6EPA
United States
Environmental Protection
Agency
EPA-600/7-86-004a
February 1986
Research and
Development
ENVIRONMENTAL ASSESSMENT OF
A WATERTUBE BOILER
FIRING A COAL/WATER SLURRY
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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EPJA-600/7-86-004a
February 1986
ENVIRONMENTAL ASSESSMENT OF
A WATERTUBE BOILER FIRING
A COAL-WATER SLURRY
Volume I
Technical Results
By
R. DeRosier and L R. Waterland
Acurex Corporation
Energy & Environmental Division
555 Clyde Avenue
P.O. Box 7555
Mountain View, California 94039
EPA Contract No. 68-02-3188
EPA Project Officer: R. E Hall
Air and Energy Engineering Research Laboratory
Research Triangle Park, North Carolina 27711
For
US. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ACKNOWLEDGEMENT
This test program was performed in cooperation with the Pittsburgh
Energy Technology Center (PETC). The help and cooperation of Y. S. Pan, D.
Snedden, G. Bellas, D. Wildman, and D. Wieczenski of PETC is greatly
appreciated. Special recognition is also extended to the Acurex field test
team of M. Chips, M. Murtiff, R. Klug, and P. Kaufmann, under the supervision
of 3. OaRos.
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CONTENTS
Acknowledgment ii
Figures v
Tables vl
1 Introduction 1-1
References for Section 1 1-9
2 Test Facility Description 2-1
3 Emission Results 3-1
3.1 Boiler Operation and Test Arrangements 3-1
3.2 Criteria Pollutant and Other Gas Phase Emissions . . 3-5
3.3 Trace Element Analysis Results 3-8
3.4 Organic Emissions 3-13
3.4.1 Total Organic Analyses 3-15
3.4.2 Infrared (IR) Spectra of Total Extracts . . . 3-17
3.4.3 LC Fractional on of Extracts 3-17
3.4.4 IR Spectra of LC Fractions 3-19
3.4.5 Low Resolution Mass Spectrometry Analysis of
LC Fractions 3-24
3.4.6 Gas Chromatography/Mass Spectrometry
Analysis of Total Sample Extracts 3-26
References for Section 3 3-31
4 Environmental Assessment 4-1
4.1 Emission Assessment 4-1
4.2 Bioassay Results 4-2
4.3 Summary 4-4
References for Section, 4 4-6
5 Test Quality Assurance and Quality Control 5-1
5.1 Cj to Cg Hydrocarbon Precision 5-1
5.2 NoO Precision 5-3
5.3 TCQ Precision 5-3
5.4 GC/MS Precision 5-3
5.5 Mercury Analysis 5-3
5.6 QA Summary 5~5
iii
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CONTENTS (continued)
Reference for Section 5 5-6
Appendix A Test Equipment and Procedures A-l
A.I Continuous Monitoring System A-l
A.2 Particulate and Sulfur Oxide Emissions . . A-l
A.3 Trace Element and Organic Emissions A-4
A.4 GI to C5 Hydrocarbon Sampling and Analysis A-6
A.6 N20 Emissions A-ll
A.7 Fuel and Ash Sampling A-12
Reference for Appendix A A-12
Appendix B Trace Element Concentrations B-l
iv
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FIGURES
Number Page
2-1 PETC combustion test facility flow diagram 2-2
3-1 N20 versus NOX emissions for external combustion
sources 3-9
A-l Schematic of particulate and SOX sampling train (EPA
Method 5 and 8) A-3
A-2 SASS train schematic A-5
A-3 Flue gas analysis protocol for SASS samples A-7
A-4 Flue gas analysis protocol A-8
A-5 Organic analysis methodology ... A-9
A-6 GI to Cg hydrocarbon sampling system A-10
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TABLES
Number Page
1-1 Completed Tests During the Current Program 1-4
2-1 Boiler Specifications 2-3
3-1 Boiler Operating Conditions 3-3
3-2 Fuel Analyses (Percent by Weight) 3-4
3-3 Criteria Pollutant and Other Gas Species Emissions . . . 3-6
3-4 Flue Gas Particle Size Distribution (Uncontrolled) ... 3-8
3-5 Fuel and Ash Stream Trace Element Analysis Results . . . 3-10
3-6 Trace Element Emissions in the Flue Gas 3-14
3-7 Summary of Flue Gas Total Organic Emissions 3-16
3-8 Summary of Ash Stream Total Organic Content 3-17
3-9 Summary of Infrared Spectra of Total Sample Extracts . . 3-18
3-10 LC Fractional on of the XAD-2 Extract 3-20
3-11 LC Fractionation of the Bottom Ash Extract 3-21
3-12 IR Spectrum Summary: XAD-2 Extract, LC 7 3-22
3-13 IR Spectra Summary: Bottom Ash Extract LC Fractions . . 3-23
3-14 LRMS Analysis Results 3-25
3-15 Compounds Sought in the GC/MS Analysis and their
Detection Limits (ng/yl injected) 3-27
3-16 PAH and Other Semivolatile Organic Priority Pollutant
Species 3-28
VT
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TABLES (continued)
Number Page
3-17 Other Compounds Tentatively Identified in GC/MS
Analysis 3-29
4-1 Flue Gas Pollutants Emitted at Concentrations Exceeding
10 Percent of Their Occupational Exposure Guideline ... 4-3
4-2 Bioassay Results 4-4
5-1 Area Counts and Relative Standard Deviations for Cj to 5-2
Cg Analyses
5-2 Area Count and Relative Standard Deviations for ^0
Analyses 5-4
5-3 Duplicate Analysis Results and Relative Standard
Deviations for the GC/MS Analyses 5-4
A-l Continuous Monitoring Equipment A-2
A-2 Gas Chromatograph Specifications A-12
vii
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SECTION 1
INTRODUCTION
This report describes and presents results of environmental assessment
tests performed for the Air and Energy Engineering Research
Laboratory (AEERL) of EPA 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 four objectives:
o Identify potential multimedia environmental effects of stationary
combustion sources and combustion modification technology
o Develop and document control application guidelines to minimize
these effects
» Identify stationary source and combustion modification R&D
priorities
9 Disseminate program results to intended users
During the first year of the NOX EA, data for the environmental
assessment were compiled and methodologies were developed. Furthermore,
\
priorities for the schedule and level of effort for 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 combustion
1-1
-------
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. 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:
o Advanced NOX controls
» Alternate fuels
o Secondary sources
o 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)
o Nonsteady-state operations
Coal-water slurries (CWS) have received attention in recent years as an
alternative to oil fuels. CWS has the advantage of allowing certain
oil-fired boilers to eliminate their oil requirements without completely
redesigning the boiler- Thus, CWS has the potential for application as a
near-term technology for conversion of certain oil-burning facilities to coal
firing and thereby offsetting high oil prices and frequently uncertain supply
situations.
1-2
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In response to the need for environmental data on burning CWS, as well
as other coal-liquid mixtures such as coal-oil-water (COW) and coal-oil
mixtures (COM), tests of two COW-fired firetube industrial boilers
(References 1-10 and 1-11), a COM-fired watertube boiler (Reference 1-12),
and two CWS-fired watertube industrial boilers (this report and
Reference 1-13) have been performed. This report presents the results of the
emissions assessment of a CWS-fired watertube boiler. The objective of this
test was to assess flue gas emissions during typical boiler operating
conditions while firing CWS.
Table 1-1 lists all sources tested in the CMEA effort, outlining the
combustion modificaton controls implemented and the level of sampling and
analysis performed in each case. Results of these test programs are
discussed in separate reports.
1-3
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TABLE 1-1. COMPLETED TESTS DURING THE CURRENT PROGRAM3
Source
Spark-ignited natural -
gas-fired reciprocating
internal combustion
engine
Compression Ignition
diesel -fired
reciprocating Internal
combustion engine
Low-N0x residential
condensing heating
system furnished by
Karl sons Blueburner
Systems Ltd. of Canada
Description
Large bore, 6 cylinder,
opposed piston, 186 kU
(250 Bhp)/cyl. 900 r\tm
Hode) 38TDS8-1/8
Large bore, 5 cylinder
opposed piston, 261 kW
(350 Bhp)/cyl. 900 rpm
Model 3BTDD8-1/B
Residential hot water
heater equipped with
M.A.N. low-NO.. burner,
0.55 ml/s (0.5 gal/hr)
firing capacity, con-
densing flue gas
Test points
unit operation
Baseline (pre-NSPS)
Increased air-fuel
ratio aimed at
meeting proposed NO,
NSPS of 700 ppm
corrected to 15
percent 02 and
standard atmospheric
conditions
Baseline (pre-NSPS)
-- Fuel Injection retard
aimed at meeting pro-
posed NOX NSPS of
600 ppm corrected to
IS percent 02 and
standard atmospheric
conditions
Low-NO, burner design
by M.A.N.
Sampling protocol
Engine exhaust:
- SASS
- Method S
-- Gas sample (C,-C6 IIC)
Continuous NO, NO CO,
C02, 02. CH4, TUHC
Fuel
Lube oil
Engine exhaust:
SASS
Method 8
- Method 5
Gas sample (C,-C6 HC)
Continuous NO. NOX, CO,
C02. 02. CH4, TUHC
Fuel
Lube oil
Furnace exhaust:
- SASS
- Method 8
- Method S
- Gas grab (Ci-C6 HC)
Continuous NO, NO,, CO,
C02. 02. CH4, TUHC
Fuel
Waste water
Test col laborator
Fairbanks Horse
Division of Colt
Industries
Fairbanks Morse
Division of Colt
Industries
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-NO, burner design
and integrated furnace
system
Furnace exhaust:
SASS
Method 8
~ Controlled condensation
Method 5
Gas sample (C^Cg HC)
Continuous NO. NO,, CO,
New test
CO... 0
Fuel
2.
TconYtTTuVd")'
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TABLE 1-1. (Continued)
Source
Pulverl zed-coal -fired
utility boiler.
Conesville station
Description
400-MH tangential ly
fired; new HSPS design
aimed at meeting 301 ng/J
MOX limit
Test points
unit operation
ESP inlet
one test
and outlet -
Sampling protocol
ESP inlet and outlet
SASS
Method 5
Controlled condensation
Test collaborator
Exxon Research and
Engineering (ER4E)
conducting cor-
rosion tests
Gas sample (Ci - C6 HO
Continuous NO, NO... CO,
C02. 02
Coal
Bottom ash
ESP ash
Nova Scotia Technical
College Industrial
boiler
1.14 kg/s steam
(9,000 lb/hr)fired with a
mixture of coal-oil-water
(COM)
-- Baseline (COW)
Controlled S02
emissions with
limestone injection
- Boiler outlet
SASS
Method 5
Method 8
Controlled
Gas sample
condensation
(C,-C6 HO
Envirocon per-
formed participate
and sulfur
emission tests
C02,
Fuel
NO,
I
in
Adelphi University
industrial boiler
1.89 kg/s steam
(15,000 Ib/hr) hot water
firetube fired with a
mixture of coal -oil -water
(COH)
Baseline (COH)
-- Controlled S02
emissions with soda
ash (Na2C03) injection
Boiler outlet
SASS
~ Method 5
-- Method 8
Controlled
Gas sample
Continuous
S02, CO
Fuel
condensation
(Cj-C« HC)
02, C02, NOX,
Adelphi University
Pittsburgh Energy
Technology Center (PETC)
industrial holler
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 &
Controlled condensation
N20 grab sample
~ Continuous 02, C02. NO.,
CO. TUHC
Fuel
PETC and General
Electric (GE)
(continued)
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TABLE 1-1. (Continued)
Source
TOSCO Refinery vertical
crude oil heater
Mohawk-Getty Oil
Industrial boiler
Industrial boiler
Industrial boiler
Description
2. 54 Ml /day
(16.000 bbl/day) natural
draft process heater
burning oil/refinery gas
8.21 kg/s steam
(65,000 Ib/hr) watertube
burning mixture of
reflnroy gas and
residual oil
2.52 kg/s steam
(20,000 Ib/hr) watertube
burning wood waste
3.16 kg/s steam
(29.000 Ib/hr)
flretube with refractory
firebox burning wood waste
Test points
unit operation
Baseline
Staged combustion
using air Injection
lances
Baseline
-- Ammonia Injection
using the noncatalytic
Thermal DeHOx
process
Dasellne (dry wood)
Green wood
Baseline (dry wood)
Sampling protocol
Heater outlet
SASS
Method 5
Controlled condensation
~ Gas sample (Ci-C6 HO
H2° 9rab sample
Continuous 02, NOX,
CO. COZ. HC
Fuel oil
Refinery gas
Economizer outlet
SASS
-- Method 5. 17
-- Controlled condensation
Gas sample (Cj-C6 HC)
Ammonia emissions
-- MgO grab sample
Continuous 0?, NO,,
CO, C02
Fuels (refinery gas and
residual oil)
Boiler outlet
SASS
-- Method 5
Controlled condensation
Gas sample (Cj-Cg HC)
~ Continuous Oo. MO.,, CO
Fuel
Flyash
Outlet of cyclone participate
collector
SASS
Method 5
Controlled condensation
-- Gas sample (Cj-Ce HC)
Continuous Oj, NOX, CO
Fuel
Bottom ash
Test collaborator
KVB coordinating
the staged com-
bustion operation
and continuous
emission
monitoring
Mohawk-Getty Oil
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
(continued)
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TABLE 1-1. (Continued)
Source
Enhanced oil recovery
steam generator
Pittsburgh Energy
Technology Center
(PETC) Industrial
boiler
Spark-Ignited, natural
gas-fired reciprocating
Internal combustion
engine nonselective
NOX reduction catalyst
Industrial boiler
Description
15-MH (50 million Btu/hr)
steam generator burning
crude oil equipped with
HHI low-NOx burner
3.03 kg/s steam
(24.000 Ib/nr) watertube
fired with a mixture of
coal-water (CHM)
610-kH (818-hp) Haukesha
rich-burn engine equipped
with DuPont HSCR system
180 kg/hr steam
(400 Ib/hr) stoker, fired
with a mixture of coal
and waste plastic
beverage containers
Test points
unit operation Sampling protocol Test collaborator
Performance mapping Steamer outlet: Getty Oil Company,
Low-N0x operation SASS CE-«atco
Method 5
Method 8
Gas sample (C]-Ce HC)
Continuous 0?, NO.. CO,
CO,
NpO grab sample
Fuel
Baseline test only Boiler outlet: PETC and General
with CHM SASS Electric
Method 5
Method 8
Gas sample (CrC6 HC)
Continuous 02, NO,, CO,
C02. TUHC
NpO grab sample
Fuel
Bottom ash
Collector hopper ash
Low NO, (with Catalyst inlet and outlet Southern California
catalyst) SASS Gas Company
15-day emissions NHi
monitoring HCN
NjO grab sample
Continuous 0?. CO?. NOX
TUHC
Lube oil
Baseline (coal) Boiler outlet Vermont Agency of
Coal and plastic waste SASS Environmental
VOST Conservation
~ Method 5
Method 8
~ HC1
Continuous Oj, NOX. CO,
CO,. TUHC
NpO grab sample
Fuel
Bottom ash
Cyclone ash
(continued)
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I
00
TABLE 1-1. (Continued)
Source
Industrial boiler
Enhanced oil
recovery steam
generator
Description
7.6 kg/s steam
(60.000 Ib/hr) waterlulie
retrofit for coal water
mixture firing
15-HW (SO million Btu/hr)
steam generator burning
crude oil, equipped with
Test points
unit operation
Baseline test with CHS
-- 30-day emissions
monitoring
-- Low NOX (with burner)
30-day emissions
monitoring
Sampling protocol Test collaborator
Holler outlet EPHl. DuPont
- SASS
VOST
Method 6
Method U
- Gas sample (Ci-C6 HC)
-- N2U grab sample
-- Continuous NOX, CO, COo,
o2, rune. so2
Fuel
Steamer outlet Chevron U.S.A..
