene            1
1,2-dichlorobenzene               1
1,2-diphenylhydrazine             1
  (as azobenzene)
1,3-dichlorobenzene               1
1,4-dichlorobenzene               1
2,4-dinitrotoluene                1
2,6-dinitrotoluene                1
2-chloronaphthalene               1
3,3'-dichlorobenzidine            5
3-methyl cholanthrene             40
4-bromophenyl phenyl ether        1
4-chlorophenyl phenyl ether       1
7,12-dimethyl benz(a)anthracene   40
N-m"trosodi-n-propylamine         5
N-nitrosodimethylamine            NA
N-nitrosodiphenylamine            1
Acenaphthene                      1
Acenaphthylene                    1
Anthracene                        1
Benzo(ghi)perylene                5
Benzidine                         20
Benzo(b)fluoranthene              1
Benzo(k)fluoranthene              1
Benzo(a)anthracene                ( 1
Benzo(a)pyrene                    1
               Benzo(c)phenanthrene
               Bi s(2-chloroethoxy)methane
               Bis(2-chloroethy!)ether
               Bis(2-chloroisopropyl)ether
               Bis(2-ethylhexylJphthalate
               Butyl benzyl phthalate
               Chrysene
               Di-n-butyl phthalate
               Di-n-octyl phthalate
               Dibenzo(a,h)anthracene
               Di benzo(c, g)carbazole
               Diethyl phthalate
               Dimethyl phthalate
               Fluoranthene
               Fluorene
               Hexachlorobenzene
               Hexachlorobutadiene
               Hexachlorocyclopentadi ene
               Hexachloroethane
               Indeno(l,2,3-cd)pyrene
               Isophorone
               Naphthalene
               Ni trobenzene
               Perylene
               Phenanthrene
               Pyrene
 5
20
20
20
 5
 1
40
 1
 1
 1
 1
 1
 1
 1
 1
 5
40
 1
 1
 1
 1
 1
 1
 1
 1
 5
 1
 1
 1
40
 1
 1
aln nanograms per microliter  injected
                                     3-19

-------
TABLE 3-11.  VOLATILE ORGANIC SPECIES EMISSIONS
Stack Gas Concentration
Compound
Benzene
Toluene
Ethyl benzene
Run 1
(vg/dscm)
128
6.3
3.2
Run 2
(yg/dscm)
42
1.1
<1
Run 3
(ug/dscm)
9
2.3
<1
Average
(wg/dscm) (ppb)
60 18
3.2 0.83
1.7 0.39
                      3-20

-------
3.4.2    TCP. GRAY, GC/MS. and IR Analyses of Sample Total Extracts
     Table 3-12 summarizes organic emissions results based on the TCO, GRAV,
and GC/MS analyses for semivolatile organics.  Total organic emissions were
relatively low, about 300 ug/dscm, and roughly equally  split among the
semivolatile (TCO) and nonvolatile (GRAV) boiling point ranges.  The levels
noted reflect the sorbent module extract analysis;  the  particulate (filter)
extract contained negligible organic content.  The  emissions noted are of  the
same order of magnitude as emissions measured from  recent  tests of a steamer
equipped with another low-NOx burner design  (the MHI burner, Reference 3-5).
Semivolatile priority pollutants detected were naphthalene, phenol, and
dimethylphthalate, all at concentrations well below 10  ug/dscm.  The
dimethylphthalate noted is most  likely a sample contaminant.
     Table 3-13 summarizes results of  the IR spectroscopy  analysis of the
SASS train extracts.  The organic sorbent module extract  spectrum suggests
the presence of aliphatic hydrocarbons and oxygenated hydrocarbons such as
aldehydes and/or ketones.  As noted  in the table,  the filter extract spectrum
showed no peaks.  A weak spectrum for  the blank suggests  the presence of
small quantities of aliphatic hydrocarbons.
3.5  EXTENDED CONTINUOUS EMISSIONS MONITORING
     Continuous monitoring of stack  gas 02,  C02, CO, NOX,  and S02 was
performed for a period extending from  January 21 to February 24, 1984.
Figures 3-3 through 3-5 illustrate the emission trends  over this test period.
The points plotted represent hourly  averages of data taken at 5- to 15-minute
intervals.  Test periods where data  gaps appear correspond to shutdown of  the
steamer.  The first shutdown occurred  during the period of February 12 to
February 15.  This was caused by concerns from the  site personnel relating to

                                     3-21

-------
  TABLE 3-12.  TOTAL ORGANIC AND  SEMIVOLATILE  ORGANIC
               PRIORITY POLLUTANT EMISSIONS
                                       Emission  levela
                                      (ng/dscm)    (pg/J)
Total semivolatile organics
  (C7 to Ci6) by TCO                    170       50

Total nonvolatile organics
  (Cl6+) by gravimetry                  130       35

    Total organics                      300       85
Semivolatile organic priority pollutantsb:

     Naphthalene                          1.4       0.40

     Phenol                               0.7       0.20

     Dimethylphthalate                    3.6       1.0

     Other priority pollutants           <0.4     <0.1

aBlank corrected.  Levels noted correspond to the
 sorbent module extract analysis; the filter
 particulate extract contained negligible organic content.
^Average of duplicate analyses
                          3-22

-------
                       TABLE 3-13.  IR SPECTRA SUMMARY

Sample
XAD-2 extract



Filter
Wave
number
(cra-1)
2930
1732
1438
1255
1165
1125


Intensity4
M
S
w
W
W
W
No peaks

Assignment
CH alky!
OO stretch
C-H bend
C-0 stretch
C-0 stretch
C-0 stretch


Possible compound
categories present
Aliphatic hydrocarbons,
oxygenated hydrocarbons
such as aldehydes
and/or ketones




XAD-2 blankb     2928
C-H aliphatic   Small  amounts of
                aliphatic hydrocarbons
aS = strong; M = medium; W = weak
bVery weak spectrum
                                     3-23

-------
accelerated tube corrosion.  These concerns  turned  out to  be  unfounded upon
inspection.  The second shutdown, starting on  February 16  and lasting to
February 21, was caused by electrical problems.  Steady operation  of  the
steamer was not again reached until February 21.
     The 03 and ($2 traces shown in Figure 3-3 indicate quite steady
operation of the steamer over the entire test period.   Flue gas  02 levels
were maintained at about 3 percent.  Only during the final day (February 24)
did the flue gas 02 increase to over 4 percent, with a corresponding  drop  in
C02 concentration.  It is not known whether  this increase  in  02  was caused by
higher secondary or primary air flow.  NOX emissions,  shown in Figure 3-4,
indicate levels generally below 80 ppm, corrected to 3 percent 02.  Average
NOX emissions for the entire test period were about 70 ppm at 3  percent 02-
 0 measurements, available only to February  11 due  to  subsequent instrument
malfunction, indicate levels generally below 30 ppm at 3 percent 02-   S02
emissions,  shown in Figure 3-5, indicate emissions  in  the  range  of about 500
to 750 ppm at 3 percent 02-  An increase in S02 emissions  seems  evident,
starting at about the half-way point of the extended test  period.   This
increase might be attributable to increased sulfur  levels  in  the crude oil,
although fuel oil samples were not collected during this time period  to
verify this.
                                     3-24

-------
    20
    16
"   12
 aot'V-rCS
1 1 	 1
10 15 2C
^S^c'flt)'
1
1 25
                                                      February 1984
      Figure  3-3.  Flue gas 03  and C02  for the extended test  period.

                                       3-25

-------
   100 -,
80 H
o~
^.
a.
c
o
E
LkJ

O
   !A rr,
   ',-r,'--1
   60 -
       Mi — wgRU i\
      mm&
      fUm i
     21       26

          January 1984
                                                           O
   Figure 3-4.  Flue gas NOX and CO for the extended test period.


                             3-26

-------
    800 -|
    700 J
           O
             ,0
*   600 -L£®
e       l>a. ?3
H •*?
                                    O
             January 1984
                                      February 1984
                                                                             I
a
w
c
0
.? 500 -
E
UJ
04
0
l/l
400 -
300 -
2
^\_J (ft -^
\2*
O O
o

~~r~ ~n i i 	 1 	 1 	
L 26 31 5 10 15 20 2
       Figure 3-5.   Flue  gas SOg  for the extended  test period.




                                     3-27

-------
                          REFERENCES FOR SECTION 3
3-1.  "Protocol for the Collection and Analysis of Volatile POHC's Using
      YOST," EPA-600/8-84-007, NTIS PB84-170042, March 1984.

3-2.  Lentzen, D.E., etal., "IERL-RTP Procedures Manual:  Level  1
      Environmental Assessment (Second Edition)," EPA-600/7-78-201,
      NTIS PB 293795, October 1978.

3-3.  Waterland, L. R., etal., "Environmental Assessment of  Industrial
      Boilers Firing Coal-Liquid Mixtures and Wood," in Proceedings of  the
      1982 Joint Symposium on Stationary Combustion NOY Control.  Volume II,
      EPA 600/9-85-OZZb, NTIS PB 85-235612, July 1985.

3-4.  44 CFR 69532, December 3, 1979.

