&EPA
United States
Environmental Protection
Agency
Industrial Environmental Research EPA-600/7-80-086
Laboratory April 1980
Research Triangle Park NC 27711
Environmental
Assessment of a Coal-fired
Controlled Utility Boiler
Interagency
Energy/Environment
R&D Program Report
•
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-80-086
April 1980
Environmental Assessment of a
Coal-fired Controlled
Utility Boiler
by
C. Leavitt, K. Arledge, C. Shih,
R. Orsini, A. Saur, W.,Hamersma,
R. Maddalone, R. Beimer, G. Richard,
S. Linger, and M. Yamada
TRW, Inc.
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2613
Task No. 8
Program Element No. EHE624A
EPA Project Officer: Michael C. Osborne
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
A comprehensive multimedia emissions assessment was performed on the
cyclone-fired La Cygne No. 1 boiler. The unit is equipped with SO^ and
particulate emission control. Level 1 and Level 2 procedures were utilized
to characterize pollutant emissions in gaseous, liquid, and solid process
streams. Results of the comprehensive assessment, in conjunction with
assumed typical and worst case meteorological conditions, were utilized to
estimate the environmental impact of emissions from this type of unit.
Principal conclusions indicated are as follows: 1) The risk of violating
National Ambient Air Quality Standard (NAAQS) for 24 hour and annual average
levels is low. However, units utilizing high sulfur fuel may exceed short
term NAAQS for SOg. 2) Little adverse health effect is anticipated as a
result of S02> S0,~, and particulate emissions projected from widespread use
of coal-fired units of the type tested. 3) Increases in the concentrations
of cadmium and lead in soil and plant tissue as a result of trace element
emissions could cause plant damage and adverse health effects to animals
consuming vegetation in the affected areas. 4) Plant damage due to NO
rt
emissions is likely to occur since estimated NO concentrations approach or
^
exceed threshold concentrations. 5) Damage to sensitive plant species may
result from predicted short-term S02 concentrations which are in the damage
threshold range.
n
-------
CONTENTS
Abstract il
Metric Conversion Factors and Prefixes 1v
1. Introduction 1
2. Summary and Conclusions 3
3. Test Setting 8
4. Assessment of a Coal-fired Utility Boiler 26
5. Environmental Impact Assessment 66
Appendices
A. Simplified Air Quality Model 105
B. Organic Analysis Methods Ill
C. Inorganic Analysis Methods 164
in
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TABLES
Number Page
2-1 Summary of Flue Gas Pollutant Emissions 4
3-1 Design Characterization of Gas Stream in the Air Quality
Control System (1 Module Only) 17
3-2 Composition of Spent Scrubber Slurry 20
3-3 Settling Pond Water Quality 21
3-4 Cooling Lake Water Quality 21
3-5 Stream Descriptions 24
4-1 Summary of Test Conditions 27
4-2 Summary of Ultimate Fuel Analysis 29
4-3 Concentration of Major Trace Elements in Coal Feedstock. . 30
4-4 Existing and Proposed Federal Emission Standards for
Coal-fired Utilities 32
4-5 Average Measured Criteria Pollutant Emissions 32
4-6 Summary of Criteria Pollutant Emissions 33
4-7 Comparison of Criteria Pollutant Emissions With EPA AP-42
Emission Factors for Coal-fired Utility Boilers (Cyclone). 34
4-8 Scrubber Inlet and Outlet Particulate Size Distribution . 38
4-9 S02, S03, and S04~ Emissions 40
4-10 Summary of Sulfate Emissions 42
4-11 Emission Concentrations of Trace Elements - Test 135 ... 43
4-12 Emission Factors for Trace Elements - Test 135 44
4-13 Spark Source Mass Spectrometer Analyses of Trace Element
Emissions - Test 135 46
4-14 ESCA Depth Profile Data for Selected Samples From the
Method 5 Sampling Train - Test 135 47
4-15 Chloride and Fluoride Emissions 49
4-16 POM Emissions From Coal Firing Prior to Scrubbing - Test
134 50
4-17 Water Quality Parameters 52
4-18 Trace Element Concentrations in Wastewater Discharges From
Coal Firing - Test 135 53
4-19 Organics in Wastewater Discharges 54
4-20 GC/MS Analyses of Organics in Wastewater Streams 55
IV
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TABLES (Continued)
Number Page
4-21 Trace Element Content of Scrubber Discharge Solids -
Test 135 57
4-22 Trace Element Content of Bottom and Fly Ash - Test 135 .. 58
4-23 Mass Balance of Trace Elements (Full Load) 60
4-24 Organics in Solid Waste Streams 61
5-1 Emission Rates From a Controlled 874 MW (Gross) Coal-fired
Utility Boiler 68
5-2 Annual Emissions 69
5-3 Comparison of Federal Air Quality Standards With Air
Quality Predicted to Result From Coal Combustion in a 874
MW Utility Boiler 71
5-4 Effects of Coal Combustion in Power Plants in Central U.S. 74
5-5 Health Impacts of Sulfate Aerosol 77
5-6 Expected Trace Element Concentrations in Vicinity of a
874 MW Controlled Coal-fired Utility Boiler 79
5-7 Annual Deposition of Trace Elements in Vicinity of
Controlled Coal-fired Utility Boilers 81
S
5-8 Long Term Effect of Controlled Coal-fired Utility Boiler
Emissions on Soil Concentrations of Trace Elements .... 81
5-9 Long Term Effect of Controlled Coal-fired Boiler Emissions
on Concentrations of Elements in Plants 82
5-10 Trace Element Concentration in Runoff Water in Vicinity of
Controlled Coal-fired Utility Boiler 85
5-11 Projected Ozone Concentrations Which Will Produce, for
Short Term Exposures, 20 Percent Injury to Economically
Important Vegetation Grown Under Sensitive Conditions. . . 87
5-12 Sensitivity of Common Plants to S02 Injury 90
5-13 Trace Element Content of Fly Ash and Bottom Slag From Coal
Firing 94
5-14 Trace Element Content of Scrubber Discharge Solids From
Coal Firing 95
5-15 Leaching Rates for Three Landfill Designs 97
A-l Stack Parameters and Plume Rise 108
A-2 Predicted Maximum Ambient Concentrations of Criteria
Pollutants 109
B-l Level 1 Data Assessment 114
B-2 General Level 1 Reporting Points 116
B-3 Level 2 Data Assessment 120
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TABLES (Continued)
Number Page
B-4 Boiling Ranges of n-Alkanes 124
B-5 TCO of Sample Concentrates and Neat Solutions 125
B-6 Sample Code for Organic Samples Analyzed 126
B-7 Gravimetry of Sample Concentrates 128
B-8 Interpretation of Infrared Spectra of Sample Concentrates 129
B-9 TCOs of Liquid Chromatography Fractions 134
B-10 Gravimetry of LC Fractions 135
B-ll Interpretation of Infrared Spectra of LC Fractions. ... 136
B-12 Results of Gas Bag Analysis 147
B-13 Probe Rinses, Particulate Extracts, Cyclone Rinses. . . . 149
B-14 Analysis of Cyclone Rinse Test 134, Scrubber Inlet
Sampling Train 150
B-15 Absorbent Resin Extracts 151
B-16 Module Rinses and Condensate Extracts 155
B-17 Acidified Process Water and Slurry Samples 157
B-18 Analysis of Selected Acidified Process Water Extracts on
OV-17 GC Column 158
B-19 Neutral and Basic Process Water Extracts (Concentration,
yg/1 of Water Sample) 162
C-l TGA/DSC Results 166
C-2 Overall Size Distributions 169
C-3 Composition of Samples 170
C-4 Spark Source Mass Spectrometry Analysis of Coal Feed -
Test 132 (132-CF) 202
C-5 Spark Source Mass Spectrometry Analysis of Coal Feed -
Test 133 (133-CF) 203
C-6 Spark Source Mass Spectrometry Analysis of Coal Feed -
Test 134 (134-CF) 204
C-7 Spark Source Mass Spectrometry Analysis of Coal Feed -
Test 135 (135-CF) 205
C-8 Spark Source Mass Spectrometry Analysis of Coal Feed -
Test 136 (136-CF) 206
C-9 Combined Spark Source Mass Spectrometry Analyses of Flue
Gas Particulates - Test 135 207
C-10 Spark Source Mass Spectrometry Analysis of Boiler Feed-
water - Test 132 (132-6-1-1) 208
VI
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TABLES (Continued)
Number Page
C-ll Spark Source Mass Spectrometry Analysis of Demister
Inlet - Test 132 (132-6-2-1) 209
C-12 Spark Source Mass Spectrometry Analysis of Settling
Pond Overflow - Test 132 (132-6-3-1) 210
C-13 Spark Source Mass Spectrometry Analysis of Inlet
Scrubber Water - Test 132 (132-6-4-1) 211
C-14 Spark Source Mass Spectrometry Analysis of Water to
Slag Pond - Test 132 (132-6-5-1) 212
C-15 Spark Source Mass Spectrometry Analysis of Lime Feed -
Test 135 (135-LF) 213
C-16 Spark Source Mass Spectrometry Analysis of Inlet Scrubber
Slurry Liquid - Test 135 (135-6-Liquid) 214
C-17 Spark Source Mass Spectrometry Analysis of Inlet Scrubber
Slurry Solids - Test 135 (135-6-Solid) 215
C-18 Spark Source Mass Spectrometry Analysis of Outlet
Scrubber Slurry Liquid - Test 135 (135-7-Liquid) 216
C-19 Spark Source Mass Spectrometry Analysis of Outlet
Scrubber Slurry Solids - Test 135 (135-7-Solid) 217
^
C-20 Spark Source Mass Spectrometry Analysis of Bottom Ash -
Test 133 (133-18-BA) 218
C-21 Summary of XRD Analyses of Coal-fired Samples 219
vn
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FIGURES
Number Page
3-1 Layout of Plant Site 9
3-2 Material Flow Diagram 10
3-3 Schematic of Boiler 11
3-4 Schematic of Burner and Cyclone 12
3-5 Scrubber System Flow Diagram 15
3-6 AQC Module 16
3-7 Flow Diagram Ash Disposal 19
3-8 Schematic of Coal-fired Boiler Showing Sampling Locations 23
5-1 Health Effects from Sulfate Levels Resulting From Coal
Combustion in Controlled Utility Boilers 75
5-2 Increase in Mortality Rates in Vicinity of Coal-fired
Utility Boilers as a Result of S02 and Total Particulate
Emissions 78
5-3 N02 Threshold Concentrations for Various Degrees of Plant
Injury 88
5-4 S02 Dose-Injury Curves for Sensitive Plant Species. ... 90
5-5 Geographical Distribution of Typical Sulfate Levels in
the United States 92
B-l Flow Chart of Sample Handling and Analysis Procedures . . 113
B-2 Retention Times Versus Boiling Points for n-Alkanes ... 123
B-3 Logic Flow Chart for Level 2 Organic Analysis 143
B-4 Analysis of Samples for Organic Content 144
B-5 Total Ion Chromatogram of Concentrated Extract of
Acidified Process Water Sample 160
C-l 135-OUT-PFa Showing the Three Types of Crystallized
Minerals Found in These Samples; Partially Uncrossed
Polars (PUP), 131X 171
C-2 133-18 Shoring the Crushed Slag; Plane Polarized Light
(PPL); 51X 173
C-3 135-IN-CYC Showing Flyash, Magnetite, and Partially
Combusted Coal; PPL, 51X 175
C-4 135-IN-CYC Showing the Same Field of View as Figure C-3
But at a Higher Magnification; PPL, 131X 176
C-5 SEM Photograph (1400X) of 135-IN-CYC Showing Cenospheres
and Air Pockets in Broken Cenosphere 177
vm
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FIGURES (Continued)
Number Page
C-6 Closeup (4000X) of Smaller Cenospheres that Fill Into
Fractured Cenosphere ................... 178
C-7 135-IN-PF Before Desiccation, Shows Flyash; PUP, 131X . . 180
C-8 135-IN-PFa Before Desiccation, Shows Flyash; PUP, 131X. . 181
C-9 135-IN-PFb Before Desiccation, Shows Flyash; PUP, 131 X. . 182
C-10 SEM Photograph of Section of 135-IN-PFa Filter Sample
With Type I Crystal in Upper Right Hand Corner ...... 183
C-ll 9000X Enlargement of Type I Crystal in Figure 3. EDX
Analysis: High, Fe, Si, S; Medium Zn; Low K, and Ca. . . 184
C-12 135-LF Showing a General View of Crushed Limestone
"Rock"; PUP, 51X ..................... 186
C-13 135-LF Showing Soil Agglomerates Which Contaminate the
"Dust" Samples; PUP, 131X ................ 187
C-14 135-6 Showing Limestone; PUP, 51X ............ 189
C-15 135-7 Showing General View of This Sample at Low
Magnification; PUP, 51X ................. 190
C-16 135-7 Showing CaSOs'l/ZHgO Laths, Limestone, Flyash, and
Magnetite; PUP, 131X ........ ' ........... 191
C-17 135-OUT-CYC Showing Type 2 Crystallized "Crust" With
Flyash Embedded in it; PUP, 51X ............. 193
C-18 SEM Photograph of 135-OUT-CYC Showing Flyash and Crystal-
line Material Aggregates ................. 194
C-19 SEM- EDX (2000X) Photograph of Crystalline Material in
135-OUT-CYC. EDX Analysis: High Fe and S; Low Si, Zn,
Ca ............................ 195
C-20 135-OUT-PF Showing the Crystal Types Present in This and
the 135-OUT-PFa Samples; PUP, 51X ............ 197
C-21 SEM of 135-OUT-PFa Filter (500X) Showing Donut-Shaped
Particles ........................ 198
C-22 SEM-EDX Enlargement (5500X) of Single Nodule from 135-
OUT-PFa. Arrow 1 EDX: High S, Fe, Zn; Low Ca, Si, K.
Arrow 2 EDX: High S, Fe, Zn; Medium Si; Low K, Ca. . . . 199
C-23 SEM-EDX of 135-OUT-PF Showing Cubic and Platelet
Materials. Arrow 1 EDX: High S, Fe, Zn; Low K. Arrow 2
EDX: High Fe, Si, Ca, Zn, S ............... 200
C-24 Outlet MRI Weight Data for Runs 135 & 136 ........ 221
ix
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METRIC CONVERSION FACTORS AND PREFIXES
To convert from
Degrees Celsius (°C)
Joule (J)
Kilogram (kg)
Kilojoule/kilogram (kJ/kg)
Megagram (Mg)
Megawatt (MW)
Meter (m)
Meter3 (m3)
Meter3 (m3)
Meter3 (m3)
Manogram/joule (ng/J)
Picogram/joule (pg/0)
Prefix
Symbol
Peta
Tera
Giga
Mega
Kilo
flilli
Micro
Nano
Pico
P
T
G
M
k
m
y
n
P
CONVERSION FACTORS
To
Multiply by
Degrees Fahrenheit (°F)
Btu
Pound-mass (avoirdupois)
Btu/lbm
Ton (2000 Ib )
m
Horsepower (HP)
Foot (ft)
Barrel (bbl)
^ •*
FootJ (ft )
Gallon (gal)
Ibm/mi11ion Btu
lbm/million Btu
PREFIXES
Multiplication
Factor
-, 15
10 °
, J2
10
IO9
IO6
IO3
, -3
10 J
io-6
io-9
io-12
t(°F) = 1.8 t(°C) + 32
9.478 x IO"4
2.205
4.299 x IO"1
1.102
1.341 x IO3
3.281
6.290
1
3.531 x IO1
2.642 x 102
2.326 x 10"3 ,
2.326 x 10"6
Example
15
1 Pm = 1 x 10 meters
12
1 Tm = 1 x 10 meters
g
1 Gm = 1 x 10 meters
1 Mm = 1 x 10 meters
1 km = 1 x 10 meters
_3
1 mm = 1 x 10 meter
1 ym = 1 x 10" meter
_o
1 nm = 1 x 10 meter -
12
1 pm = 1 x 10 meter
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SECTION 1
INTRODUCTION
Conventional methods for conversion of fuels into usable forms of
energy historically have impacted all segments of the environment. Most
conventional combustion processes emit sulfur oxides, nitrogen oxides,
carbon oxides, particulate matter and other potentially harmful pollutants
to the air. Solid wastes from the combustion process, or from control
technologies associated with it, present potential disposal problems, as
well as health and environmental problems. Adverse water-related health
and ecological effects may result when chemical compounds and heavy metals
are leached from solid residues.
Conventional fuel combustion processes are playing an increasing role
in the movement toward national energy independence. As a result, the
potential for adverse environmental impact is also increasing. In recogni-
tion of these facts, IERL-RTP established the'Conventional Combustion
Environmental Assessment program (CCEA) to conduct comprehensive assessments
of the effects of combustion pollutants on human health, ecology, and the
general environment. The assessments will result in recommendations for
control technology and standards development to control adverse effects
within acceptable limits.
This report details results of a comprehensive multimedia emissions
assessment performed at the La Cygne No. 1 utility boiler in Kansas. This
unit is a supercritical cyclone-fired boiler with a net electric generating
capacity of 820 MW. High sulfur, high ash, subbituminous coal is typically
burned in Unit No. 1. Sulfur and particulate emissions are controlled by
limestone scrubbers. Based on 1978 data, cyclone-fired units comprise only
11% of the installed generating capacity from bituminous and subbituminous
coal-fired utility boilers. The average installed capacity for cyclone-
fired boilers is 250 MW, nearly 3.5 times smaller than the test unit.
Further, 61% of all cyclone-fired units (83% on a capacity basis) utilize
electrostatic precipitators for particulate control. Hence, emissions from
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the tested unit should not be considered typical for coal-fired utility
boilers. Owing to the high ash and sulfur contents of the La Cygne fuel,
the unit's capacity and method of emission control, measured emissions from
the La Cygne No. 1 unit may be atypical for cyclones in general. Emissions
data presented herein should be considered in light of these limitations
and extrapolation should be avoided.
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SECTION 2
SUMMARY AND CONCLUSIONS
A comprehensive multimedia emissions assessment was performed on the
number 1 unit at the La Cygne power station in Kansas. This unit is
operated by Kansas City Power and Light Company (KCP&L) although it is
owned jointly by KCP&L and Kansas Gas and Electric Company. The unit is
a cyclone-fired Babcock and Wilcox supercritical, once-through boiler with
a net electrical output of 820 MW. Typically, a high sulfur, high ash
subbituminous coal is burned as fuel. Coal is obtained locally from
surface mines owned by KCP&L and operated by Pittsburgh and Midway Coal
Mining Company. Emissions of SOg and particulates are controlled by eight
venturi-absorber scrubber modules utilizing limestone slurry. Spent
2
scrubber slurry is discharged to a 0.65 km settling pond. Water for
2
cooling purposes is drawn from a 10.5 km cooling reservoir constructed
adjacent to the plant site.
Major effluent streams from the site are flue gas, combined bottom
and fly ash, scrubber solids, settling pond overflow and ash pond overflow.
With the exception of the ash pond overflow, samples were obtained from
each of these streams. Characteristics of the ash pond overflow were
estimated from analyses of liquid discharged into the ash pond from the
ash dewatering tanks.
Flue gas emissions are summarized in Table 2-1. Tabulated emissions
of NO represent lower limit values since samples were collected in bags
A
and sample degradation has since been determined significant. The apparent
NO removal by scrubbing is attributed to degradation of the bag samples
A
rather than actual removal from the flue gas. No attempt was made to
accurately measure CO emissions; indicated upper limits result from a 1000
ppm detection limit.
Measured S02 emissions indicate 78% removal by scrubbing which exceeds
the design removal efficiency of 76%. Approximately 98% of uncontrolled
sulfur emissions were as S02 while 1.1% and 0.4% were as S03 and particulate
SO-", respectively.
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TABLE 2-1. SUMMARY OF FLUE GAS POLLUTANT EMISSIONS
Pollutant
NOX* (as N02 near full load)
C0f
.
so2
**
SO,
Emission
Before Scrubber
>715
<520
***
3380 ± 400
***
48 ± 24
Factor, ng/J
After Scrubber
>385
<520
***
740 ± 90
***
10 ± 11
so,
**
ft
Total Organics
Total Parti culates**
_**
Cl
_**
***
22 ± 9.0
2.77 - 4.07
***
1090 ± 270
0.6 ± 0.4
***
***
2.7 ± 1.9
1.45 - 2.60
80
<0.14
NOX was determined by chemiluminescent analysis of bag samples (Level
2). Due to potential for NOX degradation in bag samples, measured
values are considered to be lower limit values. Apparent NOX removal
by limestone scrubbing is attributed to sample degradation.
CO was determined by gas chromatographic analysis of bag samples
(Level 2). Indicated values represent the detection limit of 1000 ppm.
_ was determined by pulsed fluorescence analysis of bag samples and
by the CCS (Level 2).
** _
S03, $04 , Cl , and F were determined by analysis of the CCS (Level
2).
" C-|-C-|(j fractions were determined by gas chromatograph while the >Cj6
fraction was determined gravimetrically (Level 1). Upper limit values
include detection limits of fractions which were not detected.
Total particulates were determined by a modified Method 5 procedure
(Level 2) and from the SASS train particulate catch (Level 1).
***
Indicated uncertainties represent one standard deviation.
-------
Total particulate emissions data indicate 91% removal by scrubbing
which is lower than the design removal of 98%. Scrubber inlet particulates
consisted primarily of particles larger than 3 ym; 13% of the particulates
were 3-10 ym and 87% were larger than 10 ym. After scrubbing, 82% were
less than 1 ym, 11% were 1-3 ym, 1% were 3-10 ym and 6% were larger than
10 ym. Scrubber removal efficiencies were essentially zero for particles
smaller than 3 ym and approximately 99% for particles larger than 3 ym.
Atomic absorption analysis (AAS) was utilized to determine concentra-
tions of 18 trace elements in the flue gas. Concentrations of most elements
exceeded health-based Discharge Multimedia Environmental Goal (DMEG) values
at the scrubber inlet. At the scrubber outlet As, Cd, Cr, Fe, Ni, Pb, and
Zn exceeded their respective health-based DMEG values. Comparison of AAS
data with spark source mass spectroscopy (SSMS) analysis indicated that SSMS
corresponds to the more accurate AAS results only to within one or two
orders of magnitude for most elements.
Speciation of organic compounds in the flue gas indicated the presence
of aliphatic hydrocarbons, substituted benzenes, ethylbenzaldehyde, dimethyl-
benzaldehyde, 2,6-pereriden-dione-4, and 2,6-dimethyl-2,5-heptadion-4-one,
and the methyl ester of long chain acid, at concentrations ranging from 0.2
to 20 g/m prior to scrubbing. Only ethylbenzaldehyde, substituted benzenes,
and aliphatic hydrocarbons were identified at the scrubber outlet. Most POM
compounds identified at the scrubber inlet are naphthalene, substituted
naphthalenes, biphenyl and substituted biphenyls. Concentrations of these
compounds were several orders of magnitude lower than their respective DMEG
values. No POM compounds were detected at the scrubber outlet.
Liquid wastes were analyzed by AAS to determine trace elements and by
gas chromatograph to determine organics. Liquid to the ash pond was found
to contain Al, Ca, Cd, Fe, V, and Zn at concentrations exceeding ecology-
based DMEG values while only Fe exceeded its health-based DMEG value. The
scrubber slurry settling pond overflow contained Ca, Cd, Mn, Ni, and Pb at
concentrations exceeding health and ecological DMEG values and, in addition,
Al, Fe, and Zn exceeded their respective ecological DMEG values. Total
organics were detected at 0.06 mg/1 in liquid to the ash pond and at 0.6
mg/1 in settling pond overflow. Liquid to the ash pond did not contain >C,g
organics while the settling pond overflow organics were primarily >C-ig.
5
-------
AAS analysis of solid wastes indicated that Al, As, Ca, Cd, Fe, Mn, Ni,
Pb, and Zn concentrations in scrubber solids, and Al, Ca, Cr, Fe, Mn, Ni,
Pb, and Zn concentrations in bottom ash/fly ash samples exceeded health-
based DMEG values. Organic concentrations in scrubber solids and bottom
ash/fly ash samples were 6.6 mg/kg and 86.2 mg/kg, respectively. No
organics >C-jg were detected. POM compounds were not detected in scrubber
solids.
Bioassay tests were performed on six samples obtained at the La Cygne
unit: 1) cyclone particulate catch (scrubber inlet); 2) raw limestone;
3) combined bottom ash/fly ash; 4) scrubber outlet slurry solids; 5) cooling
water; and 6) scrubber outlet slurry. Tests performed include Ames mutage-
nicity assay, CHO clonal toxicity, RAM cytotoxicity, WI-38 human cell cyto-
toxicity, rhodent toxicity, and freshwater toxicity assays. In general,.no
toxicity was detected. However, the RAM cytotoxicity assay indicated low
toxicity for bottom ash/fly ash, scrubber outlet solids, and the cyclone
particulate catch. Also, the scrubber outlet slurry exhibited low toxicity
in WI-38 cytotoxicity assay and moderate toxicity in the CHO cytotoxicity
assay.
An environmental impact assessment was performed based upon emission
rates measured at the La Cygne number 1 boiler and assumed typical and worst
case type meteorological parameters. Principal conclusions indicated by
this assessment are as follows:
• The environmental acceptability of emissions from coal-fired
boilers is largely dependent on site-specific factors such as
background pollution levels and meteorology. However, the
risk of violating NAAQS due to criteria pollutant emissions
from a coal-fired boiler (874 MW gross output scale) like La
Cygne utilizing a cyclone furnace appears low in terms of 24
hour and annual average levels. Units utilizing high sulfur
fuel, such as that utilized in the La Cygne number 1 boiler,
may exceed short term NAAQS for S02-
t Based on the Lundy-Grahn Model for health effects associated
with suspended sulfate levels, limited adverse health
effects would result from these emissions. Similar results
were obtained with this model considering the effects of
S0£ and total particulate emissions on people older than
30 to 40 years of age.
-------
The impact of trace element burdens on drinking water and air
quality as a result of measured emissions from this coal-fired
utility boiler is generally orders of magnitude less than
allowable or acceptable exposure levels. However, substantial
increases in Cd are predicted in soil. Similarly, substantial
increases in Cd and Pb are predicted in plant tissues. While
long-term accumulation of Cd may cause plant damage and
serious health effects to animals consuming vegetation in the
affected areas, accumulation of other trace elements is not
expected to result in concentrations which would be toxic
to human or plant life.