- SASS EEHC
- vosr
bile trn/ tti* iun-iiuy
burner
Method 8
-- Controlled condensation
-- Anderson impactor
Gas sample (Ci-C6 HC)
-- 820 grab sample
-- Continuous NOX. CO, C02,
Fuel
02> S02
Spark-ignited natural -
gas-fired reciprocating
internal combustion
engine selective NOX
1.490-kW (2,000-hp)
Inyersol 1 -Rand lean-burn
engine equipped with
Englehard SCR system
Low NOX (with
catalyst)
-- 15-day emissions
monitoring
Catalyst Inlet and outlet
SASS
VOST
NH-j
Southern
California Gas
Company
reduction catalyst
- HCN
N20 grab sample
Continuous 02, COo, CO,
HO. NOX. NOX+NH3
Lube oil
aAcronymns used In the table: EEKC, The Energy and Environmental Research Corporation; EPA IEKL-RTP, The Environmental Protection
Agency's Industrial Environmental Research Laboratory Research Triangle Park; EPHl, The Electric Power Research Institute;
HC, hydrocarbons; NSCH, nonselective catalytic reduction; NSPS, new source performance standard; SASS, source assessment sampling
system; SCR, selective catalytic reduction; TUHC, total unburned hydrocarbon; VOST, volatile organic sampling trvin
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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. 8., "Combustion Modification Controls for Residential
and Commecial Heating Systems: Volume II. Oil-fired Residential
Furnace Field Test," EPA-600/7-81-123b, NTIS PB82-231175, 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. 8. 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 PB82-231095, July 1981.
1-8. Waterland, L. R., etal., "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
PS293795, October 1978.
1-10. Castaldini, C., "Environmental Assessment of an Industrial Boiler
Burning Coal/Oil/Water Mixture," Acurex Report TR-81-86/EE, August
1984.
1-11. OeRosier, R., "Environmental Assessment of a Firetube Boiler Firing
Coal/Oil/Water Mixtures," Acurex Report TR-81-89/EE, June 1984.
1-9
-------
1-12. DeRosier, R., "Environmental Assessment of a Watertube Boiler Firing a
Coal/Oil Mixture," Acurex Report TR-81-87/EE, March 1984.
1-13. VanBuren, D., and L. R. Waterland, "Environmental Assessment of a
Coal-Water-Slurry-Fired Industrial Boiler," Acurex Draft Report
TR-84-155/EE, March 1985.
1-10
-------
SECTION 2
TEST FACILITY DESCRIPTION
The Department of Energy's Pittsburgh Energy Technology Center (PETC)
combustion test facility consists of a 3.0 kg/s steam (24,000 Ib/hr)
watertube boiler, an air-cooled steam condenser and deaerator, CWS
preparation and storage facilities, and pollution control devices.
Figure 2-1 presents a flow diagram of the test facility. The boiler is a
package, two-drum, "D"-type watertube boiler with the specifications listed
in Table 2-1. The boiler was originally designed by Nebraska Boiler Company
to fire Mo. 6 fuel oil. The furnace section has a flat integral water-cooled
floor, ceiling, side walls, and target wall. The burner wall is comprised of
13-cm (5-in.) thick interlocking tongue and groove refractory tile laid in
high temperature bonding mortar. The convection section incorporates a Boyer
type VH valve-in-head soot blower. This is a standard design normally
incorporated in the boiler by the manufacturer for firing no. 6 fuel oil. It
has kept the convective section free of ash buildup during all previous
combustion tests performed in the unit.
The coal-water slurry (CWS)1 fired in these tests was prepared in a
6,800 1 (1,800 gal) steam-jacketed mix tank which incorporated an agitator
comprised of two sets of turbine blades. A predetermined amount of water was
charged to the tank before pulverized coal was added through a vertical
gravimetric coal feeder at 910 kg/hr (2,000 Ib/hr). The CWS was then
2-1
-------
01 KIM
Mil
0«IIIM» I
lll«» 1
...«M »f^«-J
Lg I MIUAIOI A
COM HID fUMP
Figure 2-1. PETC combustion test facility flow diagram.
-------
TABLE 2-1. BOILER SPECIFICATIONS
Convection heating surface, m2 (ft2) 182 (1,956)
Radiant heating surface, m2 (ft2) 48 (518)
Furnace dimensions, m (ft) 1.92 x 4.05 x 2.26
(6.3 x 13.3 x 7.4)
Design steam capacity, kg/s (Ib/hr) 3.0 (24,000)
Design pressure, MPa (psig) 1.7 (250)
Operating pressure, MPa (psig) 1.2 (175)
Soot blower One Boyer-type VH
valve-in-head
Year installed 1978
transferred to a 10,600 1 (2,800-gal) hold tank incorporating an agitator
with one set of turbine blades. The CWS was recirculated from the bottom to
the top of the tank by a Viking rotary pump.
The fuel was driven by a variable speed CWS feed pump through flow
meters and fuel preheaters before reaching the burner. The CWS flowrate was
regulated by the adjustable-speed-drive motor driving the progressive cavity
Moyno pump. A Micro-Motion mass flow meter and a Floco positive displacement
meter measured the mass and volume flowrates.
A packaged, single-burner Model Fyr-Compak, manufactured by the Coen
i
Company, comprised the firing equipment. The original Coen Model no. 2mV,
inside-mix, steam-atomized burners were replaced with slightly different
2-3
-------
no. 2mV burners modified for abrasive service. The changes consisted of an
optional pintle in the burner body, to reduce carbon buildup inside the
burner cap, and the substitution of 440C case-hardened steel as the
construction material.
The four valves originally installed in the fuel train were removed or
replaced to avoid clogging with coal particles. The oil pressure
differential regulator and oil flow control valve were removed and the
variable speed drive CWS feed pump was used to control the fuel flowrate.
The safety shutoff solenoid valve and the oil return solenoid valve were
replaced by pneumatically actuated stainless steel full-ported ball valves.
The packaged burner incorporated an automatic air register louver control
that closed in on the register louvers at low fire to maintain air velocity
and swirl. Combustion air was supplied by a forced-draft fan.
2-4
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SECTION 3
EMISSION RESULTS
The objective of this test program was to measure flue gas emissions
from tne boiler during typical operation while burning a coal-water slurry
(C'dS). This section describes the test arrangement and presents emissions
results. Section 3.1 summarizes boiler operating conditions. Sections 3.2
through 3.5 summarize emission results by pollutant grouping; criteria and
other gas phase emissions are discussed in Section 3.2, trace elements in
Section 3.3, and organic species emissions in Section 3.4. Section 4
discusses the potential environmental significance of emissions measured and
presents results of biological testing of samples collected.
3.1 BOILER OPERATION AND TEST ARRANGEMENTS
The sampling matrix called for in the test plan consisted of the
following:
o Fuel grab sample
o Bottom ash grab sample
o Baghouse ash grab sample
o Flue gas:
Continuous monitors for 02, COg, NOX, CO, S02» and total
unburned hydrocarbons (TUHC)
Source Assessment Sampling System (SASS) sampling
3-1
-------
~ Combined EPA Method 5/8 sampling for particulate and sulfur
species emissions
-- Gas grab sampling for onsite measurement of Cj to Cg hydrocarbon
emissions
Gas grab sampling for laboratory ^0 analysis
All flue gas sampling was performed at the boiler outlet, upstream of
the facility's particulate control device (baghouse). Details of the
specific sampling protocols used are given in Appendix A.
Two separate tests were performed on the unit. During the first test,
performed with a CWS fuel containing 60.9 percent (weight) coal, difficulties
were experienced with the SASS sampling equipment. As a consequence, a
complete set of test data was not obtained for this test. Specifically, SASS
train samples were not collected in this first test. Therefore a second set
of tests, performed with the unit firing a CWS fuel containing 58.9 percent
coal, was subsequently performed. A complete set of test data was obtained
during the second test.
Table 3-1 summarizes the boiler operating conditions for both tests
performed. As noted, conditions for both tests were similar, although the
second test was run at lower excess air level.
Table 3-2 summarizes the fuel analysis results for both tests. Results
supplied for the parent coal by PETC as well as those obtained by independent
analyses of the test 2 fuel through this study are both shown.
The independent CWS compositions for the test 2 fuel (measured in this
study and calculated based on the coal ultimate analysis reported by PETC and
the CWS proportions of water and additive) were generally similar,
although the water content of the fuel in this study's analysis was lower
3-2
-------
TABLE 3-1. BOILER OPERATING CONDITIONS
Test 1 Test 2
Steam flow, kg/s 3.03 3.03
(Ib/hr) (24,000) (24,000)
Drum pressure, MPa 1.3 1.3
(psi) (189) (189)
Furnace draft, Pa 112 116
(in. H20) (0.47) (0.466)
Fuel flow, kg/s 0.410 0.39
(Ib/min) (54.2) (51.8)
Steam temperature, °C 186 188
(°F) (367) (371)
Boiler feedwaten temperature, °C 101 a
(°F) (213)
Combustion air temperature, °C 24 28
(°F) (76) (83)
Flue gas temperature °C 272 291
furnace exit, (°F) (522) (556)
Excess air percent15 14 11
aNot available
Calculated from PETC fuel composition and flue gas
02 levels
3-3
-------
TABLE 3-2. FUEL ANALYSES (PERCENT BY WEIGHT)
CWS (as fired)
Test 1
Test 2
Carbon
Hydrogen
Oxygen (by
difference)
Nitrogen
Sulfur
Ash
Additive
Water
Higher heating
value, kJ/kg
(3tu/lb)
Coal
(dry
basis)
PETCa
82.23
5.60
6.76
1.60
1.19
2.62
34,459
(14,829)
PETCb
50.08
3.41
4.12
0.97
0.72
1.60
0.50
38.60
20,986
(9,031)
This
study3
47.90
3.34
8.56
1.02
0.80
1.93
36.45
21,341
(9,184)
PETCb
48.43
3.30
3.98
0.94
0.70
1.54
0.50
40.6
20,296
(8,734)
aMeasured
^Calculated based on coal ultimate analysis and
reported proportion of coal, additive, and water
in the CWS formulation
3-4
-------
than the proportion as reported by PETC. The fuel composition measured in
this study, when available, were used in the calculations reported herein.
3.2 CRITERIA POLLUTANT AND OTHER GAS PHASE EMISSIONS
Table 3-3 summarizes emissions of CO, C02, 02, NOX, S02, TUHC, N20, and
particulate in the flue gas for the tests. As shown, average NOX (NO + N02)
emissions (corrected to 3 percent 02) with the CWS fuel ranged from an
average of 231 ppm in test 1 to 312 ppm in test 2. This difference in NOX
emissions between the two tests is not considered significant. Differences
of this magnitude often accompany minor changes in boiler operation or fuel
properties. CO and TUHC emissions were also similar for the two tests
averaging 172 ppm and 1.1 ppm respectively in test 1, and 196 ppm and
2.8 ppm respectively (all corrected to 3 percent 02) in test 2.