3-5.  Castaldini, C., et al., "Environmental Assessment of an Enhanced Oil
      Recovery Steam Generator Equipped with a Low-N0x Burner,"
      EPA 600/7-86-003 a/b, February 1986.
                                     3-28

-------
                                  SECTION 4
                 TEST QUALITY ASSURANCE AND QUALITY CONTROL

     Quality assurance  (QA) activities implemented for  this  test  included:
     •   Certification  of  the NOX continuous monitoring analyzer  using
         standard EPA Method 7  protocol for accuracy  determination of the NOX
         monitor readings
     o   Duplicate SSMS analysis of  the fuel sample and duplicate GC/MS
         analysis of SASS  extract sample for determination of analytical
         precision
     o   Duplicate Method  5/8 and controlled condensation system  (CCS)
         measurements of steamer flue gas particulate,  S02,  and $03
         concentrations under relatively constant operation
     9   Analysis of blind spiked XAD-2 resin  blank for TCO, GRAY, and GC/MS
         analytical precision
     o   Use of EPA/EMSL audit  sample in the laboratory analysis  of Method 7,
         Method 8, and  controlled condensation system samples for
         determination  of  analytical accuracy.
     The following paragraphs discuss the results of  these QA activities.
4.1  NOX MONITOR CERTIFICATION  TEST  RESULTS
     The EPA Method 7 test protocol  was used three times during the extended
continuous monitoring period to certify the accuracy  of the  NOX analyzer.
Tables 4-1, 4-2, and 4-3 show the results of the certification tests
                                     4-1

-------
      TABLE 4-1.  METHOD 7 CERTIFICATION RESULTS:  JANUARY 24, 1984
Test
no.
1
2
3
4
5
6
7
8
9
Mean
Mean
NOX
Sample
68
—a
69
77
45
56
53
30
46
reference
reference method results
1 Sample 2
80
—a
59
43
83
93
192
63
28
method test
Sample 3
65
—a
— b
55
34
47
32
53
40
value
(ppm)
Sample
average
71
—
64
58
53
65
92
49
38
61
Average
analyzer
reading
(ppm)
65
—
62
59
58
65
64
64
48

of differences
Difference
(ppm)
6
—
2
( 1)
( 5)
0
28
(15)
(10)

0.62
95 percent confidence interval of the differences = 10.8
Relative accuracy =
         Mean of differences + 95 percent confidence interval X 100
                    Mean reference method value
                  = 19 percent
^Suspected sample contamination during analysis
"Sample lost during recovery
                                   4-2

-------
     TABLE 4-2.  METHOD 7 CERTIFICATION RESULTS:  FEBRUARY 8, 1984
Test
no.
1
2
3
4
5
6
7
8
9
Mean
Mean
NOX
Sample
50
80
64
82
34
80
88
59
41
reference
reference method results
1 Sample 2
32
100
72
95
- 16
13 i
63
60
63
method test
Sample 3
24
64
62
96
80
88
54
54
—a
value
(ppm)
Sample
average
36
81
66
91
60
60
68
58
52
64
Average
analyzer
reading
(ppm)
69
72
70
75
61
65
78
68
63

of differences
Difference
(ppm)
33
(9)
4
(16)
*
1
5
10
10
11

11
95 percent confidence interval of the differences = 7.2

Relative accuracy =

          Mean of differences + 95 percent confidence interval X 100
                    Mean reference method value

                  = 28 percent


aSample lost during recovery
                                  4-3

-------
    TABLE 4-3.  METHOD 7 CERTIFICATION RESULTS:  FEBRUARY 24,  1984
Test
no.
1
2
3
Mean
Mean
NOX reference method results
Sample 1 Sample 2 Sample 3
65 55 53
70 72 99
75 33 63
reference method test value
of differences
(ppm)
Sample
average
58
81
57
65

Average
analyzer
reading
(ppm)
68
73
67


Difference
(ppm)
10
(8)
10

9.3
95 percent confidence interval of the differences = 2.9
Relative accuracy =
          Mean of differences + 95 percent confidence interval X 100
                    Mean reference method value
                  = 19 percent
                                  4-4

-------
conducted on January 24 and February 8 and 24, respectively.  Tests performed
on February 24 were abbreviated  (only three  sets of  three flasks were taken
during this certification test,  as  shown  in  Table 4-3).  Results of the
Method 7 NOX monitor certification  tests  performed on January 24 and on
February 24 indicated that the meter relative accuracy was within  the
performance specification of 20  percent.  The relative accuracy as determined
by the tests on February 8 (Table 4-2) was not.  However, if results from  the
first set of samples are disregarded, the indicated  relative accuracy of the
NOX meter is improved to 15 percent.  NOX readings indicating concentrations
below 45 ppm can be considered suspect.   Two of  the  three samples  in the
first set of Method 7 flasks in  the February 8 tests show NOX concentrations
of 32 and 24 ppm.  Sample leakage may have caused these  low values.
4.2  DUPLICATE ANALYSES
4.2.1  Trace Element Analyses
     Blind duplicate fuel samples were submitted for analysis for  trace
elements by SSMS,  supplemented by atomic  absorption  analysis for mercury and
sodium, x-ray fluorescence for sulfur, and specific  ion  electrode  analysis
for chlorine.  Precision of the  analysis  was then determined based on the
relative standard  deviation of the  replicate samples.  Table 4-4 summarizes
the results of these SSMS duplicate analyses.  The average relative standard
deviation for all  the trace elements was  42  percent;  the maximum relative
standard deviation was 113 percent.  Both are within the implied precision of
Level 1 analyses of a factor of  2 or 3.
4.2.2  Organic Analyses
     The organic sorbent module  extract from the SASS test was analyzed in
duplicate by 6C/MS for the semivolatile organic priority pollutants.  Results
                                     4-5

-------
 TABLE 4-4.  DUPLICATE SSMS ANALYSES OF TEST FUEL*, ppm
Relative standard

Element
Aluminum
Bari urn
Boron
Bromine
Calcium
Chlorine
Chromium
Cobal t
Copper
Fluorine
Gallium
Iodine
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Niobium
Phosphorus
Potassium
Rubidium
Selenium
Silicon
Sodi urn
Strontium
Sulfur
Titanium
Vanadium
Yttrium
Zinc
Zirconium
Sample
901440
9
0.8
0.2
0.2
13
25
0.4
0.6
0.7
27
0.2
0.5
10
0.6
0.5
8
0.4
2
6
0.09
4
5
0.02
0.5
19
132
0.2
11,700
3
6
0.06
2
0.2
Average relative standard
Sample
901441
1
0.3
0.08
0.06
5
21
0.4
0.2
0,7
4
0.2
0.5
5
0.5
0.2
5
0.3
0.3
20
0.03
2
3
0.02
0.4
9
104
0.2 '
11,600
4
2
0.04
2
0.06
deviation
deviation
(percent)
113
64
61
76
63
12
0
71
0
105
0
0
47
13
61
33
20
105
76
71
47
35
0
16
51
17
0
0.61
20
22
28
0
76
42
aOnly elements reported present at greater than the
 method detection limit are noted
                          4-6

-------
of these analyses are summarized in Table 4-5.  The average relative standard
deviation for these duplicate analyses was 32 percent;  the maximum relative
standard deviation was 47 percent.  Both are within the project precision
goal of 50 percent for these measurements  (Reference 4-1).
4.2.3  Particulate. SO?, and 50$ Emission Measurements
     Two sequential combined Methods 5 and 8 tests were performed on
February 1, 1984, with the  steamer operating under relatively  constant
conditions.  Both solid  (front  half) and condensible  (back half) particulate
emission levels were obtained,  as well as  S02 and $03 emissions from wet
chemical analyses of appropriate impinger  solutions.  In  addition, two
sequential CCS tests were performed on February 23, 1984, again under
relatively constant steamer operation, giving duplicate S02 and $03 emission
measurements.  Results of all these tests are summarized  in Table 4-6.
     The project precision  goal for all these measurements is  20 percent
(Reference 4-1).  The precision suggested by Table 4-6  for total particulate,
S02 by both methods, and $03 by CCS fall well within this goal.  The
precision of the Method 8 $03 measurement exceeds the goal; however, the
apparent $03 levels were quite  low.
     The precision of each  of the particulate emission  fraction measurements
(solid and condensible) exceeded the project goal, although the total
particulate result had very good precision.  Discussion in Section 3.2
suggests that changes in steamer operating conditions between  the two
Method 5 runs could have affected the split between solid and  condensible
particulate fractions.  These changes could similarly have affected
emissions as well.
                                     4-7

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        TABLE 4-5.  RESULTS OF DUPLICATE GC/MS ANALYSES OF THE
                    SASS ORGANIC SORBENT MODULE EXTRACT3
Compound
Dibutylphthalate
Dimethylphthalate
Naphthalene
Phenol
Average relative
Analysis resul
Run 1
50
100
40
20
standard deviation
ts, (ug/ train)
Run 2
50
60
20
10

Relative standard
deviation
(percent)
0
35
47
47
32
 aOnly compounds reported present at greater than the
  method detection limit are noted
TABLE 4-6.  RESULTS OF DUPLICATE PARTICULATE, S02, AND $03 MEASUREMENTS
Result (yg/dscm)
Method
Method 5
(February 1, 1984)

Method 8
(February 1, 1984)
CCS
(February 23, 1984)
Parameter
Solid particulate
Condensible particulate
Total particulate
S02
S03
S02
S03
Run 1
64
85
149
1676
43.6
1599
158
Run 2
128
14
142
1606
14.8
1627
169
Relative
standard
deviation
(percent)
47
101
3.4
3.0
70
1.2
4.8
                                  4-8

-------
     Finally, duplicate impinger solution aliquots were analyzed to give the
back half (condensible) particulate result noted in Table 4-6.  Results of
these analyses are given in Table 4-7.  As noted, analytical precision for
these analyses was within 20 percent.
4.3  ANALYTICAL RECOVERY OF BLIND SPIKES
     As part of quality assurance procedures, a sample of blank XAD-2 resin
was spiked with a mixture of polynuclear aromatic hydrocarbons  (naphthalene,
phenanthrene, and pyrene), TCO  compounds (dodecane, hexadecane  and the
naphthalene), and GRAY compounds (bis(2-ethylhexyl)phthalate, plus the
phenanthrene and pyrene noted).  This  spiked resin was then extracted and
analyzed as a separate sample to obtain recovery and analytical accuracy
information.  Table 4-8 summarizes  these data.  As shown in the table, the
recovery and analytical accuracy for all components spiked was  excellent.
The maximum deviations were +28 percent and -35 percent, well within the
project accuracy goal of -50, +100  percent for this analysis.
4.4    REFERENCE METHOD AUDIT SAMPLES
     Audit samples supplied by  EPA's Environmental Monitoring and Support
Laboratory (EMSL) were analyzed along  with the laboratory analysis of
Method 7 and Method 8 samples collected in the field to establish the
analytical accuracy of these analyses.  Results of the audit sample analyses
are summarized in Table 4-9.  Excellent accuracy is evidenced.
                                     4-9