Plant damage due to NOX emissions is likely to occur since
estimated NOX concentrations (both short and long term)
approach or exceed threshold concentrations. Predicted short
term concentrations of S02 are also in the threshold range-,
hence, SOg emissions may result in damage to sensitive plant
species. Plant damage is not likely to result from predicted
concentrations of other criteria pollutants. The effects of
secondary pollutants formed by reactions between NOX and
hydrocarbons, and the synergistic effects of 862 in the
presence of ozone are uncertain.
-------
SECTION 3
TEST SETTING
PLANT DESCRIPTION
The coal-fired utility boiler tested was the number 1 unit at the La
Cygne power station in Kansas. The unit is operated by Kansas City Power
and Light although it is owned jointly by KCP&L and Kansas Gas and Electric
Company. It burns local coal and has an air quality control system for
reducing S02 and particulate emissions.
The La Cygne Station is located about 88 km south of downtown Kansas
City, Missouri, and 0.8 km west of the Missouri state line. The plant site
was selected primarily because of availability of coal, water and limestone
locally. Figure 3-1 shows general plot plan of the entire facility.
Figure 3-2 shows the general material flow diagram for the unit tested.
Boiler
Boiler Number 1 was designed to burn coal as the primary fuel. It is
a cyclone-fired, super critical, once-through, balanced draft Babcock &
Wilcox unit rated at 46.8 Mg/s of steam. This corresponds to a maximum
heat input rate of approximately 137 GJ/s. The generator is rated at 874
MW, gross (measured at the generator with no allowance for powering fans or
pumps). The net output, that is the power leaving the plant, is 820 MW.
Construction of the unit began in 1969. Commercial operation began in mid-
1973.
Figure 3-3 is a schematic of the boiler. Figure 3-4 shows a schematic
of the burner-cyclone furnace combination. In most boilers the fuel and all or
part of the combustion air are mixed in the burner but the bulk of the actual
fuel burning occurs in the boiler (more accurately called the boiler furnace).
In cyclone-fired units the fuel-air mixture is ejected from the burner into
the cyclone furnace. The cyclone furnace is a barrel shaped plenum into
which the combustion air is injected (see Figure 3-4). Essentially complete
8
-------
vo
WAREHOUSE
TRANS. I
TOWER I
COAL STORAGE ««L
COAT STORAGE TT
FACM
0.27
•vX
AUXI
TACW
jo/y
MAINT
BUII
ESP
LLARYCZ
SCRUBBER
ABSORB
UNIT
ENANCE
.DING
1 BOILER
UNIT
NO 2
3 BOILERS
BOILER
UNIT
NO. 1
GENERATORS
(SERVICE
BLDG.
SWITCH YARD
AREA
COOLING LAKE - 2600 ACRES
Figure 3-1. Layout of Plant Site
-------
Figure 3-2. Material Flow Diagram
-------
BOILER
FURNACE
HOT
COMBUSTION
GASES
BURNER
CYCLONE FURNACE
WATER FILLED
SLAG TANK
TO ASH DISPOSAL
Figure 3-3. Schematic of Boiler
11
-------
SECONDARY^, .^^^ FURNACE
AIH ^^^^ ^--—^_ EXIT TO
BOILER
PRIMARY.
AIR
TERTIARY^ T ^^\-^ CYCLONE
AIR / \ FURNACE
/ CRUSHED
CYCLONE COAL
BURNER
Figure 3-4. Schematic of Burner and Cyclone
combustion of the fuel but relatively little heat transfer occurs in the
cyclone. The hot combustion products then enter the boiler furnace where
most of the heat is transferred to the steam. This unit has 18 such cyclone
furnaces.
Combustion air is supplied to the main boiler unit by three forced
draft fans. Combustion air enters the combustion zone at three locations.
Primary air which constitutes approximately 20% of the total, enters the
burner tangentially and imparts a swirling motion to the incoming coal.
Secondary air, approximately 75% of the total, enters the main barrel of
the cyclone furnace tangentially and imparts additional swirl and centrifu-
gal motion to the coal. Entrance velocities for secondary air of 91 m/s
are typical. Tertiary air, approximately 5% of the total, enters through
the center of the burner.
Crushed coal from overhead bunker storage is admitted at the top of
the burner. Upon entering the cyclone the fuel is burned quickly and
12
-------
essentially completely. Temperatures are high enough to melt the ash
constituents in the fuel and form a liquid slag. Because of the whirling
action in the cyclone, the liquid slag and much of the particulate matter
are propelled by centrifugal force to the outside of the cyclone. The slag
with captive particulates drains to the bottom of the cyclone and then to
the boiler furnace. On entering the boiler furnace the liquid slag begins
to cool. Prior to solidification it drains from the boiler furnace bottom
via a slag tap to a water filled slag tank where further cooling and
solidification takes place.
The boiler furnace absorbs most of the heat contained in the hot
gases produced in the cyclone furnace. Additional heat transfer occurs in
the super heaters, economizer and air heaters.
The boiler is scheduled to operate on a 24-hour per day, 7 days per
week basis. It is scheduled to be off line no less than once each year for
various types of maintenance.
The coal burned is mined locally. The mining area, located near the
site, is owned by the utility company and operated by the Pittsburgh and
Midway Coal Mining Company. The coal is surface mined and delivered to
the site by 109 Mg off-the-road trucks. The trucks bottom dump their
loads into a 908 Mg capacity receiving hopper; the typical top size of this
coal as received is 0.8 m. From the receiving hopper the coal is trans-
ported through the plant by a network of conveyors.
The coal is low grade sub-bituminous with an as-fired heating value
of 20.9 to 22.6 MJ/kg, an ash content of approximately 25%, and a sulfur
content of 5 to 6%. It is estimated that the coal deposits are approxi-
mately 63.5 Tg.
Under some circumstances coke is mixed with the coal to increase the
energy per unit weight of the fuel burned. At times 10 to 20% of the fuel
can be coke. No information as to coke supplier and analysis was available;
however, no coke was fired during testing.
There are three oil-fired auxiliary boilers which are only used inter-
mittently to provide heat for the plant when Unit No. 1 is down and for
powering a 20 MW turbine-generator to provide electricity for powering
ancillary equipment during startup.
13
-------
Scrubber
Sulfur dioxide and particulate emissions are controlled by a flue gas
scrubber system. The scrubber was designed by Babcock and Wilcox as an
integral part of the steam generation plant. It consists of eight two-stage
venturi-absorber scrubber modules. The system was designed to treat boiler
flue gas at a flow rate of 1209 Mm /s. Each module was designed to treat
151 Nm3/s per module at 413 K.
The gas handling system (boiler and scrubber) is balanced draft.
Three forced draft fans supply combustion air to the furnace and six fans
located downstream of the scrubbing system induce draft in the boiler and
scrubber.
As shown in Figure 3-5, the flue gas from the boiler enters the air
quality control system through a common plenum. From the common plenum
the gas stream is sent to the individual scrubber modules, as indicated.
No provisions exist for allowing the flue gas to bypass the scrubber.
As shown in Figure 3-6, upon entering the scrubber module the hot flue
gases pass through the venturi section, where they are sprayed with lime-
stone slurry. Up to 99% of the particulate matter is removed from the gas
stream at this point. The particles are entrained in the liquid which
drops into the bottom sump. The gas stream then makes a 180° turn and
passes through the S02 absorber section. The SC^ is removed by absorption
as the gas stream is drawn through stainless steel sieve trays which are
sprayed with the limestone slurry solution. This slurry with the absorbed
SOg drops into the bottom sump. The gas stream then passes through a
demister section in which excess moisture and mist are removed. The gas
stream then passes through a reheat section which increases the gas tempera-
ture approximately 303 K to improve gas buoyancy and to reduce the probabil-
ity of deposits on the induced draft fans. Upon exiting the scrubber module
the gas stream enters a common plenum from which it is drawn through one
of the six induced draft fans and then sent to the stack. Table 3-1 shows
typical characteristics of the flue gas before and after scrubbing, res-
pectively.
14
-------
FAN (7000 HP) TYPICAL
CTT
FLUE GAS
FROM BOILER'
Figurs 3-5. Scrubber System Flow Diagram
-------
TO OUTPUT PLENUM,
.0. FANS S STACK
122 KG/S
7KG/S
1 KG/S
1 KG/S
413 K
163 W*/S
352 K
163M3/S
»i kPa
121 KG/S
11 KG/S
0.01 KG/S
0.3 KG/S
323 K
141 M3/S
91 kPi
THROAT FLUSH
GRIT SEPARATOR
ABSORBER RECWC. PUMP
0.6M3/S
RECIRCULATION TANK
14% SOLIDS
pH-6.8
CaCO-,
FLYASH
46 KG/M3
50 KG/M3
16 KG/M3
30 KG/M3
! — DISPOSAL POND 0401 M3/S
RECIRC. PUMP O4 M It
SPENT SLURRY TO POND
ao4M3/s
TO DISPOSAL POND
37 KG/S TOTAL
FOR ALL 8 MODULES
LIMESTONE SLURRY FEED
•APPROXIMATE VALUES
Figure 3-6. AQC Module
16
-------
TABLE 3-1. DESIGN CHARACTERIZATION OF GAS STREAM IN THE
AIR QUALITY CONTROL SYSTEM (1 MODULE ONLY)
Dry Gas
H20 Vapor
Ash
so2
Temperature
Volumetric Flow Rate
Pressure
Inlet
122 kg/s
7 kg/s
1 kg/s
1 kg/s
413 K
163 m3/s
95 kPa
Outlet
121 kg/s
11 kg/s
0.01 kg/s
0.3 kg/s
323 K
141 m3/s
91 kPa
The limestone utilized in making up the scrubber slurry is mined
locally and brought to the site by off-the-road trucks. Ground limestone
is mixed with water for the slurry. The limestone processing and storage
facility is capable of supplying 15 Mg/s of slurry to the scrubber system.
2
The slurry water is recycled from the 6.5 Km settling pond. The flow
3
rate of the makeup water to the system is approximately 0.01 m /s.
Sulfur dioxide (S02) and sulfur trioxide (SOj) are removed from the
flue gas stream by reaction with the aqueous slurry of limestone. The major
component of limestone is calcium carbonate (CaCOj). The products from the
S02 reaction are carbonic acid (H2C03) and calcium sulfite hemi-hydrate
(CaS03-l/2 H20). The products from the S03 reaction are carbonic acid and
calcium sulfate dihydrate (CaS04'2H20). These reactions are shown below:
S02 + 1 1/2 H20 + CaC03 -» H2C03 + CaS03'l/2 HgO
S03 + 3 H20 + CaC03 -*• H2C03 + CaS04»2 H20
17
-------
The pH of the slurry is maintained at 5.5 to 6.0. Optimum pH for the
chemical reactions is 5.6 to 5.8. If the pH exceeds 5.8 the amount of CaCOo
O
(limestone) required increases and soft scale begins to accumulate rapidly.
If the pH drops below 5.6 a hard gypsum (CaSO^-2 HgO) scale builds up. The
pH of the slurry is controlled by adjusting the rate at which limestone is
added to the slurry.
Liquid Effluent
The plant produces three major liquid and slurry effluent streams:
0 Slurry from the slag tank containing slag and fly ash;
• Spent slurry from the scrubber;
§ Effluent from equipment wash down, especially the induced
draft fans.
The slurry from the slag tank contains suspended solids from the boiler
furnace bottom and the economizer hopper. The solids from the boiler
furnace bottom are made up of various non-volatile materials and inorganics
which were present in the fuel. The solids from the economizer hopper are
made up primarily of fly ash.
Figure 3-7 is a simplified flow diagram of the ash handling system.
3
As shown in the diagram, approximately 0.08 m /s is pumped from the cooling
water lake into the ash system. Fly ash from the economizer hoppers is
gravity fed to the mixing tanks. Fly ash and water are mixed in these tanks
and the mixture is piped to one of the slag tanks. Molten slag from the
boiler furnace is gravity fed to the liquid filled slag tank. Clinker
grinders at the bottom of the slag tank reduce the solidified slag to an
appropriate size for transport via jet pumps to dewatering bins. Transport
water is drawn from the cooling water lake. Two streams are piped from each
dewatering bin. One stream is sent directly to the ash (solid waste) dis-
posal site and the other is piped to the ash pond. Once discharged into the
ash pond the suspended solids settle out of the solution and the clear water
is recycled to the cooling lake.
The effluent from the scrubbing system is a side stream of the slurry
3
recycling system. Approximately 0.04 m /s of spent slurry is discharged
from each scrubber module and piped to the on-site settling pond. Table 3-2
18
-------
ECONOMIZER HOPPERS
vo
,. WATER
) FROM COOLING WATER LAKE
TO ASH DISPOSAL
TO ASH POND
Figure 3-7. Flow Diagram Ash Disposal
-------
gives the average analysis of the spent slurry solution. Upon entering
the settling pond the slurry is diluted and the suspended solids settle
out. The clear solution is recycled to the scrubber system and also dis-
charged into the cooling lake.
Effluents from surface housekeeping wash down and maintenance wash
downs (e.g., induce draft fan wash downs) are piped to the settling pond.
2
The settling pond is a 0.65 km pond which is used as the primary sink for
the liquid effluent from the air quality control system. Since the pond
is an open basin, surface water run-off enters the pond. However, core
tests conducted by an independent testing firm indicate that the likelihood
of leaching problems is quite remote. Typical water quality parameters for
the pond are given in Table 3-3. Part of the clarified water is used as
makeup water for the scrubber and part flows to the cooling lake.
2
The 10,5 km cooling lake is the primary source for all water used by
the facility. It receives fresh water from La Cygne Creek, surface water
run-off, settling pond overflow, ash pond overflow, and wash down water.
Typical lake water quality parameters are presented in Table 3-4. The lake
is stocked with various varieties of fish and the plant and KCP&L Company
is presently negotiating with several public agencies to open the lake to
public use for boating and fishing.
TABLE 3-2. COMPOSITION OF SPENT SCRUBBER SLURRY
CaC03
CaSOj
CaS04
Fly Ash
Total Solids
PH
Total Solids removed per day
Total Solids removed per year
Volume Displaced by Solids/year
46 kg/m3
50 kg/m3
16 kg/m3
30 kg/m3
14%
5.6
3.2 Tg
0.63 Tg
559,000 m3
20
-------
TABLE 3-3. SETTLING POND WATER QUALITY
Cations
Calcium (Ca) 808 ppm
Magnesium (Mg) 106 ppm
Sodium (Na) 53 ppm
Potassium (K) 42 ppm
Anions
Alkalinity (as HC03) 79 ppm
Chloride (Cl) 314 ppm
Sulfate (S04=) 1995 ppm
Sulfite (S03=) None detected
Silica (SiO?) 52 ppm
Others
pH 8
Conductivity 3500 micromhos/cm
Solids, suspended 5 ppm
Dissolved 3450 ppm
TABLE 3-4. COOLING LAKE WATER QUALITY
Cations
Calcium (Ca) 126 ppm
Magnesium (Mg) 16 ppm
Sodium (Na) 31 ppm
Potassium (K) 5 ppm
Anions
Alkalinity (as HC03) 112 ppm
Chloride (Cl) 45 ppm
Sulfate (S04=) 295 ppm
Sulfite (SOo3) None detected
Silica (Si02) 1 ppm
Others
pH 8
Conductivity 820 micromhos/cm
Solids, suspended 5 ppm
Dissolved 610 ppm
21
-------
Solid Wastes
The solid wastes, primarily ash, generated by combustion are removed
from the system as liquid slurries. The solids which settle to the bottom
of the settling pond are periodically dredged. The majority of the solid
waste is disposed of in a company owned landfill northwest of the facility.
COAL-FIRED UTILITY TESTS
The integrated scrubber, scrubber waste disposal and combustion waste
(ash) disposal systems at the coal-fired utility plant are extremely complex.
Because the boiler and scrubber were designed and built as an integrated
unit a large number of streams had to be sampled to allow a complete
characterization of both the boiler and scrubber. A total of 13 separate
process streams were sampled. Figure 3-8 shows the sampling location for
each stream and Table 3-5 provides stream descriptions. These 13 streams
do not constitute all possible sampling locations. However, given the time
and budget constraints, these samples did provide sufficient information to
conduct a comprehensive emissions assessment of the plant.
Emissions were characterized using EPA's phased approach to sampling
and analysis. This approach utilizes two separate levels of sampling and
analytical effort (Level 1 and Level 2). Level 1 is a sampling and analysis
procedure accurate within a factor of about 3. This level provides pre-
liminary assessment data and identifies problem areas and information gaps.
These data are then utilized in the formulation of the Level 2 sampling and
analysis effort. Level 2 provides more accurate detailed information that
confirms and expands the information gathered in Level 1. The methods and
procedures used during this study are, in some instances, modified Level 1
sampling and/or analysis procedures and are documented in the manual,
"Combustion Source Assessment Methods and Procedures Manual for Sampling
and Analysis", September 1977. The Level 2 methods and procedures included
"state-of-the-art" techniques as adapted to the needs of this site. Details
of Level 2 procedures are presented in the Appendices. Normally all Level
1 samples are analyzed and evaluated before moving to Level 2. However,
because of program time constraints, the Level 1 and Level 2 samples were
obtained during the same test period.
22
-------
All
HEAICI
ro
GJ
Figure 3-8. Schematic of Coal-fired Boiler Showing Sampling Locations.
-------
TABLE 3-5. STREAM DESCRIPTIONS
Stream Number
1
2
3
4
5
6
7
8
9
10
11
12
13
Stream Description
Coal feed
Scrubber inlet
Scrubber outlet
Stack
Boiler feedwater
Demister wash
Settling pond overflow
Scrubber make-up water
Scrubber feed slurry
Spent scrubber slurry
Thickener overflow
Thickener underflow
Limestone feed
Type of Sample
Solid fuel
Flue gas
Flue gas
Flue gas
Liquid
Liquid
Liquid
Liquid
Slurry
Slurry
Slurry
Solid ash
Solid
The Source Assessment Sampling System (SASS) was used to collect both
gaseous and particulate emission samples at the scrubber inlet and outlet
for Level 1 organic and inorganic analysis. The train was run for 6 to 8
" 3
hours until a minimum of 30 m of gas had been collected.
Previous sampling and analysis efforts had indicated possible inter-
ference of SASS train materials on certain organic and inorganic analysis
when at the lower detection limits of Level 2 methods. To avoid this
possibility, all glass sampling trains were used to collect Level 2 samples.
Two Method 5 sampling trains were modified for Level 2 organic and inorganic
sample acquisition. Each train samples approximately 10 cubic meters of
flue gas during a 6- to 8-hour run time.
A controlled condensate train (Goksoyr-Ross) was used at each location
during testing to obtain samples for S02, S03 (as H2S04), particulate
sulfate, HC1 and HF.
24
-------
During Level 2 test runs, MRI impactors were used to obtain particulate
size distribution data for the scrubber outlet gas. However, due to the
high particulate loading in the flue gas prior to scrubbing, particulate
size distribution data was obtained by polarized light microscopic analysis
(PLM) of particulate collected by the modified Method 5 procedure.
Liquid and solid samples were obtained by using appropriate composite
dipper and grab sampling techniques.
Each stream was analyzed, as appropriate, for criteria pollutants,
inorganics, organics, and wastewater parameters. A variety of analytical
techniques were employed to determine both total elemental emissions and,
in some cases, specific compounds. These techniques are discussed in detail
in the Appendices.
25
-------
SECTION 4
EMISSION ASSESSMENT OF A COAL-FIRED UTILITY BOILER
TEST CONDITIONS
Five tests were performed on the bituminous coal-fired site. In
addition to these five tests, designated 132-136, six runs were made on
other days using the Goksoyr-Ross Controlled Condensation System (CCS) to
collect supplementary data on SOg, S03, S0^~, Cl", and F~ emissions. These
runs are designated I through V and 0, and are discussed in the appropriate
sections. Specific conditions for tests 132-136 are summarized in Table
4-1. Unit loading ranged from 620 to 760 MW (gross), which corresponds to
between 71 and 87% of full-load operation. Tabulated coal feed rates are
nominal, although their accuracies have been estimated from fuel analyses
and steam production rates under the assumption of 90% thermal efficiency.
Nominal coal feed rates appear to be accurate to within 17%. Because of
possible air leakage into the flue gas bag sampling system, two sets of
oxygen concentrations were used to calculate emission factors. Oxygen con-
centrations from gas bag samples were used to calculate S02, NOX, CO, and
C-j-Cg hydrocarbon emissions, since these were also determined from grab bag
sampling. Other emissions were calculated using the average oxygen concen-
tration determined by continuous monitoring of the scrubber during runs I-V
and 0. Due to possible air leakage into upstream ducting operating at
sub-atmospheric pressure, tabulated oxygen concentrations are not necessarily
representative of concentrations at the furnace outlet. Oxygen concentra-
tions of 2.8% in the furnace after combustion are typical for this unit
during full-load operation; this corresponds to an excess air input of 15%
computed using the ultimate coal analysis. During less than full-load
operation the excess air level is higher.
Flue gas flow rates were calculated from the oxygen concentration at
the scrubber, fuel analyses, and fuel feed rates (estimated from steam
production rate data) using the following expression:
26
-------
TABLE 4-1. SUMMARY OF TEST CONDITIONS
ro
•vj
Test No.
132
133
134
135
136
Electrical
Output
(Gross)
MW
620
640
690
760
760
1! of
Maximum
Load
71
73
79
87
87
Nominal
Fuel Feed
Rate.
kg/hr
254,000
254,000
295,000
318.000
300.000
Steam
Production
Rate, ,
kg/hr x 10°
2.27
2.34
2.38
2.77
2.65
Overall t
Efficiency
X
28
28
30
28
29
Oxygen Concentration
Average Oj
at Scrubber
X
6
6
6
6
6
Average 0?
1n B»g Samples
*
7.5
9.2
8.4
8.7
9.3
Excess A1r Flue Gas
At Fumacet Flow Rate
X dscm/s
v!5 830
v!5 850
v!5 870
vlS 1,000
vIS 970
Efficiencies are based on the gross electrical output and the steam production rates, assuming
90* efficiency for steam production.
Values are for full load. For less than full load, slightly higher levels are expected.
-------
4.762 (nc + ns + .45 nN) + .9405 nH - 3.762
n
FG
1 - 4.762 (02/100)
where:
nFG = gram moles of dry effluent per gram of fuel
n- = gram moles of element j per gram of fuel
02 = volumetric 02 concentration in percent
Flue gas flow rates are expressed as dry standard cubic meters per second;
standard temperature and pressure are defined as 293 K and 101.3 kPa,
respectively.
Ultimate analyses of the fuel feed are presented in Table 4-2.
Differences among the fuel analyses for the five test days, although gener-
ally small, may result from sampling and analysis problems or may reflect
actual changes in the feed stock during the test period. However, because
of the difficulties associated with sampling large quantities of coal and
the limited number of samples acquired, the average coal analysis is
considered to be the best estimate of the fuel composition during the test
period. Hence, the average analysis was utilized to compute all emission
factors presented in this report.
Additional analyses were performed on a coal feed sample from test
135 to determine concentrations of 15 trace elements (As, Be, Cd, Co, Cr,
Cu, Hg, Mn, Ni, Pb, Sb, Se, Sr, V, and Zn) and three minor elements (Al,
Ca, and Fe). These data are presented in Table 4-3. The coal was analyzed
using atomic absorption spectroscopy (AAS), except for aluminum, which was
analyzed by neutron activation analysis (NAA).
Considering the uniformity of coal ultimate analyses obtained during
the test periods, it appears reasonable to assume that tabulated trace and
minor element analyses for test 135 are typical for the coal fired during
the five day test period. Although analyses of other coal samples from the
same source are not available for direct comparison, analyses of most trace
and minor elements presented in Table 4-3 appear to be consistent with
concentration limits typifying Appalachian and Eastern Interior Basin coals.
No coal strontium analyses were found for comparison. Calcium, lead, and
28
-------
TABLE 4-2. SUMMARY OF ULTIMATE FUEL ANALYSIS
ro
(0
Component
Moisture
Carbon
Hydrogen
Nitrogen
Chlorine
Sulfur
Ash
Oxygen
Heating Value (kJ/kg)
132
1.41
58.95
3.93
0.87
0.03
6.29
25.19
3.33
24,579
133
1.39
56.79
3.87
0.93
0.06
5.54
27.06
4.36
23,800
134
1.30
58.13
3.91
1.20
0.04
4.57
26.04
4.81
24,354
Test
135
1.23
57.36
3.79
1.07
0.05
4.91
26.24
5.35
23,986
136
1.36
55.17
3.68
0.98
0.04
5.96
28.25
4.56
23,502
Average
1.34
57.28
3.84
1.01
0.04
5.45
26.56
4.48
24,027
a*
0.07
1.28
0.09
0.12
0.01
0.64
1.03
0.66
384
a = one standard deviation.
Oxygen concentration by difference.
-------
TABLE 4-3. CONCENTRATION OF MAJOR TRACE ELEMENTS IN COAL FEEDSTOCK
Element
AT
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mn
N1
Pb
Sb
Se
Sr
V
Zn
ppm in
Coal*
2.5**
36
0.1
1.2%
24
11
41
3.3
3.0%
1.6
114
45
**
2,350
6
13
NA
35*
1,550
Typical Range
ppm
0.4-40,700
0.5-93
0.6-4.1
0-1 ,600
0.1-65
0.5-43
4-144
3-61
0.3-40,000
0.07-0.49
6-181
2-80
4-218
0.2-8.9
0.4-74
No Data
2-147
6-5,350
Reference
2,
1,
2,
1,
1.
1,
2,
1,
1,
2,
1. 2,
4
2
1
4
2
2
3
2
4
1
2
2
2
2
3
3
2
Coal sample from test 135. Except where noted, analyzed by atomic
absorption spectroscopy.
Typical ranges for Appalachian and Eastern Interior Basin coals.
* Analyzed by neutron activation (Level 2).
**
The concentration of lead appears inordinately high. However,
repeat analyses were not performed.