S02 emissions measured using the PETC continuous monitor were slightly
lower in the second test, averaging 885 ppm, than in the first test,
averaging 957 ppm. S02 emissions measured by EPA Method 8 were similar
(though lower) to the continuous monitor reading for test 2. However,
results of the Method 8 tests for test 1 were significantly lower than the
monitor reading. Measured 503 emissions for both tests were quite low.
Particulate levels in the boiler outlet gas, as measured by EPA
Method 5, apparently nearly doubled in test 2 over test 1. It is possible
that the higher mass emissions for the second test were due to lower
combustion efficiency with higher combustible losses in the flyash. The
particulate levels at the boiler outlet for test 2 corresponds to an emission
rate over 2.3 times that accountable by the ash content of the fuel (i.e., if
all the fuel ash were discharged as flyash). Although the boiler outlet flue
gas particulate was not analyzed for carbon content, the baghouse hopper ash
3-5
-------
TABLE 3-3. CRITERIA POLLUTANT AND OTHER GAS SPECIES EMISSIONS
Test 1
Test 2
Species
Range
Average
Range
Average
As measured by
continuous gas
analyzers
Oo, percent dry
C02, percent dry
N0xa, pom
CO, ppm
TUHC, ppm
S02, ppm
Grab sample
N20, ppm
Method 8
S02, ppm
S03, ppm
Corrected gaseous
emissions
NO a (as NO?)
CO
TUHC (as CH4)
S02e
N20
so2f
so3f
Solid parti cul ate
mass emissions
Method 5
SASS
2.3 to 2.9
14.6 to 15.2
196 to 293
130 to 213
0.03 to 2.6
846 to 1,060
29 to 35
b
__b
ppmc ng/Jd
231 136
172 62
1.1 0.2
957 786
30 18
310 255
0.84 0.86
mg/dscm ng/Jd
3,485 1,064
9 9
2.8
14.9
234
174
1.1
968
31
310
0.85
lb/106 Btud
0.316
0.14
0.0005
1.83
0.041
0.592
0.002
lb/106 Btud
2.47
~9
1.9 to 2.7
15.1 to 15.9
255 to 437
151 to 358
2.3 to 5.0
888 to 964
45 to 110
__b
b
ppmc ng/Jd
312 172
196 66
2.8 0.53
885 680
76 41
760 582
<0.5 <0.5
mg/dscm ng/Jd
7,255 1,991
6,820 1,872
2.1
15.7
327
206
2.9
931
81
800
<0.5
lb/106 Btud
0.400
0.15
0.00012
1.58
0.095
1.35
<0.001
lb/106 Btud
4.63
4.35
aNO + N02
DExtractive sample over test duration; range not applicable
^Corrected to 3 percent 02, dry
"Heat input basis
^Continuous monitor
fMethod 8
9No SASS test for test 1
3-6
-------
was. This ash contained 61.6 percent carbon (dry basis, average of two
analyses). The bottom ash was high in carbon content as well, 35.7 percent
dry basis. Unfortunately, no sample of the test 1 baghouse ash was
analyzed. However, if the carbon content of the test 1 participate was
significantly lower than that for test 2, the difference in measured
particulate levels might be explained on this basis. In any case, it bears
emphasis that the high (for both tests) particulate levels measured
reflect the fact that sampling was performed at the boiler outlet. Levels
measured would not be indicative of those downstream of a particulate control
device. Table 3-3 also shows quite good (within 6 percent) agreement between
the Method 5 (isokinetic traverse) and the SASS (single point) particulate
measurement result.
Table 3-4 shows the relative size distribution of the particulate as
measured by the SASS train. As shown, well over half the particulate (by
weight) was greater than 10 urn, and almost 70 percent greater than 3 urn in
diameter.
Three gas grab samples were taken during the first test and four during
the second test for N20 analysis. These averaged 30 ppm and 76 ppm
(3 percent 02, dry) respectively, as shown in Table 3-3.
Analysis results for all seven samples taken are shown plotted versus
the corresponding NOX (NO + Nt^) emission level, at the time the samples
were taken, in Figure 3-1. (NOX was measured using a chemiluminescent
continuous analyzer; this method does not respond to ^0.) Data from tests
performed on several other fossil-fuel-fired external combustion sources are
also shown in the figure. The data show that ^0 emission levels are
generally about 20 percent of the corresponding NOX emission level. In fact,
3-7
-------
TABLE 3-4. FLUE GAS PARTICLE SIZE
DISTRIBUTION (UNCONTROLLED)
Emission rate
Particle size
>10ym
3 to lOum
1 to Sum
Filter (
-------
140
co
VO
120
100
80
C Coal-fired commercial boiler (Reference 3-4)
O Coal-water-slurry-fired industrial boiler (Reference 3-5)
V EOR steamer equipped with a low-NO burner (Reference 3-6)
O EOR steamer equipped with the EPA low-NO burner (Reference 3-7)
I r J x
100 200 300 400
NOX (ppm, 3% 02, dry)
500
600
Figure 3-1. ^0 versus NOX emissions for external combustion sources.
-------
TABLE 3-5. FUEL AND ASH STREAM TRACE ELEMENT ANALYSIS RESULTS
Concentration (yg/g)
Flue gas parti cul ate
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bi smuth
Boron
Bromine
Cadnri urn
Calcium
Cerium
Cesium
Chlorine
Chromium
Col bait
Copper
Dysprosium
Erbium
Europl urn
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Hoi mi urn
lodi ne
Iridium
Iron
Lanthanium
Lead
Lithium
Lutecium
Magnesium
Manganese
Fuel a
13,400
0.40
1.0
25
0.40
0.03
0.50
1.0
<0.04
38,100
1.0
0.20
3.0
2.0
1.0
3.0
0.10
0.10
0.07
5.0
0.20
2.0
0,50
__
<0.30
0.10
0.70
700
2.0
2.0
0.70
0.01
>100
2.0
Bottom
ash
60,700
21
110
1,000
7.0
3.0
54
8.0
9.0
14,200
120
1.0
110
620
21
270
8.0
4.0
1.0
71
5.0
45
5.0
__
5.0
5.0
4.0
-_
43,500
93
5,200
38
0.80
2,800
500
10 + 3 urn
31,300
11
30
1,000
8.0
__b
8.0
35
6.0
4,400
85
3.0
410
170
14
110
9.0
4.0
2.0
160
5.0
15
4.0
_-
4.0
6.0
4.0
_-.
24,100
75
150
25
2.0
1,200
92
1 ym + filter
73,300
18
440
1,600
4.0
2.0
120
30
30
2,380
61
0.30
8,400
170
270
710
3.0
1.0
1.0
180
2.0
430
53
__
0.80
2.0
3.0
__
40,500
54
77
74
0.60
4,500
>530
Baghouse
hopper ash
43,000
13
100
1,000
16
0.80
51
85
4.0
8,300
140
2.0
620
230
190
330
6.0
3.0
4.0
86
7.0
160
22
_-
2.0
4.0
5.0
--
36,100
200
450
35
1.0
1,900
500
(continued)
aAsh content of fuel was 1.93 percent
''Double dashes denote less than detection limit, generally 0.1 ug/g
3-10
-------
TABLE 3-5. (continued)
Concentration (ug/g)
Flue gas parti cul ate
Element
Mercury
Molybdenum
Neodymi urn
Nickel
Niobium
Osmium
Palladium
Phosphorus
Platinum
Potassium
Praesodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Si 1 ver
Sodium
Strontium
Sulfur
Tantal urn
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Fuel a
1.0
0.60
2.0
0.50
__
377
10,300
0.30
--
0.20
__
0.30
0.30
0.30
69,200
0.20
100
34
8,000
0.10
0.20
0.06
0.20
0.50
<0.02
0.04
63
0.10
0.50
3.0
0.10
Bottom
ash
57
23
190
35
--
--
6,000
5,000
11
39
--
9.0
47
11
104,000
<3.0
13,300
300
5,500
8.0
1.0
2.0
7.0
22
0.20
41 '
2,500
9.0
18
2,000
4.0
10 + 3 um
70
16
30
19
--
1,600
2,100
21
39
--
17
11
15
60,600
<0.60
8,200
1,000
5,500
15
1.0
3.0
31
0.30
1.0
2,500
9.0
16
180
6.0
1 urn + filter
76
6.0
480
9.0
--
--
2,800
4,500
6.0
18
5.0
61
29
124,000
4.0
34,600
300
5,200
4.0
0.40
0.60
6.0
9.0
0.40
6.0
4,000
3.0
8.0
400
3.0
Baghouse
hopper ash
28
55
60
51
--
--
2,300
2,500
51
21
--
21
32
44
63,000
<2.0
11,600
300
5,500
100
0.60
2.0
3.0
42
0.30
9.0
3,000
12
19
2,000
6.0
aAsh content of fuel was 1.93 percent
bDouble dashes denote less than detection limit, generally 0.1 ug/g
3-11
-------
TABLE 3-5. (continued)
Concentration (ug/g)
Flue gas part icul ate
Element
Yttrium
Zinc
Zirconium
Fuel a
4.0
2.0
2.0
Bottom
ash
270
4,600
130
10 + 3 ym
79
88
230
1 urn + filter
120
73
45
Baghouse
hopper ash
320
160
160
aAsh content of fuel was 1.93 percent
''Double dashes denote less than detection limit, generally 0.1 yg/g
3-12
-------
residue of the fuel (the fuel levels noted in Table 3-5 divided by the ash
content of the fuel 1.93 percent).
Given the trace element concentrations as determined by laboratory
analysis, trace element flue gas emission concentrations (mg/dscm) and
flowrates normalized to heat input (ng/J) were computed. Table 3-6 shows
the emission results on these bases. (Elemental mass balances were not
computed since bottom ash and baghouse hopper ash flowrates were not
measured).
As shown in Table 3-6, the elements silicon, aluminum, iron, sodium,
calcium, titanium, potassium, magnesium, and phosphorus were present in
concentrations exceeding 10 mg/dscm (2.7 ng/J) in the flue gas. These 10
elements were also found in high concentrations in the fuel, as noted in
Table 3-5. Most of the element emission levels noted were associated with
the flue gas particulate sample. Recalling that sampling was done at the
boiler outlet, the levels noted in Table 3-5 would not reflect those
downstream of a particulate control device.
3.4 ORGANIC EMISSIONS
Organic analyses were performed on specified flue gas samples according
to EPA Level 1 protocol (Reference 3-8) as outlined in Appendix A. The SASS
train particulate, 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 species 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. The XAD-2
3-13
-------
TABLE 3-6. TRACE ELEMENT EMISSIONS IN THE FLUE GAS
Emissions
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmi urn
Calcium
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Dysprosium
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Hoi mi urn
lodi ne
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
(mg/dscm)
297,000
90
1,060
7,950
45
4
290
238
34
25,300
526
14
19,600
1,190
640
2,030
47
20
11
1,300
27
978
130
__
20
32
26
__
201,000
470
850
270
10
15,000
>1,700
a
200
(ng/J)
82
0.02
0.3
2
0.01
0.001
0.08
0.06
0.009
6.9
0.14
0.004
5.4
0.33
0.17
0.56
0.01
0.006
0.003
0.36
0.007
0.27
0.03
__
0.005
0.009
0.007
--
55
0,13
0.23
0.07
0.003
4.1
>0.47
_.a
0.05
Element
Neodynrium
Nickel
Niobium
Osmium
Palladium
Phosphorus
Platinum
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Urani urn
Vanadium
Ytterbi urn
Yttrium
Zinc
Zirconium
Emissions
(mg/dscm)
87
1,330
107
«
13,200
19,300
113
220
88
185
167
537,000
9.6
>111,000
1,090
>37,900
77
5
15
13
161
2
23
19,900
48
90
1,670
34
618
632
1,160
(ng/J)
0.024
0.37
0.03
3.6
5.3
0.03
--
0.06
0.02
0.05
0.04
148
0.003
>31
0.3
>10.4
0.02
0.001
0.004
0.003
0.04
0.0006
0.006
5.4
0.01
0.02
0.46
0.009
0.17
0.17
0.32
aDouble dashes indicate that emissions were below detection limit
3-14
-------
and boiler bottom ash extracts were subjected to further separation by liquid
column (LC) chromatography followed by TCO, GRAV, and IR analysis of eluted
fractions. Direct insertion probe low resolution mass spectrometry (LRMS)
analyses were also performed on selected LC fractions. In addition, volatile
organic gas phase species with boiling points in the nominal C^ to £5 range
-160 to 100°C (-260° to 212°F) were measured by multiple analyses of flue gas
samples onsite using gas chromatography. A discussion of the analytical
results follows.
3.4.1 Total Organic Analyses
TCO and gravimetric analyses were performed on the SASS train cyclone,
filter, XAD-2 sorbent, and organic module condensate (OMC) extracts. The
results of these and the onsite GC analyses for Cj to CQ hydrocarbons are
summarized in Table 3-7. The total concentration of organic matter in the
flue gas was 48 mg/dscm. Approximately 70 percent of the organic matter was
in the nonvolatile (C^5+) boiling point range. Total organic emissions in
these tests were over an order of magnitude higher than the range of 0.12 to
4.3 mg/dscm reported for oil- and coal-fired boilers in a report summarizing
results of other comprehensive field tests (Reference 3-9). These high
emissions are consistent with the poor boiler efficiency and high combustible
losses (especially high carbon carryover in the flyash) noted previously.
Table 3-7 also shows the Cj, to CQ hydrocarbon data obtained during
test 1 (the SASS train sampling was not successful for test 1). The test 1
data are quite comparable to those of test 2. Most of the hydrocarbon
emitted in this volatile boiling point range was low molecular weight Cj and
G£ compounds.