-------
TABLE 4-7.  DUPLICATE METHOD 5 CONDENSIBLE PARTICIPATE ANALYSIS  RESULTS
            Method 5
             train
               1
               2
                       Analysis result  (yg/train)
Test 1   Test 2
13.70
26.31
13.42
20.92
               Relative
               standard
               deviation
               (percent)
 1.5
16
              TABLE 4-8.  SPIKE XAD-2 RESIN ANALYSIS RESULTS
       Analyte spiked
  Spiked amount   Recovered amount   Percent
      (mg)              (mg)         recovery
TCO compounds

  (400 yg dodecane,
   400 yg hexadecane,
   400 yg naphthalene)

GRAY compounds

  (10 mg bis(2-ethylhexyl)
   phthaiate, 400 yg
   pyrene, 400 yg
   phenanthrene)

Polynuclear aromatics

  Naphthalene

  Phenanthrene

  Pyrene
      1.20
     10.8
      0.40

      0.40

      0.40
              0.784
             11.0
              0.42

              0.40

              0.51
             65
            102
            105

            100

            128
                                   4-10

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           TABLE 4-9.  EMSL AUDIT SAMPLE ANALYSIS RESULTS
                Audit sample
Pollutant   Lot no.   Sample no.
                      Reported      Known
                        value      valuea      Percent
                      (mg/dscm)   (mg/dscm)   difference
   S02
   N02
0881

0881

0481
2337

3333

5501
1294.9      1296.4

 200.7       190.7

 297.3       298.6
0.12

5.2

0.44
aAs certified by EMSL
                                  4-11

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                           REFERENCE FOR SECTION 4
4-1.  "Quality Assurance Plan for the Combustion Modification Environmental
      Assessment," Acurex Corporation under EPA Contract 68-02-2160,
      September 10, 1982.
                                     4-12

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                                  SECTION  5
                                    SUMMARY

     Field tests were performed  on  a  16-MW (55  X  106  Btu/hr)  thermally
enhanced oil recovery (EOR)  steamer equipped with  the  EPA  low-NOx burner.
This burner was developed  under  EPA sponsorship to achieve  NOX emissions at
or below 85 ppm at 3 percent Q£  with  acceptable CO and smoke  emissions when
burning high-nitrogen fuel oils.  These  tests were performed  in  conjunction
with the field demonstration tests  by the  Energy and  Environmental  Research
Corporation (EERC), the  burner developers.  Two series of  tests  were
performed:  a comprehensive  test program to characterize flue gas emissions
from the steamer with burner operating conditions  set  to achieve the  field
demonstration goals of less  than 85 ppm  NOX and low combustible  emissions,
and an extended flue gas monitoring program spanning about  30 days  to measure
the low-NOx burner performance under  typical steamer operation.
     During the 1-day comprehensive tests, NOX  emissions averaged about
70 ppm at 3 percent 0£, with CO  emissions  below 30 ppm while burning Kern
County crude oil with a  nitrogen content of about  1 percent.  SOg emissions
measured by a continuous monitor averaged  about 550 ppm, also at 3  percent
02-  Other S0£ measurements  with extractive sampling trains indicate
relatively good agreement  between the continuous monitor and these methods.
Solid partlculate emissions  were  measured at about 27  ng/J  (96 mg/dscm).
Condensible paniculate emissions were at about 14 ng/J (50 mg/dscm).  These

                                      5-1

-------
results correspond to  the average of  two separate measurements.   Particle
size distribution data indicate that  about 90 percent of  the particulate had
a mean particle diameter less than 1  to 10 urn (two determinations).  Trace
element analyses performed on the fuel oil indicate sodium, silicon, nickel,
fluorine, and chlorine are the major  elements present at  levels greater than
10 ug/g.  In the flue gas, sodium, chlorine (condensed chlorides), copper,
iron, nickel, and zinc contributed the highest emission levels, with emission
concentrations greater than 100 ug/dscm.
     Volatile organic analyses of flue gas samples indicated benzene,
toluene, and ethylbenzene as the detected compounds, with emissions in the
2 to 60 ug/dscm (0.4 to 20 ppb) range.  Semivolatile organic compounds
detected were naphthalene and phenol  in the 1 ug/dscm (0.3 ppb) range.  Total
organic emissions were relatively low, at 300 ug/dscm, and relatively evenly
distributed between the semivolatile  (boiling point of about 100° to 300°C)
and nonvolatile (boiling point of greater than about 300°C) categories.
     Extended continuous monitoring of flue gas criteria emissions spanned a
period of 33 days.   During this monitoring period, NOX emissions were
generally below 80 ppm, with an average of about 70 ppm at 3 percent $2-  c^
emissions were also low, generally less than 30 ppm at 3 percent 03.
                                     5-2

-------
                                 APPENDIX A
                       SAMPLING AND ANALYSIS METHODS

     Emissions test equipment was provided by Acurex Corporation.  Onsite
equipment included a continuous monitoring system for emissions measurements
of gaseous criteria pollutants; the source assessment sampling system (SASS)
train for particulate mass, trace elements, and semivolatile and nonvolatile
organics; the EPA Method 5 with modified impingers for 503 and $03
measurements by EPA Method 8; a volatile organic sampling train (VOST) for
volatile organic species; a controlled condensation system (CCS) sampling
train for SC>2 and sulfuric acid mist measurement; gas grab sampling equipment
for determining N20 emissions by subsequent laboratory gas chromatography and
sampling equipment for validation of NOX analyzer measurements with EPA
Method 7.  The following sections summarize the sampling and analysis
equipment and methods used in the field and laboratory.
A.I  CONTINUOUS MONITORING SYSTEM
     Figure A-l illustrates a simplified schematic of the gas conditioning
and monitoring system.  The monitoring capability included 03, C02, CO (high
and low concentrations), NO, NOX, and $03.  The heated sample gas was treated
for moisture removal using a permeation dryer.  Table A-l lists the
instrumentation constituting the continuous monitoring and flue gas
extractive sampling system.  A datalogger was used in addition to strip
charts to record data continuously.
                                     A-l

-------
                                         011-1*11 llr
Figure A-l.  Schematic for continuous  extractive sampling  system.
                                A-2

-------
    TABLE A-l.  CONTINUOUS MONITORING EQUIPMENT IN THE MOBILE LABORATORY
Instrument
NO
NOX
CO (1)
CO (2)
C02
Principle of
operation Manufacturer
Chemi luminescence Thermo Electron
Nondispersive ANARAD
infrared (NDIR)
Nondispersive ANARAD
infrared (NDIR)
Nondispersive ANARAD
infrared (NDIR)
Instrument
model Range
10 AR 0-2.5 ppm
0-10 ppm
0-25 ppm
0-100 ppm
0-250 ppm
0-1,000 ppm
0-2,500 ppm
0-10,000 ppm
500R 0-1,000 ppm
500R 0-10 percent
(10,000 ppm)
AR500 0-20 percent
S02
Pulsed
Fluorescence
Thermo Electron    40
0-100 ppm
0-1,000 ppm
0-5,000 ppm
0-10,000 ppm
02
Fuel cell
Teledyne
0-5 percent
0-10 percent
0-25 percent
Datalogger    Electronic
                    'Acurex/Autodata    10
                               99 channels
Sample gas    Permeation
conditioner   dryer
                    Permapure
                   E-4G-SS     10 scfm
Strip chart   Dual pen
recorders     analog
                    Linear
                   400
0-10 mV
0-100 mV
0-1V
0-10V
                                     A-3

-------
A. 2  TRACE ELEMENT AND SEMIVOLATILE AND NONVOLATILE ORGANIC EMISSIONS
     Emissions of semivolatile and nonvolatile organics were sampled using
the source assessment sampling system (SASS).  Designed for Level 1
environmental assessment (Reference A-l), the SASS collects large quantities
of gas and solid samples required for subsequent analyses for inorganic and
organic emissions.
     The SASS, illustrated in Figure A-2, is generally similar to the system
utilized for total particulate mass emission tests (a high-volume Method 5
train), with the exception of:
     o   The addition of a gas cooler and organic sampling module
     o   The addition of necessary vacuum pumps to allow a sampling rate of
         2 1/s (4 cfm)
Particulate cyclones shown in Figure A-2 were not used for these tests
because of low particulate loading in the flue gas.
     Schematics outlining the standard sampling and analytical procedures
using the SASS equipment are presented in Figures A-3 and A-4.  The following
paragraphs briefly describe analytical procedures used in measuring trace
elements and organic emissions.
     Inorganic analyses of solid (particulate and organic sorbent) and liquid
(impinger solution) samples from the SASS train were performed with spark
source mass spectroscopy (SSMS) for most of the trace elements.  Atomic
absorption spectrometry (AAS) was used for analyses of volatile mercury (Hg),
antimony (Sb), and arsenic (As) and for backup analyses for those elements
identified as major components by SSMS.  Additional backup techniques used to
quantitate elements identified as major components by SSMS were specific ion
                                     A-4

-------
                                     Heated oven
                                                       Filter
          Stainless
            steel
           sample
           nozzle
                              Organic module



                             Gas temperature T.C.

                                Teflon  line
Ol
           Stack
         velocity
       AP magnehellci
          gauges   I
                                                                                Teflon
                                                                                line
                                                                                Isolation
                                                                               ball valve
                     Stainless steel
                      probe  assembly
                                                              Oven T.C

                                                 Sorbent cartridge

                                              Heater controller

                                                               	1
              Teflon  lirfe
            Condensate '
         collector  vessen
                                                                          Imp/cooler trace    .X
                                                                        element collector
                                                                               Coarse adjustment
                               All orifice plate
                   Fine adjustment
                     valve
                               Orifice AH
                              magnehelic
                               gauge
i   »di.uuin iiumpi
1(10  ftVmln each)
                                                                                                                   Implnger
                                                                                                                     T.C.
            Ice bath
            COO grains
            silica gel
             deslcant
            500 ml
             0.2  H AgNOi
             0.2  H (Nll4)2
            500 ml
             30S  H202
Heavy wall
vacuum line
                   |	Control jodulV-^  _°O^
       Note:   T.C.  = Thermocouple
                                Figure A-2.   Source assessment sampling train  schematic.