30
-------
mercury were found to be present at higher concentrations than are indicated
to be typical by the limited published data. Beryllium was found to be at
a somewhat lower than typical concentration.
FLUE GAS EMISSIONS
Criteria Pollutants
Federal New Source Performance Standards (NSPS) currently in effect
define allowable emission rates of NOX (as NOg), S02 and total particulates
from fossil fuel fired utility boilers having 25 MW or greater output. More
stringent limitations have been proposed by EPA for NO , S0« and total
particulate emissions. Federal NSPS currently address neither CO nor total
hydrocarbon emissions. Existing NSPS and corresponding proposed emission
standards for coal-fired utility boilers are summarized in Table 4-4. It
should be noted that this plant is not required to meet NSPS; they are
presented for comparison only.
A total of 5 tests were performed to determine the emissions from the
coal-fired boiler. A summary of the criteria pollutant emissions data for
the 5 test series is presented in Table 4-5. Criteria pollutant emissions
data for the individual tests are presented in Table 4-6. Additionally,
the average scrubber inlet data are compared with the EPA AP-42 emission
factors for uncontrolled sources (5) in Table 4-7. The emissions data are
discussed by specific pollutant in the ensuing subsections.
Nitrogen Oxides—
NOV emissions from the coal-fired boiler were determined by chemilu-
X
minescence analysis of grab bag samples. The measured NO emission factors
A
near full load conditions were 715 ng/J prior to scrubbing. HOX data
generally indicate a significant reduction of NO across the scrubber.
A
However, it has been recently established that NO decay inside these grab
A
bags is rapid with respect to time in the presence of air (6). Due to the
proximity of the stack sampling location, delays between bag sample acquisi-
tion and analysis were at least 30% longer for outlet samples than for inlet
samples. Hence, NOV removal by the FGD system at the coal-fired power plant
A
was probably not a real phenomena but, rather, the result of NO degredation
A
in bag samples. Additional data from on-line monitoring would be needed
31
-------
TABLE 4-4. EXISTING AND PROPOSED FEDERAL EMISSION STANDARDS
FOR COAL-FIRED UTILITIES
Pollutant
NSPS
Proposed Standard
NOX (as N02)
SO,
Total
Particulates
300 ng/J
(0.7 Ib/MM Btu)
520 ng/J
(1.2 Ib/MM Btu)
43 ng/J
(0.10 Ib/MM Btu)
260 ng/J (0.60 Ib/MM Btu)
for bituminous coal;
220 ng/J (0.50 Ib/MM Btu)
for sub-bituminous coal.
.520 ng/J (1.2 Ib/MM Btu)
max. with 85% reduction to
85 ng/J (0.20 Ib/MM Btu).
13 ng/J (0.03 Ib/MM Btu)
max. with 99% reduction.
TABLE 4-5. AVERAGE MEASURED CRITERIA POLLUTANT EMISSIONS
Pollutant
Emission Factor (ng/J)
Before Scrubber
After Scrubber
N0¥ (as NO? near
x full Toad)
CO*
SO,
**
J.4.
Total Organics
Total Particulates'
3380
2.77-4.07**
1090
>385n
740
1.45-2.60**
80
NOX was determined by chemi luminescent analysis of bag samples (Level 2).
Tabulated NOX emissions are from tests 135 and 136. These two tests were
performed at 87% boiler load. Due to possible NOX degradation in the
sampling bags, these values represent lower limit emissions.
CO was determined by gas chroma to graphic analysis of bag samples (Level 2).
S0£ was determined by two Level 2 methods: 1) pulsed fluorescence analysis
of bag samples, and 2) wet chemical analysis of the controlled condensation
system's impinger catch.
J.J,
The Ci-C-jg fractions were determined by gas chromatographi c analysis while
the >Cl6 fraction was determined gravimetrically (Level 1).
** Upper limit values include detection limits of fractions which were not
detected.
Total particulates were determined by a modified Method 5 procedure (Level
2) and from the SASS train parti culate catch (Level 1).
JL- i i
32
-------
TABLE 4-6. SUMMARY OF CRITERIA POLLUTANT EMISSIONS
CO
Toct* No
1 Co L I1U •
132 Inlet
132 Outlet
133 Inlet
133 Outlet
134 Inlet
134 Outlet
135 Inlet
135 Outlet
136 Inlet
136 Outlet
Average Inlet
Average Outlet
Emission Factor (ng/J)
MA
X
(as N02)
460
300
250
190
480
380
700
370
730
400
520
330
+
CO
S500
1500
1500
1500
*500
1500
*550
1550
1550
1550
1520
1520
4.
SO/
2
3210
640
3440
820
2970**
240
3650
ND*
2560
770
3380tf
740
r -f
Ll L6
Organics
ND*
ND*
ND*
ND*
1-2.3
0.85-2.0
ND*
ND*
ND*
ND*
1-2.3
0.85-2.0
r* r
7 1 6
Organlcs
ND*
ND*
ND*
ND*
0.45
0.12
ND*
ND*
ND*
ND*
0.45
0.12
>r
>U16
Organlcs
ND*
ND*
ND*
ND*
1.32
0.48
ND*
ND*
ND*
ND*
1.32
0.48
Total
Organics
ND*
ND*
ND*
ND*
2.77-4.07
1.45-2.60
ND*
ND*
ND*
ND*
2.77-4.07
1,45-2.60
Total
Particulates
ND*
ND*
ND*
ND*
1280
ND*
900
80
ND*
ND*
1090
80
CO emission factor was based on the detection limit of 1000 ppm.
S02 emissions were determined from grab bag sampling for test Nos. 132-134, and from the Implnger
solution of the controlled condensation system for test Nos. 135 and 136.
ND - data not available.
Determination of SOg emissions at the scrubber outlet for test No. 134 appears to be in error. This
data point was Judged to be an outlier at 90% probability level by the method of Dixon, and discarded
in the computation of average SOg emissions.
^Additional data were used to calculate this average; see Table 4-9.
**
-------
TABLE 4-7. COMPARISON OF CRITERIA POLLUTANT EMISSIONS
WITH EPA AP-42 EMISSION FACTORS FOR
COAL-FIRED UTILITY BOILERS (CYCLONE)
Emission Factor (ng/J)
Pollutant Test Data AP-42
Before Scrubber Emission Factor
NOV (as N02 near
x full load)
CO*
so2
Total Organ ics
Total Parti culates
>715
<520
3380
2.8-4.1
1090
1020
18.5
4440
5.5
980
*
No effort was made to accurately determine CO emissions.
to confirm any NO reduction across the scrubber. Although inlet NOV
A X
samples may also be subject to degradation, concentrations determined from
these samples may be utilized as lower limit values.
The measured NOX emissions at both the scrubber inlet and the scrubber
outlet exceed the NSPS limit of 300 ng/J for coal-fired utility boilers.
The relatively high NOX emissions are attributed to: (1) higher thermal
NOX generation in cyclone furnaces because of extremely high heat release
rates and the resulting high furnace gas temperatures, and (2) high fuel
nitrogen content in the coal.
The Environmental Protection Agency is currently developing a low-NO
A
coal burner for utility boilers. This burner relies on a distributed fuel/
air mixing concept in which fuel and primary air are injected with a moderate
axial component. A surrounding secondary air stream is injected with a swirl
component for stabilization. Tertiary air for burnout is added axially
around the burner periphery. Pilot tests conducted have shown that the EPA
burner is capable of reducing NO emissions to less than 86 ng/J (7).
A
However, these burners are designed for pulverized coal firing and are not
applicable to cyclone furnaces.
34
-------
Carbon Monoxide-
No effort was made for accurate determination of CO from the coal-fired
boiler. The reported CO emission factor of less than 520 ng/J for the coal-
fired boiler was based on detection limit of the instrumentation. However,
CO emissions should be comparable in magnitude to the AP-42 tabulations.
Sulfur Dioxide—
S02 emissions were determined by two methods during the test period.
Bag samples of flue gas from the inlet manifold and stack were analyzed for
S02 by pulsed fluorescence during tests 132 through 134. The controlled
condensation system (CCS) was utilized for S02 determination during tests
135 and 136.
Average S02 emissions were 3380 ng/J prior to scrubbing. These un-
controlled emission factors are lower than the AP-42 value of 4440 ng/J for
coal firing. Average S02 emission rates from the coal-fired boiler were
740 ng/J after scrubbing. This represents a mean scrubber efficiency of
78% for S02 removal. For comparison, the NSPS units for S02 emissions after
scrubbing are 520 ng/J for coal-fired utility boilers.
The AP-42 value for uncontrolled coal firing is based on approximately
95% of the fuel sulfur being converted to S02, whereas the present study
found only 75% of the fuel sulfur as S02, using the gas bag and the con-
trolled condensation system (CCS) impingers as sampling devices. The
remaining sulfur was not accounted for by S03 or particulate sulfate and
was not detected in other effluent streams. Tests performed recently under
the EPA sponsored project "Environmental Assessment of Conventional
Combustion Sources" at three lignite-fired utility boilers using the gas
bag sampling technique have demonstrated problems with this technique.
S02 apparently degraded in the gas bag to such an extent that expected S02
concentrations of 390, 230 and 670 ng/J were reduced to 96, <1 and <1 ng/J,
respectively. These data indicate that the gas bag sampling method is
probably not adequate for accurate S02 determinations. However, results
from bag samples correspond well with S02 data from the CCS. This correla-
tion appears to mutually validate these analytical techniques and associated
02 measurements despite the fact that incomplete sulfur recovery was
obtained.
35
-------
Total Organics—
In the determination of organic emissions, gas chromatographic analyses
were performed on grab bag samples of flue gas and catches from the Level 1
sampling (SASS train). Additionally, gravimetric analyses were performed
on Level 1 samples to quantify high molecular weight organics. Each bag
sample was collected over an interval of 30 to 45 minutes, with a single
sample being collected per test. These samples were utilized to measure
C^ to Cg hydrocarbons. The SASS train collects approximately 30 m3
of flue gas which are drawn isokinetically during the test. Samples from
the SASS train were analyzed to determine organics higher than Cg. The Cj
to C,g fraction was determined by gas chromatograph while organics higher
than C.jg were determined gravimetrically.
Average organic emissions were 2.8-4.1 ng/J for coal firing prior to
scrubbing. The higher organic value includes the detection limit concen-
trations for fractions which were not detected and, as such, represents an
upper limit. The measured organic emission corresponds well with the AP-42
value of 5.5 ng/J for coal-fired utility boilers.
Emissions of organics after scrubbing were 0.85-2.0 ng/J for the C,-Cg
fraction, 0.12 ng/J for the Cy'C-ig fraction, and 0.48 ng/J for the high
molecular weight fraction. The data indicate scrubber removal efficiencies
of 14% for the C-j-Cg fraction, 72% for the Cy-C-jg fraction, and 63% for
higher molecular weight fractions.
Total Particulates--
Average emissions of total particulates were 900 ng/J for coal firing
prior to scrubbing. The particulate emission factor for the coal-fired
boiler tested is in excellent agreement with the AP-42 value of 980 ng/J
for coal-fired cyclone boilers. Total particulate emissions after scrubbing
were 80 ng/J. This corresponds to 91% particulate removal efficiency for
the scrubber. The NSPS limit for utility boilers is 43 ng/J.
Particulate Size Distribution
Size distributions of particulates at the scrubber inlet and outlet
were determined by two methods. Due to the high particulate loading at the
scrubber inlet, polarized light microscopic analyses (PLM) were utilized
to obtain a size distribution in terms of optical diameter and number of
36
-------
particles per size range. All other participate size distribution deter-
minations involved streams with substantially lower solids loadings and,
therefore, a Meteorology Research Institute (MRI) cascade impactor was used.
The cascade impactor data differs from PLM analyses in that size distribu-
tions are determined in terms of aerodynamic diameter and weight percent in
each size range. Thus, data from the two methods cannot be directly
compared. For this reason, the PLM data have been converted to the same
basis as the impactor data by assuming that particulate density is inde-
pendent of particle diameter. This is generally a reasonable assumption
because the major components of the particulates generated from coal com-
bustion, the aluminosilicates and iron oxides, are known to partition
equally among small and large particulates.* With the constant density
assumption, the weight distribution in each size range would be proportional
to the product of the number distribution and the particulate volume
representing the size range. The particulate volume was calculated based
on the geometric mean diameter for the size range.
Particulate size distribution data from tests 135 (inlet) and 136
(outlet)* are summarized in Table 4-8. These data show a significant
change in particulate size distribution before and after scrubbing. The
increase in the fraction of finer particulates across the scrubber indicates
that coarse particulates were removed more efficiently than fine particu-
lates. Particulates larger than 3 ym were removed with efficiencies of
greater than 99% while particulates smaller than 3 ym actually showed a net
increase in emission rates across the scrubber. This net increase raises
the possibility that fine particulates may be generated within the scrubber,
or that the particulate size distribution may be modified during the high
energy scrubbing process. It is more probable that the high particulate
loading at the inlet caused agglomeration of the fine particulates on the
test train filter. PLM analysis of the resulting sample may not be able to
Although data presented subsequently indicate that partitioning of Al may
occur, this simplifying assumption was required in order to present all size
distribution data in terms of a common basis. The error associated with
this assumption is unknown. Raw data from PLM analyses are presented in
Appendix C.
The reason for this choice of runs is discussed in Appendix C.
37
-------
TABLE 4-8. SCRUBBER INLET AND OUTLET PARTICULATE SIZE DISTRIBUTION*
CO
00
Aerodynamic
D1 ameter
Size Range,
Microns
< 1
1 - 3
3-10
> 10
Total
Weight %f
Scrubber
Inlet
<0.01
<0.3
13
87
100
Scrubber
Outlet
82
11
1
6
100
Emission Factor (ng/J)
Scrubber
Inlet
<0.1
<3
117
783
900
Scrubber
Outlet
65.6
8.8
0.8
4.8
80
Removal
Efficiency,
<0
<0
99.3
99.4
91.1
*
Determined by Level 2 methods.
'''Size distribution data from test 135 were used for the scrubber Inlet while data from test 136
were used for the scrubber outlet. Total particulate loadings from test 135 were used to compute
emission factors. The reason for this choice of runs is discussed in Appendix C.
-------
distinguish the agglomerated fine participates from the larger participates,
and the distribution is probably weighted towards the larger particulates.
Since there was no similar problem with the outlet size distribution,
removal efficiencies calculated from these data could be less than zero.
In a recent draft document issued by the Health Effects Research
Laboratory (HERL) of EPA (8), it is stated that larger particulates (from
3 to 15 ym) deposited in the upper respiratory system (in the nasopharynx
and conducting airways) can also be associated with health problems. This
is in contrast to the past belief that particulates of health consequence
were those less than 3 ym size and deep-lung penetrable. The area of
concern now is particulates which are 15 ym and less, which have been
designated as "inhalable particulates" (IP). Emissions of inhalable parti-
culates after scrubbing were approximately 75 ng/J.
Sulfur Compounds: SOp, S03, and SO^"
Sulfur species were determined using several methods. Bag samples of
flue gas from the inlet manifold and stack were analyzed for S02 using the
pulsed fluorescent analyzer during tests 132-134. The CCS was used at the
same sampling points during tests 135 and'136 to collect S02, SOg, and SO^"".
Additional testing was performed at the inlet and outlet of one of the eight
scrubbers (module "H") using the CCS. These tests are designated I through
V (inlet) and 0 (outlet). The above data are listed in Table 4-9. An
average of 98.4% of the output sulfur is emitted as S02 during uncontrolled
coal firing while approximately 1.1% and 0.4% are emitted as S03 and parti-
culate sulfate, respectively. Average removal efficiencies were computed
by comparing the average inlet and outlet values for each species. The SOg
and S04~ values from test 0 were discarded because of probable entrainment
of particulate.su!fate at the scrubber outlet sampling point. The outlet
S09 value for test 134 was also discarded. This low value is thought to be
^ *
due to sample degradation in the gas bag . The removal efficiency for S02
by the scrubber system averaged 78%, which compares with 76% design removal
efficiency (9). About 80% of the S03 was also removed by the scrubber.
Degradation of SO? in gas bags has been suspected in other cases as well,
as discussed previously.
39
-------
TABLE 4-9. SOg, S03, AND SO^ EMISSIONS*
Sul fur
Compound
SO,
z
so.
•)
so4-
Test No.
132
133
134
135
136
I
II
HI
IV
V
0
Average
135
136
I
II
III
IV
V
0
Average
135
136
I
II
III
IV
V
0
Average
Sampling Sampling
Points Method
Plenum/Stack Gas bag
»
•
Plenum C S
H
Nodule H
H
H
H
H
H
Plenum/Stack CCS
n
Nodule H
Plenum/Stack CCS
•
Module H
Coal Mr
Inlet
ng/J
3210
3440
2970
3650
2560
3260
3450
3980
3640
3610
3380
99.4
53.7
49.3
39.3
23.6
35.3
38.6
48.5
15.5
18.2
41.2
22.2
24.2
18.6
15.3
22.2
ng
Outl et
ng/J
643
824
238t
NO
NO
766
744
17.2
1.87
18.8*
9.54
5.09
2.39
15.9*
3.74
Mole i of Total Removal
Sulfur Species Efficiency,
In Flue Gas <
._
—
--
97.6
97.8
98.0
98.7
99.1
98.9
98.8
98.4 78.1
2.13
1.64
1.18
0.899
0.470
0.767
0.846
1.13 80.3
0.276
0.464
0.826
0.423
0.402
0.337
0.277
0.429 83.1
Level 2 procedures were utilized.
This value was not used 1n computing averages, as sample degradation In the sample bag was
suspected.
These values were not used 1n computing averages, as the sampling point was close enough to
the scrubber that entralnment of participate sulfate was probable.
-------
This figure appears to be high as S03 is usually associated with water
present as fine aerosols in the flue gas stream, which are less efficiently
scrubbed. The removal efficiency for S04= averaged 83%, which is lower than
the total particulate removal efficiency. This indicates that the SO^" may
be associated with the fine particulates in the flue gas stream, which are
less efficiently scrubbed.
Sulfate emissions broken down into water- and acid-soluble fractions
are presented in Table 4-10. This distribution was changed somewhat by
scrubbing, as 97% of the inlet sulfates and 99% of the outlet sulfates were
water-soluble.
Inorganics
Trace elements present in the flue gas were determined using atomic
absorption spectroscopy (AAS). Concentrations of 18 major trace elements
present in the flue gas are presented in Table 4-11. To assess the hazard
potential of these emissions, the emission concentrations are compared with
the Discharge Multimedia Environmental Goal (DMEG) values. The DMEG values are
emission level goals developed under direction of EPA, and can be considered
as concentrations of pollutants in undiluted emission streams that will
not adversely affect those persons or ecological systems exposed for short
periods of time (10). The DMEG values tabulated represent air concentra-
tions which were derived from human health considerations based on the
most hazardous compound formed by the element in question. Analysis of the
flue gas indicates that 16 elements exceeded their respective DMEG values
at the scrubber inlet and 7 exceeded their DMEG values at the scrubber out-
let. These seven elements which are of potential concern are arsenic,
cadmium, chromium, nickel, lead, iron, and zinc. The DMEG value for arsenic
is low because it is a cumulative poison producing chronic effects in humans.
Considerations for the potential carcinogenic, oncogenic, and teratogenic
effects of cadmium upon humans have led to a low DMEG value for this element.
Chromium and nickel have low DMEG values due to considerations of potential
human carcinogenicity. Lead is a cumulative poison which results in lesions
in human organs.
Emission factors for the 18 trace elements analyzed are presented in
Table 4-12, as are scrubber removal efficiencies for each element. An
overall removal efficiency of 94% was obtained for these trace elements.
41
-------
TABLE 4-10. SUMMARY OF SULFATE EMISSIONS^
ro
Test No.
135
136
I
II
III
IV
V
0
Average
Sampling
Point
Plenum/Stack
H
Module H
•
H
II
H
N
Scrubber Inlet
Water Soluble Sul fates
ng/J I of Total
>15.5
16.7
>41.2
>22.2
23.0
17.1
>15.3
>21.6
>99.5
91.4
>99.6
>99.5
94.9
92.2
>99.5
96.7
Acid Soluble Sul fates
ng/I i of Total
<0.07
1.6
<0.1
<0.1
1.2
1.4
<0.08
.6
<0.5
8.6
<0,4
98,6
52.9
>99,5
>99.3
Acid Soluble Sulfates
ng/J S^oT Total
«0.07 <1.4
1.1 47.1
<0.07
-------
TABLE 4-11. EMISSION CONCENTRATIONS OF TRACE ELEMENTS - TEST 135
3
Concentration, mg/m
El etnent
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mn
Ni
Pb
Sb
Se
Sr
V
Zn
Scrubber
Inlet
130
0.98
0.021
49
5.1
0.19
1.3
1.2
400
0.095
0.70
2.0
11
0.78
0.37
0.46
0.78
100
Scrubber
Outlet
3.0
0.94
0.0018
2.0
0.58
0.013
0.12
0.19
13
0.0057
0.15
0.054
2.9
0.27
0.088
0.038
0.083
21
DMEG For Air
(Health Basis),
mg/m3
5.2
0.002
0.002
16
0.010
0.050
0.001
0.20
1.0
0.050
5.0
0.015
0.15
0.50
0.20
3.0
0.50
4.0
Discharge
Scrubber
Inlet
25
500
10
3.1
520
3.7
1000
6.0
400
1.9
0.14
130
73
1.6
1.8
0.15
1.6
26
Severity
Scrubber
Outlet
0.58
500
0.9
0.13
58
0.26
100
0.95
13
0.11
0.03
3.6
19
0.54
0.44
0.013
0.17
5.2
Level 2 procedures were utilized.
* Discharge severity is defined as the ratio of the discharge
concentration to the DMEG value.
43
-------
TABLE 4-12. EMISSION FACTORS FOR TRACE ELEMENTS - TEST 135
Emission Factor, nq/J
Element
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mn
N1
Pb
Sb
Se
Sr
V
Zn
Total
Scrubber
Inlet
49
0.37
0.0079
18
1.9
0.069
0.48
0.45
150
0.035
0.26
0.73
4.1
0.28
0.14
0.17
0.29
39
265
Scrubber
Outlet
1.1
0.35
0.00067
0.73
0.21
0.0047
0.046
0.072
4.9
0.0021
0.054
0.020
1.1
0.099
0.033
0.014
0.030
7.7
17
Removal
Efficiency,
%
98
4
91
96
89
93
90
84
97
94
79
97
74
66
76
92
89
80
94
Level 2 procedures were utilized.
44
-------
Because removal efficiencies for Al, Ca, Fe, and Ni are higher than
the average trace element removal efficiency of 94%, concentrations of these
elements in the particulate appear to be lower at the scrubber outlet than
at the scrubber inlet. Similarly, concentrations of non-volatile elements
removed with less than average efficiency must be higher in the scrubber
outlet particulate than in the scrubber inlet particulate. Highly volatile
trace elements such as Hg and Se may not be associated with particulates but
may, at least in part, be present as elemental vapors. As such, no conclu-
sion may be drawn regarding particulate concentrations of these elements.
Spark source mass spectrometry (SSMS) analysis results are presented
in Table 4-13 for the 17 elements which were also analyzed by AAS (mercury
was not analyzed by SSMS). Also presented are ratios of SSMS analyses to
AAS analyses. Analysis by SSMS is generally used as a screening tool, and
is considered to be less accurate than AAS. Comparison of the 17 elements
analyzed by both methods shows good agreement (values within a factor of
two) for inlet and outlet concentrations of Co, Ni, Sb, Se, and V. Order
of magnitude agreement was obtained for Ca, Cd, Be, Fe, Mn, Pb, Sr, and Zn.
SSMS analysis of other elements, such as Al, As, Cu, and Cr, correspond to
the AAS values only to within approximately two orders of magnitude.
To characterize the distribution of the major elements present in the
flue gas particulates and to look at the depth profile of these elements in
the particulates, Electron Spectroscopy for Chemical Analysis (ESCA) and
x-ray diffraction (XRD) were performed on particulate samples. ESCA depth
profile data are presented in Table 4-14 for selected Method 5 train particu-
late catches (test 135 inlet and outlet). The data are presented as atom
percentages, normalized to 100%, of iron, oxygen, calcium, carbon, silicon,
and aluminum. These are relative values, not absolute concentrations, since
not all elements present in the particulate are included. However, tentative
conclusions may be drawn under the assumption that the elements analyzed con-
stitute the major surface components. The Method 5 filter catches were
analyzed on the silicon-containing filter which may have caused some inter-
ference.
Data presented in Table 4-14 indicate that the concentration of sulfur
in both the scrubber inlet and outlet particulate is enriched at the surface
and decreases with increasing depth. A possible mechanism which is consistent
45
-------
TABLE 4-13. SPARK SOURCE MASS SPECTROMETER ANALYSES
OF TRACE ELEMENT EMISSIONS - TEST 135
Element
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Mn
N1
Pb
Sb
Se
Sr
V
Zn
Concentration
Scrubber
Inlet
1.9
> 95
0.0034
180
0.86
0.088
> 0.97
> 2.0
>130
> 1.6
> 1.0
>100
0.89
0.38
> 1.7
1.0
>130
, mg/m
Scrubber
Outlet
> 0.14
> 9.0
0.001
>44
0.32
0.007
>26
>26
>63
0.02
0.036
>90
0.12
0.13
0.047
0.13
>76
SSMS
Scrubber
Inlet
0.015
>97
0.16
3.7
0.17
0.46
> 0.75
> 1.6
> 0.34
> 2.3
> 0.52
> 9.1
1.1
1.0
> 3.6
1.3
> 1.3
* +
/AASf
Scrubber
Outlet
> 0.05
> 9.6
0.6
22
0.54
0.54
>220
>140
> 4.8
0.1
0.67
> 31
0.43
1.5
1.2
1.5
> 3.6
SSMS Is a Level 1 analysis.
AAS is a Level 2 analysis for cations.