3-15
-------
TABLE 3-7. SUMMARY OF FLUE GAS TOTAL ORGANIC EMISSIONS
Volatile orgam'cs analyzed in the field
by gas chroma tography
Cl
£2
r3
r4
r5
C6
Total Ci to Cg
Semi volatile orgam'cs analyzed by TCO
XAO-2 and organic module condensate
Total Cy to Cis
Nonvolatile organics analyzed by
gravimetry
10 + 3um cyclones
lum cyclone + filter
XAO-2 and organic module condensate
Total Cis+
Total organics
Test 1 Test
(mg/dscm) (ng/J) (rag/dscm)
3.5 1.07 3.0
10.5 3.20 5.8
0.3
14.0 4.27 9.1
~a a 5.9b
5.9
0.67
0.45
32.0
~a a 33.1
48.1
2
(ng/J)
0.82
1.60
0.08
2.50
1.62P
1.62
0.18
0.12
8.78
9.09
13.2
aSASS train sampling not performed for test 1
"Average of duplicate analyses
3-16
-------
Table 3-8 summarizes the total organic analysis results for the ash
stream samples taken. As noted, the organic content of the bottom ash sample
was quite high, again consistent with the evident poor combustion efficiency
existing during test 2. The relative organic contents of the bottom ash and
the baghouse hopper ash was consistent with their relative carbon content
(61.0 percent for the bottom ash and 35.7 percent for the baghouse hopper
ash).
3.4.2 Infrared (IR) Spectra of Total Extracts
The results of the IR analyses of the GRAV residue of the total extract
samples are summarized in Table 3-9. As noted, only the spectra of the
XAD-2 and bottom ash extracts were sufficiently strong to be interpreted.
The spectra for both extracts were consistent with the presence of aliphatic
hydrocarbons and oxygenated species, such as carboxylic acids, aldehydes, and
alcohols.
3.4.3 1C Fractionation of Extracts
The XAD-2 and bottom ash sample extracts contained greater than 15 mg of
total organic, so they were separated into seven polarity fractions via
TABLE 3-8. SUMMARY OF ASH STREAM TOTAL ORGANIC CONTENT
Test 2 (mg/kg)
Semi volatile organics analyzed by TCP
Bottom ash 1,600
Baghouse hopper ash 7.2
Nonvolatile organics analyzed by gravimetry
Bottom ash 6,400
Baghouse hopper ash <100
3-17
-------
TABLE 3-9. SUMMARY OF INFRARED SPECTRA OF TOTAL SAMPLE EXTRACTS
Extract
sample
10y + 3n
participate
Filter + In
participate
Wave number
(cm-1) Assignment
No peaks
No peaks
Possible compound
categories present
XAD-2 + OMC
3600 to 3000
1640
1410
1160 to 1060
1000
0-H stretch
C=Ca stretch
0-H bend
C-0 stretch
Not assigned
Oxygenated hydrocarbons such
as carboxylic acids,
aldehydes, alcohols; possible
aromatics.
Bottom ash 3400
2940
2860
1730
1610
1460
1380
1280
820
750
Baghouse ash No peaks
0-H stretch
C-H alkyl
C-H alkyl
C=0 stretch
C*"C aromatic3
C-H bend
C-C stretch
C-0 stretch
Not assigned
C-H rock
Aliphatic hydrocarbons;
oxygenated hydrocarbons such
as carboxylic acids, ketones,
aldehydes, alcohols; possible
aromatics.
tentative assignment, not supported by other absorbances
3-18
-------
liquid column chromatography. The gravimetric and TCO content of each
fraction are summarized in Tables 3-10 (XAD-2) and 3-11 (bottom ash).
Table 3-10 shows that very poor recovery was achieved in the LC fractionation
of the XAD-2 extract (about 16 percent), with recovery of the TCO fraction
being especially poor- Most of the material appeared to be retained on the
chromatography column. The analyst noted that the XAD-2 extract appeared to
consist of two distinct liquid phases. It is possible that one of these
phases could not be eluted from the column with the specified series of
solvents. Most of the XAD-2 extract which did elute from the column occurred
in LC fraction 7. This fraction generally contains carboxylic acids and
other polar (e.g. oxygenated) compounds.
The bottom ash extract exhibited a more even distribution of organic
content among the LC fractions. LC 1 accounted for most of the total organic
and virtually all of the semivolatile (TCO) content. Other fractions showed
considerable, though lesser, amounts of nonvolatile (GRAV) organics.
Fractionation recovery, at 119 percent, was considerably better for this
sample.
3.4.4 IR Spectra of LC Fractions
The results of the IR analysis of the GRAV residue of the eluted LC
fractions are summarized in Table 3-12 (XAD-2 extract) and in Table 3-13
(bottom ash extract). For the XAD-2 extract, only the LC 7 residue had an IR
\
spectrum sufficiently strong to interpret. This spectrum is consistent with
the presence of polar oxygenated species such as carboxylic acids, which
elute in LC 7. Comparing Table 3-12 with Table 3-9 confirms that the LC 7
IR spectrum is essentialy the same as that obtained for the total sample
extract.
3-19
-------
TABLE 3-10. LC FRACTIONATION OF THE XAD-2 EXTRACT
TCO
(mg)
Total sample 53
Fraction
1
2
3
4
5
6
7
Total
Taken for
Recovered
TCO (
Analyzeda
<0.02
<0.01
<0.01
0.13
0.03
<0.01
<0.01
0.16
LC 15
0.16
mg)
Corrected
to total
sample
<0.07
<0.03
<0.03
0.45
0.10
<0.03
<0.03
0.55
GRAV
(mg)
285
83
15.4
GRAV
Analyzed9
0.8
0.4
0.6
0.6
0.4
0.6
12.0
15.4
TCO + GRAV
(mg)
338
98
16
(mg)
Corrected
to total
sample
2.8
1.4
2.1
2.1
1.4
2.1
41.2
53.1
Concentration
(mg/dscm)
37.8
11.0
1.8
TCO + GRAV
(mg)
2.8
1.4
2.1
2.6
1.5
2.1
41.2
53.7
Concentration
(mg/dscm)
0.31
0.16
0.23
0.29
0.17
0.23
4.62
6.01
aBlank corrected
3-20
-------
TABLE 3-11. LC FRACTIONATION OF THE BOTTOM ASH EXTRACT
TCO
(mg)
Total sample 40
Fraction
1
2
3
4
5
6
7
Total
Taken for
Recovered
TCO
Analyzed3
3.3
0.10
0.06
0.09
0.09
<0.01
<0.01
3.6
LC 20
3.6
(mg)
Corrected
to tbtal
sample
6.6
0.20
0.12
0.18
0.18
<0.02
<0.02
7.3
GRAV
(mg)
160
80
115.8
GRAV
Analyzed3
34.0
23.0
15.6
10.4
11.0
16.2
5.6
115.8
TCO + GRAV
(mg)
200
100
119.4
(mg)
Corrected
to total
sample
68.0
46.0
31.2
20.8
22.0
32.4
11.2
231.6
Concentration
(mg/kg)
8,000
4,000
4,780
TCO + GRAV Concentration
(mg) (mg/kg)
74.6
46.2
31.3
21.0
22.2
32.4
11.2
238.9
2,980
1,850
1,250
850
890
1,300
450
9,560
aBlank corrected
3-21
-------
TABLE 3-12. IR SPECTRUM SUMMARY: XAD-2 EXTRACT, LC 7a
Wave
number
(cra-1)
3400
1640
1550
1390
1220
1100
Intensity15
S
S
w
M
W
W
Assignment
0-H stretch
C=C stretch
Not assigned
0-H bend
C-0 stretch
C-0 stretch
Possible compound
categories present
Oxygenated hydro-
carbons such as
carboxylic acids
aOnly LC 7 had a spectrum sufficiently strong to interpret
bS = strong, M = moderate, W = weak
3-22
-------
TABLE 3-13. IR SPECTRA SUMMARY: BOTTOM ASH EXTRACT LC FRACTIONS
Wave number
(cm-1)
3500
3450
3300
3060
2950
2870
1740
1620
1480
1390
1290
1200
1140
1080
1040
960
880
820
760
710
to
to
to
to
to
to
to
to
to
to
3400
2940
2860
1720
1610
1460
1380
1270
1020
750
Intensity3
Assignment
0-H
0-H
0-H
C-H
C-H
C-H
C=0
C=C
C-H
C-H
0-H
C-0
C-0
C-0
C-0
C-0
C-C
C-H
C-H
C-H
Not
stretch
stretch
stretch
stretch
stretch
stretch
stretch
stretch
bend
bend,
bend
stretch
stretch
stretch
stretch
stretch
stretch
rock
rock
rock
assigned
LC 1
S
M
W
M
W
W
W
W
LC 2 LC 3
W
W
M
S S
M
M S
M
W
W
W
W
W M
W M
M M
W
LC 4
W
S
M
W
M
W
M
W
W
W
W
W
W
W
LC 5
M
S
S
M
M
W
M
M
M
W
W
W
W
LC 6
M
S
M
M
M
M
M
W
W
W
LC 7
W
S
M
M
W
W
W
aS = strong, M moderate, W = weak, blank = absorbance not in spectrum
3-23
-------
The IR spectra of the bottom ash fractions are summarized in Table 3-11.
The spectra of LC 1 and 2 are consistent with the presence of aliphatic
hydrocarbons, which elute in those fractions. The spectra of LC 3 and 4 are
consistent with the possible presence of aldehydes and ethers which elute in
those fractions. The spectra of LC 5, 6, and 7 suggest the presence of more
polar oxygenates, such as ketones, esters, phenols, and carboxylic acids
which elute in those fractions.
Comparing the Table 3-13 summary with Table 3-9 shows that all
absorbences found in the total extract sample are accounted for among the
eluted LC fractions. In fact, a few fractions had weak to moderate
absorbences that could not be elucidated in the total extract spectrum.
3.4.5 Low Resolution Mass Spectrometry Analysis of LC Fractions
Direct injection probe LRMS was performed on various combinations of LC
fractions of the XAD-2 and bottom ash extract samples and the total baghouse
hopper ash extract. The results of these analyses are presented in
Table 3-14. Specific compound categories were identified as being present
only in two LC fractions of the bottom ash extract and the baghouse ash
extract. Alkyl aromatics were identified in all three samples. The results
from the bottom ash extract are in reasonable agreement with the IR spectra
results in that they indicate carboxylic acids and alkyl aromatics in the LC
fraction where they are expected to be found.
The inability to identify any compound categories in the LRMS analyses
of the XAD-2 extract LC fraction is no doubt due to the very poor recovery of
the LC fractionation performed, although one might have expected some
identifications in the total extract and perhaps the LC 7 extract, as these
contained moderate organic content. Similarly, some identifications might
3-24
-------
TABLE 3-14. LRMS ANALYSIS RESULTS
Sample
Compound category
MW range Intensity
Composite particulate
extract
None identified
XAD-2 + condensate:
Total extract
LC 1 + 2 + 3
LC 4 + 5 + 6 ,
LC 7
None identified
None identified
None identified
None identified
Bottom ash extract:
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
None identified
None identified
None identified
None identified
Alkyl aromatics
Alkyl aromatics
Carboxylic acids
None identified
106 to 148
106 to 148
100
100
100
Baghouse ash extract
Alkyl aromatics 106 to 148 100
Halogenated aliphatics 100
3-25
-------
have been expected for the LC 1 through 4 fractions of the bottom ash
extracts. The authors have no explanation for these Inabilities to identify
major component categories.
3.4.6 Gas Chromatography/Mass Spectrometry Analysis of Total Sample
Extracts
6C/MS analyses of the SASS train sample extracts (10 plus 3 urn
particulate, 1 urn plus filter particulate, XAD-2 and organic module
condensate) and extracts of the bottom ash and baghouse ash were performed to
detect and quantify the 58 semi volatile organic priority pollutant species, a
class which contains several polynuclear aromatic hydrocarbon (PAH) compounds
of interest in combustion source emissions. The compounds sought in the
analysis and their detection limits are listed in Table 3-15. Table 3-16
lists the compounds detected in terms of a mass concentration (mg/kg) and a
flue gas concentration (yg/dscm), as appropriate. The greatest quantity of
PAH and other organic priority pollutant compounds occurred in the bottom
ash. This is consistent with the high TCO and 6RAV analysis results noted in
Section 3.4.1. In fact, of the PAH compounds, only naphthalene was found in
samples other than the bottoh ash. The phthalates noted in the table are
suspected contaminants.