-------

                            X
                            HI
GC FOR S ft OTHER GAS
ORGANIC |bp<100 Cl
ORV. WEIGH
SOXHLET EX
GRAV


TCO


LC-IR-L
ARR/ACIO DIGESTION
                                                                                                     s
SAMPLE










SPLIT \
SCRAMS
AniiFniit rflnnFfKATF .A..,-,- AQUEOUS PORTION
>y ORGANIC EXTRACT




•_^^_^«__




COMBINE
... \






*
SECOND AND THIRD

IMPINGERS COMBINED
-•—•
     TOTALS
                                                                    5   2   S
 8   1
   • If nquirad. umpto ihould b« wt Mid. for biologkal «nalyftt M thb point.


   Thn IMP • raqund to drfln* ttw tonl RUM of pwiiculM* catch. If ttM •mpto .xoNd* 10% of rtio teal cyetorw and

   Iilt«r umpto «Mi«M. proewd to •mryM. It tin •rnipte it Ma then 10% of th. catch, hold in •
             Figure  A-3.   Flue gas analysis protocol  for SASS  samples.
                                                A-6

-------
rnont AND
 CYCLONE
  HINSl
  OnOANIC'
J
 INORGANIC
                rAHTICULATE
                    COMHINE
         II  INOHOANICS  I
         L—I—'
                     DIOASSAY
                     onoANics
                                         FLUE SOUItCE
                                                               or ACHY
OASES



                              Figure A-4.   Flue  gas sample analysis protocol.

-------
electrode methods for fluorine and chlorine, x-ray fluorescence for  sulfur,
and a wet chemical (colorimetrie) method for phosphorous.
     Quantitative information on total organic emissions was obtained by  gas
chromatography/flame ionization detector for total chromatographable organics
(TCO), that fraction with boiling point between about 100° and 300°C, and by
gravimetry (GRAY) of sample extracts for that fraction with boiling  point
greater than 300°C.  Infrared spectroscopy  (IR) was used for identification
of organic functional groups in the GRAV residue of extract samples  and gas
chromatography/mass spectroscopy (GC/MS) was used to quantitate the
semivolatile organic priority pollutant species in extract samples.  This
class contains several of the polynuclear aromatic hydrocarbon (PAH)
compounds of interest from combustion sources.  Figure A-5 illustrates the
organic analysis methodology used.
     Passivation of the SASS train with 15 percent by volume HN03 solution
was performed prior to equipment preparation and sampling to produce
biologically inert surfaces.  Detailed descriptions of equipment preparation,
sampling procedures,  and sample recovery are discussed in Reference  A-l and
will not be repeated here.
A.3  VOLATILE ORGANIC EMISSIONS
     A volatile organic sampling train (VOST), shown schematically in
Figure A-6, was used to measure the low-molecular-weight volatile organic
compounds (boiling points 
-------
                  Organic Extract
                       or
                Neat Organic Liquid
                    Concentrate
                     Extract
                       I
                                              TCO
                                            Analysis
      n

      vS

      fi

      •^
1
EC/MS Analysis,
POM, and other
organic species

LRMS

Infrared
Analysis

Gravimetric

Repeat TCO
Analysis
if necessary
Figure A-5.  Organic analysis methodology.

                        A-9

-------
               T' bore stopcock
 I
H-*
O
Glass wool
participate
filter
 Stack
 (or test
 system)
                                           Charcoal
                                           backflush  trap
       Thermocouple
       Insert port
                    Condensate
                    trap impinger
                                                            Vacuum
                                                            Indicator
                                                    Tenax/
                                                    charcoal
                                                    trap
                                                     Empty
                                                     Impinger
                                                                                                     Exhaust
                                                                                         Dry gas
                                                                                         meter
                Figure  A-6.   Schematic of  volatile organic  sampling  train  (VOST).

-------
and petroleum-based charcoal.  Prior to  their use in the field, each trap was
conditioned to remove organic compounds.  Conditioning consisted of baking
each trap at 190°C with a N2 purge  for an 8-hr  period.  The  traps were  then
desorbed at 190°C directly  into a GC/FID.   If a trap showed  no contaminant
peaks greater than 20 ng as benzene or toluene,  it was considered ready  for
sampling.  The trap was then sealed at each end with compression fittings,
placed  in clean, muffled culture tubes,  and sealed in a metal can with  a
charcoal packet  for shipping.
     Before the  field testing,  the  entire system was leak-checked at ~15 to
20 in.  of vacuum.  A leakage rate of 0.05 1/min was considered acceptable.
Ambient airNwas  drawn through a charcoal-filled tube to prevent organic
contamination while bringing the system  back to ambient pressure.
     One set of  samples  (three  trap pairs), a field blank, a trip blank, and
a lab blank were obtained for the test program. The gas  sample was obtained
at the  stack location.  A total sample volume of 20 1 was  taken over a  40-min
period  (0.5 1/min) for each trap pair.   Upon completion of the test, the
sample  traps were removed from  the  train, sealed, returned to their original
culture tubes, and stored in a  metal can on ice. The VOST samples were
analyzed by thermal desorption, purge and trap  GC/MS according to the EPA
VOST protocol.   Each pair of traps  used  was analyzed for  the EPA Method 624
(volatile) priority pollutants  (Reference A-3). Each trap in a trap pair was
analyzed separately.
A.4  PARTICULATE TESTS
     Particulate mass emission  tests were performed using  the EPA Method 5
with the impinger train modified according  to EPA Method  8 for S02 and  S03
measurements.  The sampling train used is illustrated in Figure A-7.  Solid
                                     A-ll

-------
ro
                Sample nozzle
                 Probe T.C.
                                      Probe
             \_  "S" type
                  pilot tube
             AP Hagnchellc
             gauge
                                           142 mm (diameter)
                                           filter
                                         Filter
                                         oven
  If
   Oven
   T.C.
                                                                i
                            Teflon
                            connecting
                            line
                                Fritted
                                glass
                                filter
Proportional
temperature
controllers
      Ice/water
      bath

       100 ml
       BOX  I PA
Smith-Greenberg
impinger
"T
   !   •
                 mrtnrin'
                                    AH orifice
                                    plate      ~\
                                                                                                           Check
                                                                                                           valve
                                                                                                 Implnger
                                                                                                 thermocouple
                                                                                                       Silica  gel
                                                                                                       desslcant
3X M2fl,
                                                                                                    Modified
                                                                                                 — Smith-Greenberg
                                                                                                    Impinger
                    Gas meter  thermocouples
                                          Fine adjustment
                                          bypass valve
                Digital  temperature
                Indicator
                                                             Vacuum line

                                                             Vacuum gauge

                                                           4—Coarse adjustment valve

                                                             Airtight vacuum pump
                            Figure A-7.   Participate  and  SQX sampling train (EPA Method 5  and 8).

-------
particulate matter collected in the probe, cyclone, and filter were
determined by gravimetric analyses of these samples. Condensible particulate
matter was obtained from gravimetric analysis of  impinger liquids and
impinger rinses.  Sulfur oxide emissions were determined by bariun-thorin
titration of appropriate impinger solutions per EPA Method 8 protocol.
A.5  SULFUR OXIDE EMISSIONS
     Sulfur oxide emissions  (S02 and $03) were also measured using the
controlled condensation system illustrated in Figure A-8.  This sampling
system, designed primarily to measure vapor phase  concentrations of 503 as
H2$04, consists of a  heated  Vycor probe, a Goksoyr/Ross condenser
(condensation coil),  impingers, a pump, and a dry  gas  test meter.  By using
the Goksoyr/Ross condenser,  the gas is  cooled to  the dew point where $03
condenses as H2S04.   S02 interference is prevented by  maintaining the
temperature of the gas above the water  dew point.  Sulfur dioxide is
collected in a 3 percent hydrogen peroxide solution.   Both S02 and $03  (as
H2S04) are measured by titration with a 0.02 N NaOH, using bromophenol blue
as the indicator.  A  more detailed discussion of  the sampling and analytical
techniques for the controlled condensation system  is given in Reference A-4.
A,6  N20 SAMPLING AND ANALYSIS
     The stack gas grab samples were extracted into stainless-steel cylinders
for laboratory analysis for  N20 using the sampling apparatus illustrated in
Figure A-9.  For analysis, each sample  cylinder was externally heated to
120°C  (250°F), then a 1-ml sample was withdrawn with a gas-tight syringe for
injection into the gas chromatograph (GO equipped with an electron capture
detector (ECO).  The  GC column used was a 10 ft x  1/8  in. stainless-steel
column packed with 80/100 mesh chromosorb 101.  The flow of nitrogen was
                                     A-13

-------
                           • 1/h" quart! noirle

                              316 stainless fleet union
                                                                      -IIInn tcwperiture
                                                                         iMtlni) m*nlle
                                                                                            Coksoyr/Rnti
                                                                                             condtnter
 I
t-»
*.
                                                                                                    tonrtrnter f.C.
                                                                                      Heavy Mil
                                                                                      1/4* I.D.
                                                                                     late* lubinq
                                                                       Submrtlbte wtlcr
                                                                       clrcuUtlon
                                                                      Dl.pUl  I
                                                                        rradnul
                               Proportion*! temperature
                                     controllers      Gtt
                                                                                                     Sta Inlets steel
                                                                                                      condrnier heat
                                                                                                        eiclianqer
                    gauqe
         Coarse adjustment
             valve
Air tight vacuum pump
                               Orifice AP
                            •uqnehellc gauge
                                                   Dry test meter
            Greenberg
   (•plnqer (100 nt 3: H2n


    Cupty Mdlfled SaiUh-
    •Crcenberg Inplnner
1 1 lea gel des leant trap
                                                   Control module
                                               Figure  A-8.   Controlled  condensation  system.