46
-------
TABLE 4-14. ESCA DEPTH PROFILE DATA FOR SELECTED SAMPLES
FROM THE METHOD 5 SAMPLING TRAIN - TEST 135*
Scrubber Inlet (Atom Percent)
Sample
135-IN-CYC
135-IN-CYC
135-IN-CYC
135-IN-CYC
135-IN-CYC
135-IN-CYC
135-IN-CYC
135-IN-PFb
135-IN-PFb
135-IN-PFb
135-IN-PFb
135-IN-PFb
135-IN-PFb
135-IN-PFb
135-IN-PFb
Depth
0
100 A
150 A
200 A
300 A
400 A
500 A
0
50 A
100 A
150 A
200 A
300 A
400 A
500 A
Fe
2,5
4.1
4.3
4.4
5.6
4.8
4.1
1.3
4.4
4.6
5.0
5.1
5.6
5.1
4.0
0
47.4
38.0
35.0
35.3
34.9
34.9
35.6
51.7
60.9
60.5
60.9
60.7
58.2
60.4
62.0
Ca
1.3
1.7
1.7
1.6
2.3
2.3
2.5
0.7
2.4
2.7
2.4
3.0
3.2
4.1
3.8
C
28.0
36.0
38.1
38.3
40.7
41.2
38.1
20.6
8.3
5.5
4.1
4.0
3.4
<1
-------
with this observation involves adsorption or deposition of sulfur-containing
compounds on the surface of parti culates. Scrubber inlet particulates were
found to contain CaS04 by XRD analysis. Formation is probably by H2S04
adsorbing on and reacting with calcium compounds after combustion, which
would result in surface enrichment of sulfur relative to bulk parti cul ate
concentrations. The presence of carbon in the bulk of the inlet and outlet
cyclone parti cul ate catches indicates unburned coal particles. Bulk con-
centrations of carbon in the inlet and outlet filter catches appear to be
at least an order of magnitude lower than those in the cyclone catches based
on data at depths of 200 A to 1000 A. This may indicate that unburned coal
particulates are mostly found in the larger size fractions. Surface enrich-
ment of carbon relative to bulk concentrations in the filter catches may
result from adsorption of organics or, in the case of scrubber outlet
particulates, deposition of
Chloride and Fluoride Emissions
Specific am* on analysis was performed on extracts from parti cul ate
catches and impinger solutions from the Goksoyr-Ross sampling train.
Emissions data for chloride and fluoride are presented in Table 4-15. HC1
and HF concentrations are measured from the impingers and incorporated in
the chloride and fluoride emission factors reported in Table 4-15. Fluo-
rides are removed at greater than 62-84% efficiencies by the scrubber.
Computation of chloride removal efficiency is not possible because the
chloride concentrations were below the detection limit. Assuming that the
chloride level is just below the detection limit, 8% of the fuel chlorine
was analyzed in the parti cul ate extract, and the remainder was found in the
impinger solution as HC1 .
Specific Organic Compounds
Selected samples were analyzed by combined gas chromatography/mass
spectrometry (GC/MS) for the identification of organic compounds present.
The organic compounds identified include aliphatic hydrocarbons, substituted
benzenes, ethyl benzaldehyde, dime thy Ibenzaldehyde, 2,6-pereriden-dione-4,
and 2,6-dimethyl-2,5-heptadion-4-one, and the methyl ester of long chain
acid, at concentration levels ranging from 0.2 to 20 yg/m in the flue gas
48
-------
TABLE 4-15. CHLORIDE AND FLUORIDE EMISSIONS*
CT
Test InletOutletRemoval InletOutlet Removal
Efficiency Efficiency
ng/J ng/J % ng/J ng/J %
135 <0.1
136 <0.1
<0.1 ~ 0.37 <.l
<0.1 ~ 0.9 <.l
4 >62
4 >84
Level 2 procedures were utilized.
prior to scrubbing. With the exception of ethylbenzaldehyde, substituted
benzenes, and aliphatic hydrocarbons, none of the other organic compounds
were identified at the scrubber outlet.
Emissions of polycyclic organic matter (POM) determined by GC/MS are
summarized in Table 4-16. Most of the POM compounds identified are
naphthalene, substituted naphthalenes, biphenyl, and substituted biphenyls.
No POM compounds were identified at the scrubber outlet. POM compounds
found at the scrubber inlet are at levels several orders of magnitude below
their respective DMEG values.
LIQUID WASTE
The two major wastewater streams are wastewater discharge from the
slag tank to the ash pond and overflow from the settling pond for spent
scrubber slurry. The flow rates for these two wastewater streams are
approximately 2.89 Gg/hr and 0.77 Gg/hr, respectively. Two additional
streams were sampled, although these streams are not actually wastewater
streams because they are not discharged from the site. These streams are
the scrubber make-up water and the scrubber discharge liquid. The scrubber
make-up water stream is taken from the settling pond and its analysis
should be similar to the settling pond overflow. The scrubber discharge
stream is the scrubber slurry liquid and discharges to the1settling pond.
49
-------
TABLE 4-16. POM EMISSIONS FROM COAL FIRING
PRIOR TO SCRUBBING - TEST 134*
Emission
Compound Concentration
yg/m3
Decahydronaphthalene
Dltert-butyl naphthalene
Dimethyl Isopropyl naphthalene
Hexamethyl blphenyl
Hexamethyl, hexahydro Indacene
Dlhydronaphthalene
CIO substituted naphthalene
CIO substituted decahydro-
naphtha1enet
Methyl naphthalene
Anthracene/phenanathrene
1-1 ' blphenyl
9,10-dlhydronaphthalene /
1-T dlphenylethene
I,l-b1s(p-ethyl phenyl)-ethane/
tetramethyl blphenyl *
j, j,
5-methyl -benz-c-acr1d1 ne
2,3 dimethyl decahydro-
naphthalenet
0.1
0.3
0.3
0.6
1.0
0.03
0.06
1.0
1.6
0.3
4.0
0.2
9.0
0.2
<0.03
DMEG
Value
yg/m3
130,000
230,000
230,000
1,000
No data
130,000
230,000
130,000
130,000
1,590
1,000
130,000
1,000
11,000
130,000
Discharge
Severity
<0.0001
<0.0001
<0.0001
0.0006
<0.0001
<0.0001
<0.0001
<0.0001
0.0002
0.004
<0.0001
0.009
<0.0001
< 0.0001
Total 18.7
Level 2 procedures were utilized.
The DMEG values for decahydronaphthalene, dlhydronaphthalene and any
substituted decahydronaphthalene are assumed to be the same as that for
tetrahydronaphthalene.
The DMEG values for alkyl naphthalenes are assumed to be the same as
that for methyl naphthalene.
**
The DMEG value for hexamethyl blphenyl 1s assumed to be the same as
that for blphenyl.
The DMEG value for 5-methyl-benz-c-acr1d1ne-1s assumed to be the same
as that for benz(c)acn'd1ne.
50
-------
Water Quality Parameters
Table 4-17 summarizes the waste water parameters for the sampled
streams.
Inorganics - Wastewater
Analysis results of major inorganic cations in the wastewater stream
from the slag tank to the ash pond and the scrubber slurry settling pond
overflow are presented in Table 4-18. Also presented are the analysis
results for the scrubber make-up water obtained from the settling pond, and
for the scrubber discharge liquid (filtrate from the spent slurry). Of the
18 elements analyzed, iron exceeds its health DMEG value and iron, calcium,
aluminum, cadmium, vanadium and zinc exceed their respective ecological
DMEG values for the wastewater stream to the ash pond. For the scrubber
slurry settling pond overflow, calcium, cadmium, manganese, nickel, and
lead exceed both their health and ecological DMEG values, and additionally
aluminum, iron, and zinc exceed their respective ecological DMEG values.
Comparison of the inorganic data for the scrubber slurry pond overflow and
the scrubber make-up water (from the settling pond) indicates that the
trace element concentrations for these two streams are almost identical.
This agreement supports the reliability and accuracy of sampling and
analysis of trace elements for the wastewater streams.
Organics - Wastewater
Concentrations of C, to C,g organics and high molecular weight (>C-j6)
organics measured in the wastewater streams are summarized in Table 4-19.
The total organics detected are low, ranging from 0.06 mg for the
wastewater to the ash pond to 0.6 mg for the scrubber slurry settling
pond overflow.
GC/MS analyses were performed to identify the organic compounds present
in the wastewater streams. In the extraction of the aqueous samples, the
samples were first acidified to pH 2 and extracted with methylene chloride.
The samples were then adjusted to pH 7 and reextracted with methylene
chloride. A final extraction was made at pH 11.
The results of the GC/MS analyses are presented in Table 4-20. In
general, the detected compounds consist of oxygenates such as ketones,
51
-------
TABLE 4-17. WATER QUALITY PARAMETERS
Oi
IVi
Test
No.
pH
Conductivity TSS
umhos/cm wg/1
Hardness
(as CaC03)
Alkalinity Acidity Acidity
(as CaCO-j) (methyl orange (phenol phtaleln
as CaCO-)) as CaCOa)
mg/1 mg/1 mg/1
Ammonia
Nitrogen
mg/1
Cyanide Nitrate
mg/1 mg/1
Phosphate
mg/1
so3-
mg/1
pg/i
132
133
135
136
132
133
135
136
6.5
6.5
7.4
6
7.0
6.5
7.8
6.5
3500
3600
4000
4000
850
870
800
820
150
82
15
0
0
5
15
5
2750
2350
2800
2800
400
400
315
410
0 33 1.85
0 R5
74 Q
65 0
-00
— 0
112 0
105 0
2.5
»
1.1
0.59
0.45
0.32
0.68
0 0
0 1
1
0 1
0 0
0 0
0
0 0
.9
.3
.7
.4
.5
.2
.7
.7
0.30
0.45
4.2
0.3
0.22
0.25
4.3
0.31
1750
0
0
150
0
1.0
0
5
6000
35
2250
2050
150
4.0
200
290
Level 1 procedures were utilized.
-------
TABLE 4-18.
TRACE ELEMENT CONCENTRATIONS IN WASTEWATER DISCHARGES
FROM COAL FIRING - TEST 135*
en
DMEG Value, ma/1
Element
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
N1
Pb
Sb
Sr
V
Zn
Health
80
0.250
0.030
240
0.050
0.75
0.25
5.0
1.5
0.010
90
0.2S
0.23
0.25
7.5
46
2.5
25
Ecology
1.0
0.050
0.055
16
0.001
0.25
0.25
0.050
0.25
0.250
86
0.10
0.010
0.05
0.20
No HATE
0.15
0.10
Hater to Ash Pond
mg/1
3.5
0.012
0.0003
150
0.020
0.002
0.012
0.008
3.0
< 0.0002
13.8
<0.38
0.01
0.030
0.002
0.84
0.25
0.13
Discharge
Health
0.044
0.048
0.010
0.61
0.40
0.003
0.048
0.002
2.0
<0.02
0.15
<1.5
0.04
0.12
0.0003
0.018
0.10
0.0052
Severi ty
Ecology
3.5
0.24
0.005
9.1
20
0.008
0.048
0.2
12
<0.0008
0.16
<3.8
1
0.6
0.01
_.
1.7
1.3
Settling Pond Overflow
mg/1
1.5
0.021
<0.0008
930
0.059
0.043
<0.002
0.004
1.1
<0. 00008
N/A
1.9
0.70
0.60
0.044
6.4
0.064
2.2
Discharge
Health
0.019
0.084
<0.03
3.9
1.2
0.057
<0.008
0.0008
0.73
<0.008
—
r.e
3.0
2.4
0.0059
0.14
0.026
0.088
Severity
Ecology
1.5
0.42
<0.01
58
60
0.17
<0.008
0.08
4.4
<0.0003
—
19
70
10
0.22
--
0.43
22
Scrubber Make-up
mg/1
1.2
0.017
0.0001
910
0.052
0.047
0.001
0.003
0.63
<0. 00008
11
1.7
0.86
0.024
0.041
5.9
0.080
1.7
Discharge
Health
0.015
0.068
0.003
3.8
1.0
0.063
0.004
0.0006
0.42
<0.008
1.2
6.8
3.7
0.096
0.0055
0.13
0.032
0.068
Water
Severi ty
Ecology
1.2
0.34
0.002
57
50
0.19
0.004
0.06
2.5
<0.0003
1.2
17
86
0.5
0.21
—
0.53
17
Scrubber Discharge
mg/1
0.083
0.06
0.0011
380
0.0005
0.005
0.004
0.004
0.014
<0. 00008
270
<0.38
0.20
. 0.03
0.063
3.4
0.095
0.005
Discharge
Health
0.0010
0.24
0.037
1.6
0.01
0.007
0.02
0.0008
0.0097
<0.008
3.0
1.5
0.87
0.1
0.0084
0.074
0.038
0.0002
Liquid
Severity
Ecology
0.083
1.2
0.020
24
0.5
0.02
0.02
0.08
0.058
<0.0003
3.1
3.8
20
0.6
0.31
--
0.63
0.05
* Determined by Atomic Absorption Spectroscopy (Level 2).
-------
TABLE 4-19. ORGANICS IN WASTEWATER DISCHARGES
Concentration, mg/1
C7
C8
C9
C1n
10
cn
11
C12
C13
C1A
14
C15
C16
>C16
Total
Water to
Ash Pond
0
0.02
0
0
0.02
0
0
0
<0.01
0.01
0
0.06
Settling
Pond
Overflow
0
0
0
0
0.04
0.01
0
0
<0.01
0.01
0.5
0.6
Scrubber
Make-up
Water
0
0
0
0
0.04
0
0
0
<0.01
0.01
0.3
0.4
Scrubber
Discharge
Liquid
0
0
0
0
0
0
0
0
0
0
0.1
0.1
Level 1 procedures were utilized.
54
-------
TABLE 4-20. GC/MS ANALYSES OF ORGANICS IN WASTEWATER STREAMS*
en
en
Compound
Water to Ash Pond Settling Pond
Add . Neutral Basic Overflow
Extract" Extract Extract Acid Extract
Scrubber Make-up Water
NeutralBasic
Extract Extract
Olefln or ketone; Cg - C^
Tetrachloropropane (possible)
e-chloro-N-ethyl-N'-O-methyl ethyl)-l,3,5-
tr1az1ne-2,4-d1am1ne
8-methy1-3a-d1hydronaphthalene-one
3a.7a-d1hydro-5-raethyl-1ndene-l,7(4h)-d1one
Qulnollne
Butyl naphthalene(4) (plus a possible alkyl
substituted naphthalene)
l-chloro-2,4-hexad1ene
Cg nltrlle or Cj alcohol
01-2-ethyl-hexyl ester of nonane dfolc acid
2,2,5,5-tetramethyl hexane
01phenylheptane (possible)
4 vg/1
0.5 wg/1
0.3 yg/1
2 ug/1
Scrubber
Discharge Liquid
Basic Extract
Level 2 procedures were utilized.
f Identified compounds are present In this extract at concentrations below 15 yg/1.
-------
alcohols, ethers, and cyclic ethers. Some of these are lightly halogenated.
Typical DMEG values for these classes of compounds are greater than 1000
yg. Thus, the levels of organics present in the wastewater streams
from coal firing do not appear to warrant any environmental concern.
SOLID WASTE
The two major solid waste streams generated are bottom slag/fly ash
from the slag tank and scrubber sludge from the FGD operation. These two
solid wastes are generated at the rates of 0.11 Gg/hr and 0.13 Gg/hr,
respectively, on a dry basis at full load.
Inorganics
The scrubber sludge is composed predominantly of relatively insoluble
solids: 45-60% limestone, 30-45% CaSO,-l/2 H90, 5-10% fly ash, 5-10%
J *- *
magnetite, and <2% partially combusted coal on a dry basis . Trace elements
in the fly ash may contribute to the leachate from the scrubber sludge and
are of special concern. The concentrations of 18 trace and minor elements
in the scrubber discharge solids are presented in Table 4-21. With respect
to the human health based DMEG values for solids, 9 elements exceeded their
DMEG values. Eleven elements exceeded their ecology based DMEG values.
This is the consequence of transforming a high volume, low concentration
pollution stream to a low volume, high concentration stream which can be
more readily contained. The discharge severity for over half of the trace
elements analyzed is sufficiently high to warrant disposal of these solid
wastes in a specially designed landfill.
The concentrations of 18 trace and minor elements present in the bottom
slag/fly ash from coal firing are presented in Table 4-22. In 8 cases, the
trace element concentration exceeds its human health based DMEG value for
solids, and in 12 cases the ecology based DMEG value is exceeded. Again,
specially designed landfills should be considered for disposal of these
wastes.
*
From PLM analysis.
56
-------
TABLE 4-21.
TRACE ELEMENT CONTENT OF SCRUBBER
DISCHARGE SOLIDS - TEST 135*
El ement
AT
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Hn
Ni
Pb
Sb
Sr
V
Zn
Concentration
mg/kg
24,000
no
2.5
51 ,000
36
22
52
190
50,000
< 1.0
0.49
560
96
1,100
38
990
190
6,500
DMEG value
Health
16,000
50
6
48,000
10
150
50
1,000
300
2
18,000
50
45
50
1,500
9,200
500
500
, mg/kg
Ecology
200
10
11
3,200
0.2
50
50
10
50
50
17,400
20
2
10
40
NDf
30
20
Discharge
Health
1.5
2.2
0.4
1.1
3.6
0.15
1.0
0.19
170
< 0.5
0.000027
11
2.1
22
0.025
0.11
0.38
13
Severi ty
Ecology
120
11
0.22
16
200
0.44
1.0
19
1,000
< 0.02
0.000028
28
5
no
0.95
6.3
320
Level 2 procedures were utilized.
ND - data not available.
57
-------
TABLE 4-22. TRACE ELEMENT CONTENT OF BOTTOM AND FLY ASH - TEST 135*
El ement
AT
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Ni
Pb
Sfa
Sr
V
Zn
Concentration
mg/kg
82,000
11
8.2
66,000
1.2
44
210
820
170,000
< 1
ND*
700
330
160
7.0
280
86
1,500
DMEG value
Health
16,000
50
6
48,000
10
150
50
1,000
300
2
18,000
50
45
50
1,500
9,200
500
500
. mq/kq
Ecol ogy
200
10
11
3,200
0.2
50
50
10
50
50
17,400
20
2
10
40
NDf
30
20
Discharge
Health
5.1
0.21
1
1.4
0.12
0.29
4.2
0.82
580
< 0.5
14
7.3
3.2
0.0047
0.03
0.17
3.0
Severity
Ecology
410
1.1
0.75
21
6
0.88
4.2
82
3,500
< 0.02
35
200
16
0.17
2.9
75
Level 2 procedures were utilized.
* ND - data not available.
58
-------
An overall mass balance for these trace and minor elements is presented
in Table 4-23. The percent of the trace element in the influent streams
which could be located in the effluent streams is taken as a measure of mass
balance closure. Very good mass balance closure was obtained for aluminum,
arsenic, and strontium. Closures for most other elements were within a fac-
tor of two, but recoveries for beryllium and copper values were >700%, and
mercury and lead values were low. Stream flow rates were obtained from
several sources and it is possible that uncertainties in several of these
which were obtained from design values, contributed to poor mass balance
closure for some elements. However, process streams of principal importance
to the trace element balance are feed coal, bottom ash, and scrubber slurry
solids (inlet and outlet). The generally acceptable trace element balances
obtained tend to validate flow rates for these streams. Hence, large closure
discrepancies may be the result of analytical problems.
Organics - Solid Waste
Concentrations of Cy to C^g organics and high molecular weight
organics measured in the solid wastes are summarized in Table 4-24. The
total organics amount to 86.2 mg/kg for the combined bottom ash/fly ash
and 6.6 mg/kg for the scrubber discharge solids. High molecular weight
organics were not detected for either solid waste.
Organics present in the bottom ash/fly ash are probably the result of
incomplete combustion, or the adsorption of organics by fly ash particulates.
Organics are present in the scrubber discharge solids because of the partial
removal of these compounds from the flue gas stream in the FGD system. GC/
MS analysis of the scrubber discharge solids did not reveal the presence of
any POM. Although no other specific organic compound identification in-
formation is available, the high trace element content of these solid wastes
far outweighs the concern for the organic content. Disposal in specially
designed landfills should be satisfactory to handle the potential degree
of hazard.
BIOLOGICAL TESTING
Selected process samples including solid, liquid, and slurry samples
were submitted for bioas say testing. A listing of the samples tested is as
f ol 1 ows :
59
-------
TABLE 4-23. MASS BALANCE OF TRACE ELEMENTS (FULL LOAD)
cn
o
Influent Streams
Element
A1
As
Be
C«
Cd
Co
Cr
Cu
Fe
Hg
Mn
N1
Pb
Sb
Sr
V
Zn
Coal
Feed
kg/hr
11,600
17
0.046
5.566
U.I
5.1
20
1.5
13,921
0.72
53
21
1,091
2.9
20
41
720
Ash
Water
kg/hr
2.1
O.H
0.0013
1,718
0.11
0.085
0.0061
0.015
1.8
2.4x10'4
3.3
0.85
0.072
0.072
13
0.13
3.0
SI urry
Solids
1.000
1.8
0.022
23.772
0.17
0.071
3.5
15
742
0.091
47
2.2
1.8
0.71
135
6.4
2.85
Inlet, kg/hr
Liquids
3.7
7x1 O*4
3x1 O"4
240
0.0015
0.0015
7x1 O'4
0.0011
6x1 0"4
2x1 O"4
0.14
0.022
0.0037
0.0018
3.6
0.0084
0.011
Scrubber
Water.
kg/hr
0.40
0.022
2xlO"4
331
0.023
0.016
0.0012
0.0029
0.35
SxlO'5
0.64
0.16
0.014
0.014
2.4
0.023
0.58
Total
kg/hr
12,606
18.9
0.070
31 .627
11.40'
5.27
23.5
16.5
14,665
0.811
104
24.2
1.093
3.7
174
47.6
726
Bottom
Ash,
kg/hr
9,063
1.1
0.91
7,291
0.10
4.9
23
91
19.238
0.11
77
37
17
0.77
31
9.5
167
Ash
Water
kg/hr
10.5
0.11
9.1x10"4
443
0.060
0.0061
0.037
0.024
9.1
6.1x10"4
1.1
0.030
0.91
0.0061
2.5
0.76
0.39
Effluent Streams
Scrubber
Solids
3.170
15
0.33
6,737
4.8
2.9
6.9
25
6,605
0.13
75
13
143
5.0
131
25
857
Slurry, kg/hr
liquids
0.056
0.040
7x1 O'4
259
3x1 O'4
0.0034
0.0027
0.0027
0.0098
5x1 0'5
0.26
0.13
0.020
0.043
2.3
0.064
0.0034
Flue Gas
kg/hr
12
3.9
0.0076
8.2
2.4
0.053
0.52
0.81
55
0.024
0.61
0.22
12
1.1
0.15
0.35
86
Total
kg/hr
12,256
20.15
1.25
14,738
7.36
7.86
30.5
116.8
25,907
0.265
154
50.4
173
6.9
167
35.7
1.110
Recovery
97
106
>1 .000
47
65
149
130
707
177
33
148
208
16
187
96
75
153
* Level 2 procedures were utilized.
-------
TABLE 4-24. ORGANICS IN SOLID WASTE STREAMS
Carbon
Number
C7
C8
C9
C10
cn
c12
C13
C14
C15
C16
>C16
Total
Concentration
Bottom Ash/
Fly Ash
0
33.0
28.8
0
0
0
0
0
0
24.4
0
86.2
, mg/kg
Scrubber
Discharge Solids
0
0
4.7
1.9
0
0
0
0
0
0
0
6.6
Level 1 procedures were utilized.
61
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• Cyclone participate catch (test 136 scrubber inlet gas)
• Raw limestone (composite of tests 135 and 136)
• Fly ash/bottom ash (test 133)
• Scrubber outlet slurry solids (composite of tests 135 and 136)
• Cooling water (composite of tests 132, 133, 135, and 136)
0 Scrubber outlet slurry (composite of tests 134 and 136)
Detailed test descriptions and analytical results have been reported
by Litton Bionetics (11). A summary of the bioassay test results is
provided in the ensuing paragraphs.
The six samples were examined for their mutagenie activity as well as
for their toxicity effects in the in vitro microbial assays employing
Salmonella indicator organisms (Ames mutagenicity assay). The genetic
activity of a sample is measured by its ability to revert Salmonella indi-
cator strains from histidine dependence to histidine independence. The
toxicity is measured by the reduction in number of colonies growing on n
nutrient agar plates. The samples were tested directly and in the presence
of liver microsomal enzyme preparations from Aroclor induced rats (referenced
as S9).
The samples did not exhibit toxicity with any of the indicator organisms
employed directly or in the presence of S9. The tests with all the samples
were repeated because of inconsistent population counts with some of the
indicator strains in the initial test. The results of the repeat tests
indicated that these six samples were not toxic to the indicator strains at
any of the doses tested.
The results of mutagenicity assays conducted on these six samples in
the presence and absence of metabolic activation systems were negative in
the initial as well as in the repeat tests. The repeat tests were con-
ducted with all the samples because of inconsistent population counts
observed in the initial test. The tests performed with raw limestone and
fly ash/bottom ash were repeated once again with the indicator strain TA1535
in the presence of S9 because of an increase in the number of revertants
observed at all doses in the repeat test. The final repeat test performed
with this strain using duplicate plates per dose level were negative.
62
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Effects of the two liquid-containing samples, cooling water and
scrubber outlet slurry, on the colony-forming ability of cultured Chinese
hamster cells (CHO) were determined. Test materials were applied to cell
cultures for 24 hours at five concentrations from 10 ml/1 to 600 ml/1.
The cooling water sample caused only a small depression in the colony-
forming ability of the CHO cells. This effect was nearly constant from
30 ml/1 to 600 ml/1 and did not reduce the relative cloning efficiency
below about 85%. Therefore, there was no concentration of cooling water
which would reduce the colony number by 50% (EC50), and the cooling water
was classified as having nondetectable toxicity.
The limestone scrubber slurry test material was toxic at all applied
concentrations. The relative cloning efficiency was 71.6% at the lowest
applied concentration of 10 ml/1, and no survivors were obtained at 100
ml/1. Since the EC50 value was determined to be 19 ml/1, the slurry was
moderately toxic to CHO cells. It was not established whether the cells
responded to the particulate or soluble fractions of the slurry.