In addition to specific quantification of semivolatile organic priority
pollutants in the GC/MS analyses, major peaks representing other organic
species in the GC chromatograms present at significant concentrations were
identified and approximately quantitated. Table 3-17 shows the organic
compounds identified in each sample and their concentrations. Most of those
noted are aromatic organics, fused ring aromatics, or alkyl derivatives of
these. As in other analyses, the greatest number and greatest quantities of
3-26
-------
TABLE 3-15. COMPOUNDS SOUGHT IN THE GC/MS ANALYSIS AND THEIR DETECTION
LIMITS (ng/yl injected)
2,4,6-trichlorophenol
p-chloro-m-cresol
2-chlorophenol
2,4-dichlorophenol
2,4-dimethylphenol
1,2,4-trichlorobenzene
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,
1,
1,
1,
2,
1
2-dichlorobenzene 1
2-diphenylhydrazine 1
(as azobenzene)
3-dichlorobenzene 1
4-dichlorobenzene 1
4-dim"trotoluene 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-nitrosodi-n-propylamine 5
N-nitrosodimethylamine NA
N-nitrosodiphenylamine 1
acenaphthene 1
acenaphythylene 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)phenathrene
bi s(2-chloroethoxy)methane
bis(2-chloroethyl)ether
bis(2-chloroisopropyl )ether
bi s(2-ethylhexyl)phthalate
butyl benzyl phthalate
chrysene
di-n-butyl phthalate
di-n-octyl phthalate
dibenzo(a,h)anthracene
dibenzo(c,g)carbazole
diethyl phthalate
dimethyl phthalate
fluoranthene
fluorene
hexachlorobenzene
hexachlorobutadiene
hexachlorocyclopentadi ene
hexachloroethane
i ndeno(1,2,3-cd)pyrene
isophorone
naphthalene
nitrobenzene
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
3-27
-------
TABLE 3-16. PAH AND OTHER SEMIVOLATILE ORGANIC PRIORITY POLLUTANT SPECIES
DETECTED
Species
Sample
10 + 3 mi
participate
1 um + filter
parti cul ate
XAD +
condensate
extract
Bottom
ash
Baghouse
ash
(nig/kg) (ug/dscm) (mg/kg) (pg/dscm) (ug/dscm) (mg/kg) (mg/kg)
PAH'S
Acenaphthene a
Acenaphthylene
Anthracene
Benz{a)anthracene
Benzo(j+k)f1uoranthenes
Chrysene
Fluoranthene
Fluorene
Naphthalene 0.2
Phenanthrene
Pyrene
Other priority pollutants
Bis(2-ethylhexyl)phthalate <0.15
Butylbenzylphthalate <0.07
Diethylphthalate
0.9
<0.7
<0.3
3.7
3.4
0.2
0.4
7.7
7.2
0.4
0.8
7.8
2
1
2
1
0.4
0.4
0.8
2
2
42
11
2
84
120
0.3
0.3
0.08
0.04
2, 4-dimethy! phenol
Detection limit
<0.2
0.05
<0.9
0.2
<0.4
0.05
<0.8
0.1
<7
1.1
5
0.4
<0.2
0.04
aDouble dashes denote less than detection limit noted
3-28
-------
TABLE 3-17. OTHER COMPOUNDS TENTATIVELY IDENTIFIED IN GC/MS ANALYSES
Concentration
Sample
10 + 3 urn parti cul ate
1 urn + filter participate
\
XAD + condensate extract
Bottom ash
Compound
No peaks identified
C3~alkyl benzene
Trimethyl benzene
C/^-aklyl benzene
Benzothiazole
Benzoic acid
Ethyl benzoic acid
Ethyl benzaldehyde
Sulfur
Methyl naphthalene
Ethyl naphthalene
Di methyl naphthal ene
Trimethyl naphthalene
Dibenzofuran
4-methyl di benzof uran
(mg/kg)
4.7
2.0
0.8
3.9
100
110
14
29
47
13
17
(yg/dscm)
9.8
4.1
1.7
8.2
290
58
17
Baghouse ash
No peaks identified
3-29
-------
these species were found in the bottom ash. The presence of these compounds,
as indicated by GC/MS confirms the results of the LRMS analysis which
indicated the presence of alkyl aromatics in the bottom ash extract.
3-30
-------
REFERENCES FOR SECTION 3
3-1. DeRosier, R., "Environmental Assessment of a Watertube Boiler Firing a
Coal/Oil Mixture," Acurex Report TR-81-87/EE, March 1984.
3-2. DeRosier, R., "Environmental Assessment of a Crude-Oil Heater Using
Staged Air Lances for N0y Reduction," Acurex Report TR-82-94/EE, March
1984. X
3-3. Castaldini, C., et a!., "Environmental Assessment of NHq Injection for
an Industrial Package Boiler," Acurex Draft Report TR-82-94/EE, March
1984.
3-4. DeRosier, R., et al., "Environmental Assessment of a Commercial
Boiler Firing a Coal/Plastic Waste Mixture," Acurex Draft Report under
EPA Contract 68-02-3188, February 1985.
3-5. VanBuren, D., and L. R. Water!and, "Environmental Assessment of a
Coal-Water-Slurry-Fired Industrial Boiler," Acurex Draft Report
TR-84-155/EE, March 1985.
3-6. Castaldini, C., et al., "Environmental Assessment of an Enhanced Oil
Recovery Steam Generator Equipped with a Low-N0x Burner," Acurex Draft
Report TR-84-161/EE, September 1984.
3-7. Castaldini, C., et al., "Environmental Assessment of an Enhanced Oil
Recovery Steam Generator Equipped with the EPA Low NOX Burner," Acurex
Draft Report TR-85-174/33D, January 1985.
3-8. Lentzen, D. E., et. al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)", EPA 600/7-78-201, NTIS
PB293795, October 1978.
3-9. Waterland, L. R. et al., "Environmental Assessment of Stationary Source
NOX Control Technologies Final Report," EPA 600/7-82-034, NTIS
PB82-249350, May 1982.
3-31
-------
SECTION 4
ENVIRONMENTAL ASSESSMENT
This section discusses the potential environmental significance of
firing a coal-water slurry in the boiler tested and also discusses the
results of the bioassay testing of samples collected during the tests. As a
means of ranking species discharged for possible further consideration, flue
gas stream species concentrations are compared to occupational exposure
guidelines. Bioassay analyses were conducted as a more direct measure of the
potential health effects of the emissions and effluent streams. Both of
these analyses are aimed at identifying potential problem areas and providing
the basis for ranking pollutant species and discharge streams for further
consideration.
4.1 EMISSION ASSESSMENT
To obtain a measure of the potential significance of the discharge
streams analyzed in this test program, discharge stream concentrations were
compared to an available set of health-effects-related indices. For the flue
gas discharge, the indices used for comparison were occupational exposure
guidelines. Two sources of such guidelines were used: the time-weighted-
average TLV's defined by the American Conference of Governmental Industrial
Hygienists (AGCIH) (Reference 4-1) and 8-hr time-weighted-average exposure
limits established by the Occupational Safety and Health Adminstration (OSHA)
(Reference 4-2).
4-1
-------
The comparisons of discharge stream species concentrations to these
indices should only be used for ranking species emission levels for further
testing and analyses.
Table 4-1 lists those polluant species emitted in the flue gas at levels
greater than 10 percent of their occupational exposure guideline. As noted
in the table, many trace elements were present at the boiler outlet at
significant levels. However, flue gas particulate accounts for the major
fraction of these elements in the flue gas at this location. Ultimate flue
gas discharge concentrations would be significantly reduced after passage
through a particulate control device.
For comparison, the gaseous criteria pollutants $03 and NOX were emitted
at levels much higher than their occupational exposure guidelines. NOX
emissions were at levels about 100 times its occupational exposure guideline.
S02 emissions were at levels about 500 times its occupational exposure
guidelines.
4.2 BIOASSAY RESULTS
Health effects bioassay tests were performed on the SASS organic sorbent
(XAD-2) extracts and particulate sample, the bottom ash and the baghouse
hopper ash. The bioassay tests performed were (Reference 4-3) (1) the Ames
assay, based on the property of Salmonella typhinurium mutants to revert due
to exposure to various classes of mutagens, and (2) the cytotoxicity assay
(CHO) with mammalian cells in culture to measure cellular metabolic
impairment and death resulting from exposure to soluble toxicants.
Table 4-2 summarizes the results of these tests. The results suggest
that the XAD-2 extract was of low mutagenicity and undetermined (low or less)
4-2
-------
TABLE 4-1. FLUE GAS POLLUTANTS EMITTED AT CONCENTRATIONS EXCEEDING
10 PERCENT OF THEIR OCCUPATIONAL EXPOSURE GUIDELINE
Species
Flue gas
concentration
(mg/dscm)
Occupational exposure
guideline*
(mg/m3)
S02
Iron, Fe
Phosphorus, P
Aluminum, Al
NOX (as N02)
Arsenic, As
Silicon, Si
Vanadium, V
Chromium, Cr
Beryllium, Be
Copper, Cu
Lead, Pb
Barium, Ba
Nickel, Ni
Calcium, Ca
Lithium, Li
Potassium, K
Cobalt, Co
CO
Titanium, Ti
Uranium, U
Magnesium, Mg
Silver, Ag
Selenium, Se
Cadmium, Cd
Sodium, Na
Manganese, Mn
Germanium, Ge
Zirconium, Zr
Antimony, Sb
Zinc, Zn
Thallium, Tl
2,480
201
13.2
297
626
1.06
537
1.67
1.19
0.045
2.03
0.85
7.95
1.33
25.3
0.27
19.3
0.64
240
20
0.09
15
0.0095
0.167
0.0338
1.09
>1.7
0.13
1.16
0.0899
0.632
0.0126
t
5
1
0.1
2
6
0.01C
10b
0.05
0.05
0.002
0.1C
0.05C
0.5
0.1
2
0.025
2d
0.1
55
10b
0.05C
10
0.010
0.2
0.05d
2d
5d
0.6
5
0.5
1
0.1
aTime-weighted-average TLV (Reference 4-1) unless noted
bFor nuisance parti culate
c8-hr time-weighted-average OSHA exposure limit (Reference 4-2)
dCeiling limit
4-3
-------
TABLE 4-2. BIOASSAY RESULTS
Ames
Sample mutagenicity
10 + 3 urn parti cul ate
1 wn + filter participate
XAD-2 + organic module condensate
total extract
Bottom ash
Baghouse ash
NO
ND
L
ND
ND
CHU
clonal toxicity
L/M
ND/L
U(L)
L/M
L
Note
NU No detectability mutagenicity/toxicity
L Low mutagenicity/toxicity
M Moderate mutagenicity/toxicity
U Undetermined toxicity. Exact toxicity range could not be
determined due to insufficient amount of sample. Test results
indicate low toxicity or less.
toxicity. The other samples showed no detectable mutagenicity and low to
moderate toxicity. The positive Ames response for the XAD-2 extract is
typical for XAD-2 from SASS tests of combustion sources. Current studies
sponsored by EPA's Industrial Environmental Research Laboratory, Research
Triangle Park, are investigating whether such a response is due to artifact
compounds formed when combustion product gas containing NOX is passed over
XAO-2 resin.
4.3 SUMMARY
A comprehensive emissions testing program was performed on a watertube
industrial boiler fired with a coal-water slurry (CMS). The slurry fired
contained nominally 60 percent coal by weight. Two tests were performed: an
abbreviated set of tests with the unit fired at about 2.8 percent flue gas 02
4-4
-------
(test 1), and a comprehensive set of tests with the unit fired at about
2.1 percent 02 (test 2).
NOX, S02, CO, and TUHC emissions (corrected to 3 percent 03) averaged
about 230 and 310 ppm, 880 and 960 ppm, 170 and 200 ppm, and 1 and 3 ppm,
respectively for test 1 and 2, respectively. The apparent emission
differences for these pollutants between the two tests are not considered
significant. N20 levels in the flue gas were generally 15 to 25 percent of
the corresponding NOX emission level.
Particulate levels at the boiler outlet (upstream of the unit's
particulate control device) were quite high. These also apparently increased
from about 3.5 g/dscm in test 1 to 7.3 g/dscm in test 2. The increase is
attributed to greatly increased combustible losses in the flyash in test 2.
Confirming this is the fact that the emitted particle size distribution was
dominated by coarse particulate; over 60 percent (weight) of the boiler
outlet particulate was larger than 10 pm, almost 70 percent was larger than
3 pm.
Total organic emissions in test 2 (the comprehensive emissions test)
were quite high, almost 50 mg/dscm. About 70 percent of this organic matter
was in the nonvolatile (greater than 300°C, ^5+) boiling point range.
The bottom ash organic content was quite high as well, 8 g/kg, with
80 percent of this being in the nonvolatile boiling point range. Alky!
aromatics and carboxylic acids were the major compound categories identified
in the bottom ash organic fraction.
Of the polynuclear aromatic hydrocarbon (PAH) compounds analyzed, only
naphthalene was found in flue gas samples (on the particulate), with emission
4-5
-------
levels of 8.6 yg/dscm. Several PAH's were found in the bottom asti at levels
ranging from 0.4 to over 40 mg/kg.
REFERENCES FOR SECTION 4
4-1. "Threshold Limit Values for Chemical Substances and Physical Agents in
the Work Environment with Intended Changes for 1983-84," American
Conference of Governmental Industrial Hygienists, Cincinnati, Ohio,
1983.
4-2. OSHA Safety and Health Standards, 29 CFR 1910, Subpart Z.
4-3. Brusick, D. J., and R. R. Young, "IERL-RTP Procedures Manual: Level 1
Environmental Assessment, Biological Tests," EPA-600/8-81-024, NTIS
PB81-228766, October 1981.
4-6
-------
SECTION 5
TEST QUALITY ASSURANCE AND QUALITY CONTROL
Quality assurance (QA) activities, implemented for this test included:
9 Duplicate injections for Cj_ to C6 hydrocarbons
9 Duplicate injections for N20
» Duplicate total chromatographable organics (TCO) analysis
» Duplicate gas chromatography/mass spectrometry (GC/MS) analysis for
the semivolatile organic priority pollutant
» Blind standard analysis for Hg analysis
The following paragraphs discuss the results of these QA activities.