-------
H-«
cn
                        0.7 \m sintered  stainless-steel filter
                             1/4-ln. stainless-steel
                               probe
                                                                          Teflon diaphragm pump

                                                                            Pressure gauge


                                                                                 Inlet valve
500-cm  stainless-steel
  sample cylinder
                                                                  Ceramic Insulation -'
                                                                    and heat  tape

                                                                          Resistive heat tape
                                                                                                                          Outlet
                                                                                                                            valve
                                                                                                                  Thermocouple
                                                   Figure A-9.   ^0  sampling  system.

-------
20 ml/min with the column kept at 45"C (112°F).  Elution time for N20 was

approximately 5 min.

A.7  NOX MONITOR CERTIFICATION SAMPLING AND ANALYSIS

     Certification of the continuous NOX monitor was performed using the

standard EPA Method 7 equipment and protocols.
                           REFERENCES FOR APPENDIX A

 A-l.  Lentzen, D. E.,  et al., "IERL-RTP Procedures Manual:  Level 1
       Environmental Assessment (Second Edition)," EPA-600/7-78-201,
       NTIS PB 293795,  October 1978.

 A-2.  "Protocol for the Collection and Analysis of Volatile POHC's Using
       YOST," EPA-600/8-84-007, NTIS PB84-170042, March 1984.

 A-3.  "Methods for Chemical Analysis of Water and Wastes," EPA-600/4-79-020,
       NTIS PB 297686,  March 1979.

 A-4.  Maddalone, R. and N. Gainer, "Process Measurement Procedures:
       H2S04 Emissions," EPA-600/7-79-156, NTIS PB80-115959, July 1979.
                                     A-16

-------
                                 APPENDIX  B
                        TRACE ELEMENT CONCENTRATIONS

     The following  tables present  sample trace element analysis  results  and
trace element discharge stream concentrations.  The tables  labeled  "ppm"
represent elemental analysis results (ug/g or wg/ml)  for each  sample
analyzed.  Compositions for the steamer crude oil and all SASS train  samples
(filter, XAD-2 resin, and first impinger)  are noted.  Other  tables  give
corresponding sample element concentrations  in units  of yg/dscm  (labeled
MCG/DSCM) and ng/J  (labeled NG/J)  heat input.  A  final set  of  tables  gives
corresponding trace element flowrates in ug/s (labeled MCG/SEC), with the
mass balance ratio  (out/in) noted  in the last table (labeled STEAMER  MASS
BALANCE).
     Symbols appearing in the table include:
     DSCM   Dry standard cubic meter at 1  atm and 20°C
     MCG    Mi crogram
     PPM    Parts per million by weight
     SEC    Second
     <      Less than
     >      Greater than
     Trace elements having concentrations  less than the detectable  limit or
having a blank value greater than  the sample value were given an arbitrary
concentration of zero.
                                     B-l

-------
     Detection limits for  the various  SASS  samples  were:
     •   Filter:                <0.1 ug/g
     •   XAD-2:                 <0.08  wg/g
     •   Impinger and organic   <0.008 wg/ml
         module condensate:
     «   Fuel oil:              <0.7 ng/g
     SASS and steamer operating data used for  the calculation  of trace
element emissions were as  follows:
     •   Fuel flowrate --  388 ml/s  (3,073 Ib/hr)
     •   Heat input -- 16.6 MW (56.63  x 106 Btu/hr)
     •   Flue gas flowrate — 4.62  dscm/s (9,779 dscfm)
     •   SASS gas volume collected  —  22.5 dscm  (796  dscf)
     •   Particulate on filter — 0.5129 g
     •   XAD weight — 130 g
     •   Impinger 1 volume — 547 ml
     •   Impinger 2 and 3  volume — 840 ml
     •   Heating value of  fuel — 42.78 MO/kg  (18,430 Btu/lb)
                                      B-2

-------
DO
oo
                     PPM BLANK CORRECTED

                     ELEMENT

                     ALUMINUM
                     ANTIMONY
                     ARSENIC
                     BARIUM
                     BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM

CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT

COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE

GADOLINIUM
GALLIUM
GERMANIUM
HOLMIUM
 IODINE

 IRON
 LANTHANUM
 LEAD
 LITHIUM
 LUTETIUM

 MAGNESIUM
 MANGANESE
 MERCURY
 MOLYBDENUM
 NEODYMIUM

 NICKEL
 NIOBIUM
 PHOSPHORUS
 PLATINUM
 POTASSIUM

 PRASEODYMIUM
 RUBIDIUM
 SAMARIUM
 SCANDIUM
 SELENIUM
EOR STEAMER
1 BASELINE
PPM
FUEL
.500E401
. 000E400
. 600E-02
. 550E+00
<.100E-01
.000E+00
. 1 40E+00
.130E400
. 000E+00
.900E401 U
. 000E400
. 000E400
. 230E+02
. 400E400
. 400E400
. 700E400
.000E+00
. 000E400
.000E400
.160E-f02
. 000E400
. 200E400
<.200E-01
. 000E4 00
. 500E400
.750E401
. 000E400
.550E400
.350E400
.000E400
.650E+01
. 350E400
< . 400E+00
. 120E+01
. 000E400
.130E+02
.600E-01
.300E+01
. 100E+01
.400E+01
. 000E400
.200E-01
. 000E400
.600E-0I
.450E+00



FILTER
. 232E404
.800E+01
. 158E402
.800E401
. 400E+00
. 200E400
. 000E+00
.600E401
. 000E400
. 000E400
.119E402
. 400E400
.315E405
. 280E402
.557E402
.600E401
.400E401
. 000E400
. 400E400
.106E403
.400E401
.117E402
.190E401
.200E401
. 000E400
.715E404
.I58E402
.300E401
.162E402
. 400E400
. 154E404
. 180E402
.200E-01
. 100E402
.120E402
. 236E405
. 600E400
. 408E403
. 000E400
. 100E401
.380E401
. 700E400
.400E401
.370E401
.380E401
 XAD-2

. 100E401
. 000E400
.300E-01
. 400E400
. 000E400

. 000E400
. 500E400
. 000E400
.000E400
.400E401

. 000E400
. 000E400
. 000E400
. 000E400
. 000E400

. 000E400
.000E400
.000E400
.000E400
.000E400

. 000E400
. 000E400
. 100E-01
. 000E400
. 100E-01

.000E400
. 000E400
. 400E400
.000E400
.000E400

. 100E401
. 100E400
. 120E400
. 100E400
. 000E400

. 100E400
. 000E400
.000E400
.300E400
.800E40t

.000E400
.000E400
.000E400
.000E400
.000E400
                                                                                1ST IMPINGER   2ND ft 3RD IMPINGERS
  .850E400
  .210E-01
  .480E-01
  .180E400
  .000E400

  .000E400
  .180E-01
  .192E400
<.2C0E-0I
  .160E401

  .000E400
  .400E-02
  .000E400
  .299E401
<.600E-02

  .719E+02
  .000E400
  .000E400
  .000E400
  .590E400

  .000E400
  .370E-01
  .880E-01
<.200E400
  .700E-01

  .594E401
  .000E400
  .000E400
  .700E-01
  .000E400

  .000E400
  . 190E400
  .000E400
  .970E400
  .000E400

  .299E401
<.360E-01
  . 100E401
  .000E400
  . 180E401

  .100E-01
  .100E-01
  .000E400
  .495E400
  494E400
.000E400
.000E400
.700E-02
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
. 000E400
. 000E400
.000E400
.000E400

.000E400
. 000E400
. 000E400
.000E400
. 000E400

. 000E400
. 000E400
. 200E-02
. 000E400
. 000E400

.000E400
. 000E+00
.000E400
.000E400
. 000E400

. 000E400
.000E400
. 000E400
. 000E400
. 000E400

-------
   PPM BLANK CORRECTED

   ELEMENT               FUEL
EOR STEAMER
BASELINE
PPM
   SILICON             . 140E+02
   SILVER              .000E+00
   SODIUM              .118E+03
   STRONTIUM           .200E+00
   SULFUR              .104E+04

   TANTALUM            .000E+00
   TELLURIUM           .000E+00
   TERBIUM             .000E+00
   THALLIUM            .000E+00
   THORIUM             .000E+00

   THULIUM             .000E+00
   TIN                 .000E+00
   TITANIUM            .350E+00
   TUNGSTEN            .000E+00
   URANIUM             .000E+00

   VANADIUM            .400E+00
   YTTERBIUM           .000E+00
   YTTRIUM             .500E-01
   ZINC                .200E+01
   ZIRCONIUM           .130E+00
             FILTER

            .000E+00
            .100E+01
            .113E+04
            .120E+02
            .650E+02

            .200E+01
            .300E+01
            .800E+00
            .400E+00
            .800E+01

            .400E+00
            .400E+01
            .200E+02
            .400E+00
            .100E+01

            .937E+03
            .100E+01
            .232E+02
            .600E402
            .000E+00
 XAD-2

.C00E+00
.000E+00
.000E+00
. 110E+00
.500E+01

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.200E-01
.000E+00
.000E+00
.230E+01
.000E+00
1ST IMPINGER   2ND & 3RD IMPINGERS
 .340E+0I
 .900E-01
 .496E+04
 .970E-01
 .687E+04

 .000E400
 .840E-01
 .000E+00
 .000E+00
 .000E+00

 .000E+00
 .000E+00
 .960E+00
 .000E+00
 .600E+01

 .470E-01
 .000E+00
 .100E-01
 .300E+02
 .S00E-01
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E400
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
CO