Cytotoxic effects of the four solid samples on cultured rabbit alveolar
macrophanges (RAM) were determined. Test samples were applied to primary
cell cultures for 20 hours at concentrations ranging from 3 mg/1 to 1000
mg/1. Five cellular parameters were monitored: percent viability; viabi-
lity index; total protein; total ATP; and ATP/106 cells. Of these five
parameters, the ATP content was the most sensitive. Concentrations that
reduced the culture ATP content by 50% (EC50) were 250 mg/1 for the cyclone
particulate catch, 370 mg/1 for the scrubber solids, and 1000 mg/1 for the
fly ash/bottom ash sample. These samples are evaluated to have low toxi-
city. The raw limestone samples had little effect on the cells and, at the
highest dose of 1000 mg/1, all five assay parameters were approximately 90%
of the negative control values. As such, the raw limestone had no detectable
toxi ci ty.
Rhodent toxicity effects of five samples (the cyclone particulate catch
was not tested) were determined by oral administration of sample aliquots
at a dose level of 10 g/kg. Test results indicate that the samples are
non-toxic when administered to young rats at this dose level. Because
neither the male nor female rats died during the 14-day test period, LD50
concentrations for these samples is greater than 10 g/kg.
63
-------
The cytotoxic effects of the cooling water and scrubber slurry samples
on cultured VII-38 human cells were determined. Sample material was applied
to cell cultures for 20 hours at concentrations ranging from 3 ml/I to
600 ml/I. Five cellular parameters were examined: percent viability;
viability index; total protein; total ATP; and ATP/10 cells. The cooling
water sample had little effect on the cells at concentrations up to 600 ml/1;
the viability index was the most sensitive assay parameter and it decreased
at the 600 ml/1 dose level to 60% of the negative control. Hence, the
cooling water sample was evaluated as having nondetectable toxicity to the
WI-38 cells. The limestone scrubber slurry reduced the culture ATP content
by 50% at 180 ml/I (EC50 value). The EC50 for the viability index was 350
ml/1 and the ATP per 10 cells parameter gave about 340 ml/1. Thus, the
scrubber slurry sample was evaluated as having low toxicity. The slurry
sample produced a strong color reaction with the Lowry reagents and pre-
vented determination of the protein content by this method.
The acute toxicities of raw limestone, fly ash/bottom ash, and scrubber
solids were determined for freshwater fish (fathead minnows), invertebrate
(Daphnia pulex), and algae (selenastrum capricornutum). Fish toxicity tests
were conducted using static acute 96-hour tests, Daphnia tests were con-
ducted using 48-hour static acute tests, and algal assays were bottle tests.
In addition, algal assays were also conducted on scrubber slurry and cooling
water.
For all samples, no detectable toxicity was observed. For the fish
acute assays, LC50 values were greater than 1000 mg/1. For the Daphnia
assay with raw limestone, the LC50 was greater than 1800 mg/1 and for the
other samples LC50 values were greater than 1000 mg/1. Results of the algal
assays for the solid and slurry samples indicate that population growth at
nominal concentrations of 100, 180, 320, 560, and 1000 mg/1 of the test
materials was not significantly different from the controls. Assays per-
formed in 100% cooling water indicated 8-15% less growth than lower concen-
trations or the control. Growth in 10, 32, and 56% cooling water was
statistically the same as in the control. Growth in 18% cooling water was
5-15% greater than growth in the control. Algal assays therefore indicated
no detectable toxicity.
64
-------
REFERENCES FOR SECTION 4
1. Magee, E.M., H.J. Hall, and G.M. Varga, Jr. Potential Pollutants in
Fossil Fuels. Report prepared by ESSO Research and Engineering Co.
for EPA under contract No. 68-02-0629. June 1973.
2. Ruch, R.R., H.J. Gluskoter, and N.F. Skimp. Occurrence and Distribu-
tion of Potentially Volatile Trace Elements in Coal: A Final Report.
Illinois State Geological Survey Environmental Geology Notes. Number
72. August 1974.
3. Hamersma, J.W. and M.L. Kraft. Applicability of the Meyers Process
for Chemical Desulfurization of Coal: Survey of Thirty Five Coals.
Report prepared by TRW Systems Group for EPA under contract No.
68-02-0647. September 1975.
4. Koutsoukos, E.P., M.L. Kraft, R.A. Orsini, R.A. Meyers, M.J. Santy,
and L.J. Van Nice. Meyers Process Development for Chemical Desulfur-
ization of Coal, Vol. I. Report prepared by TRW Systems Group for EPA
under contract No. 68-02-1336. May 1976.
5. Compilation of Air Pollution Emission Factors, AP-42, Part A. Third
Edition. U.S. Environmental Protection Agency. August 1977.
6. Emissions Assessment of Conventional Combustion Systems. Progress
Report No. 21. Prepared by TRW Energy Systems Group for U.S. Environ-
mental Protection Agency. June 1978.
7. U.S. Environmental Protection Agency. NOV Control Review. Vol. 3,
No. 4. Fall 1978. x
8. Miller, S.S. Inhaled Particulates. Environmental Science and Tech-
nology 12 (13): 1353-1355. December 1978.
9. Melia, H. et al. EPA Utility FGD Survey: August-September 1978.
Report prepared by PEDCo Environmental, Inc. for the U.S. Environmental
Protection Agency. EPA-600/7-79-022a. January 1979.
10. Cleland, J.G. and G.L. Kingsbury. Multimedia Environmental Goals for
Environmental Assessment. Volumes 1 and 2. EPA-600/7-77-136a.
November 1977.
11. Level 1 Bioassays on Six Conventional Combustion Samples, Final Report.
Report prepared by Litton Bionetics, Inc. for the U.S. Environmental
Protection Agency under contract No. 68-02-2681, TON 104. July 1979.
65
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SECTION 5
ENVIRONMENTAL IMPACT ASSESSMENT
Future energy policies will affect the social, economic, energy, and
physical environments. One of the major policy issues involves intensifica-
tion of coal utilization. It is essential that the effects of increased coal
utilization be determined so that national energy policies may be developed.
This section evaluates the impacts of emissions resulting from coal
combustion in utility boilers, based on the La Cygne station test results.
As indicated previously, La Cygne is unique with respect to several charac-
teristics including boiler size and furnace type. Hence, environmental
impacts estimated from La Cygne data may not be indicative of other coal-
fired utility boilers. The analysis is conducted in five parts. The first
part introduces background information pertinent to the development of the
environmental assessment, including a review of relevant studies, plant emis-
sions, and air quality forecasts. In the succeeding parts, the major health,
ecological, and economic impacts resulting from coal firing in controlled
utility boilers of the type tested are estimated. The final section assesses
the implications of the impacts for energy development by considering: 1)
the additional controls which may be needed to mitigate the expected damage
levels, and 2) the potential effect of such control needs on energy cost and
energy resource development.
INTRODUCTION
Economic and environmental concerns over the nation's energy develop-
ment policies have precipitated several research efforts to evaluate the
consequences of all phases of energy development, from fuel production to
fuel end use. To organize the various efforts into a systematic, coordinated,
environmental assessment structure, the Environmental Protection Agency is
implementing a Conventional Combustion Environmental Assessment (CCEA)
Program. This program has been established for the purpose of integrating
together separate data generated by past and current studies into a complete
environmental assessment of conventional combustion processes. The integra-
tion procedure involves coordination and information exchange between EPA
66
-------
related studies to: 1) determine the extent to which the total environmental,
economic, and energy impacts of conventional combustion process can be
assessed, 2) identify additional information needed for complete assessment,
3) define the requirements for modifications or additional developments of
control technology, and 4) define the requirements for modified or new
standards to regulate pollutant emissions. The CCEA Program coordinates
and integrates current and future studies encompassing a wide spectrum of
environmental assessment areas and conventional combustion processes.
Integration of these studies, including the present effort, will provide
the basis for energy policies which result in the expanded use of conven-
tional combustion processes at reasonable environmental, economic, and
energy costs.
AIR QUALITY
Model Plant Emissions
Air quality impacts were estimated based on a hypothetical model plant.
The model plant was characterized using emission factors derived from the
La Cygne plant test data and assumed meteorological parameters. The model
plant was assumed to have the same fuel and boiler characteristics as the
La Cygne plant. The criteria pollutant emission rates utilized are shown
in Table 5-1. Comparison of the measured trace element emission concentra-
tions with DMEG values revealed that the flue gas contained 7 trace elements
which exceeded their DMEG values. Hence, these trace elements were also
included in this analysis.
Annual Emissions
Estimated annual emissions for hypothetical coal-fired plants generating
874 MW are presented in Table 5-2. These estimates are based on the emis-
sion factors determined for the La Cygne coal-fired plant. The hypothetical
plant was assumed to operate at 87% of its maximum load with 29% overall
efficiency.
Impact on Air Quality
The duration of exposure is important in determining effects of changing
air quality. The highest concentrations occur for short periods (usually
less than one hour) under meteorological conditions causing plume trapping.
67
-------
TABLE 5-1. EMISSION RATES FROM A CONTROLLED 874 MW
(GROSS) COAL-FIRED UTILITY BOILER*
Pollutant Emissions, gm/sec
S02 1 ,940
NO
X
Parti culates 200
Organics 3.80 - 6.82
As1" 0.92
Cd1" 0.55
Crf 0.12
Fef 13
Nif 0.052
Pbf 2.9
Znf 20
*
These emission rates are based upon data from a cyclone-
fired boiler burning high sulfur, high ash coal. This
unit is not required to meet NSPS and, as such, emission
rates may be considered to represent worst case values.
Trace element concentration in the flue gas exceeded the
DMEG value.
68
-------
TABLE 5-2. ANNUAL EMISSIONS
Pollutant
Emission Rate, kg/year
Scrubber Inlet
Scrubber Outlet
Gaseous N0>
SO,
SO,
so]
CO
Total Organics
8
>4.24 x 10'
2.00 x 10
2.87 x 106
1.32 x 106
<3.08 x 107
1.64xl05 - 2.41xl05
>4.24 x 10'
4.39 x 107
5.65 x 105
2.22 x 105
<3.08 x 107
8.59xl04 - 1.54xlOJ
crce
VC16
>C16
Total Parti culates
10y
5.93x10
2.
7.
6.
<
<
6.
4.
H
67
82
46
6
2
93
64
1
x
x
X
X
X
X
X
.36x10°
104
104
107
103
105
106
107
5.04x10* -
7
2
4
3
5
2
•
•
•
•
•
•
11
84
7
99
2
5
8
1
x
x
X
X
X
X
X
.19x1
103
104
106
106
105
104
105
Liquid (1) Wastewater:
Slag tank to ash pond
(2) Scrubber Slurry:
Settling pond overflow
1.57 x 10
4.21 x 10-
10
Solid (1) Bottom Slag/Fly Ash
(2) Scrubber Sludge
6.01 x 10
7.10 x 10
Coal-fired plants generating 874 MW (gross) operating 6278 hours/year,
69
-------
The stack emissions are trapped under an inversion layer, with the plume
spreading downward. The frequency of occurrence and the severity of such
trapping conditions varies depending on the site. As a conservative worst
case estimate in this study, plume trapping conditions were assumed to
persist for periods as long as three hours. Typical 24 hour maximum con-
centrations were estimated assuming Gaussian steady state plume dispersion
under conditions of low wind speed and stable atmosphere. Typical 24 hour
levels were translated to annual expected concentrations by applying ratios
for the one day maximum and annual mean as empirically derived from the
Continuous Air Monitoring Project (1, 2, 3, 4). The effective stack height
was estimated based on assumed meteorological conditions, and the actual
stack height.
Table 5-3 shows the maximum predicted levels for criteria pollutants
in the vicinity of the model plant. Estimated ambient concentrations result-
ing from the controlled coal-fired boiler are in excess of the air quality
standards for short term SO- emissions, while concentrations of other
/\
criteria pollutants are in conformance with the air quality standards.
Carbon monoxide was not accurately measured during testing and will not be
considered in this section. It should be noted, however, that CO emissions
typically are insignificant relative to NAAQS. For any of the pollutants,
the short term maximum concentrations present the most significant air
pollution problem. It should be noted that the short term maximum concen-
trations generally occur infrequently depending on site meteorology, and
are usually of very brief duration (about 1 hour or less). The maximum
concentration levels are localized within a distance of about one-half to
four miles from the boiler stack. These concentrations diminish to about
one-half the peak level another one to eight miles further downwind.
The absolute value of the predicted concentrations depends on many
variables, not the least of which are assumptions of adverse case meteoro-
logical conditions employed in the theoretical air quality models. Stack
height is also an important factor which may vary greatly among units, and
will generally depend on prevailing meteorology at the boiler site. Meteo-
rological parameters were selected conservatively in the present analysis,
resulting in predicted air quality which may be overstated in terms of
70
-------
TABLE 5-3. COMPARISON OF FEDERAL AIR QUALITY STANDARDS
WITH AIR QUALITY PREDICTED TO RESULT FROM
COAL COMBUSTION IN A 874 MW UTILITY BOILER
3
Concentration, yg/m
Pollutant
Annual Average
NOV
X
so2
Total Organics
Total Particulates
24 Hour1"
NOV
X
so2
Total Organics
Total Particulates
1-3 Hour*
NOV
X
so2
Total Organics
Total Particulates
Model
Plant
12
12
0.05
1
46
48
0.2
5
2800
2900
10
310
NAAQS
100
80
—
75
• •»•
365
—
260
« M
1300
160
— — —
PSD Increments**
Class I Class II Class III
_«.• «»••. •••_
2 20 40
— — —
5 19 37
••»• B«W • • •
5 91 182
— — —
10 37 75
«M» rm • •» ^ ^ ^
25 512 700
— — —
— — — — — — — — —
**
The expected annual average levels were estimated based on the conser-
vative end of the range of typical ratios for 24 hour maximum to annual
as reported in the Air Quality Criteria Documents (1, 2, 3, 4).
Based on typical meteorological conditions for 24 hour period.
Based on worst case meteorological conditions (plume trapping).
Prevention of significant deterioration standards (PSD).
71
-------
adversity. However, the calculated levels of air pollutants do illustrate
the potentially high concentrations which may occur in the vicinity of some
controlled coal-fired utility boilers, and this underscores the necessity
for careful siting and design of utilities to avoid potential violations of
the NAAQS. Concentrations of total organics are seen to be negligible
relative to short term NAAQS. Hence, these emissions will not be considered
further.
Federal standards limiting deterioration of air quality are generally
more restrictive than the NAAQS. Included in Table 5-3 is a list of the
allowable increments of deterioration for the three classes of growth and
development areas. Hence, depending on the existing air quality and the
allowable deterioration increment, emissions of total particulates from
the model plant may not be acceptable in certain locations. Again, siting
of the plants would be a major consideration in their environmental accept-
ability, since areas which already experience marginally acceptable air
quality could not tolerate the increases projected to occur.
HEALTH IMPACT
The health effects of exposure to high concentrations of the various
pollutants are well known and have been tabulated throughout the literature
(5). However, the specific extent to which health is affected by ambient
pollutant exposure levels (dose-response relationships) is unclear. More-
over, it is unclear how pollutant specific dose response curves may be
related to the overall health effects of the gas-aerosol complex associated
with fossil fuel combustion products.
Most attempts to establish dose response functions for ambient pollu-
tion levels involve the formulation of some indicator which is then assumed
to represent the entire spectrum of primary and secondary pollutants pre-
sent. The indicator (usually sulfur dioxide, total particulates, or sulfates)
is then related to mortality or morbidity data for various areas by various
statistical approaches designed to factor out effects of other variables
(e.g., population age, climatology, etc.). Dose-response curves derived
from these studies are then employed to estimate health effects of air
quality changes-resulting from proposed projects.
72
-------
Recently, the health effects model by Lundy and Grahn (6) has been
developed for application in the National Coal Utilization Assessment
Studies being conducted at Argonne National Laboratories. The model com-
bines mortality functions for suspended sul fates as developed by Finch and
Morris (7) and age-dependent and established response curves for cigarette
smoke. The mortality dose-response functions for suspended sulfates are
based on statistical studies of various populations experiencing different
sulfate exposures. Unlike the dose-response air pollution studies, inves-
tigations of smokers have been relatively well controlled with respect to
age, degree of exposure, and effect. Thus, to expand the predictability
of the sulfate dose-response curves to populations of different age distri-
bution (e.g., future populations), the cigarette response curves are ad-
justed to fit the observed mortality/sulfate data, resulting in a model
which predicts age-specific death rates. This elaboration is important
because death rates vary exponentially with age, and shifts in the age
distribution of a population will result in substantial shifts in total
mortality. Accordingly, the Lundy-Grahn Model utilizes projections of the
population age distribution to estimate the age-specific and total death
rates due to air pollution at any specific time in the future. The basic
relationship of the model is:
bX
B(X' Xo> = -
where B is the number of excess deaths per year for the population of age
o
X which was exposed to the sulfate concentration S (in ug/m ) since age Xo.
The constants a,b,c and d are coefficients to fit the model to cigarette
smoking mortality data and response data for a specific population subgroup
exposed to air pollution.
The Lundy-Grahn Model is being used in the ongoing National Coal Utili-
zation Assessment Program to estimate excess mortality resulting from in-
creased coal utilization. Air diffusion modeling was conducted first to
predict a population-weighted exposure increase for suspended sulfates. The
Lagrangian Statistical Trajectory Model of Argonne National Laboratory (8)
73
-------
which assumes a constant transformation of S02 to sulfate, is employed in
the estimation procedure. Then, based on the predicted exposure increase
and projections of the population age distribution, excess death rates are
calculated for each age and summed to yield the expected mortality asso-
ciated with coal combustion. Table 5-4 shows the estimated effects of an
3
average exposure increment of 8.95 yg/m suspended sulfates predicted to
result from coal-firing of power plants throughout the Central United
States. The plants are assumed to emit sulfur oxides at the ceiling levels
of the NSPS, and the degree of power plant coal firing is assumed to in-
crease in the region from the current level of 161 Tg/y to 744 Tg/y in 2020,
The projected levels of power plant coal utilization are predicted to cause
significant health effects in future years.
TABLE 5-4. EFFECTS OF COAL COMBUSTION IN POWER
PLANTS IN CENTRAL U.S.*
Year
1985
2000
2020
Increase in Death Rate,
Number of deaths/
Million persons/Year
28-130
181-809
150-665
Reduction In
Expectation of Life
At Birth t
17 - 79 days
136 days -1.7 years
160 days - 1.8 years
Reference 30.
The range of values represents the expected and upper 80%
confidence limit given by Finch and Morris (7). The effects
are calculated corresponding to an expected average exposure
increment of 8.95 ug/m3 suspended sulfates.
74
-------
Figure 5-1 shows the expected health effects caused by air pollution
(as indexed by suspended sulfates) which might result from coal-fired
utility boilers emitting S02 at the rate observed in this study, and also1
the effects which would be expected under coal-firing conforming to the
ceiling levels of the NSPS. The maximum impact is expected to occur in
the year 2000, when the proportion of population in the highest risk age
groups will be greatest. For each million persons, the number of increased
deaths expected to occur annually due to accelerated use of coal-fired
utility boilers is 222 in the year 2000.
Effect of coal-fired, power plant and
associated 11.0 yg/m^ ambient sulfate
exposure from model plant emissions.
Effect of coal burning power
plants emitting S02 at NSPS
and creating 9 yg/m3 ambient
sulfate exposure.
1985
2000
2020
YEAR
Figure 5-1. Health effects from sulfate levels resulting from
coal combustion in controlled utility boilers.
75
-------
Health effects caused by sulfate levels may also be expressed in terms
of morbidity. Table 5-5 presents data for increases in incidents of health
disorders due to ambient sulfate exposures. In those areas which already
experience high sulfate levels, respiratory disease may increase signifi-
cantly with increases of suspended sul fates due to increased fuel consumption,
3
For example, in areas where the threshold level 10 yg/m is exceeded
3
regularly, the contribution of 11.0 ug/m of sulfate concentration associated
with controlled coal -fired boilers would be estimated to produce a 150%
increase in the incidence of chronic respiratory disease caused at the
threshold level. Based on the expected ambient exposure attributable to
coal firing of power plants, other mortality effects (aggravation of asthma,
living disease, etc.) would also occur.
In addition to potential health effects created by long range sulfate
levels from utility boilers, high concentrations of pollutants in the pro-
ximity of the power plant pose a potentially serious health problem. The
Lundy-Grahn model may also be applied to estimate mortality effects caused
by ambient levels of S02 and total suspended parti culates. The model gives
the following relationships when fitted to Lave and Seskin dose response
data (5) for S02 and total suspended particulates (TSP):
c
per 10b males: - o/v YA\ (-835 TSP + .715 S09)
1 + lOOe v '
f ncco*
per 10b females: - otv yn\ (-835 TSP + .715 SOJ
~*A~AO;
If the model is applied for average concentrations expected to occur in the
vicinity of a power plant (Table 5-3), the expected increase in mortality
is appreciable. Figure 5-2 illustrates the estimated impact on mortality.
For example, when boilers are coal -fired, populations of the age 50 are
predicted to experience increases in death rates of 176 male and 29
female deaths per million persons per year.
76
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TABLE 5-5. HEALTH IMPACTS OF SULFATE AEROSOL
Pollutant and
Health Effect
S'j1 fates
T.ortaTity
Aggravation of
Heart and lung
Disease in Elderly
Aggravation of
Asthnia
Lo*or Respiratory
Disease in Children
Chronic Respiratory
Disease
Hons^.okers •
Smokers
Population at Risk .
Total Population-
Same as above for
oxidonts function
Sarce as above for
oxidants function
Sane as above for
nitrogen dioxide
function
62 percent of
population age 21
or older
33 percent of
population age 21
or older
Assumed Baseline
Frequency of
Disorder v.'ithin
' Population at Risk
Daily death rate of
2.58 per 100,000
Same
Same
Same
Two percent
prevalence
Ten percent
prevalence
Pollutant
Concentration
Threshold
For Effect
25 vg/m3 for
one day or
more
9 vg/n3 for
one day or
rore
6 tJfi/m3 for
one* day or
mere
13 vg/m3 for
several years
10 uci/ni3 for
several years
15 ug/m3 for
several years
Effect Increase as ~
of Saseline Per
Folluinnt Unit Above
Thrc:.'~old
2.5S per 10 vg/n3
14.12 par 10 vg/ir;*
33.5- per 10 vg/n3
76.9% per 10 vg/rc3
134^ per 10 pg/n3
73.8S per 10 vg/n3
Reference 9.
-------
O UJ
•z. >-
LU CO
CO
•— « o
300
250
200
150
100-
50-
0
Male response
/* Female response
30 40 50
POPULATION AGE
60
Figure 5-2. Increase in mortality rates in vicinity of coal-fired
utility boilers as a result of S02 and total particulate
emissions.
Effect of Trace Elements--
Trace elements from coal combustion emissions enter the atmosphere and
are then dispersed to the upper atmosphere or deposited in the environment
around the sources. The principal routes of entry to man are by inhalation,
drinking water and food.
Table 5-6 summarizes estimates of the annual average atmospheric
concentrations of various elements expected in the vicinity of a single
controlled coal-fired utility boiler of 874 MW capacity. The elements
included in this listing are those which exhibited stack concentrations
78
-------
TABLE 5-6. EXPECTED TRACE ELEMENT CONCENTRATIONS IN VICINITY
OF A 874 MW CONTROLLED COAL-FIRED UTILITY BOILER
Element
As
Cd
Cr
Fe
Ni
Pb
Zn
Annual Ambient
Concentration,
ug/m
0.006
0.003
0.001
0.08
OoOOOS
0.02
0.1
Typical
Urban Air
Concentration *
u9/m3
.010
.300
.010
1.60
1.40
2.40
.67
Allowable
Exposure
Level t
yg/m3
50
20
50
1000
100
20
500
Based on data reported in References 10, 11 and 12.
Based on ambient air objectives proposed for hazardous
waste management facilities (13).
exceeding the DMEG values. Also included in Table 5-6 is a listing of
concentrations considered acceptable for continuous ambient exposure. The
allowable concentrations are based on proposed regulations for control of
air pollution from hazardous waste management facilities, as required by
Section 3004 of the Resource Conservation and Recovery Act. It is clear
that the air concentrations of elements resulting from operation of the
utility boiler are several orders of magnitude (3 to 6) below the allow-
able exposure level. Moreover, the predicted maximum concentrations are
also less than typical urban ambient background levels.
A primary concern in emissions of trace elements is the contribution
of these elements to body burden due to exposure to water and food. To
estimate this contribution, pollutant deposition rates are approximated by
the product of the ambient concentrations and the deposition velocity of
the pollutant. The deposition rate is dependent on particle size. Test
results of the present study show that particles emitted from the controlled
79
-------
coal-fired boiler are predominantly three vm or less in diameter.
The deposition velocity of particles this size over grass surfaces is appro-
ximately 0.1 to 0.2 cm/sec (14). Accordingly, the deposition rates of the
various trace elements were approximated and are shown in Table 5-7.
The significance of the deposition rates is evaluated by considering
the associated effect on drinking water and diet. The pathway to drinking
water is by run-off of soil particles containing deposits of trace elements,
and the pathway to the diet is by plant uptake from trace elements in the
soil. In either pathway, the incremental concentration of elements in the
soil determines the extent of the potential impact. Table 5-8 summarizes
the maximum predicted soil concentration in the vicinity of coal-fired
utility boiler of 874 MW capacity. The concentrations are estimated by
assuming mixing of the deposited elements to a depth of 10 cm, and over a
period of 40 years. For the majority of the trace elements, only minor
increases over the background soil levels would be expected. However, the
concentration of cadmium may increase significantly. It is predicted that
coal firing will cause an 80% increase in the cadmium soil concentration.
The significance of elevated soil concentrations is evaluated by considering
the associated increase in trace element concentration in plant tissues and
drinking water.