5.1 C]_ to C6 HYDROCARBON PRECISION
Replicate injections were performed for the Ci to C$ calibration
standards and at least one duplicate injection of sample per test. The area
counts and relative standard deviations (RSD) from these injections are
presented in Table 5-1. The replicate standard injections were performed
with a gas mixture including the six normal C^ to C5 hydrocarbons. In all
cases, the percent RSD is below the QA objective of 15 percent precison for
the standard injections (Reference 5-1). The duplicate sample injection for
test 2 had an RSD of 26 percent, which failed the QA objective. Both
duplicate injections from test 1 met the QA objective. Thus, of a total of
15 determinations, all but one met the QA precision goal, for a percent
completeness of 93 percent, exceeding the QA objective of 90 percent.
5-1
-------
TABLE 5-1. AREA COUNTS AND RELATIVE STANDARD DEVIATIONS
FOR Ci TO C6 ANALYSES
Test 1
Injection number area count
Calibration
standards
Cl
C2
C3
C4
C5
C6
Samples
(total count)
1
7,192
9,299
10.211
17,917
23,420
29,567
1,560
4,808
2
6,605
9,263
10,239
17,874
23,095
30,115
1,554
4,316
3
7,076
9,184
10,107
17,819
23,103
30,902
4
7,195
9,215
10,477
18.212
23,603
29,835
5
6,966
9,235
10,258
17,996
24,080
29,104
RSD
(percent)
3.5
0.5
1.3
0.9
1.7
2.2
0.3
7.6
Test 2
Injection number area count
Calibration
standards
Cl
C2
C3
C4
C5
C6
Samples
(total count)
1
7,860
9,503
10,417
18,491
23,987
30.131
1,616
2
7,497
9,516
10,769
18.606
24,000
29,793
2,337
3
7,644
9.732
10,872
18,969
24,391
30,948
4
7,290
9,486
10,380
18,561
25,759
30,900
5
8,507
10,149
10,681
18,821
24,385
30,513
6
8,131
10,427
12,675
19,184
24,947
30,986
7
9,017
10,511
11,078
19,160
24,630
30,120
RSD
(percent)
7.6
4.5
7.2
1.5
2.5
1.6
25.8
5-2
-------
5.2 N20 PRECISION
Replicate injections were performed for N20 standards and samples.
Table 5-2 summarizes the area counts for N20 and the percent RSU for these
runs. All of the standard injections met the QA objective of 20 percent RSU
(Reference 5-1). The replicate injections of the samples also met the QA
objectives.
5.3 TCO PRECISION
Duplicate injections of the XAD-2 plus organic module condensate extract
were performed in the quantisation of total semivolatile organics. Results
of the duplicate injections were 57 and 49 mg TCO per SASS train. This
corresponds to an RSD of 10.7 percent, just failing QA objective of
10 percent RSD for this analysis.
5.4 GC/MS PRECISION
Duplicate injections of the XAD-2 plus organic module condensate extract
were performed in the GC/MS analysis for the semivolatile organic priority
pollutants. Quantitation results (only the two compounds identified and
quantitated) are summarized in Table 5-3. The average RSD is within the QA
objective (Reference 5-1) of 50 percent for this analysis. The objective was
failed for one compound quantitation; however, this compound was only found
at the detection limit of the analysis.
5.5 MERCURY ANALYSIS
A NBS reference flyash with a 0.13 mg/kg mercury concentration was
submitted to the analytical laboratory as a blind sample for analysis. The
reported concentration was 0.09 mg/kg, corresponding an accuracy of
-30 percent. This is outside the QA objective of ±20 percent.
5-3
-------
TABLE 5-2. AREA COUNT AND RELATIVE STANDARD DEVIATIONS
FOR N20 ANALYSES
Sample
Injection number area count
RSD
4 (percent)
Calibration
standards
Test 1
Sample 1
Sample 2
Sample 3
Test 2
Sample 1
Sample 2
Sample 3
Sample 4
79,597
10,258
71,978
24,016
28,974
21,196
55,252
73,009
88,851
36,812
79,456
10,154
60,990 67,879 57,102
23,984
28,501
27,177 23,624
78,040 81,048
72,283
91,203
37,539
0.1
0.7
10.9
0.1
1.2
12.5
19.7
0.7
1.8
1.4
TABLE 5-3. DUPLICATE ANALYSIS RESULTS AND RELATIVE STANDARD
DEVIATIONS FOR THE GC/MS ANALYSES
Analysis result (pg/ml)
Compound quantitated
bis (2-ethylhexyl)
phthalate
butyl benzyl phthalate
Run 1
6
3
Run 2
6
1
RSD
(percent)
0
70.7
Average
35.4
5-4
-------
5.6 QA SUMMARY
In summary, of all QA activities performed to challenge the precision of
analytical techniques employed, results were within the project QA objectives
in all instances except two. One failure was in the duplicate TCO analysis,
where measured precision was 10.7 percent compared to a project objective of
10 percent. This very small failure to obtain the QA objective is not
considered significant, and has no effect on conclusions derived from data
obtained in the tests.
The second failure was in the GC/MS analysis, where for one compound
method precision was 71 percent compared to the project objective of
50 percent. However, the quantisations for this compound were at the
detection limit of the analytical techniques, an area where precision is
always poor- This QA objective failure is also not considered significant,
and has no effect on conclusions derived from data obtained in the tests.
In the one test performed to challenge the accuracy of the cold vapor
AAS technique employed to measure mercury concentration, analysis of a blind
audit sample gave a result with accuracy of -30 percent, compared to a
project objective of ±20 percent. This failure has no effect on test program
conclusions since mercury was not detected in any test sample analyzed.
5-5
-------
REFERENCE FOR SECTION 5
5-1. "Quality Assurance Plan for the Combustion Modification Environmental
Assessment," prepared under EPA Contract No. 68-02-3188, September 10,
1982.
5-6
-------
APPENDIX A
TEST EQUIPMENT AND PROCEDURES
A.I CONTINUOUS MONITORING SYSTEM
Flue gas compositon of 02, C02, CO, S02, NOX, NO, and unburned
hydrocarbons were measured continuously by instrumentation at the test
facility. Flue gas samples were drawn by a pump suction through a Pall
particulate filter into a compressed air dryer. The samples were further
dried by a Perma Pure Dryer before delivery to the gas analyzers. Table A-l
lists the instrumentation available at the test facility for this test
program.
A.2 PARTICULATE AND SULFUR OXIDE EMISSIONS
Particulate mass emissions and sulfur oxides tests were conducted in
accordance with EPA Reference Methods 5 and 8. The Acurex High Volume Stack
Samples (HVSS), illustrated schematically in Figure A-l, was used in this
program. A 1.52m (5-ft) heated stainless steel glass-lined probe was
maintained at 120°C (250°F) as required by EPA Method 5. A glass fiber
142-mm (5.59-in.) diameter filter was used to capture the particulate in the
heated oven. The impinger train consisted of four glass impingers equipped
with Teflon caps and 316 stainless steel stems, collector tubes, and
fittings. The first impinger contained 100 ml of 80 percent isopropanol in
distilled water, the second and third impinger contained 100 ml of 3 percent
H202 and the fourth contained a known amount of silica gel. A fritted glass
A-l
-------
TABLE A-l. CONTINUOUS MONITORING EQUIPMENT
Flue gas Principle of
component Analyzer operation Mode Range^
02 Beckman Oxygen Magnetic Model 755 0 to 25 percent
Analyzer susceptibility
S02 MSA LIRA Infrared Model 303 0 to 2,000 ppm
C02 Infrared absorption 0 to 25 percent
CO Analyzer 0 to 1,000 ppm
NO/NOX Beckman Chemiluminescent Model 951 0 to 1,000 ppm
NO/NOX
Analyzer
THC Beckman Flame ionization Model 400 0 to 100 ppm
Hydrocarbon
Analyzer
Operating ranges during the COM test burn on February 19, 1981
A-2
-------
-Sample nozzle
Probe
142 m (diameter) Tcflon
/ filter
V
\_ "S" type
pilot tube
r~ "]
-x
*/
4 '
J Filter
J 1 oven
U
<=T="
Oven
T.C.
w\
coiiuei,Lini|
/line
/
Ice/water
bath ^\^
100 ml -^_
80% I PA ^x
Smith-Greenberg ^Z-
impinger
"""" ' 1 1UU II
Proportional , 3j ){
temperature | 2
controllers [_
-1
$
X
^-
1
°2
Fritted
glass
filter
AP Magnehelic
gauge
Gas meter thermocouples
AH orifice
plate
Check
valve
linpinger
thermocouple
Silica gel
dessicant
Modified
Smith-Greenberg
impinger
Fine adjustment |
bypass valve
Digital temperature
indicator
Control module
Orifice AH
Magnehelic
Vacuum line
Vacuum gauge
I
JCoarse adjustment valve
Dry test meter
Airtight vacuum pump
Figure A-l. Schematic of participate and SQ% sampling train
(EPA Method 5 and 8).
-------
filter is placed between the first and second impingers. The control module
was equipped with maynahelic gauges and digital thermocouple readouts, and a
dry gas flowmeter for monitoring pressure and temperature in the stack and
total gas sampled.
Sample collection took place in the uninsulated stack above the ID fan.
The particulate tests were performed at 12 sampling points in accordance with
EPA Method 1. Each test point was sampled for 6 min, hence a 72-min total
sampling time.
SU2 and $63 emissions were measured by titration of the impinger
solutions per EPA Method 8. Sulfuric acid mist and any vapor phase 803 is
trapped in the isopropanol impinger with the backup filter trapping any
carryover mist. S02 is absorbed in the \\-^2 impingers. After completion of
a test, the filter is rinsed with isopropanol and the rinse solution added to
the isopropanol impinger solution. Absorbed $03 in the isopropanol and SU2
in the ^02 are determined separately by barium-thorin titration.
A.3 TRACE ELEMENT AND ORGANIC EMISSIONS
Emissions of inorganic trace elements and organic compounds were sampled
with 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 of inorganic and
organic emissions as well as particle size measurement.
The SASS, illustrated in Figure A-2, is generally similar to the system
utilized for total particulate mass emission tests (HVSS) with the exception
of:
« Particulate cyclones heated in the oven with the filter to 230°C
(450°F)
A-4
-------
Ul
Stack T.C.
Stainless
steel
sample
nozzle
Heated oven
r
I iI lor
Stainless steel
probe assembly
Stack ,
velocity TX.
AP magnehelici
gauges
1/2" fefloJ
I ine I
Isolation |
ball valve
Sorbent cartridge
Heater controller
Gas meter T.C.
Organic module
f>
j
-------
The addition of a gas cooler and organic sampling module
The addition of necessary vacuum pumps
Schematics outlining the sampling and analytical procedures using the
SASS equipment are presented in Figures A-3 and A-4. The following briefly
describes analytical procedures used in measuring boiler outlet trace
elements and organic emissions.
Inorganic analyses of solid and liquid 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.
Quantitative information on total organic emissions was obtained by gas
chromatography for total chromatographable organics (TCO) and by gravimetry
(GRAV) of particulate, sorbent module (XAD-2), and condensate trap organic
extracts. Infrared spectroscopy (IR) was used for identification of organic
functional groups and gas chromatography/mass spectroscopy (GC/MS) was used
to quantitate the semi volatile 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-6 illustrates
the organic analysis methodology followed during the current program.
A.4 G! TO C6 HYDROCARBON SAMPLING ANU ANALYSIS
Samples of flue gas were collected for C^ to 5 hydrocarbon analysis
using a grab sampling procedure.
The samples were collected using the apparatus illustrated in
Figure A-6. The equipment consisted of a heated, 0.64-cm (1/4-in.) 00
pyrex-lined, stainless-steel probe fitted with a 0.7-wn sintered stainless
A-6
-------
SAMPLE
3y CYCLONE
PROBE WA3M FTP
SORBENT CARTRIDGE -
AQUEOUS CONDENSATE
FIRST IMPINGES
SECOND AND THIRD
lutotuccoe rnntatucn
2 z
u o 2
u ST g y
x
x u ce c a
u u o a M
^ g^ SPLIT
^^r ^^s^-
a. ^ ^^^
*
\
/
SPLIT \
5 GRAMS
.» AQUEOUS PORTION
\^_ ORGANIC EXTRACT
2
o
H
M
UI
a
a <
« y 5 >
J 5 < a
5 C «E tn > 4
< o t e S a 3
5^2 2 1 5 <
.^
^
A . -. A
_^_ A A
COMBINE
\
» « >*
/
TOTALS
5 2 S
' If 'nuirad. lamol* should b. Mt aiida for biological analyin at tha point.
Thii
-------
Figure A-4. Flue gas analysis protocol.
-------
Organic Extract
or
Neat Organic Liquid
1
i
Concentrate
Extract
* t
GC/M.S Analysis,
POM, and other Infrared Analysis
organic species
t t
Repeat TCO
Gravimetric Analysis
if necessary
i
Aliquot containing
15-100 mg
\
Solvent
Exchanae
1
-
Liquid
Chroma tograohic
Separation
t M
' t t t
Seven Fractions
t :
Infrared Analysis
,
»
Mass Snectra
Analysis
TCO
Gravimetric
Analysis
Figure A-5. Organic analysis methodology.
A-9
-------
-Teflon diaphragm pump
Pressure gauge
Inlet valve
0.7 urn sintered stainless-steel filter
l/4~1n. stainless-steel
probe
500-crn stainless-steel
sample cylinder
Ceramic Insulation
and heat tape
Outlet
valve
Thermocouple
Figure A-6. Cj to 65 hydrocarbon sampling system.