-------
   CONCENTRATION

   ELEMENT

   ALUMINUM
   ANTIMONY
   ARSENIC
   BARIUM
   BERYLLIUM

   BISMUTH
   BORON
   BROMINE
   CADMIUM
   CALCIUM

   CERIUM
   CESIUM
   CHLORINE
   CHROMIUM
   COBALT

   COPPER
   DYSPROSIUM
   ERBIUM
   EUROPIUM
   FLUORINE

   GADOLINIUM
co GALLIUM
   GERMANIUM
   HOLMIUM
   IODINE

   IRON
   LANTHANUM
   LEAD
   LITHIUM
   LUTET1UM

   MAGNESIUM
   MANGANESE
   MERCURY
   MOLYBDENUM
   NEODYMIUM

   NICKEL
   NIOBIUM
   PHOSPHORUS
   PLATINUM
   POTASSIUM

   PRASEODYMIUM
   RUBIDIUM
   SAMARIUM
   SCANDIUM
   SELENIUM
i
en
FILTER

 .528E+02
 .182E+00
 .360E+00
 .182E400
 .910E-02

 . 455E-02
 .000E+00
 . 137E+00
 .000E400
 .000E-V00

 .27 IE-fee
 .910E-02
 .716E+03
 .637E+00
 .127E+01

 .137E-l-0e
 .910E-01
 .000E+00
 .9ieE-«2
 .241E+01

 .910E-01
 .266E+00
 .432E-01
 .455E-01
 .000E+00

 .163E+03
 .360E+C0
 .6B3E-01
 .369E+00
 .910E-02

 .350E+02
 .410E+00
 .455E-03
 .228E+00
 .273E+00

 .536E+03
 .137E-ei
 .928E+01
  .000E+00
 .228E-01

  .865E-01
  .159E-01
  .910E-81
  .842E-01
 .865E-B1
                               EOR STEAMER
                               BASELINE
                               MCG/DSCM
XAD-2

 .577E+B1
 .000E+00
 .173E+00
 .231E+01
 .000E+00

 .000E+00
 .288E+01
 .000E+00
 .000E+00
 .231E+02

 .000E+00
 .000E+00
 . 000E+00
 . 000E+00
 .000E+00

 .000E-1-00
 .000E+00
 .000E+00
 .000E+00
 .000E+00

 .000E+00
 .000E+00
 .577E-01
 .000E+00
 .577E-01

 .000E+00
 .000E+00
 .231E+01
 .000E+00
 . 000E+00

 .577E+ei
 .577E+00
 .692E+00
 .577E+ee
 .000E+00

 .577E+00
 .000E+00
 .000E+00
 .173E+01
 .461E+02

 .000E+00
 .000E+00
 .000E+00
 .000E-f00
 .000E+00
                                                              1ST 1MPINGER   2ND t 3RD  IMPINGERS
                                                                 . 206E+02
                                                                 .510E+00
                                                                 . 116E+01
                                                                 .000E+00

                                                                 .000E+00
                                                                 . 437E+00
                                                                 .466E+01
. 388E+02

. 600E+00
.971E-01
. 000E+00
. 726E+02
.146E+00

.174E+B4
.000E+00
. C00E+00
.000E+00
. 143E+02

.000E+00
. 898E+ ee
. 214E+01
                                                                  .170E+ei

                                                                  . 144E403
                                                                  . 000E+00
                                                                  .000E+00
                                                                  . 170E+01
                                                                  . 000E-H00

                                                                  .000E+00
                                                                  .461E-I-01
                                                                  .000E+00
                                                                  . 235E+02
                                                                  . 000E+00

                                                                  .726E+02
                                                                  . 874E+00
                                                                  .243E+02
                                                                  .000E+«0
                                                                  . 437E+02

                                                                  .243E+00
                                                                  . 243E+00
                                                                  . 000E+00
                                                                  . 1 2BE+B2
                                                                  . 120E+02
.000E+00
.000E+00
.261E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
. 000E+00

.000E+00
.000E+00
. 000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.745E-B1
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
   STACK OUTLET

       .792E+02
       .692E+«0
       .196E+01
       .6B6E+01
       .910E-02

       .455E-fl2
       .332E+01
       .480E401
     < .485E400
       .619E+02

       .271E+00
       .106E+00
       .716E+03
       .732E+02
. 127E+0KX<.141E+ei

       . 174E+04
       .910E-01
       . 000E400
       .910E-02
       .167E+02

       .910E-01
       .1J6E+01
       .224E+01
.455E-0KX<.490E-t-01
       .176E+01

       .307E+03
       .360E+00
       .238E+01
       .207E+01
       .910E-02

       .408E+02
       .560E+01
       .767E+00
       .243E+02
       .273E+00

       .609E+03
. 137E-0KX<.887E+00
       .336E+02
       .173E+01
       .898E+02

       .329E400
       .259E+00
       .910E-01
       . 121E+02
       . 121E+02

-------
    CONCENTRATION

    ELEMENT

    SILICON
    SILVER
    SODIUM
    STRONTIUM
    SULFUR

    TANTALUM
    TELLURIUM
    TERBIUM
    THALLIUM
    THORIUM

    THULIUM
    TIN
    TITANIUM
    TUNGSTEN
    URANIUM

    VANADIUM
    YTTERBIUM
    YTTRIUM
    ZINC
    ZIRCONIUM
FILTER

 . 000E400
 .228E-01
 .258E402
 .273E400
 .14BE401

 .455E-01
 .683E-01
 . 182E-01
 .910E-02
 .182E400

  910E-02
  910E-01
 . 455E400
 .9J0E-02
 .228E-01

 .213E+C2
 .228E-01
 .528E400
 .137E+01
 .000E400
       EOR STEAMER
       BASELINE
       MCG/DSCM
XAD-2

 .000E400
 . 000E400
 .000E400
 .634E400
 . 288E-I-02

 .000E400
 .000E400
 .000E400
 .000E400
 .000E400

 .000E400
 .000E400
 .000E400
 .000E+00
 .000E+00

 .115E+00
 .000E+00
 .000E+00
 .U3E402
 .000E+00
1ST IMPINGER   2ND & 3RD IMPINGERS
   . 825E402
   . 218E401
   . 120E+06
   .235E401
    167E406

   . 000E400
   .204E+01
   . 000E400
   .000E400
   . 000E400

   . 000E400
   . 000E400
   . 233E+02
   . 000E400
   . 146E403

    114E401
   . 000E400
   . 243E400
   . 728E+03
    121E+01
. 000E400
. 000E400
. 000E400
. 000E400

. 000E400
. 000E400
. 000E400
. 000E400
. 000E400

.000E400
.000E400
.000E400
. 000E400
.000E400

.000E400
.000E400
. 000E400
. 000E400
.000E400
STACK OUTLET

    .B25E402
    .221E401
    .120E406
    .326E401
    .167E406

    .455E-01
    .211E401
    .182E-01
    .910E-02
    . 182E400

    .910E-02
    .910E-01
    . 238E402
    .910E-02
    . 146E403

    . 226E402
     228E-01
    .771E400
    .742E403
    . 121E401
oo
i

-------
MASS/HEAT INPUT

ELEMENT

ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM

BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM

CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT

COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE

GADOLINIUM
GALLIUM
GERMANIUM
HOLMIUM
 IODINE

 IRON
 LANTHANUM
 LEAD
 LITHIUM
 LUTETIUM

 MAGNESIUM
 MANGANESE
 MERCURY
 MOLYBDENUM
 NEODYMIUM

 NICKEL
 NIOBIUM
 PHOSPHORUS
 PLATINUM
 POTASSIUM

 PRASEODYMIUM
 RUBIDIUM
 SAMARIUM
 SCANDIUM
 SELENIUM
FUEL
       EOR STEAMER
       BASELINE
       HG/J
 .117E+00
 .000E+00
 . 140E-03
 .128E-01
 .2J3E-03

  000E+00
 .327E-82
 .303E-02
 .000E+00
 .210E+00

 .000E+00
  000E+00
 .537E+00
 .933E-02
 .933E-02

 .163E-01
 .000E+00
 .000E+00
 .000E+00
 .373E+00

 .000E+00
  .467E-02
  .467E-03
  .000E+00
  .117E-01

  .175E+00
  .000E+00
  . 128E-01
  .B16E-02
  .000E+00

  .152E+00
  .B16E-02
:  .933E-02
  .280E-01
  .000E+00

  .303E400
  .140E-02
  .700E-01
  .233E-01
  .933E-01

  .000E+00
  .467E-03
  .000E+00
  .J40E-02
  .105E-01
  STACK OUTLET

       .220E-01
       .192E-03
       .545E-03
       .191E-02
       .253E-05

       .127E-05
       .923E-03
       .133E-02
     <  .135E-03
       .172E-01

       .753E-04
       .295E-04
       .199E+00
       .204E-01
.352E-03
-------
   MASS/HEAT INPUT

   ELEMENT

   SILICON
   SILVER
   SODIUM
   STRONTIUM
   SULFUR

   TANTALUM
   TELLURIUM
   TERBIUM
   THALLIUM
   THORIUM

   THULIUM
   TIN
   TITANIUM
   TUNGSTEN
   URANIUM

   VANADIUM
   YTTERBIUM
   YTTRIUM
   ZINC
   ZIRCONIUM
FUEL
      EOR STEAMER
      BASELINE
      NG/J
.327E+00
.000E+00
.275E+01
.467E-02
.243E+02