The concentration of elements in plant tissues is related to the
biologically available fraction of the elements in the soil. This is often
expressed as the soluble concentration in the soil, and is some fraction of
the total concentration reported in Table 5-8. Plant possess the ability
to concentrate elements from dilute soil solutions. This ability is de-
pendent on the concentration of elements in the soil, and usually increases
with decreasing soil concentrations. The ratio of concentration of elements
in plants to the concentration in the soil is known as the concentration
ratio. Table 5-9 lists average plant concentration ratios for various
elements. The data are based on various published data as compiled in a
study by Battelle (15). The effect of increased trace element soil loadings
(caused by 40 years of boiler emissions) on concentration of the elements
in plants is then estimated by assuming that the soluble portion of the
loadings are available for plant takeup. For all elements except chromium
80
-------
TABLE 5-7. ANNUAL DEPOSITION OF TRACE ELEMENTS IN VICINITY OF
CONTROLLED COAL-FIRED UTILITY BOILERS
Element
Annual Deposition Rate, g/m -yr
As
Cd
Cr
Ni
Pb
Zn
3.8 x 10"4
1.9 x 10"4
6.3 x 10"5
1.9 x 10"5
1.1 x 10"3
7.8 x 10"3
Calculated by assuming a particulate deposition velocity of
0.2 cm/sec. The deposition velocity is multiplied by the
annual average concentration to estimate the total deposition
rate. The deposition rate is calculated for the location
where the maximum average annual concentration occurs.
TABLE 5-8. LONG TERM EFFECT OF CONTROLLED COAL-FIRED
UTILITY BOILER EMISSIONS ON SOIL
CONCENTRATIONS OF TRACE ELEMENTS
Increased Soil
Element Concentration
After 40 Years,*
mg/kg
Typical
Soil .
Concentration
mg/kg
Increase Over
Average Soil
Concentrations, %
As
Cd
Cr
Ni
Pb
Zn
0.1
0.05
0.02
0.01
0.3
2
6.0
0.06
40
40
10
50
2
80
0.05
0.02
3
4
* Based on deposition rate (Table 5-7), an assumed mixing depth of 10 cm
and soil density of 1.5 Mg/m3.
* Based on data compiled in Reference 13.
81
-------
TABLE 5-9. LONG TERM EFFECT OF CONTROLLED COAL-FIRED BOILER
EMISSIONS ON CONCENTRATIONS OF ELEMENTS IN PLANTS
Element
As
Cd
Cr
N1
Pb
Zn
Concentration
Ratios*
4.2
222
250
331
2
40
Solubility
Of Elements*
%
9
40
0.004
0.1
—
8
Typical Con-
centration
in plants,*
mg/kg
.08- .55
.04- .50
.23
3
2.7
100
Increase in
Concentration
of plants ,t
mg/kg
0.04
4
.0.0002
0.003
0.6
7
Extracted from Reference 15. 3.
Calculated by multiplying concentration ratio by the incremental
increase in soil concentration (Table 5-8) by the fraction of the
element which is soluble.
and nickel, coal firing appears to exert an appreciable impact on trace
element plant burden. The elements predicted to produce the most notable
burdens in plant tissue are cadmium and lead. Coal firing is predicted to
result in plant concentrations of cadmium about 8 to 100 times greater than
the endogenous levels, and is expected to produce a 20% Increase in lead
concentrations.
Cadmium is considered highly toxic to plants and animals. Mammals
tend to absorb cadmium continually, accumulating high body levels which ad-
versely affect the respiratory, cardiovascular, nervous, and reproductive
systems, disrupt kidney and liver functions, and cause intestinal disorders,
Cadmium levels as low as 15 mg/kg in plants may cause injury to man (16).
Cadmium levels in some areas are believed to be approaching threshold
levels, and it is believed that cadmium concentrations in cigarettes might
82
-------
cause smokers to exceed thresholds of observable symptoms of cadmium
poisoning if exposed to additional sources of cadmium (17). Consequently,
the addition of cadmium to the environment in significant quantities is
a serious concern.
In contrast to cadmium, lead is considered to exhibit a lower order of
toxicity. Both natural and agricultural vegetative species have been found
growing in soil with lead concentrations exceeding 700 mg/kg. Soil concen-
trations of 1000 mg/kg are suspected to be lethal to lettuce. Domestic
animals tend to exhibit considerable susceptibility to lead concentration
in some situations. It is believed that lead concentrations of 300 mg/kgin
foliage will induce lead poisoning in grazing animals. By contrast, animal
populations in the wild have been observed in areas with high background
levels of lead in soil and vegetation (200-400 mg/kg in the soil and 121
mg/kgin leaves) with no adverse health effects reported.
The actual impact of trace element emissions on plant burden depends
greatly on many site-specific variables, such as temperature, precipitation,
soil type, water chemistry, and plant species at a given site. Of major
concern are the concentrations of elements in soil, water, and the atmos-
phere. Where trace element concentrations are approaching threshold limits,
emissions from power plants will exert a greater influence on health impacts<
This consideration is particularly relevant with respect to environmental
buildup of cadmium because high background levels of this element already
exist in many areas. It is anticipated that long term accumulation of
cadmium emissions from coal firing would cause serious health effects to
animals consuming vegetation grown in the affected areas. Accumulation of
other trace elements in nearDy soils is not expected to result in soil
concentrations which would be toxic to plants or in plant concentrations
toxic to man.
Trace elements also enter the plant via foliar absorption. Intake
from the leaf surface to the interior occurs through stomatal openings,
walls of epidemal cells, and leaf hairs. Although relatively little is
known regarding the efficiency of foliar intake, it would appear that the
plant burden produced by soils containing long term deposits is several
orders of magnitude greater than that which could be transferred from
83
-------
foliar interception of trace elements in the atmosphere. Soil concentra-
tions are the result of accumulation of elements over the long-term, and
crops raised in these soils tend to concentrate the trace elements in the
plant tissue. By contrast, the foliar intake rate can be no greater than
the deposition rate on the plant surface, and there is much uncertainty
regarding the efficiency of the plant in absorbing the deposited particles.
Thus, it is clear that the soil uptake scenario (Table 5-8) represents the
more adverse case for plant uptake of trace elements. This scenario assumes
no interference (e.g., animal or crop uptake) with trace element buildup in
soils over a 40 year period, and a fixed concentration of elements in the
soil despite crop uptake.
Trace element emissions also affect the quality of drinking water. The
impact of trace element particle deposition on runoff water concentration
will be related to the relative increase in soil concentration due to long
term atmospheric deposition of elements. The actual runoff concentrations
may be estimated by applying average sediment burden rates for representative
runoff per unit of watershed area. The sediment is assumed to carry the
cumulative deposits of metals originating from the boiler emissions. Table
5-10 summarizes estimates of increased soluble metals concentrations for
runoff waters in the vicinity of the model plant. The estimated concentra-
tions are substantially less than the standards for livestock drinking water
and potable water. The concentration of lead is predicted to approach
background concentrations in runoff water after 40 years of coal firing.
However, hazard to human health by drinking water impacts appears remote.
IMPACT ON ECOLOGY
The ecological environment will be affected by air emissions and by
solid waste residuals generated by air pollution control equipment.
Effects of Air Emissions
A major ecological impact category most likely to be affected by
utility boiler emissions is plant life. Of the major gaseous pollutants
emitted by fossil fuel combustion, plant life is most affected by S02 and
NOV in the concentration ranges expected. Concentrations of CO and hydro-
J\
carbons produced by coal firing of utility boilers would be expected to
84
-------
TABLE 5-10.
TRACE ELEMENT CONCENTRATION IN RUNOFF WATER IN
VICINITY OF CONTROLLED COAL-FIRED UTILITY BOILER
Element
As
Cd
Cr
Ni
Pb
Zn
Typical
Background
Concentration
of Soluble
Metals In
Runoff Water*
mg/1
4 X 10"4
1 X 10"4
1 X 10"5
1 X 10"4
7 X 10"4
3 X 10"3
Increase In
Soluble Metals
Concentration
In Soil After
40 yearst
mg/kg
9 x 10"3
2 x 10"2
8 x 10~7
1 x 10"5
3 x 10"1
2 x 10"1
Increase In
Soluble Metals
Concentration
In Runoff Water*
After 40 years
mg/1
9 x 10"6
2 x 10"5
8 x ID"10
1 x 10"8
3 x 10"4
2 x 10"4
EPA Proposed
Maximum
Acceptable
Concentration
For Livestock
mg/1
2 X 10"1
5 X 10"2
1
• •» w
1 X 10"1
25
Standard
As Critical
Concentration
In Potable
Water
mg/1
1 X 10"2
1 X 10"2
2 X 10~2
5 X 10"2
1 X 10"2
5 X 10"2
00
en
Based on average soil particulate runoff rate of 1000 mg/1 of runoff water, and soluble endogenous
concentration of metals in soils (15).
'''Based on increase in trace element concentration (Table 5-7) and solubility of elements (Table 5-8).
*Based on average soil particle runoff rate of 1000 mg/1 of runoff water, and increased soluble
metals concentration in soil after 40 years.
-------
cause negligible impact on vegetation (4, 18). The maximum levels of NO
A
and SOp expected to occur in the vicinity of utility boilers are near or
exceed the threshold injury values for these pollutants. Sensitive plants
in the vicinity of the utility boiler could suffer injury, although such
injury would be limited to a downwind sector a few miles from the plant.
The secondary pollutants (ozone and peroxyacytylnitrates} formed by
reaction of hydrocarbons and nitrogen oxides are considerably more toxic
than either of the precursors alone. The formation of secondary compounds
in boiler stack plumes and the impact of the boiler nitrogen oxides emis-
sions on urban photochemical smog depend on complex relationships which are
not yet totally understood. Therefore, it is not possible to reliably
estimate the effect of NO emissions levels on levels of photochemical
A
compounds. However, based on typical regional emissions figures, it appears
that emissions from power plant fuel combustion provide a significant source
of the regional emissions of NOX necessary for photochemical smog. Approxi-
mately 28% of the nation's NO emissions are produced by combustion in
A
power plants (19).
If NOY emissions from utility boilers are a significant contributor to
/v
photochemical smog, then there is valid concern that boiler emissions may
contribute to plant injury. The effects of photochemical air pollution on
plant life have been observed frequently at various different severities
throughout the United States. In addition, the effect of the major consti-
tuents of photochemical smog (products of nitrogen oxides and organic com-
pounds) on plants has been investigated separately. The pigmentation of
small areas of palisade cells is characteristic of ozone injury, and a
bronzing of the undersurface of leaves is typical for peroxyacytylnitrate
injury. Table 5-11 illustrates the relatively low levels of ozone which
will produce significant plant injury to crops. The concentrations shown
are typical of many areas experiencing photochemical air pollution, and
suggest the necessity for concern over sources emitting high levels of NOX.
Nitrogen oxides may also cause injury to vegetation by direct contact.
The significant oxides of nitrogen are NO and NOg. The major oxide in com-
bustion emissions is NO. However, after residence in the atmosphere, NO is
86
-------
TABLE 5-11. PROJECTED OZONE CONCENTRATIONS WHICH WILL PRODUCE, FOR
SHORT TERM EXPOSURES, 20 PERCENT INJURY TO ECONOMICALLY
IMPORTANT VEGETATION GROWN UNDER SENSITIVE CONDITIONS*
Concentrations
Time, Hr
0.2
0.5
1.0
2.0
4.0
8.0
producing injury
Sensitive
0.40-0.90
0.20-0.40
0.15-0.30
0.10-0.25
0.07-0.20
0.05-0.15
in three types
Intermediate
0.80-1.10
0.35-0.70
0.25-0.55
0.20-0.45
0.15-0.40
0.10-0.35
of plants, ppm
Resistant
1.00 and up
0.60 and up
0.50 and up
0.40 and up
0.35 and up
0.30 and up
*
Reference 20.
converted to N02 by photolysis and by photochemical interaction with hydro-
carbons. The effect of N0£ on plant life has been studied under controlled
laboratory conditions. Acute injury is characterized by collapse of cells
and subsequent development of necrotic patterns. Chronic injury, caused by
exposure to low concentrations over long periods, is characterized by
chlorotic or other pigmented patterns in leaf tissue. Such injury results
in reduction of growth and reproduction. Only limited data are available
to characterize the effect of NO on plants. Generally, it appears that NO
leads to effects somewhat similar to those observed for N02, but at slight-
ly higher threshold concentrations. Therefore, for worst case evaluations
of the impact of ambient NOX levels, it is assumed that NOX exists as N0£,
and that the NOX levels are not depleted by the photochemical reactions
which typically occur in urban areas.
Figure 5-3 illustrates the threshold concentrations at which various
degrees of damage result from exposure to N02- Based on the expected con-
centration of NOX in the vicinity of the coal-fired utility boiler, and
the assumption it is converted entirely to N02, it appears that acute leaf
damage may be anticipated to occur as a result of short term plume trapping.
87
-------
0.01
0.1
DAYS
1.0
1000
ex
a.
o
z
u.
o
100
3 1.0
0.1
10
100.
THRESHOLD FOR FOLIAR LESIONS -
0.1
METABOLIC AND GROWTH EFFECTS
•i
10
i
fcr
HOOO
CO
E
cv;
o
4-10
r-1.0
1000
10.000
DURATION OF EXPOSURE (HOURS)
Figure 5-3. NOg threshold concentrations for various
degrees of plant injury (21).
Chronic effects, including growth and yield reductions, may also be noticed
over the long term. However, the extent of the damages would be localized
within a few miles of the boiler, and would be expected to occur to those
plants most sensitive to NO, injury (i.e., cotton, navel orange, spinach,
etc.).
88
-------
Acute short term injury to vegetation by S02 exposure is characterized
by damaged leaf areas which first appear as water soaked spots, and later
appear as bleached white areas or darkened reddish areas. Chronic S(L injury
is usually characterized by chlorosis (yellowing) which develops from lower
concentrations over extended periods of time. Either acute or chronic S02
injury may result in death or reduced yield of the plant if the extent of
the damaged tissue exceeds 5 to 30 percent of the total amount of foliage.
The impact of the expected SOg concentrations varies with the plant
species. Threshold injury in sensitive plants may be caused by short term
o
S02 levels as low as 30 yg/m (22). Table 5-12 summarizes the broad cate-
gories of sensitivity for different plants. Grain, vegetable, pasture, and
forage crops are susceptible to SOg damage for most of the growing season.
These crops may suffer yield reductions in areas where power plants such as
that of the present study are located, although the damage would be relati-
vely localized. Data presented in Figure 5-4 indicate that peak SOg
concentrations expected to occur near the coal-fired boiler may possibly
cause leaf damage to occur in the more sensitive plant species.
It should be noted that the plant damage thresholds illustrated by
Figure 5-4 apply to conditions of temperature, humidity, soil moisture,
light intensity, nutrient supply, and plant age which cause maximum sus-
ceptibility to injury. The occurrence of such conditions are rare. In
tact, in the unlikely event that all such conditions are met, the dose-
response curves indicate that plant injury could occur without a violation
of the federal air quality standard for the 3 hour or 24 hour concentration
of SOg. Additional susceptibility may also result from synergistic effects
of sulfur dioxide and other pollutants. Particularly relevent to the urban
environment are combinations of sulfur dioxide and ozone. Moderate to
severe injury of tobacco plants have been observed for four hour exposures
to concentrations of 0.1 ppm (262 yg/rn^) S02 in combination with 0.03 ppm
ozone. Because high ozone levels are a frequent problem in the vicinity
of urban areas, susceptibility to plant injury by S02 pollution is greater
when utility boilers are also sited in urban areas. One of the major con-
cerns associated with fossil fuel utilization is acid precipitation result-
ing from wet deposition of suspended sulfur and nitrate compounds. Data
89
-------
TABLE 5-12. SENSITIVITY OF COMMON PLANTS TO
INJURY
r - -
Sensitive
i l.'riilc pine
Gclder.rcd
Cntlor-tfOOd
Viroir.ia creeper
.V.'.or
i Sosscberry
Elr-
Wild grcpe
Arericd'i eln
Wnite ash
i Virginia pine
I Tulip tree
Vecetetion
Jntcrr.;c-tliate Rcsistarit
Kaple Sugar maple
Virt|inia creeper Phlox '
KM to oak fok
Elm fe pic-
Short leaf pine Shrubby willow
Aster
Linden
* "
Crops
Sensitive
Alfalfa
Bsrlpy
Oats
Rye
Ki,e?.t
Sweet potato
Soybean
Sweet clever
Cotton Tobacco
Clover
JnterneJiatc Resistant
Irish Potato Corn
Clover .Sorjhysi
Sweet clover
Reference 23.
SO, DOSE-INJURY CURVES
FOR SENSITIVE PLANT SPECIES
DAMAGE LIKELY
INJURY OR DAMAGE
POSSIBLE
(THRESHOLD RANGE!
2 345 6
DURATION OF EXPOSURE. l»»
Figure 5-4. S02 dose-injury curves for sensitive
plant species (22).
90
-------
show that there has been an intensification of acidity in the northeastern
region of the U.S. since the mid 1950's. Precipitation in a large portion
of the eastern U.S. averages between pH 4.0 and 4.2 annually. Values
between pH 2.1 and 3.6 have been measured for individual storms at distances
several hundred miles downwind of urban centers. The areas experiencing
highest acidity are typically downwind of the areas where sulfur emissions
are highest (17, 21).
Acid rain affects plant life in varying degrees depending on the pH
and-the type of plant species. Experiments show that the effects on plants
may include reduction in growth or yield, leaf damage, death, and chlorosis.
Acid rain also has been shown to affect aquatic organisms, and it is be-
lieved that thousands of lakes are now experiencing reductions in fish
population due to acidification between pH 5.0 and 6.0 (21).
The impact of fossil fuel combustion in controlled utility boilers on
acid precipitation and plant damage is potentially significant. In the
previous discussion, it was estimated that controlled coal-fired boilers
3
could account for a level of 11.0 u9/m suspended sulfate in the central
region of the U.S. This level is approximately equivalent to ambient
sulfate concentrations associated with areas experiencing significant acid
precipitation. Typical ambient sulfate levels prevalent in the U.S. are
shown in Figure 5-5 .
Vegetation may also sustain injury from elevated levels of trace
elements. As shown previously (Table 5-9), concentrations of cadmium in
vegetation near coal-fired utility boilers may exceed levels observed to
be toxic in plants. The effects of cadmium toxicity in plants are wilting,
chlorosis, necrosis, and reduction of growth. Substantial declines in
yield of the soybean, wheat and lettuce have been observed when the tissue
concentration of cadmium in foliar parts of these species was as low as
7, 3, and 11.5 mg/kg, respectively. Based on tests of the utility boiler
of this study, it appears that emissions from coal firing may result in
high cadmium plant burdens and potential plant injury.
91
-------
(A) Urban Levels
<-v*- •
{::-.:;::-' b.O --6.
tiol^Cu
? 7.0 - 8.9M/mJ
(B) Rurc-,1 Levels
Figure 5-5. Geographical distribution of typical sulfate
levels in the United States (23).
92
-------
Effect of Solid Wastes
A major environmental concern involving the use of fossil fuels is the
generation of coal ash and flue gas desulfurization (FGD) sludges. The
quantity of such wastes depends on the proportion of coal utilization and
the amount of S02 removed from stack gases. It has been estimated that by
1985 coal ash will be generated at a rate of 83 Tg/y and FGD sludges at a
rate of 30 Tg/y (dry basis). Landfill is the common means of disposal for
these wastes. By 1980, it is estimated that 2000 to 3000 m2 of land per MW
of boiler capacity will be required for disposal purposes (24). The compo-
sition of the wastes will depend on the fuel source, the boiler design, and
the flue gas desulfurization system. Most FGD processes generate a waste
sludge consisting predominantly of calcium sulfite and sulfate. Various
trace elements are also found in the FGD sludge. The trace elements originate
from reagents used in SO removal, from process water, from trace elements
yv
in the combusted coal, and from fly ash which is collected by the FGD system.
Fly ash and bottom ash usually consist of about 80 percent silica, alumina,
iron oxide, and lime. The composition of trace elements found in bottom
and fly ash is similar.
Based on tests of the coal-fired boiler, the rate of generation of
solid waste from a 874 MW coal-fired boiler would be 0.11 Gg/hr of bottom
slag/fly ash and 0.13 Gg/hr of scrubber sludge from the FGD operator.
The concentrations of trace elements in the combined fly ash/bottom
slag and in the scrubber sludge are shown in Table 5-13 and 5-14. For
almost all elements, the concentrations far exceed both the health and
ecological DMEG values for both solids. The waste is considered hazardous,
creating difficult waste disposal problems.
FGD scrubber wastes and coal ash are usually disposed in impoundment
ponds or landfills. The major concern in either disposal approach is the
release of trace elements to ecosystems in localized areas surrounding the
disposal sites. Lateral and upward movement of trace elements through the
soil to plant rooting zones may be possible, and contamination of ground
and surface waters may occur. Additional adverse consequences include the
diversion of land from other uses, and aesthetic degradation at the dis-
posal site.
93
-------
TABLE 5-13. TRACE ELEMENT CONTENT OF FLY ASH AND
BOTTOM SLAG FROM COAL FIRING
El ement
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Ni
Pb
Sb
Sr
V
Zn
Concentration
mg/kg
82,000
11
8.2
66,000
1.2
44
210
820
170,000
< 1
*
ND
700
330
160
7%0
280
86
1,500
DM EG value
Health
16,000
50
6
48,000
10
150
50
1,000
300
2
18,000
50
45
50
1,500
9,200
500
500
, mg/kg
Ecology
200
10
11
3,200
0.2
50
50
10
50
50
17,400
20
2
10
40
NDf
30
20
Discharge
Health
5.1
0.21
1
1.4
0.12
0.29
4.2
0.82
580
< 0.5
14
7.3
3.2
0.0047
0.03
0.17
3.0
Severity
Ecology
410
1.1
0.75
21
6
0.88
4.2
82
3,500
< 0.02
35
200
16
0.17
2.9
75
Level 2 procedures were utilized.
f ND - data not available.
94
-------
TABLE 5-14. TRACE ELEMENT CONTENT OF SCRUBBER DISCHARGE
SOLIDS FROM COAL FIRING
El ement
Al
As
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Ni
Pb
Sb
Sr
V
Zn
Concentration
mg/kg
24,000
110
2.5
51 ,000
36
22
52
190
50,000
< 1.0
0.49
560
96
1,100
38
990
190
6,500
DMEG value
Health
16,000
50
6
48,000
10
150
50
1,000
300
2
18,000
50
45
50
1,500
9,200
500
500
, mg/kg
Ecology
200
10
11
3,200
0.2
50
50
10
50
50
17,400
20
2
10
40
NDf
30
20
Discharge
Health
1.5
2.2
1
1.1
3.6
0.15
1.0
0.19
170
< 0.5
0.000027
11
2.1
22
0.025
0.11
0.38
13
Severity
Ecology
120
11
0.22
16
200
0.44
1.0
19
1,000
< 0.02
0.000028
28
5
110
0.95
6.3
320
Level 2 procedures were utilized.
ND - data not available.
95
-------
Because of the limited experience concerning land disposal of wastes,
and the long time lags preceding future potential adverse impacts, there
is significant uncertainty regarding the level of restrict!"veness necessary
to assure the environmental adequacy of various land disposal methods.
Because of such uncertainty, it seems likely that stringent waste disposal
regulations will be proposed to prevent the migration of waste sludges
in the terrestrial environment and the movement of leachate to
underground water sources.
Disposal of FGD sludges and coal ash is already subject to regulations
at the state level. Recent federal legislation (the Resource Conservation
and Recovery Act) now requires that criteria be developed to classify wastes
and suitable disposal management techniques. Under the proposed criteria
it is plausible that FGD sludges and coal ash may be classified as
hazardous waste, and that disposal of these wastes will be restricted by
the stringent requirements now being proposed for hazardous waste
management facilities. Typically, these requirements would restrict
the land disposal of hazardous wastes to "secure landfills" de-
signed to provide protection for all-time of the quality of ground and
surface waters. By definition, the secure landfill would prevent signifi-
cant adverse impact to certain environmental sectors (i.e., public health
and ecology). Unfortunately, the secure landfill, is, by definition, an
ideal design which cannot be attained except at very great cost. There is,
therefore, a need to define reasonably attainable land disposal designs
which offer a high level of environmental protection.
Various recent efforts have been conducted to define appropriate land-
fill criteria. In one pertinent study (25), the effectiveness of three
scenario landfill designs for the disposal of FGD scrubber cake were
evaluated. The scrubber cake considered is that generated by the Double
Alkali FGD system utilized at the reference industrial boiler of this study.
Migration of leachate to the groundwater and the loading rate of dissolved
solids into the groundwater were estimated by considering the permeability
of the landfill layers and the solubility of solids as determined from
laboratory tests. Table 5-15 summarizes the analysis of the three landfill
cases. As indicated, permeability of the soils and the scrubber waste is
96
-------
TABLE 5-15. LEACHING RATES FOR THREE LANDFILL DESIGNS
Case
I
II
III
h
(m)
5.5
5.5
6.1
L2
(m)
0.6
0.6
0.3
L3
(m)
3.0
3.0
3.0
Kl
(m/sec)
10'7
io~7
io-7
K2
(m/sec)
ID'10
ID'8
ID'11
K3
(m/sec)
ID'6
io-10
io-6
Keff
(m/sec)
7.7 x 10"8
1.5 x 10'10
3.0 x 10"10
t
(years)
1
200
100
12
(years)
20
6000
3000
Q
(kg/m2/yr)
5.08
0.016
0.032
Liner or
Cor;;p;r.cted
Filter Cake
Double
Alkali
Filter Cake
f •.'•' . ', v . '.' • :' .'•'• ' .';'•! ' '•'. '• '.'• •'.
} Soil
VI
• ' 't
7>
L2
*
A ( Ground
(Water
Table
L, = Depth of uncompacted filter cake (m)
L- = Depth of compacted filter cake or liner (Case III) (m)
1-2 = Depth of soil (m)
Kl' K2' K3 = Coeff''cients of permeability of layers 1, 2, and 3, respectively
(m/sec)
Effective permeability of overall filter cake plus soil layers (m/sec)
Time for migration of leachate to groundwater table (years)
Time for washout of major dissolved solids from filter cake (years)
o
Loading rate of total dissolved solids to groundwater (kg/m /yr)
97
-------
the primary factor in initiating leachate migration. In the first case,
all net precipitation becomes leachate, and the time to reach groundwater
is about one year while the time to wash out the major portion of the
soluble solids is about 20 years. The overall washout rate of soluble
2
solids during the 20 year period is calculated to be 5.08 kg/m /yr. Con-
tamination of groundwater sources over significant landfill areas at this
washout rate is clearly unacceptable. In the second and third cases, 200
and 100 years elapse before leachate reaches groundwater, and leaching of
—2 2
soluble substances occurs at the low loading rate of 1.6 x 10 kg/m /yr
2 2
and 3.2 x 10 fc kg/m /yr, respectively. The time for total washout of all
soluble solids would be 6000 and 3000 years, respectively. The extent of
impact of such a leaching rate would depend on the size of the landfill
and the flow of the underground aquifer. For example, for case II, a 1
acre landfill over a small underground water source flowing at one million
gallons per year would cause an increase of 2 ppm in the dissolved solids
content of the underground water. Most of the 2 ppm increase would be
composed of lime and sodium sulfate and sulfite salts. As indicated by
Tables 5-13 and 5-14 trace element would comprise a small fraction of the
incremental increase, and considering the low solubility of the trace
elements, their concentration in the underground water would be at least
three orders of magnitude less than the lime, sulfate, and sulfite con-
centrations, and well below the standard for potable water (see Table 5-10).