-------
steel filter at the probe inlet. The outlet of the probe was directly
attached to a diaphragm vacuum pump which was in turn attached to a 500 ml
heated stainless steel sampling cylinder. The sampling cylinder was
insulated with heat tape powered by a varying voltage controller. The heated
jacket kept the sample gas above the dew point to minimize sample loss due to
water condensation.
Prior to sampling, the gas cylinder was purged with stack gas for 3 min
and then sealed. The trapped flue gas was then analyzed onsite with a Varian
Model 3700 gas chrornatograph (GC) equipped with a flame ionization detector.
Table A-2 lists the design specifications of the Varian GC. A 1.85m (6-ft)
long, 0.32-cm (1/8-in.) diameter stainless-steel column packed with Porapak
Q 60/80 mesh was used to separate the hydrocarbons into their respective
components (C]_ to C6). The GC was calibrated with repeated injections of a
standard yas containing C^ to Cg hydrocarbons (each having a concentration of
15 ppm). The chromatographic responses for the standards and the samples
were recorded on a Hewlett-Packard Model 3390A reporting integrator.
A.6 N20 EMISSIONS
Stack gas grab samples were extracted into stainless steel cylinders,
similar to those used for C^ to C5 hydrocarbon sampling, for laboratory
analysis for N20. For the 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 a gas chromatograph. The analytical equipment
consisted of a Varian 3700 gas chromatograph equipped with a 63Ni
electron capture detector and a 5.5-m (18-ft) stainless-steel column packed
for 3.7m (12-ft) with Poropak R 80/100 mesh and 1.8m (6-ft) with Poropak
Super Q. The injector temperature was kept at 120°C, the detector at 350°C,
A-ll
-------
TABLE A-2. GAS CHROMATOGRAPH SPECIFICATIONS
Vari'an Model 3700 Gas Chromatograph
Sensitivity 1 x 10~12 A/mV at attenuation 1 and range 10~12 A/mV
Zero range -10"11 to 10-9 A (reversible with internal switch)
Noise (input capped) 5 x 10~15 A; 0.5 yV peak to peak
Time constant 220 ms on all ranges (approximate is response to
99 percent of peak)
Gas required Carrier gas (helium), combustion air, fuel gas
(hydrogen)
and the column temperature at 39°C. Elution time for ^0 was approximately
7.5 min.
A.7 FUEL AND ASH SAMPLING
Fuel samples were taken from the line running between the fuel tank and
the boiler. Ash samples were collected from the boiler and the baghouse
after the test.
REFERENCE FOR APPENDIX A
A-l. Lentzen, D.E., et a!., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201,
NTIS PB293795, October 1978.
A-12
-------
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 element analysis results (ug/g or ug/ml) for each sample analyzed.
The composition of the coal-water slurry fuel, the bottom ash, the baghouse
hopper ash, and all SASS train samples (10 + 3 urn particulate, 1 pm + filter
particulate, XAD-2, first impinger, and second and third impingers) are
noted.
The tables labeled "concentration" give the calculated flue gas
concentration (yg/dscm) of each element corresponding to each SASS train
sample, along with the total flue gas concentration (the sum of individual
SASS train samples) in the column labeled "flue gas." The tables labeled
"mass/heat input" give calculated flue gas concentrations (ng/J) of each
element in each SASS train sample, again with the total flue gas
concentration (sum of SASS train samples) in the column labeled "flue gas."
Symbols appearing in the tables include:
dscm Dry standard cubic meter at 1 atm and 20°C
meg Microgram
ppm Part per million by weight
ng/J Nanogram per Joule
< Less than
B-l
-------
> Greater than
N Element not analyzed
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. Values in the form A < x < B were determined by
letting elements reported as less than some concentration be represented by a
concentration of zero for the low value and the reported (less than)
concentration as the high value.
Detectability limits for the various samples were the following:
o Filter <0.1 yg/g
e XAD-2 <0.01
Impinger and organic
module concentrate <0.002 yg/ml
o Coal-water slurry <0.01
» Bottom ash <0.2 yg/g
o Baghouse hopper ash <0.2 yg/g
At standard conditions (20°C (68°F) and 1 atm), one molecular weight
of an ideal gas occupies 24.04&.
Fuel feedrate kg/s 0.410
(Ib/hr) (3,250)
Heat input MW 8.75
(million Btu/hr) (29.9)
Stack gas flowrate dscm/s 2.40
(dscfm) (5,120)
Gas collected (SASS) dscm 8.93
(dscf) (317)
Stack gas molecular weight dry 30.36
wet 28.44
B-2
-------
Water in stack gas (percent) 15.6
02 (percent dry) 2.08
B-3
-------
O3
PPM
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
PETC
COAL-WATER-SLURRY
PPM
FUEL-CWS
.134E+05
.400E+00
.100E+01
.250E+02
.400E+00
.300E-01
.500E+00
.10.100E+03
.200E+01
N.000E+00
.100E+01
.600E+00
.200E+01
.500E+00
.370E+02
.103E+05
.300E+00
. 200E+00
. 300EH-00
.300E+00
.300E+00
BAGHOUSE ASH
.430E+05
.130E+02
.100E+03
.100E+04
.160E+02
.800E+00
.510E+02
.850E+02
.400E+01
.830E+04
.140E+03
.200E+01
.620E+03
.230E+03
.190E+03
.330E+03
.600E+01
.300Ef01
.400E+01
.860E+02
.700E+01
.160E+03
.220E+02
.200E+01
.400E+01
.500E+01
.361E+05
.200E+03
.450E+03
.350E+02
.100E+01
.190E+04
.500E+03
N.000E+00
.280E+02
.550E+02
.600E+02
.510E+02
. 230E+04
. 250E+04
.510E+02
.210E+02
.210E+02
. 320E+02
.440E+02
BOTTOM ASH
.607E+05
-210E+02
.110E+03
.100E+04
.700E+01
.300E+01
.540E+02
.800E+01
.900E+01
.142E+05
.120E+03
.100E+01
.110E+03
.620E+03
.210E+02
.270E+03
.800E+01
.400E+01
.100E+01
.710E+02
.500E-I-01
.450E+02
.500E+01
.500E+01
.500E+01
.400E+01
.435E+05
.930E+02
.520E+04
.380E+02
.800E+00
.280E+04
.500E+03
N.000E+00
.570E+02
. 230E+02
.190E+03
.350E+02
.600E+04
.500E+04
.110E+02
.390E+02
.900E+01
.470E+02
.110E+02
-------
PPM
ELEMENT
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
PETC
COA L-WAT ER-S LURRY
PPM
FUEL-CWS
.692E+05
. 200E+00
.100E+03
.340E+02
.440E+04
.100E+00
.200E+00
.600E-01
. 200E+00
.500E+00
<.200E-01
.400E-01
.630E+02
.100E+00
.500E+00
.300E+01
.100E+00
.400E+01
.200E+01
.200E+01
BAGHOUSE ASH
.630E+05
<.200E+01
.116E+05
.300E+03
.550E+04
.100E+03
.600E+00
.200E+01
.300E+01
.420E+02
.300E+00
.900E+01
.308E+04
.120E+02
.190E+02
.200E+04
.600E+01
.320E403
.160E+03
.160E+03
BOTTOM ASH
.104E+06
<.300E+01
.133E+05
.300E+03
.550E+04
.800E+01
.100E+01
.200E+01
.700E+01
.220E+02
.200E+00
.410E+02
. 250E+04
.900E+01
.180E+02
.200E+04
.400E+01
.270E+03
.460E+04
.130E+03
DO
en
-------
PPM
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
«, GERMANIUM
l HAFNIUM
01 HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
10
PETC
COAL-WAT ER-S LURRY
PPM
3 MICRON 1U + FILTER
.313E+05
.110E+02
.300E+02
.100E+04
.800E+01
.000E+00
.800E+01
.350E+02
.600E+01
.440E+04
.850E+02
.300E+01
.410E+03
.170E+03
.140E+02
.110E+03
.900E+01
.400E+01
.200E+01
.160E+03
.500E+01
.150E+02
.400E401
.400E+01
.600E+01
.400E+01
.241E+05
.750E+02
.150E+03
.250E+02
.200E+0I
.120E-f04
.920F+02
N.000E+00
.200E+02
.160E+02
.300E+02
.190E+02
.160E+04
.210E+04
.210E+02
.390EH02
.170E+02
.110E+02
.150E+02
.733E+05
.180E+02
. 440E-4-03
.160E+04
.400E+01
200E+01
120E+03
300E+02
.300E+01
.238E+04
.610E+02
.300E+00
.840E+04
.170E+03
.270E+03
.710E+03
.300E+01
.100E+01
.100E+01
.180E+03
.200E+01
.430E+03
.530E+02
.800E+00
.200E+01
.300E+01
.405E+05
.540E+02
.770E+02
740E+02
600E+00
450E+04
> 530E403
N 060FI09
IF. 102
.600t+0l
480E+03
900E+01
.280E+04
.450E+04
.600E+01
.180E+02
.500E-I-01
.610E+02
.290E+02
XAD
.400E+00
.000E+00
.000E+00
.300E+00
.000E+00
.000E+00
.200E-01
.140E+00
.000E+00
.100E+01
.600E+00
.000E+00
.300E+01
.300E+00
.400E-01
.100E+00
.000E+00
.000E+00
.000E+00
.800E+00
.000E+00
.200E+08
.000E+00
.000E+00
.000E+00
.900E-01
.190E+02
.900E+00
.300E-01
.100E-01
.000E+00
.250E+01
.170E+00
N.000E+00
.540E+00
.700E-01
.400E+00
.000E+00
.480E+00
. 600E+01
.300E+00
.000E+00
.000E+00
.200E-01
.600E-01
FIRST IMPINGER
.600E-01
.900E-02
. 200E-0?