.eeeE+ee
.000E+00
.eeeE+ee
.000E+00
.000E+00

.ee0E+ee
.000E+00
.816E-02
.000E+00
.000E+00

.933E-02
.000E+00
.117E-02
.467E-01
.303E-02
STACK OUTLET

    .229E-01
    .614E-03
    .335E+02
    .907E-03
    .464E+02

     127E-04
    .586E-03
    .506E-05
    .253E-05
    .506E-04

    .253E-05
    .253E-04
    .661E-02
    .253E-05
    .405E-01

    .628E-02
    .633E-05
    .214E-03
    . 206E+00
    . 337E-03
cx>
i
00

-------
  MASS/HEAT  INPUT

  ELEMENT

  ALUMINUM
  ANTIMONY
  ARSENIC
  BARIUM
  BERYLLIUM

  BISMUTH
  BORON
  BROMINE
  CADMIUM
  CALCIUM

  CERIUM
  CESIUM
  CHLORINE
  CHROMIUM
  COBALT

  COPPER
  DYSPROSIUM
   ERBIUM
   EUROPIUM
   FLUORINE

   GADOLINIUM
   GALLIUM
"> GERMANIUM
10 HOLMIUM
   IODINE

   IRON
   LANTHANUM
   LEAD
   LITHIUM
   LUTETIUM

   MAGNESIUM
   MANGANESE
   MERCURY
   MOLYBDENUM
   NEODYMIUM

   NICKEL
   NIOBIUM
   PHOSPHORUS
   PLATINUM
   POTASSIUM

   PRASEODYMIUM
   RUBIDIUM
   SAMARIUM
   SCANDIUM
   SELENIUM
FILTER

 .147E-01
 .506E-04
 .100E-03
 .506E-04
 .253E-05

 .127E-05
 .000E+00
 .380E-04
 .600E-I-00
 .000E+00

 .753E-04
 . 253E-05
 . 199E400
 .177E-03
 .352E-03

 .380E-04
 .253E-04
 .000E+00
 .253E-05
 .671E-03

 .253E-04
 .740E-94
 .120E-04
 .127E-04
  000E+00

 .452E-01
 .100E-03
 .190E-04
 .103E-03
 .253E-05

  .975E-02
  .114E-03
  .127E-06
  .633E-04
  .759E-04

  .149E+00
  .380E-05
  .258E-02
  .000E+00
  .633E-05

  .240E-04
  .443E-05
  .253E-04
  .234E-04
  .240E-04
       EOR STEAMER
       BASELINE
       NG/J
XAD-2

 .160E-02
 .000E+00
 .481E-04
 .642E-03
 .000E+00

 .000E+00
 .802E-03
 .000E+00
 .000E+00
 .642E-02

 .000E+00
 .000E+00
 .000E+00
 .000E+00
 .000E+00

 .000E+00
 .000E+00
 .000E+00
 .000E+00
 .000E+00

 .000E+00
 .000E+00
 .160E-04
 .000E+00
 .160E-04

 .000E+00
 .000E+00
 .642E-03
 .000E+00
 .000E+00

 .160E-02
 .160E-03
 .192E-03
 .160E-03
 .000E+00

 .160E-03
 .000E+00
 .000E+00
 .481E-03
 .128E-01

 .000E+00
 .000E+00
 .000E+00
 .000E+00
 .000E+00
1ST IMPINGER   2ND It 3RD IMPINGERS
   .574E-02
   .142E-03
   .324E-03
   .121E-02
   .000E+00

   . 000E+00
   .121E-03
   .130E-02
   .135E-03
   .108E-01

    000E+00
   .270E-04
   .000E+80
   .202E-01
   . 405E-04

   .485E+00
   .000E+00
   .000E+00
   .000E+00
   .398E-02

   .000E+00
   .250E-03
   .594E-03
   .135E-02
   .472E-03

   . 401E-01
   .000E+00
   . 000E400
   .472E-03
   . 000E+00

   .000E+00
   .128E-02
   .000E+00
   .655E-02
   .000E+00

   .202E-01
   .243E-03
   .675E-02
   .000E+00
   .121E-01

   .675E-04
   .675E-04
   .000E+00
   .334E-02
   .333E-02
.000E+00
.000E+00
.726E-04
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
. 000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.207E-04
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
   STACK OUTLET

       .220E-01
       .192E-03
       .545E-03
       .191E-02
       .253E-05

       .127E-05
       .923E-03
       .133E-02
     < .135E-03
       .172E-0)

       .753E-04
       .295E-04
       .199E+00
       .204E-01
.352E-03
-------
   MASS/HEAT INPUT

   ELEMENT

   SILICON
   SILVER
   SODIUM
   STRONTIUM
   SULFUR

   TANTALUM
   TELLURIUM
   TERBIUM
   THALLIUM
   THORIUM

   THULIUM
   TIN
   TITANIUM
   TUNGSTEN
   URANIUM

   VANADIUM
   YTTERBIUM
   YTTRIUM
   ZINC
   ZIRCONIUM
FILTER

 .000E+00
 .633E-05
 .718E-02
 .759E-04
 .411E-03

 .127E-04
 .190E-04
 .506E-05
 .253E-05
 .506E-04

 .253E-05
 .253E-64
 .127E-03
 .253E-65
 .633E-05

 .593E-02
 .633E-05
 .147E-03
 .3B0E-03
 .000E+00
       EOR STEAMER
       BASELINE
       NG/J
XAO-2

 .000E+00
 . 000E+00
 .000E+00
  176E-03
 .802E-02

  000E+00
  000E+00
  000E+00
 .000E+00
  000E+00

 .000E+00
 .000E+00
 .000E+00
 .000E+00
 .000E+00

 .321E-04
 .000E+00
 .000E+00
 .369E-02
 .000E+00
1ST IMPINGER   2ND * 3RD IMPINGERS
   .229E-01
   .607E-03
   .335E+02
   .655E-03
   .464E+02

   .000E+00
   .567E-03
   .000E+00
   .000E+00
   .000E+00

   .000E+00
   .000E+00
   .648E-02
   .000E+00
   .405E-01

   .317E-03
   .000E+00
   .675E-04
   .202E+00
   .337E-03
.000E+00
. 000E+00
.000E+00
.000E400
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E+00
.000E+00
.000E+00
.000E+00

.000E+00
.000E-I-00
.000E+00
.000E+00
.000E+00
STACK OUTLET

    .229E-01
    .614E-03
    .335E+02
    .907E-03
    .464E+02

    .127E-04
    . 586E-03
    .506E-05
    .253E-05
    .S06E-04

    .253E-05
    .253E-04
    .661E-02
    .253E-65
    .405E-01

    .628E-02
    .633E-05
    .214E-03
    .206E+00
    .337E-03
 I
o

-------
  MASS FLOWRATE

  ELEMENT

  ALUMINUM
  ANTIMONY
  ARSENIC
  BARIUM
  BERYLLIUM

  BISMUTH
  BORON
  BROMINE
  CADMIUM
  CALCIUM

  CERIUM
  CESIUM
  CHLORINE
  CHROMIUM
  COBALT

  COPPER
  DYSPROSIUM
  ERBIUM
  EUROPIUM
  FLUORINE

  GADOLINIUM
  GALLIUM
Y GERMANIUM
— HOLMIUM
   IODINE

   IRON
   LANTHANUM
   LEAD
   LITHIUM
   LUTETIUM

   MAGNESIUM
   MANGANESE
   MERCURY
   MOLYBDENUM
   NEODYMIUM

   NICKEL
   NIOBIUM
   PHOSPHORUS
   PLATINUM
   POTASSIUM

   PRASEODYMIUM
   RUBIDIUM  .
   SAMARIUM
   SCANDIUM
   SELENIUM
FUEL
       EOR  STEAMER
       BASELINE
       MCG/SEC
 . 194E404
 .000E400
 .233E401
 .213E+03
 .388E401

 .000E+00
 .543E402
 .504E402
 .000E+00
 .349E+04

 .000E400
 .000E400
 .891E404
 .155E403
 .155E403

 .271E403
 .000E400
 .000E+00
 .000E400
 . 620E404

 .000E+00
 .775E402
 .775E401
  .000E+00
  .194E403

  .291E404
  .000E+00
  213E+03
  136E403
  .000E+00

  .252E+04
  .136E+03
I  .155E+03
  .46SE403
  .000E+00

  .504E+04
  .233E+02
  .116E+04
  .3B8E+03
  .155E+04

  .000E+00
  .775E+01
  .000E+00
  .233E+02
  .174E+03
  STACK OUTLET

       .366E+03
       .320E401
       .905E+01
       .317E402
       .421E-01

       .210E-01
       . 153E+02
       .222E+02
    <  .224E+01
       .286E+03

       .125E+01
       .491E+00
       .331E+04
       .338E+03
.586E+0KX<.653E+01

       . 806E+04
       .421E+00
       .000E+00
       .421E-01
       .773E+02

       .421E+00
       .538E+01
       .103E+02
.210E+00
-------
                               EOR STEAMER
  MASS  FLOWRATE                BASELINE
                               MCG/SEC
  ELEMENT               FUEL            STACK OUTLET

  SILICON               .543E+04             .381E403
  SILVER                .000E+00             .102E+02
  SODIUM                .457E+05     '        .556E+06
  STRONTIUM             .775E+02             .151E+02
  SULFUR                .403E+06             .770E+06

  TANTALUM              .000E+00             .210E+00
  TELLURIUM             .000E+00             .973E4BI
  TERBIUM               .000E+00             .841E-01
  THALLIUM              .000E+00             .421E-01
  THORIUM               .0B0E+00             .841E+00

  THULIUM               .000E+00             .421E-01
  TIN                   .000E+00             .421E+00
  TITANIUM              .136E403             .I10E+03
  TUNGSTEN              .000E+00             .421E-01
  URANIUM               .000E+00             .673E+03

  VANADIUM              .155E+03             104E+03
  YTTERBIUM             .000E+00             .105E+00
  YTTRIUM               .194E+02             356E+01
  ZINC                  .775E+0J             .343E+04
  ZIRCONIUM             .504E+02             .561E+01
ro
i

-------
DO
I
MASS FLOWRATE

ELEMENT

ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM

BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM

CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT

COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE

GADOLINIUM
GALLIUM
GERMANIUM
HOLMIUM
 IODINE

 IRON
 LANTHANUM
 LEAD
 LITHIUM
 LUTETIUM

 MAGNESIUM
 MANGANESE
 MERCURY
 MOLYBDENUM
 NEODYM1UM

 NICKEL
 NIOBIUM
 PHOSPHORUS
 PLATINUM
 POTASSIUM

 PRASEODYMIUM
 RUBIDIUM
 SAMARIUM
 SCANDIUM
 SELENIUM
FILTER

 .244E+03
 .841E+00
 .166E401
 .841E400
 .421E-81

 .210E-01
 .eeeE+ee
 .631E+00
 .000E400
 .000E400

 .125E401
 .421E-01
 .331E404
 .294E401
 .586E+01

 .631E400
 .421£400
 .000E400
 .421E-01
 .111E+02

 .421E400
 .123E401
 .200E400
 .210E400
 .000E400

 .751E403
 . 166E-I-01
 .315E400
 .170E401
 .421E-01

 .162E403
 .189E401
 . 210E-02
 .105E+01
 .126E+01

 .248E404
 .631E-01
 .429E+02
 .000E400
 .105E400

 .399E400
 .736E-01
  .421E+00
  .389E+00
 .399E400
                                 EOR STEAMER
                                 BASELINE
                                 MCG/SEC
XAD-2