The rate of leaching can be minimized still further by mixing bentonite
with a layer of soil to provide a layer over the filter cake after it has
been landfilled to the desired level. The bentonite soil mixture achieves
a low permeability of 10"11 m/sec. By contrast, the permeability of silty
clay and permeable soils is about 10"10 m/sec, and 10" m/sec, respective-
ly. The permeability of the double alkali scrubber cake is 10" m/sec,
whereas it is about 10"6 m/sec for lime/limestone type scrubber sludges.
Estimated leaching rates can be confirmed by tracking the migration
of leachate in the landfill. In one experimental landfill used for dis-
posal of FGD scrubber wastes (25), and which contains no seal or barrier
other than the native clay silt (permeability of 10 m/sec), tests show
that no leachate has migrated as far as six inches below the disposal layer
after the first year of operation. The results and analyses indicate that
98
-------
landfills of untreated scrubber cake can be constructed such that signifi-
cant adverse impacts will not occur. Moreover, it is conceivable that a
completed landfill can be reclaimed for use as a park or farmland, provided
a sufficient soil cover is applied and care is exercised not to disrupt
the stabilized waste or to permit its migration entry into the terrestrial
environment.
The environmental concerns associated with the wastewater holding and
settling ponds for the fly ash/bottom slag and scrubber sludges are similar
to those of the landfill operation. Leaching of water soluble constituents
of the wastewater into the underlying soil, and into the groundwater, can
occur. In one study (26) of the Teachability of trace elements from ash
and scrubber sludge settling ponds, samples of leachate from five different
coal-fired generating stations were found to contain concentrations of
trace elements exceeding proposed EPA standards for Public Water Supply
Intake. The rate of leakage is affected by the type of element, soil type,
and depth of water table. To prevent leakage, settling ponds are often
lined with impervious material. As with landfills, evidence has shown that
the absorption capacity of impervious soils can reduce concentrations of
elements in the leachate before reaching the water table (26). With pro-
per design of the settling ponds, it is expected that the impact of leach-
ing can be minimized to an insignificant degree. It is expected that such
designs will become mandatory under rules established by the authority of
the Resource Conservation and Recovery Act.
ECONOMIC IMPACT
The direct economic impacts associated with residuals of fuel combus-
tion involve the costs of damages (or benefits) sustained when the residuals
enter the environment. Second order economic impacts associated with the
residuals involve the alterations that occur in employment, the tax base,
energy prices, income, and land values due to the damages (or benefits)
resulting from combustion residuals. The quantification of direct economic
impacts involves the difficult task of ascribing economic values to environ-
mental changes. Quantification of second order economic effects are yet
more difficult because of gaps in knowledge which make it impossible to
determine the complex relationships between cost and the numerous socio-
economic factors involved.
99
-------
A number of ongoing energy related studies are attempting to develop
sophisticated economic models which will predict the cost of environmental
damages (6, 23, 27). The models address the cost of visibility reduction,
health effects (morbidity and mortality), and certain second order effects.
Utilization of the models requires substantial input data involving regional
demography and emission source distributions. The models require further
refinement and are currently under continuing development. The data base
or scope of the present program did not permit the adaption and utilization
of such models.
The extent of the economic impacts resulting from residuals of coal-
fired utility boilers is proportional to the extent of the environmental
damages which occur. The analyses have shown that the impact of emissions
from coal-fired boilers tested in this study is substantial. Ambient con-
centrations of gaseous pollutants and trace elements are estimated to be
significant in the vicinity of the model coal-fired boiler. In fact, based
on the worst case circumstances assumed for the analysis of maximum ambient
concentrations, federal ambient air quality standards for sulfur oxides may
be violated in the vicinity of the plant. Trace element concentrations in
soils (i.e., especially cadmium) near coal-fired boilers may result in
toxic accumulation of these elements in plants. Localized crop damage will
be significant, and additional land requirements will be required at coal-
fired plants for disposal of wastes. The cost of these impacts will be
significant in the affected areas. Higher medical costs and loss of
productivity will be experienced in the area of coal firing. Annual cost of
cleanup and maintenance for soiling damages will be greater in the affected
areas, revenue for crop sales will be reduced somewhat, and esthetic blight
in the area of landfills will diminish the value of land and activities
nearby.
Whatever the extent to which additional controls may be required for
coal-fired boilers, the comparative cost of such controls will probably be
significant compared to the overall operating cost of a boiler and other
factors affecting the overall costs. Control of NOX emissions from cyclone-
fired units would probably require either thermal decomposition or catalytic
reduction; the cost of these technologies is rather uncertain at this time.
100
-------
Costs of NO control for these units may be on the order of those for SO
/v " y\
control. Even when predicted pollutant loadings meet environmental standards,
it is not entirely clear whether the increasing use of fossil fuels may be
continued at the forecasted levels of control technology without potential
long term environmental damages. If it is found that long term effects of
pollution (e.g., trace metals accumulation, lake acidity, land use) are
unacceptable, then more stringent environmental regulations can be expected,
and it is clear that energy costs will increase with increasing control
requirements.
101
-------
REFERENCES
1. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Sulfur Oxides. AP-50. March 1967.
2. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Nitrogen Oxides. January 1971.
3. U.S. Department of Health, Education and Welfare. Air Quality Criteria
for Particulate Matter. January 1969.
4. U.S. Department of Health, Education and Welfare. Air Quality Criteria
for Carbon Monoxide. March 1970,
5. Waldbott, G. Health Effects of Environmental Pollutants. 1973.
6. Lundy, R.T. and D. Grahn. Argonne National Laboratory. Predictions
of the Effects of Energy Production on Human Health, a paper presented
at the Joint Statistical Meetings of the American Statistical Associa-
tion Biometric Society, Chicago, Illinois. August 1977.
7. Finch, S. and S. Morris. Brookhaven National Laboratory. Consistency
of Reported Health Effects of Air Pollution, BNL-21808.
8. Shin, C. Application of a Langrangian Statistical Trajectory Model to
the Simulation of Sulfur Pollution over North Eastern United States.
Preprints of Third Symposium on Atmospheric Turbulence, Diffusion, and
Air Quality. 1976.
9. Nelson, W., Knelson, J,, Hasselblad, V. Health Effects Research
Laboratory of Environmental Protection Agency. Air Pollutant Health
Effects Estimation Model, EPA Conference on Environmental Modeling
and Simulation. Cincinnati. April 1976.
10. Effects of Trace Contaminants from Coal Combustion. Proceedings of a
Workshop Sponsored by Division of Biomedical and Environmental Research
and Development Administration. August 1976. Knoxville, Tennessee.
11. Sullivan, R.J. Litton Systems, Inc. Air Pollution Aspects of Iron
and Its Compounds. U.S. Department of Commerce/National Bureau of
Standards. September 1969.
12. Athanassiadis, Y.C. Litton Systems.. Inc. Air Pollution Aspects of
Zinc and Its Compounds, U.S. Department of Commerce/National Bureau
of Standards. September 1969.
102
-------
13. Draft of proposed rules for "Standards Applicable to Owners and
Operators of Hazardous Waste Treatment, Storage and Disposal
Facilities," obtained from Office of Solid Waste, Environmental
Protection Agency. March 1978.
14. Sehmel, G. Battelle Pacific Northwest Laboratories, Pacific Northwest
Laboratory Annual Report for 1972, BNWL-1751, Vol. II. 1973.
15. Vaughan, B., et al. Battelle Pacific Northwest Laboratories, Review
of Potential Impact on Health and Environmental Quality from Metals
Entering the Environment as a Result of Coal Utilization. August
1975.
16. Berry, W. and A. Wallace. Trace Elements in the Environment - Their
Role and Potential Toxicity as Related to Fossil Fuels, University of
California Laboratory of Nuclear Medicine and Radiological Biology.
1974.
17. Argonne National Laboratory, Assessment of the Health and Environmen-
tal Effects of Power Generation in the Midwest, Vol. II Ecological
Effects. April 1977.
18. Department of Health Education and Welfare, Air Quality Criteria for
Hydrocarbons. March 1970.
19. U.S. Environmental Protection Agency, 1975 National Emissions Report.
May 1978.
20. Department of Health, Education and Welfare, Air Quality Criteria for
Photochemical Oxidants. March 1970.
21. Glass, N. Office of Health and Ecological Effects, Ecological Effects
of Gaseous Emissions from Coal Combustion. November 1977.
22. Argonne National Laboratory, The Environmental Effects of Using Coal
for Generating Electricity, prepared for Nuclear Regulatory Commis-
sion, Washington, D.C. May 1977.
23. Argonne National Laboratory, A Preliminary Assessment of the Health
and Environmental Effects of Coal Utilization in the Midwest. January
1977.
24. Environmental Protection Agency, Office of Research and Development,
Office of Energy Minerals and Industry, Health and Environmental
Impacts of Increased Generation of Coal Ash and FGD Sludges, Report
to the Committee on Health and Ecological Effects of Increased Coal
Utilization. November 1977.
25. Krizek, R. and J. Fitzpatric. Northwestern University, Double Alkali
Landfill Tests Evaluation, Technical Report 120. April 1976.
103
-------
26. Holland, W.F. Environmental Effects of Trace Elements from Ponded Ash
and Scrubber Sludge, Report 202, Electric Power Research Institute,
Palo Alto, California. 1975.
27. Ford, A. and H.W. Lorber. Los Alamos Scientific Laboratory,
Methodology for the Analysis of the Impacts of Electric Power Pro-
duction in the West. January 1977.
28. Argonne National Laboratory, Environmental Control Implications of
Generating Electric Power from Coal, Technology Status Report
Volume I, Coal Utilization Program. December 1976.
29. Science and Public Policy Program, University of Oklahoma, Energy
Alternatives: A Comparative Analysis. May 1975.
104
-------
APPENDIX A
SIMPLIFIED AIR QUALITY MODEL
Simple ambient air quality models were used to estimate the maximum
expected ground level concentrations of criteria pollutants. It is impor-
tant to recognize that these air quality values are estimates only, based
upon simplifying assumptions, as discussed below. Two sets of meteoro-
logical conditions were considered: worst case and typical. Conditions
were selected that are representative of what could reasonably be expected
to occur almost anywhere in the country but are not specific to the area of
the plant from which the pollutant emission rates were obtained. It was
assumed that all species were inert. No photochemical reactions were
considered.
There are several meteorological conditions which can produce high
ground level pollutant concentrations. These conditions can result in plume
coning, looping, fumigation, and trapping, all of which can cause high
ambient concentrations. In the case of coning, high levels occur along the
plume centerline. Looping causes high ground level concentrations at points
where the plume impacts the ground. Fumigation causes high ground level
concentrations which are generally lower than those from plume trapping.
For this study it was assumed that plume trapping constituted the worst
case in terms of ground level concentrations.
Trapping conditions occur when an inversion layer or stable air aloft
inhibits upward dispersion of the plume. Although the plume is trapped by
the capping stable layer at height L, the plume distribution is still
Gaussian in the horizontal and uniform in the vertical directions. Ambient
concentrations can be estimated by the following equation (1):
105
-------
E
-l |_
P -i/2 + exp -1/2
N-l "z
exp -1/2 + exp
°z °z
Where: X (x,y,z;H) = Concentration at point (x,y,z) assuming an
effective stack height of H, yg/m3
H - Effective stack height, m
Q = Pollutant emission rate, kg/hr
y = Mean wind speed, m/s
a = Concentration distribution within the plume
in the horizontal (oy) and vertical (oz)
directions, m
z = Height above the ground, m
J = Maximum wind speed class index, unitless
N = Wind speed class index, unitless
L = Height of the stable layer, m
At ground level (z = 0) and at the plume center line (y = 0)
Equation (1) reduces to:
- zf]+
(2)
/ U OWI I «- I I
+ exp -1/2|
For typical conditions, ground level concentrations were calculated
using a Gaussian solution to the convective diffusion equation (2):
X (x,y,o) = ^-fy- exp - {(H2/2az2) + (y2/2ay2)| (3)
106
-------
3
where X = Concentration, g/m
Q = Pollutant release rate, g/s
a ,o = Crosswlnd and vertical plume standard deviations, m
£s = Mean wind speed, m/s
H = Effective stack height, m
x,y = Downwind and crosswind distances, m
At the plume center! ine, Equation (3) reduces to:
* (x....) - "P ' - M)
The maximum value of this equation occurs at the distance where
In Equations (3) and (4!), H is defined by:
H = HS + AH (5)
Where H = physical height of the stack and H = plume rise, both expressed
in meters. There are more than 30 plume-rise formulas in the literature.
All of which require empirical determination, of one or more constants. For
the purpose of this study, the Briggs plume rise formula was chosen to cal-
culate the final plume rise in stable conditions,
1/3
AH-2.6f-f-\ (6)
Where: AH = Plume rise, m
y = Wind speed, m/s
s = Stability parameter, unitless
F = Buoyancy flux.
The stability parameter, s, is defined as:
S=*- (7)
* 0 9z V '
-------
atmosphere of -0.0065 K/m, a value of ,0033 K/m was
80
employed for -r— in this study.
oZ
The buoyancy flux, F, is defined as:
F=flgwr2 (8)
s
Where AT = Stack temperature minus the ambient air temperature, K
Ts = Stack temperature, K
g = Gravitational constant, m/s2
w = Stack exit velocity, m/s
r = Inside radius of the stack, m.
The plume rise was calculated using Equation (6), The data used for
the calculations are shown in Table A-l. The values selected for wind speed
are discussed below.
TABLE A-l. STACK PARAMETERS AND PLUME RISE
Stack temperature, K 463
Ambient temperature, K 293
Stack exit velocity, m/s 33
Stack area, irr 41
Stack height, m 213
Equation (2) was used to estimate maximum ambient concentrations result-
ing from short term meteorological conditions causing plume trapping. As a
worst case estimate for this study, plume trapping conditions were assumed to
persist for periods as long as three hours. Equation (4) was used to
estimate maximum ambient concentrations for conditions which could
typically persist over a 24 hour period. For the 24 hour concentration
forecasts, typical conditions of wind speed (4 m/sec) and atmosphere sta-
bility (Class D stability) were assumed to persist. For the short-term
plume trapping, conditions of low wind speed (1 m/sec) and a moderately
108
-------
unstable atmosphere (Class B stability) were assumed to persist throughout
the applicable averaging period. These conditions were selected because
they produce high ground level concentrations. The inversion inducing plume
trapping was assumed to be at an elevation equivalent to the effective
stack height (817 m). Results of these calculations are presented in
Table A-2.
TABLE A-2. PREDICTED MAXIMUM AMBIENT CONCENTRATIONS
OF CRITERIA POLLUTANTS
Pollutant
Pollutant Concentration,
•]ig/rt|3
24 hour period:
NOX
CO
S02
Particulates
Total organics
Plume trapping:
NOX
CO
S02
Particulates
Total organics
46
<34
48
5
0.2
2800
<2100
2900
310
10
109
-------
REFERENCES FOR APPENDIX A
1. Bierly, E. W., and E. W. Hewson. Some Restrictive Meteorological
Conditions to be Considered in the Design of Stacks, Journal Applied
Meteorology, 1,3, 383-390, 1962.
2. Slade, D. H. Meteorology and Atomic Energy, U. S. Atomic Energy
Commission, 1968.
110
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APPENDIX B
ORGANIC ANALYSES FROM COAL FIRING
Sample Preparation
For coal firing, samples were prepared for both phases (Level 1 and 2)
of organic analyses at the same time and aliquots were divided to meet the
requirements of each phase. Runs 133 and 134 were made using the SASS
train and were to supply all the organic samples. However, only 134 was
prepared and fully analyzed because this sampling was taken when the
facility was operating at a slightly higher percentage of capacity. The
full data assessment, therefore, has been generated only for run 134 and
is representative of organic emissions from this source.
The compound identification phase of this effort (Level 2) used gas
chromatography/mass spectrometry (GC/MS) as the only analytical technique.
Compounds of low volatility, high molecular weight or with a strong
affinity to those GC columns used would not have been identified. There-
fore, for this environmental assessment, closure with the Level 1 non-
volatile organics (> C^g) was not expected.
Samples were prepared using procedures detailed in Reference B-2 with
modifications whenever required to ensure Level 2 quality data would be
produced. The steps involved for each sample type are summarized below.
Water samples: Samples were taken on each of six sampling days at the
site. Ten t composites were prepared for each sample stream. Each compo-
site was extracted three times with a total of 450 ml of methylene chloride
at each of three pH levels. First the water was acidified to a pH of 2 with
HC1; then it was neutralized to pH 7; and finally, it was made basic to
pH 11 with NaOH.
XAD-2 module condensates: Each sample was extracted three times with
methylene chloride at each of three pH conditions: 2, 7, and 11. The volume
of methylene chloride used was 10 percent of the condensate volume.
Ill
-------
Solids (filters and loose participate): Each sample was extracted
with methylene chloride in a Soxhlet apparatus for 24 hours.
XAD-2 resins: Each sample was extracted in a Soxhlet apparatus for
24 hours with methylene chloride.
Slurries: The solids and liquids were separated by filtration and a
liquid composite was made for each stream to represent the total sampling
period of six days. The water composite was extracted three times with a
total of 450 ml of methylene chloride at each of three pH conditions. In
this case, the pH was first adjusted to 11, then the water acidified to
pH 7; and finally to pH 2. A portion of the solid composites was extracted
1n a Soxhlet apparatus for 24 hours with methylene chloride.
1 ml aliquots were taken of each methylene chloride extract for TCO
and GC/MS analyses. Then the solutions were concentrated to 10 ml in
Kuderna-Danish evaporators. Aliquots taken for analyses included 1 ml for
TCO and GC/MS and 1 ml for GRAV/IR. The flow diagram in Figure B-l shows
the sample handling and analysis procedures used.
Summary
Level 1 —
Table B-l is a complete overview of Level 1 data generated from the
SASS sampling, run 134, both into (IN) and out of (OUT) the scrubber. The
resultant Level 1 weight data are tabulated under "Level 1 Data Assess-
3 3
ment, 134 IN, yg/m and 134 OUT, yg/m ". These data have been compared to
the most toxic MEG compound for that Level 1 reporting point. The Level 1
reporting points are C1-C6, C7-C17 and LC1-LC7. The C1-C6 and C7-C17 cate-
gories are organized by boiling point ranges and the LC1-LC7 are organized
by column separation fractions. Table B-2 gives a general outline of
the Level 1 reporting points.
The results of this Level 1 assessment, by MEG categories and DMEG
concentrations are:
• The Level 1 reporting points which were identified for Level 2
based on the presence of low probability (not likely present
under these source conditions) MEG compounds were C3, C5, C6,
C9, CIO, LC5, and LC6.
112
-------
ORGANIC
RINSE OR
EXTRACT
DRY
1 ML ALIQUOT
SOLUTION
rBULK
TCO
GC/MS [
KUDERNA
DANISH
CONCENTRATION
^ 1 ML ALIQUOT
< 8 ML ALIQUOT 1 ML ALIQUOT^
IS THE
SAMPLE
ADEQUATELY
CHARACTERIZED
SPECIAL
ANALYSES
SPECIAL
ANALYSES
Figure B-1. Flow chart of sample handling and analysis procedures
113
-------
TABLE B-l. LEVEL 1 DATA ASSESSMENT
Level 1
SampHng
Point
CI-C6 Cl
C2
C3
C4
C5
C6
Total C1-C6
C7-C16 C7
CB
C9
CIO
Cll
•
C12
C13
C14
CIS
C16
Total C7-C16
134 In 134 Out
1.8x10? 1.2x10?,
< 6.5x10 (O ppm) < 6.5x10^
7 ")
< e.Sxlo'M ppm) < 6.5x10^
7.4x10? 6.5xlQ2
< 6.5x10' < 6.510*
< e.sxio2 < e.sxio2
Z.SxlO3 to 1.9xl03
5.2x10* to ,
4.5xlOJ
4.7xl02 2.3xl02
1.3x10 4.0x10
2.6xl02 1.9x10
S.OxlQ2 1.5x10
7.1x10 1.2x10
7,4
2.4
2.7x10 S.OxlO"1
4.2x10 7.1
•» •»
1.2xlOJ 3.3xlOJ
Most Toxic
MEG Compound
Methane
Acetylene
Ethylen*1mine
Ethylamtne
Acroleln
N,N-D1methy1-
hydrazlne
Tetramethyl
Lead
Malelc Add
N-N1troso-
dlflethylamlne
N-Nltroso-
dlethylamine
Hexachloro-
cyclohexane
2.4-D1chloro-
Hexachloro-
cyclo-
pentadlene
An1s1d1ne$
4-Amtnob1phenyl
Phthalates
DMEGj
3.2x10?
5.3X10"1
3.3xl02
1.8x10?
2.5xlO£
3.7x10
l.SxlO2
l.OxlO3
1.2
1.2x10
S.OxlO2
7.0xl03
l.lxlO2
S.OxlO2
4.5xlOJ
S.OxlO3
Probable
MEG Category
1. Aliphatic Hydro
1. Aliphatic Hydro
10. Amines
10. Amines
7. Aldehydes/
Ke tones
11. Azo Compounds
26. Organo-
MetalKcs
8. Carboxyltc
Acids
12. N1trosam1nes
12. N1trosam1nes
2. Halogens ted
Aliph.
Hydrocarbons
19. Halophenols
2. Halogenated
AHph.
Hydrocarbons
10. Amines
10. Anines
8. Carboxyllc
Adds and
Esters
Sample
DMEG
134 In 134 Out *»«"«nt Notes
'.< 1 « 1 Level2 not required -
« 1 « 1 Difference between IN
and OUT within SiA
accuracy.
< 2 < 2 Most Toxic MEG
compound Is reactive •
the nonresctlve com-
pound Is a factor of 10
higher
6.5x10?) Formaldehyde at
1.6x10 ). Level 2 required
< 1 « 1 Level 2 not required -
c 2.6 < 2.6 Difference with IN and OUT
within SiA accuracy.
Host toxic MEG Is reactive
and ratio Is within SiA
uncertainty - next most
toxic Is Methyl Iodine
at 8.5x10 . Level 2
required.
'20 < 20 Most toxic MEG Is
reactive - next most toxic
1s dlchloro-propenes at
1.1 xlO' Level I required.
Solvent contaminants were
Q B „ - the major cau« of these
concentrations.
10.0 33.0 Most toxic MEG Is
reactive - next most toxic
Is chloropyridine at
4.8xl03 - IN and OUT
within SSA uncertainty
22.0 1.5 Host toxic MEG Is
reactive - next most toxtc
1s trlbromomethane at
0.6 0.03 Level 2 not required.
« 1 « 1 Level 2 not required.
« 1 « 1 Level 2 not required.
"1 "1 Level 2 not required.
« 1 =< 1 Level 2 not required.
« 1 « 1 Level 2 not required
-------
TABLE B-l (Continued)
cn
Level 1
Sampling
Point
LC1-LC7 LCI
LC2
LC3
LC4
LC5
LC6
LC7
134 In
ug/m
1.6x10
6.3x10
2.4x10
2.4xl02
l.OxlO3
5.7xl02
3.1xl02
134 Out
ug/m
1.0x10
3.0
9.0
2.6x10
6.2xl02
Z.OxlO2
5.4x10
Host Toxic
MEG Compound
Tetraethyl Lead
PolychloHnated
Blphenyls
Benzo(a)pyrene
4-Nitrobiphenyl
n-Methyl-
n-n1trosoan1Hne
Perchloromethyl-
mereaptan
Pentachlorophenol
1-Amlnonaphthalene
DMEG
ug/m
l.OxlO2
S.OxlO2
2.1xlO-z
1.3xl03
1.3xl03
S.OxlO2
S.OxlO2
5.5x10?
Probable
MEG Category
26. Organometallics
16. Halogenated
21 . Fused Aromatic
Hydrocarbons
17. Aromatic Nltro
Compounds
12. N1trosam1nes
13. Mercaptans
19. Halophenols
10. Amines
Sample
DMEG
134 In 134 Out
« 1 « 1
1 1
l.lxlO3 4.3
1 1
0.77 0.5
0.71 0.25
0.62 0.11
0.56 0.1
Assessment Notes
Level 2 not required (IR
Identified aliphatic
hydrocarbons.)
Level 2 not required (IR
Identified aliphatic and
aromatic hydrocarbons)
POM screening necessary.
Level 2 required for POM
species.
Level 2 not required.
Most toxic compound
reactive - next most toxic
Dlnltrotoluene at 1.5xl03
- Level 2 required (IR
Identified hydrocarbons,
alcohols, esters and MEG.)
Level 2 required.