.000E400
. 000E400
.000E400
.800E-02
.700E-01
.000E+00
.700E+00
.000E+00
.000E+00
.000E+00
.291E+00
.480E-01
. 180E+00
.000E+00
. 000E+00
.000E+00
. 940E+00
.000E+00
.250E-01
. 200E-02
.000E+00
. 000E+00
.000E+00
.298E+02
.000E+00
.000E+00
.000E+00
.000E+00
. 000E+00
.898E+00
N.000E+00
.250E+00
.000E+00
.990E+00
.800E-02
. 100E+00
.950E400
. 000E+00
.190E-01
.000E+00
.320E-01
. 196E+00
-------
PPM
ELEMENT
10 +
PETC
COAL-WATER-SLURRY
PPM
3 MICRON 1U + FILTER
XAD
FIRST 1MP1NGER
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
.606E+05
:.600E+00
.820E+04
.100E+03
.550E+04
.150E+02
.100E+01
.300E+01
.000E+00
.310E+02
.300E+00
.100E+01
.250E+04
.900E+01
. 160E+02
.180E+03
.600E+01
.790E+02
.880E+02
.230E+03
. 1 24E+06
.400E+01
.346E+05
. 300E+03
. 520E+04
400E+01
. 400E+00
. 600E+00
.600E+01
. 400E+00
.600E+01
. 400E+04
.300E+01
.800E+01
. 400E+03
.300E+01
. 1 20E+03
.730E+02
. 450E+02
. 100E+01
.800E-01
. 110E+01
. 000E+00
. 400E+01
. 000E+00
. 000E+00
. 000E+00
. 000E+00
.000E+00
. 000E+00
. 000E+00
. 600E+00
. 000E+00
. 000E+00
.300E-01
.000E+00
.400E-01
. 700E+00
. 600E+00
.500E+00
.000E+00
>.680E+01
.350E-01
>.930E+01
.000E+00
.000E+00
.000E+00
.000E+00
.000E400
.000E+00
.300E-01
.200E-01
.000E+00
.000E+00
.150E-01
.000E400
. 190E-01
.350E+00
.000E+00
CXI
i
-------
CO
I
00
CONCENTRATION
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTET1UM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
10
PETC
COA I.-WAT ER-S LURRY
MCG/DSCM
+ 3 MICRON 1U + FILTER
.144E+06
.505E+02
.138E+03
.459E+04
.367E+02
.000E+00
.367E+02
.161E+03
.275E+02
.202E+05
.390E+03
.138E+02
.188E+04
.780E403
.642E+02
.505E+03
.413E+02
.183E+02
.917E+01
.734E+03
.229E+02
.688E+02
.183E+02
.183E+02
.275E+02
.183E402
.111E+06
.344E+03
.688E+03
.115E+03
.917E+01
.550E+04
.422E+03
.000E+00
.917E+02
.734E+02
.138E+03
.871E+02
.734E+04
.963EH-04
.963E+02
.179E+03
.780E+02
.505E+02
.688E+02
.154E+06
.377E+02
.923E+03
.335E+04
.839E+01
.419E+01
.252F.+03
.629E+02
.629E+01
.499E+04
.128E+03
.629E+00
.176E+05
. 356E+03
566E+03
.149E-f04
.629E+01
.210E+01
.210E+01
.377E+03
.419E+01
.902E+03
.111E+03
.168E+01
.419E+01
.629E-1-01
.849E+05
.113E+03
. 161F.+03
.155E+03
.126E+01
.944E+04
.111E+04
. 000E+00
,545E+02
.126E+02
.101E+04
.189E+02
.587E+04
.944E+04
.126E+02
.377E+02
.105E+02
.128E+03
.608E+02
XAD
.583E+01
.000E+00
.000E+00
.437E+01
.000E+00
.000E+00
.291E+00
.204E+01
.000E+00
. 146E-f02
.874E+01
.000E+00
.437E+02
.437E+01
. 583E+00
. 146E+01
.000E+00
.000E+00
.000E+00
.117E+02
.000E+00
.291E+01
.000E+00
.000E+00
. 000E+00
.131E+01
. 277E+03
.131E+02
.437E+00
.146E+00
. 000E+00
.364E+02
.248E+01
. 000E+00
.786E+01
.102E+01
.583E+01
.000E+00
.699E+01
.874E+02
.437E+01
.000E+00
.000E+00
.291E+00
.874E+00
FIRST IMPINGER
.111E+02
.167E+01
.371E+00
.000E+00
.000E+00
.000E+00
.148E+01
.130E+02
. 000E+00
.130E+03
.000E400
.000E400
.000E400
.540E+02
.890E+01
.334E+02
.000E+00
.000E+00
.000E400
.174E+03
.000E+00
.464E+01
.371E+00
.000E+00
.000E+00
.000E+00
.553E+04
.000E400
.000E+00
.000E+00
.000E400
.000E400
.166E403
N .000E+00
.464E+02
.000E+00
.184E+03
.148E+01
.185E402
.176E+03
.000E+00
.352E+01
.000E+90
.593E+01
.363E+02
FLUE GAS
. 297E+06
.899E+02
. 106E+04
.795E+04
.451E+02
.419E+01
. 290E+03
. 238E+03
.338E+02
. 253E+05
.526E+03
.144E+02
.195E+05
.119E+04
.640E+03
.203E+04
.476E+02
.204E+02
. 113E+02
. 130E+04
.271E+02
. 978E+03
. 130E+03
.200E+02
.317E+02
.259E+02
.201E+06
.470E+03
.850E403
.278E+03
.104E+02
. 150E+05
> .170E+04
.000E+00
.200E+03
.870E+02
.133E+04
.107E+03
.132E+05
.193E+05
.113E+03
. 220E+03
.885E+02
. 18SE+03
.167E+03
-------
"CONCENTRATION
ELEMENT
10
PETC
COAL-WATER-SLURRY
MCG/DSCM
+ 3 MICRON 1U + FILTER
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
.278E+06
.275E+01
.376E+05
.459E+03
.252E+05
.688E+02
.459E+01
. 138E-I-02
. 000E400
.142E40.3
.138E401
.459E+01
.115E405
.413E+02
.734E+02
.826E403
.275E402
.362E403
.404E403
.105E404
. 259E+06
.839E401
.725EH-05
.629E+03
109E+05
.839E+01
839E400
. 126E+01
. 126E+02
. 189E+02
.839E+00
. I26E+02
.839E+04
.629E+01
.168E+02
.839E403
.629E+01
.252E+03
.153E+03
.944E+02
D3
I
VO
XAD
FIRST IMPINGER
FLUE GAS
. 146E+02
. 117E+01
. 160E+02
. 000E+00
. 583E+02
. 000E+00
.000E+00
.000E+00
. 000E+00
. 000E+00
. 000E+00
.000E+00
.874E401
. 000E+00
. 000E+00
.437E+00
. 000E+00
. 583E+00
. 102E+02
.874E+01
.927E+02 .537E+06
.000E+00 .955E+0KX<.123E+02
.126E+04 > .111E+06
.649E+01 .109E+04
.172E+04 > .379E+05
.000E+00 .772E+02
.000E+00 .543E+01
.000E400 .150E+02
.000E+00 .126E+02
.000E+00 .161E+03
.000E+00 .221E+01
.556E+01 .227E+02
.371E+0t .199E+05
.000E+00 .476E+02
.000E+00 .902E+02
.278E401 .167E+04
.000E+00 .338E+02
.352E+01 .618E+03
.649E+02 .632E+03
.000E+00 .116E+04
-------
03
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
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
PI: re
i -WAIER-SI
10
:i'./J
1 3 MICRON
39-H1+02
l.'.8E-fll
.378E-01
. 126E4-01
.101E-01
.000E+00
.101E-01
.441E-01
.755E-02
.554E+01
.107E+00
. 378E-02
.516E+00
.214E-f00
.176E-01
.138E+00
.113E 01
.504E-02
.252E-02
.201E+00
.630E-02
.189E-01
.504E-02
.504E-02
. 755E-02
.504E-02
.303E+02
.944E-01
.189E+00
.315E-01
.252E-02
. 151E+01
.116E+00
.000E+00
.252E-01
.201E-01
.378E-01
.239E-01
.201E+01
.264E+01
.264E-01
.491E-01
.214E-01
.138E-01
.189E-01
HI + FILTER
-122EH02
1R4F.--01
.253EI00
921IH 00
,'30F-02
.1 I5E-02
.691E-01
.173E-01
.173E-02
.137E+01
.351E-01
.173E-03
.483E+01
.978E-01
.155E+00
.409E+00
.173E-02
.576E-03
.576E-03
.104E+00
.115E-02
.247E+00
.305E-01
.460E-03
.115E-02
.173E-02
.233E+02
.311E-01
.443E-01
.426E-01
.345E-03
.259E+01
> .305E+00
N .000E+00
.150E-01
.345E-02
.276E+00
.51BE-02
.161E+01
.259E+01
.345E-02
.104E-01
.288E-02
.351E-01
.167E-01
XAD
.160E-02
.000E+00
.000E+00
.120E-02
.000E+00
.000E+00
.800E-04
.560E-03
.000E+00
.400E-02
.240E-02
.000E+00
.120E-01
.120E-02
.160E-03
. 400E-03
.000E+00
.000E+00
.000E+00
.320E-02
.000E+00
.800E-03
.000E+00
.000E+00
.000E+00
.360E-03
.760E-01
.360E-02
.120E-03
.400E-04
.000E+00
.100E-01
. 680E-03
. 000E+00
.216E-02
. 280E-03
.160E-02
.000E+00
.192E-02
.240E-01
.120E-02
.000E+00
.000E+00
.800E-04
. 240E-03
FIRST IMPINGER
. 305E-02
. 458E-03
. I02E-03
.000E+00
.000E+00
.000E+00
.407E-03
.356E-02
.000E400
.356E-01
.000E+00
. 000E+00
. 000E+00
.148E-01
.244E-02
.916E-02
. 000E+00
.000E+00
. 000E+00
.478E-01
.000E+00
. 127E-02
.102E-03
.000E+00
.000E+00
.000E+00
.152E+01
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.457E-01
N .000E+00
.127E-01
.000E+00
.504E-01
.407E-03
.509E-02
.484E-01
.000E+00
.967E-03
.000E+00
.163E-02
.998E-02
FLUE GAS
.B16E+02
.247E-01
.291£400
.218E+01
.124E-01
.115E-02
.796E-01
.655E-01
.928E-02
.695E401
.145E-H00
.395E-02
.536E+01
.328E+00
.I76E+00
.557E+00
.131E-01
.561E-02
.309E-02
.356E+00
.745E-02
. 268E+00
.356E-01
.550E-02
.871E-02
.712E-02
. 552E+02
. 129E+00
.233E+00
-741E-01
.286E-02
.411E+01
> .467E+00
.000E+00
.550E-01
.239E-01
.366E+00
.295E-01
.363E+01
.531E+01
.311E-01
.604E-01
.243E-01
.507E-01
.458E-01
-------
MASS/HEAT INPUT
ELEMENT
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
10
PETC
COA L-WAT ER-S LURRY
NG/J
+ 3 MICRON 1U + FILTER
.763E402
.755E-03
.103E+02
.126E+00
.692E+01
.189E-01
.126E-02
.378E-02
.000E+00
.390E-01
.378E-03
.126E-02
.315E+01
.113E-01
.201E-01
.227E+00
.755E-02
.995E-01
.111E+00
.290E+00
.712E+02
.230E-02
.199E+02
. 173E+00
.299E+01
.230E-02
.230E-03
.345E-03
. 345E-02
.518E-02
. 230E-03
.345E-02
. 230E+01
.173E-02
.460E-02
.230E+00
.173E-02
.691E-01
.420E-01
.259E-01
TO
i
XAD
FIRST IMPINGER
FLUE GAS
. 400E-02
. 320E-03
.440E-02
.000E+00
.160E-01
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.240E-02
.000E+00
.000E+00
.120E-03
.000E+00
.160E-03
.280E-02
.240E-02
.254E-01 .148E+03
.000E+00 .262E-02 .306E+02
.178E-02 .300E+00
.473E+00 > .104E+02
.000E+00 .212E-01
. 000E-I-00 . 149E-02
.000E+00 .412E-02
.000E+00 .345E-02
.000E+00 .442E-01
.000E+00 .608E-03
.153E-02 .624E-02
.102E-02 .545E+01
.000E+00 .131E-01
.000E+00 .247E-01
.763E-03 .458E+00
.000E+00 .928E-02
.967E-03 .170E+00
.178E-01 173E+00
.000E+00 .318E+00
-------
CO
I
ro
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
OYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
SELENIUM
run
I-"T 1C
(OA| WAITR-SIURRY
Nf.,',1
|'WS FlUf GAS
. I87C-OI
.468F.-01
.117E401
.187E-01
.140E-02
.234E-01
468E-01
< 187E-02
1 7RE-104
if.ni. 01
'U6E-02
140E+00
.936E-01
468E-01
.140E+00
.468E-02
. 468F.-02
.328E-02
.234E+00
.936E-02
.936E-01
.234E-01
< .140E-01
.468E-02
.936E-02
.328E+02
.936E-01
.936E-01
.328E-01
,468E-03
> .468E+01
.936E-01
I .000E+08
.468E-01
.281E-01
.936E-01
.234E-01
.173E+01
.482E+03
.140E-01
.936E-02
.140E-01
.140E-01
.140E-01
.8ISE.+0?
.247F -01
.29 I El00
218E4-0I
. 124E-01
.115E-02
.796E-01
.655E-01
.928E-02
.695E+01
.145E+00
.395E-02
.536E+01
.328E-f00
.176E+00
.557E+00
.131E-01
.561E-02
.309E-02
.356E+00
.745E-02
.268E+00
.356E-01
.550E-02
.B71E-02
.712E-02
.552E+02
.129E+00
.233E+00
.741E-01
.286E-62
.411E+01
.467E+00
.000E+00
.550E-01
.239E-0t
.366E+00
.295E-01
.363E+01
.531E+01
.311E-01
.604E-01
.243E-01
.507E-01
.458E-01
-------
CO
I
MASS/HEAT INPUT
ELEMENT
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
COAI
HiV.I
FUFl -i. VI'..
V4I.»(U
q ,M.-*V
468EHH
1591.101
, 206F-I-03
. 468E-02
.936E-02
.281E-02
.936E-02
.234E-01
< .936E-03
. 187E-02
.295E+01
. 468E-02
.234E-01
. 140E+00
. 468E-02
.187E+00
.936E-01
.936E-01
f'LTC
WATTR SI 'WRY
Fllll f.AS
I48EI03
262E-02''X<. 338E-02
> .306Et02
. 300E+00
> .104E+02
.212E-01
.J49E-02
.412E-02
.345E-02
.442E-01
. 608E-03
.624E-02
545E-V01
. 1.31E-01
.247E-0)
. 458E+ 00
.928E-02
170E+00
173E400
318E400
OJ
-------
TECHNICAL REPORT DATA
(Please read lauructions on the reverse before completing)
NO.
.
EPA-600/7-86-004a
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Environmental Assessment of a Watertube Boiler
Firing a Coal/Water Slurry; Volume I. Technical
Results
5. REPORT DATE
February 1986
6. PERFORMING ORGANIZATION COOE
7. AUTHOR(S)
R. DeRosier and L. R. Waterland
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Aourex Corporation
P. O. Box 7555
Mountain View, California 94039
10. PRC'GRAM 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; 1/84-3/85
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES AEERL project o'fflcer is Robert E.
2477. Volume II is a data supplement.
Hall, Mail Drop 65, 919/541-
16. ABSTRACT
repOrt describes results from field testing a watertube industrial boi-
ler firing a coal /water slurry (CWS) containing about 60% coal. Emission measure-
ments included continuous monitoring of flue gas emissions; source assessment sam-
pling system (SASS) sampling of the flue gas, with subsequent analysis of samples to
obtain total flue gas organics in two boiling point ranges, compound category infor-
mation within these ranges, specific quantitation of the semivolatile organic priority
pollutants, and flue gas concentrations of 73 trace elements; EPA Methods 5/8 sam-
pling for particulate, SO2, and SOS emissions; and grab sampling of fuel and ash for
inorganic composition. NOx, SO2, CO, and TUHC emissions were in the 230-310,
880-960, 170-200, and 1-3 ppm ranges (corrected to 3% O2), respectively, over the
two tests performed. Particulate levels at the boiler outlet (upstream of the unit's
baghouse) were 7.3 g/dscm in the comprehensive test. Coarse particulate (>3 mic-
rometers) predominated. Total organic emissions were almost 50 mg/dscm, with
about 70% of the organic matter in the nonvolatile (>300 C) boiling point range. The
bottom ash organic content was 8 mg/g, 80% of which was in the nonvolatile range.
Of the PAHs, only naphthalene was detected in the flue gas particulate, with emis-
sion levels of 8. 6 micrograms/dscm. Several PAHs were found in the bottom ash.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Held/Group
Pollution
Water Tube Boilers
Slurries
Coal
Assessments
Pollution Control
Stationary Sources
Industrial Boilers
Environmental Assess-
ment
13B
13 A
11G
08G, 21D
14B
is. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
90
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
B-14
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