 .266E+02
 .000E+00
 . 799E400
 .107E402
  000E+00

 .000E400
 .133E402
  000E+00
 .000E400
 .107E403

 .000E400
  000E400
 .000E+00
 .000E400
 .000E+00

 .000E+00
 .000E400
 .000E+00
 .000E+00
 . 000E400

 .000E400
 .000E400
 .266E400
 .000E400
 .266E400

 .000E400
 .000E400
 .107E402
 .000E400
 .000E400

 .266E402
 .266E401
 .320E401
 .266E401
 .000E400

 .266E401
 .000E400
 .000E400
 .799E401
 .213E403

 .000E400
 .000E400
 .000E400
 .000E400
 .000E400
                                                                1ST IMPINGER   2ND & 3RD IMPINGERS
.953E402
.235E401
.538E401
. 202E402
.000E400

.000E400
.202E401
.215E402
. 224E401
.179E403

.000E400
. 448E400
.000E400
.335E403
.673E400

.806E404
.000E400
.000E400
.000E400
.661E402

.000E400
.415E401
.987E401
.224E402
.785E401

.666E403
.000E400
.000E400
.785E401
.000E400

.000E400
.213E402
. 000E400
.109E403
.000E400

.335E403
.404E401
.112E403
.000E400
.202E403

.112E401
 112E401
.000E400
.555E402
.554E402
.000E400
.000E400
.121E+01
.000E400
.000E400


.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.344E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400


.000E400
.000E400
.000E400
.000E400
.000E400
   STACK OUTLET

       .366E403
       .320E401
       .905E401
       .317E+02
       .421E-01

       .210E-01
       . 153E402
       . 222E402
     < .224E401
       . 286E403

       .125E401
       . 491E400
       .331E404
       .338E403
.586E40KX<.653E401

       .806E404
       .421E400
       . 000E400
       .421E-01
       . 773E402

       .421E400
       .538E401
       .103E402
. 210E400
-------
       MASS  FLOWRATE

       ELEMENT

       SILICON
       SILVER
       SODIUM
       STRONTIUM
       SULFUR

       TANTALUM
       TELLURIUM
       TERBIUM
       THALLIUM
       THORIUM

       THULIUM
       TIN
       TITANIUM
       TUNGSTEN
       URANIUM

       VANADIUM
       YTTERBIUM
       YTTRIUM
       ZINC
       ZIRCONIUM
FILTER

 .000E+00
 .105E+00
 .119E+03
 .126E+01
 .6B3E+01

 .210E400
 .315E+00
 .841E-01
 .421E-01
 .841E400

 .421E-01
 .421E+00
 .210E+01
 .421E-01
 .105E400

 .985E+02
 .105E+00
 .244E+01
 .631E+01
 .000E+00
       EOR STEAMER
       BASELINE
       MCG/SEC
XAD-2

 . 000E400
  000E400
 .000E400
 .293E+01
 .133E+03

 .000E+00
 .000E+00
 .006E+00
 .000E+00
 .000E+00

  000E+00
 .000E+00
 .000E+00
 .000E+00
 .000E+00

 .533E+00
 .000E+00
 . 000E+00
 .613E+02
 .000E+00
1ST IMPINGER   2ND Jc 3RD IMPINGERS
   .381E403
   .101E+02
   .556E+06
   .109E+02
   .770E+06

   .000E+00
   .942E40t
   .000E400
   .000E400
   .000E400

   .000E+00
   .000E400
   .108E+03
   .000E400
   .673E+03

   .527E+01
   .000E+00
   . 112E+01
   .336E+04
   .561E+01
.000E+00
.000E+00
. 000E+00
.000E+00
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400

.000E400
.000E400
.000E400
.000E400
.000E400
STACK OUTLET

    .381E403
    .102E402
    .556E406
    . 151E402
    .770E406

    .210E400
    .973E401
    .841E-01
    .421E-01
    .841E400

    .421E-01
    .421E400
    . H0E403
    .421E-01
    .673E403

    . 104E403
    . 105E400
    .356E401
    .343E404
    .561E401
oo
i

-------
                            EOR STEAMER
                            BASELINE
ELEMENT
                   STEAMER
STEAMER MASS BALANCE
              TOTAL IN
                                     INPUT = FUEL
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
03 GADOLINIUM
.1 GALLIUM
en GERMANIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
PLATINUM
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
. 194E+04
.233E+B1
.213E+03
X< 388E+01
. 543E+02
. 504E+02
. 349E+04
.891E+04
.155E+03
.155E+03
.271E+03
. 620E+04
. 775E+02
X<.775E+01
. 194E403
.291E+04
.213E+03
.136E-I-03
. 252E+04
. 136E+03
X<.155E+03
. 465E+03
.504E+04
. 233E+02
. 116E+04
.388E+03
. 155E+04
.775E+01
. 233E+02
.174E+03
     OUTPUT = STACK GAS
   TOTAL OUT

.366E+03
.320E+01
.905E+01
.317E+02
.421E-61

.210E-01
.153E+02
.222E+02
        X<.224E+01
.286E+03

.125E+01
.491E+00
.331E+04
. 338E+03
.586E+0KX<.653E+01

.806E+04
.421E+00

.421E-01
.773E+02

.421E+00
.538E+01
.103E+02
.210E+00
-------
                                 EOR STEAMER
                                 BASELINE
     ELEMENT

     SILICON
     SILVER
     SODIUM
     STRONTIUM
     SULFUR

     TANTALUM
     TELLURIUM
     TERBIUM
     THALLIUM
     THORIUM

     THULIUM
     TIN
     TITANIUM
     TUNGSTEN
     URANIUM

     VANADIUM
     YTTERBIUM
     YTTRIUM
     ZINC
     ZIRCONIUM
                   STEAMER
STEAMER MASS BALANCE
              TOTAL IN

         .543E+04

         .457E+05
         .775E+02
         .403E+06
                                          INPUT = FUEL
         .136E+03
         .155E+03

         .194E+02
         .775E+03
         .504E+02
     OUTPUT = STACK GAS
   TOTAL OUT

 381E+03
 102E+02
 556E+06
 151E+02
 770E+06

 210E+60
 973E+01
 841E-0)
.42IE-01
.84IE4-00

.421E-01
.421E+00
 110E+03
.421E-01
.673E+03
.104E+03
.105E+00
.356E+01
.343E+04
.561E+01
MASS BALANCE (OUT/IN)

.703E-01
         •
 122E+02
.194E+00
.191E+01
.809E+00
.673E+00

 184E+00
.442E+01
.111E+00
CO
i

-------
                                TECHNICAL REPORT DATA
                          (Please read Inuructions on the reverse before completing)
 . REPORT NO.
 EPA-600/7-86-013a
                           2.
                                                      3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Environmental Assessment of an Enhanced Oil
 Recovery Steam Generator Equipped with an EPA
 Heavy-oil Low-NOx Burner; Volume I*
                                                      5. REPORT DATE
                                                       April 1986
                                                      6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)    	

 C. Castaldini, L. R. Waterland,  and R.  De Rosier
                                                      8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
A cur ex Corporation
Energy and Environmental Division
P. O. Box 7044
Mountain View,  California  94039
                                                      10. PROGRAM ELEMENT NO.
                                                      11. CONTRACT/GRANT NO.
                                                       68-02-3188
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Air and Energy Engineering Research Laboratory
 Research Triangle Park, NC 27711
                                                      13. TYPE OF REPORT AND PERIOD COVERED
                                                       Final; 1/84 - 1/85
                                                      14. SPONSORING AGENCY CODE
                                                        EPA/600/13
is. SUPPLEMENTARY NOTES AEERL projectofficeris Joseph Ai McSorley,  Mail Drop 65,  919 /
541-2920.  Volume jj is a data supplement. (*) Volume I is Technical Results.
io. ABSTRACT
          The report gives results of comprehensive emission measurements and
30-day flue  gas monitoring on a 16-MW (55 million Btu/hr) enhanced oil recovery
steam generator equipped with the EPA low-NOx burner firing high-nitrogen crude.
The 1-day comprehensive measurements included quantification of semivolatile or-
ganics  and 73 trace elements; volatile organic sampling train quantisation of volatile
organic priority pollutants;  EPA Method 5/8 for particulate and SOx;  controlled con-
densation for SOx; Andersen impactors for particle size distribution; grab samples
for N2O; and continuous flue gas monitoring.  NOx emissions averaged 70 ppm at 3%
O2, well below the target of 85 ppm.  CO emissions were below 30 ppm,  and SO2
averaged about 550 ppm. Solid particulates were emitted at about 27 ng/J (96 mg/
dscm); condensible particulates were about half that. Volatile organics (benzene,
toluene, and ethylbenzene)  were measured in the 0.4 to 20 ppb range.  Semivolatile
organics (naphthalene and phenol)  were detected at about 0. 3 ppb. Subsequent contin-
uous monitoring of flue gas  criteria emissions showed  NOx below 80 ppm at 3% O2
with  an average of 70 ppm.  CO emissions were generally less than 30 ppm.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                          b.lDENTIFIERS/OPEN ENDED TERMS
                                                                  c. COSATI Field/Group
 Pollution
 Assessments
 Boilers
 Oil Recovery
 Crude Oil
 Combustion
                                          Pollution Control
                                          Stationary Sources
                                          Environmental Assess-
                                           ment
                                          Low-NOx Burners
                        13B
                        14B
                        ISA
                        081.11H

                        21B
                                                                  21. NO. OF PAGES
                                                                      100
13. DISTRIBUTION STATEMENT
 Release to Public
19. SECURITY CLASS (This Report)
Unclassified     	
                                          20. SECURITY CLASS (This pagt)
                                          Unclassified
                                                                  22. PRICE
EPA Form 2220-1 (»-73)
                                        B-17

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