Level 2 required on
134 IN
TOTAL LC1-LC7 2.2xl03 9.2xl02
TOTAL LC2HC3+LC6 6.6x102 2.1xlOZ
-------
TABLE B-2. GENERAL LEVEL 1 REPORTING POINTS
General Level 1
Sample Classes
Level 1
Reporting Point
Inorganics
• SSMS data in yg/m for each element
3
t Hg, As, Sb data in yg/m
Organics
C1-C6 on site in yg/m for each
boiling point range
C7-C12 in yg/m for each boiling
point range
LC1-LC8 in yg/m3 for each MEG
category
LC Fraction
1
MEG Category Present
(Theoretically Predicted Compounds)
1. Aliphatic Hydrocarbons (HCs)
2. Halogenated Aliphatic HCs
2. Halogenated Aliphatic HCs
15. Benzene, Substituted Benzene HCs
16. Halogenated Aromatic HCs
21. Fused Aromatic HCs
22. Fused Nonalternate Polycylic HCs
15. Benzene, Substituted Benzene HCs
16. Halogenated Aromatic HCs
21. Fused Aromatic HCs
22. Fused Nonalternate Polycyclic HCs
23. Heterocyclic Nitrogen Compounds
116
-------
TABLE B-2 (Continued)
LC Fraction
MEG Category Present
3. Ethers
4. Halogenated Ethers
9. Nitriles
17. Aromatic Nitro Compounds
21. Fused Aromatic HCs
22. Fused Nonalternate Polycyclic HCs
23. Heterocyclic Nitrogen Compounds
25. Heterocyclic Sulfur Compounds
7. Aldehydes, Ketones
9. Nitriles
13. Mercaptans
17. Aromatic Nitro Compounds
18. Phenols
24. Heterocyclic Oxygen Compounds
5. Alcohols
7. Aldehydes, Ketones
8. Carboxylic Acids, Derivatives
9. Nitriles
10-. Amines
18. Phenols
19. Halophenols
117
-------
TABLE B-2 (Continued)
LC Fraction
MEG Category Present
18. Phenols
20. Nitrophenols
8. Carboxylic Acids, Derivatives
10. Amines
11. Azo Compounds, Hydrazine Derivatives
8*
8. Carboxylic Acids, Derivatives
14. Sulfuric Acid, Sulfoxides
Recent studies have shown that fraction 8 does not actually contain these
theoretically predicted categories. Sulfuric acid and sulfoxides may not
be removed from the samples by the original extraction process.
118
-------
• The Level 1 reporting points which were identified for Level 2 by
weight criteria only and did not have supportable infrared (IR) or
low resolution mass spectral (LRMS) data to indicate that toxic
species were present were LC5 and LC6.
• The Level 1 reporting point clearly requiring Level 2 analysis
based both on high probability and IR and LRMS were LC2 and LC3
for the Halogenated Aromatic Hydrocarbons and the Fused Aromatic
Hydrocarbons.
• For the C1-C7 species the Level 1 "IN" and "OUT" concentration
variations are within the sampling and analytical accuracy. For
reporting points CIO, Cll, C13, C15, C16, LC2, LC3, LC4 and LC7
the "OUT" concentrations are lower than the "IN" concentrations.
Even though In most cases the "IN" concentrations do not exceed a
DMEG criterion, the scrubber has reduced organic emissions.
Level 2—
Compounds identified and quantified have been organized on Table B-3
by Level 1 reporting points. This provides for some comparison with the
Level 1 data.
An important analytical decision which was made when conducting this
data evaluation was to remove from consideration and tabulation most of the
common background compounds, e.g., phthalate esters, silicones and freons.
Therefore, the data reported are adjusted for background variations except
when a good deal of uncertainty existed.
The Level 2 effort identified unusual background contributions: In the
C8 range, acetone condensation products; and 1n the LC2 and LC3 fractions,
resin contributions. These are clearly identified on Table B-3.
The Level 2 analytical phase therefore:
t Verified that in the C1-C6 range, with good closure to the Level 1
data, the compounds emitted were not the most toxic for these
reporting points. Those emitted did not exceed DMEG concentrations.
• Identified that the C8 and C9 species were condensation products
of the SASS rinse solvents and not source related.
t Identified those Fused Aromatic Hydrocarbons and Aromatic Hydro-
carbons required in LC2 and LC3 and those compounds identified as
source emissions did not exceed DMEG concentrations.
In general the organic emissions were low and compounds did not exceed
DMEG concentrations.
119
-------
TABLE B-3. LEVEL 2 DATA ASSESSMENT
Level 1
Sampling Point
Cl
C2
C3
C4
C5
134 In
Level 2 Compound Identified vg/m3
None
None
Dichlorofl uoromethane
Vinyl Chloride
None
Methyl ene Formate -
134 Out
ug/m3
1.3 x 102
8.0 x 10
1.0 x 102
C6
TOTAL C1-C6
C7
C8
C9
CIO
Cll
C12
C13
C14
CIS
C16
TOTAL C7-C16
Diethyl Ether
Carbon TetrachloHde
Tetrahydrofuran
Hethylmethacrylate
C7 Hydrocarbon
Unsaturated Hydrocarbon
Hydrocarbon
Toluene
Tr1chloroethylene
MethylIsobutyl Ketone
(Solvent Source)
3-Methylene-2-pentanone
(Solvent Source)
Trlmethylbenzene
1.1 x 10J
1.8 x 102
3 x 103
4.3 x 103
4.0 x 10
5.0 x 103
6.6 x 102
1.1 x 103
4.0 x 103
2.5 x 103
1.0 x 102
0.6
1.8 x 10'
1.0 x 103
1.5 x 103
4.0 x 10
5.0 x 102
4.0 x TO2
1.3 x
9.4 x 10£
120
-------
TABLE B-3 (Continued)
Level 1
Sampling Point
LCI
LC2
Level 2 Compound Identified
Phenyl (2.2.3-trlmethyl
134 In
ug/m3
2.0
134 Out
wg/m3
LC3
TOTAL Per LC3
LC5
LC6
TOTAL Per LC6
LC7
TOTAL LC2+LC3+LC6
cyclopentlUdene)
Methane
4(2-Butenyl}-l ,2-d1methyl-
benzene
Decahydronaphthalene
D1-tert-buty1naphthalene
DimethylIsopropylnaphthalene
Hexaroethylbiphenyl
Cyclohexylbenzene
Hexamethyl, hexahydrolndacene
Trimethylna phthalenylsllane
1,3-D1ethylbenzene
Cg Substituted Benzene
Dlhydronaphthalene
1,3,5-TH ethyl benzene
Cio Substituted Naphthalene
Cio Substituted Decahydro-
naphthalene
Methyl naphthalene (2 Isomers)
Anthracene or Phenanthrene
l-r-B1phenyl
9,10-D1hydropheiwnthrene or_
1-1'-Dlphenylethene
1,1-Bis (p-ethyl phenyl)-
ethane or tetramethyl-
blphenyl (three Isomers)
"Another" tetramethylblphenyl
2-phenylnaphtha1ene
Tetramethylbenzene
5-Methy1benz-c-acr1d1ne
2,6-D1methy1-2,5-heptad1on-4-one
Phthalates
Benzole Add
Aromatic Hydrocarbons
Butylacetate
2,6-PI perlden-d1one-4,4-
dlmethyl
Long Chain Acid; Methyl Ester
2,3-D1methy1decahydronaph-
thalene
Ethylbenzaldehyde
Dimethylbenzaldehyde
2,4-Dlmethylacetophenone
Trimethylcydohexenone
Nitric Acid Decylester
o-Methylbenzaldeoxlm* (C=N-OH)
Methyl Ester of Carboxyllc
Add
3.0 x 10'1
1.0 x lO"1
3.0 x 10']
3.0 x 10-'
6.0 x 10-]
3.0 x 10"'
3.0 x 10-1
1.0
2.0
1.0
3.0 x 10-2
3.0 x 10-1
6.0 x ID"2
1.0
1.6
3.0 x 10-1
4.0
,-1
2.0 x 10'
8.0
1.0
2.0 x TO"1
1.0 x 10
^
2.3 x 10
Not Quantltated
2.0 x 10
2.0 x 10-1
< 3.0 x 10-2
4.0
6.0 x 10-'
4.0 x 10
Not Quantltated
6.5 x 10
3.0 x 10
-1
< 3 x TO"2
Not Quantltated
3.0 x 10-1
3.0
6.0 x lO'1
1.0
3.0 x ID'1
8.0
3.0 x 10-1
8.3
121
-------
Level 1 Data
Total Chromatographable Organics Analysis--
The gas chromatographic analyses (6C-TCO) were performed using either
a Perkin-Elmer Sigma 1, a Varian 1860, or a Varian 5860 chromatograph with
differential flame ionization detectors. The operating parameters were as
fol1ows:
t Column-10 percent OV-101 on Supelcoport, 100/120 mesh,
0.32 X 183 cm stainless steel.
• Temperatures-detectors, 300°C; injectors, 200°C; column, begin
and hold at ambient for 5 min., then program temperature increase
from 30°C to 250°C at 15°C/min.
• Flowrates-column, 30 mi/min. He; detectors, 300 m«./min air and
30 ma/min H2-
• Electrometer-! X 10-10 A/mV
• Recorder- 1 mV full scale
• Injections-1 p£.
These conditions provide a lower detectable limit of 0.7 ng/y£ for
n-alkanes. This is equivalent to a hydrocarbon concentration of 2 X 10~4
mg/m3 in 30 rr>3 of sample gas (the quantity of gas required in these tests)
or 7 X 10-4 mg/£ in 10 i of a water sample.
The instrument is calibrated so that results can be expressed in terms
of the quantity of n-alkanes boiling in the temperature ranges shown in
Table B-4. Calibration of the GC requires synthetic mixtures of the appro-
priate n-alkanes be chromatographed. A plot of retention times versus
normal boiling points is then constructed, as illustrated in Figure B-2. The
retention time intervals corresponding to the boiling points of interest
are then determined graphically.
Quantisation of the peak areas on the chromatograms is based upon the
instrument response to n-decane. A thorough description of the calibration
1s given In Reference B-2. Data reduction and quantitation of chromatograms
obtained from the actual samples are done In two steps; First, all peak
areas observed within the overall retention time Interval of interest are
added together. The total concentration of chromatographable organic
122
-------
ro
oo
r
320
7flO
240
200
160
120
,
40
• t
i -
• I
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if"
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a
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il;
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15
i
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9
r
iii
rr<
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':.
I.
X^
i
- -
80
^
V
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••
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>
1
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^l
f?'
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tf?
0
9
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g
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c
50
i^
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ft
/
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<}
1C
: |
(j
^5
40
'
3
_
1
2C
1
20
3
;-|
i
1
Retention Time, Sec.
Figure B-2. Retention times versus boiling points for n-alkanes
-------
TABLE B-4. BOILING RANGES OF n-ALKANES
C7
C8
C9
C10
Cll
90-110°C
110-140°C
140-160°C
160-180°C
180-200°C
C12
C13
C14
C15
C16
200-220°C
220-240°C
240-260°C
260-280°C
280-300°C
material (TCO) In the sample Is determined by dividing the total peak area
by the sensitivity of n-decane and then multiplying by the appropriate
3
dilution sample volume factors. Whenever the TCO is greater than 75 wg/m ,
the concentration of all peaks in each n-alkane equivalent boiling range
fraction is determined. Peak areas are summed within each specific retention
Interval and the response factor for the corresponding n-alkane is used to
determine the weight of material eluted from the GC. As before, the total
amount of material in each sample is determined by multiplying the concen-
tration by the sample volume and the fraction of sample extracted.
All samples were analyzed both prior to and after the Kuderna-Danlsh
concentration step. The results of these Cj - C16 analyses are given in
Table B-5. (An explanation of sample codes is given in Table B-6.)
Gravimetry for C^y and Higher Hydrocarbons--
Gravimetric determinations were performed on the concentrates of sol-
vent rinses and extracts in accordance with the procedure in Reference B-2:
a one milliliter aliquot was taken from each sample and evaporated to dry-
ness in an aluminum pan. The residues were then weighed on a microbalance.
The results are presented in Table B-7.
Infrared Analyses (IR) on Samples Concentrated in Kuderna-Danish Evaporators--
Each of the concentrates weighing more than 0.5 mg was also scanned by
infrared (IR) spectroscopy. After the final weighing, the residue in each
weighing bottle was redissolved in methylene chloride and smeared onto a
NaCl window. The resulting spectra and the compound classes whose presence
was identified are summarized in Table B-8.
124
-------
TABLE B-5. TCO OF SAMPLE CONCENTRATES AND NEAT SOLUTIONS
Sample Hydrocarbon Content
C7 C8 C9 CIO Cll C12 C13 C14 C15 C16
132/6-1-LE-GC -- --..-.-„
132/6-2-LE-GC -- ........
132/6-3-LE-GC -- ........
132/6-4-LE-GC -- -- - ---.
132/6-5-LE-GC -- --.-.---
132/6-61-LE-GC -- --------
132/6-6S-SE-GC -- -- - .---
132/6-7L-LE-GC -- -- - ....
132/6-7S-SE-GC -- --------
134-IN-CD-LE-GC -- -- - .---
134-OUT-CD-LE-GC -- ........
134-IN-PR-GC - 1313 - - - ... -
134-OUT-PR-GC - 507 44.2 - 6.1 - - - 1.1
134-IN-MR-GC -LB -- - ....
134-OUT-MR-GC -- -10.5- - - --
134-IN-CYR-GC - 7460 - 55.9 37.3 37.3 - - -
134-IN-XR-SE-GC - - - - 52.7 39.5 - - -
134-OUT-XR-SE-GC . - - - - - - --
134-IN-1C-SE-GC -- -- - .---
134-IN-3C-SE-GC -- - - - - ...
134-IN-10C-SE-GC -- -- - .---
134-IN-PF-SE-GC - - --------
. 134-OUT-PF-SE-GC -- -- - ....
133-18-SE-GC -- --------
132/6-1-LE-KD-GC - - ... 0.02 - g/i
0 ng/£
0 ing/i
0 ng/ii
0 ing/kg
0 ing/t
0 mg/kg
0 ug/m3
0 vg/m3
1313 Ug/m3
558 vg/m3
0 ug/i*3
10.5 ug/m3
7590 ug/m3
92.2 ug/m3
0 ug/m3
0 ug/m3
0 ug/m3
0 yg/m3
o ug/m3
0 ug/n3
0 ing/kg
0.02 mg/i
0.14 Dg/i
0.06 mg/l
0.05 ng/i
0.05 mg/l
0 ng/t
0 «g/kg
0 «g/i
6.6 »g/kg
0 pg/"3
1.6 ug/»3
26 ug/"3
139 Ug/n3
318 vS/»3
26. -3 ug/m3
626 ug/n3
189 us/"3
14.9 ug/»3
0 vg/ti3
0 »g/»3
o ug/»3
0 vg/n3
146 iig/n3
86.2 «9/kg
125
-------
TABLE B-6. SAMPLE CODE FOR ORGANIC SAMPLES ANALYZED
SAMPLE CODE
- XX - XX - X
Site Identification
Sample Type
Sample Preparation
First Level Analysis
•Second Level
Analysis
Third Level
Analysis
132-1N, each test at
Inlet to
scrubber
133- IN
134-IN
135-IN
136- IN
132-OUT, each test
at scrubber
outlet
133-OUT
134-OUT
135-OUT .
136-OUT
132/5 represents
composites of all
sanples taken
1 - boiler feedMater
2 - tnlet to demlsters
3 - settling pond over-
flow
4 - scrubber water Inlet
5 - water to slag pond
6L - scrubber makeup
liquid
7L - scrubber out liquid
65 - scrubber makeup
solids
75 - scrubber out sol Ids
CD - condensate from
XAD-2 module
PR - solvent probe rinse
CAR - cyclone rinse
MR - solvent XAD-2 'module
rinse
HM - HNOa XAD-2 module
rinse
HI - H202 Implnger
AI - APS 1mp1ngers
XR - XAD-2 resin
PF - fllter(s)
1C - l-3u cyclone
3C - 3-10u cyclone
IOC - >10p cyclone
CF - solid fuel feed (coal)
Number and corresponding
preparation steps are as
follows:
0 - no preparation
LEA - liquid-liquid
extraction, ad-
fled sample
SE - solvent extraction
A - acidified aliquot
B - basic aliquot
PB - Parr bomb com-
bustion
HW - hot water extrac-
*4nn
t ion
AR - aqua reals
extraction •
LEN - liquid-liquid
extraction, neu-
tralized sample
LEB - liquid-liquid
extraction, basl-
fled sample
Numbers and corresponding
procedures are as follows:
Organic
0-no cone
require
GC-C7-C17
KD-K-D Cor
Inorganic
SS-SSHS
AAS-Hg,As,Sb
S04-S04
N03-N03
CF-C1.F
Organic analyses on
cone samples will
be coded as follows:
GM-GC/MS for PAHs
GI-Grav., IR
HS-LRHS
LC-LC separation
Resulting LC
fractions for
grav./IR/LRMS
analyses will be
numbered In
order, 1-8
ro
CTi
-------
TABLE B-6 (Continued)
ro
Water Samples:
132/6-1-LEA
132/6-2-LEA
132/6-3-LEA
132/6-4-LEA
132/6-5-LEA
Slurry Samples:
132/6-6L-LEA
132/6-6S-LE
132/6-7L-LEA
132/6-7S-LE
SASS Train Samples:
134-IN-PR
134-OUT-PR
134-IN-1C-SE
134-IN-3C-SE
134-IN-10C-SE
134-IN-CYR
134-IN-PF-SE
134-OUT-PF-SE
134-IN-XR-SE
134-OUT-XR-SE
134-IN-MR
134-OUT-MR
134-IN-CD-LEA
134-OUT-CD-LEA
Blanks
H20 Blank-LEA
133-MCB
133-MAB
133-XRB-SE
133-PFB-SE
COB
132/6-1-LEN
132/6-2-LEN
132/6-3-LEN
132/6-4-LEN
132/6-5-LEN
132/6-6L-LEN
132/6-7L-LEH
134-IH-CD-LEN
134-OUT-CO-LEN
H20 Blank-LEH
132/6-1-LEB
132/6-2-LEB
132/6-3-LEB
132/6-4-LEB
132/6-5-LEB
132/6-6L-LEB
132/6-7L-LEB
134-IN-CO-LEB
134-OUT-CD-LEB
H20 Blank-LEB
-------
TABLE B-7. GRAVIMETRY OF SAMPLE CONCENTRATES
Sample
132/6- 1-LE-KD-GI
132/6-2-LE-KD-GI
132/6- 3-LE-KD-GI
132/6-4-LE-KD-GI
132/6- 5-LE-KD-GI
132/6- 6L-LE-KD-GI
132/6-6S-SE-KD-GI
132/6- 7L-LE-KD-GI
132/6-7S-SE-KD-GI
133-18-SE-KD-GI
134-IN-CD-LE-KD-GI
134-OUT-CD-LE-KD-GI
134-IN-PR-O-KD-GI
134-OUT-PR-O-KD-GI
134-IN-MR-O-KD-GI
134-OUT-MR-O-KD-GI
134-IN-CYR-KD-GI
134-IN-1C-SE-KD-GI
134-IN-3C-SE-KD-GI
134-IN-10C-SE-KD-GI
134-IN-PF-SE-KD-GI
134-OUT-PF-SE-KD-GI
134-IN-XR-SE-KD-GI
134-OUT-XR-SE-KD-GI
133-XRB-SE-KD-GI
133-MCB-O-KD-GI
133-MAB-O-KD-GI
133-CDB-LE-KD-GI
132/6-LEB-LE-KD-GI
Weight
mg/nu
0.4
0
0.5
0.3
0
0.2
0.2
0.1
0.1
0
0.4
0.4
0.9
0.1
0.9
0.8
7.5
0
0
0
0
0.52
1.89
3.65
0.47
0.1
0
0.3
0
Corrected
for Blank
mg/m£
0.4
0
0.5
0.3
0
0.2
0.1
0.1
0
0
0.3
0.4
0.9
0.1
0.9
0.8
7.5
0
0
0
0
0.26
1.45
3.17
Aliquot
Factor
X10
X10
XI 0
X10
XI 0
X10
X10
X10
XI 0
XI 0
X10
X10
X10
X10
X10
XI 0
X10
XI 0
X10
X10
X10
XI 0
X10
XI 0
Sample
Volume
10JI
10*
104
10*
10£
8.5£
10. 2g
8.U
10. 6g
6.2g
31.1m3
36.5m3
31.1m3
36.5m3
31.1m3
36.5m3
31.1m3
31.1m3
31.1m3
31.1m3
31.1m3
36,5m3
31.1m3
36.5m3
Net
Gravimetry
0.4 mg/Ji
0
0.5 mg/£
0.3 mg/a
0
0.2 rng/A
98.0 mg/kg
0.1 mg/£
0
0
96.5 yg/m3
109.6 yg/m3
289 yg/m3
27.4 yg/m3
289 yg/m3
219 yg/m3
2412 ug/m3
0
0
0
0
71.2 yg/m3
446 yg/m3
868 yg/m3
128
-------
TABLE B-8. INTERPRETATION OF INFRARED SPECTRA OF SAMPLE CONCENTRATES
Sampl e
Identification
134-IN-XR-SE-
KD-GI
134-OUT-XR-SE-
KD-GI
Band
Location
cm"1
3280
2920
1695
1600
1450
1365
1320
1270
1170
1130-1050
925
855
795
750
700
2910
2650
2560
1680
1600,1580
1450
1420
Band
Intensity
W
S
S
W
M
W
W
S
W
M
W
w)
J
w(
«)
M
W
W
S
W
. w
M
Compound
Classification
OH or NH or C=0
overtone
C-H stretch
C=0
aromatics
-CH2
-C(CH3)X
S=0 antisym stretch
C-O-C stretch
S=0 sym stretch
ester and ether
unas signed
aromatics
Indicates: esters,
aldehydes/ketones,
ether, sulfone -
significant amount of
aromatic species
C-H stretch
acid
acid
C=0
aromatics
CH2
acid
129
-------
TABLE B-8 (Continued)
Sample
Identification
134-OUT-XR-SE-
KD-GI (con't.)
134-IN-CYR-KD-GI
Band
Location
cm"1
1320
1285
1175
1130-1055
1020
925
800
705
680
660
3400
2920
1745-1650
1600
1510
1455
1390-1355
1270-1010
1235
1170
1110
Band
Intensity
M
S
W
W
W
M
vA
M(
W (
w/
M
S
S
W
w
M
M
S
S
M
M
Compound
Classification
sulfone S-0 antisym
stretch
C-O-C stretch
sulfone, S=0 sym.
stretch
ester and ether
unassigned
acid
aroma tics
indicates: esters,
carboxylic acids, ether
& sulfone (reasonable
amount of aromatic
species)
OH, NH
C-H stretch
C=0
aromatics
benzene rings or nitro
compound
-CH2
-C(CH3)x & nitro com-
pound
not sufficiently
resolved
ester, acid sulfate or
C-O-C in ring
ester, sulfate, phenol
alchol
130
-------
TABLE B-8 (Continued)
Sample
Identification
134-IN-CYR-KD-GI
(Con't).
134-OUT-PF-SE-
KD-GI
Band
Location
cm-1
1030
830
2910
1740-1675
1640,1630
1605
1505
1460
1410
1385-1360
1290
1235
1180
1135-1090
1035
825
Band
Intensity
M
W
S
M
W
W
S
M
W
W
W
S
S
M
M
M
Compound
Classification
S=0 sulfoxide
1,4-disubst benezene
C-H stretch
C=0
C=C (mono or disubst.)
aromatic
aromatic nitro
compound (or benzene
ring)
-CH2
carboxylic acid
-C(CH3)x
C-O-C stretch
C-O-C stretch for
ester or alkyl acid
sulfate or C-O-C in
ring
C-O-C stretch for
ester, sulfate or
C-O-C in ring
ether
S=0 stretch, sulfoxide
1,4 disubst. benzene
Indicates: esters,
aldehydes/ ketones,
carboxylic acid,
ether, covalent
sulfate, alkyl acid
sulfate, sulfoxide,
possible nitro
compound/significant
aromatic character
131
-------
TABLE B-8 (Continued)
Samp] e
Identification
134-IN-MR-KD-GI
134-OUT-MR-KD-GI
134-IN-PR-KD-GI
Band
Location
cirri
2920
2920
1725
1650
1450
1290-1210
1120-1060
2920
1690
1730
1505
1460
1290
1230
1180
Band
Intensity
W
S
S
W
M
M
W
S
S
M
W
W
W
M
W
Compound
Classification
C-H stretch
no identifiable
species
C-H stretch
C=0
C-C (mono or disubst.)
-CH2
C-O-C stretch
ester or ether
Indicates: ester,
possible ether
C-H stretch
C-0
C=0
benzene ring or^nitro
compound
-CH2
unassigned
C-O-C stretch
unassigned
Indicates:
unsaturated aldehyde
or ketone & ester
132
-------
Liquid Chromatographic (LC) Separations and Subsequent Analyses —
Liquid chromatographic separations are performed on only those samples
3
having an organic content in excess of 500 yg/m as determined by the gravi-
metric and TCO analyses. Whenever more than 10 percent of the total organic
content is observed in the chromatographable portion, i.e., volatile mate-
rials represent a significant portion of the sample, special precautions
are taken in preparing the sample for fractionation, and additional GC-TCO
analyses are performed on the resultant samples. Using this criterion, a
liquid chromatographic fractionation was needed and performed on samples
134-IN-XR-SE-KD, 134-OUT-XR-SE-KD and 134-IN-CYR-O-KD. In order to preserve
volatile organics, all samples were introduced onto the LC column using
the solvent exchange procedure described in Reference B-2. The seven
fractions collected from the XAD-2 resin sample were analyzed for TCO
just as were the original samples. The results of these C,-C,g analyses
are presented in Table B-9. All fractions were then evaporated to dryness in
tared aluminum dishes. After the residues were weighed, an infrared analy-
sis was done on all having a weight greater than 0.5 mg. The procedures
followed were the same as used on the original samples. The gravimetric
results for nonvolatile materials are shown in Table B-10. Table B-ll summa-
rizes the classes of compounds identified in the infrared spectra produced
by the residues.
Low Resolution Mass Spectroscopy (LRMS) —
Only fraction 5 of sample 134-OUT-XR contained enough material to
require LRMS. Phthalates, benzoic acid, and aromatics, including the
possibility of a nitro compound were reported as present.
Level 2 Data
Introduction—
With a few exceptions discussed below, the samples were prepared and
extracted according to the procedures for Level 2 comparative assessment.
These procedures are discussed elsewhere (Reference B-l). Details of special
handling which is different from the Level 2 procedures are discussed in the
following subsections. Compound identifications were made on the basis of
the computerized mass spectral search of the 25,000 plus compounds in the
133
-------
TABLE B-9. TCOs OF LIQUID CHROMATOGRAPHY FRACTIONS
134-IN-XR-LC1
LC2
LC3
LC4
LC5
LC6
LC7
134-IN-CYR-LC1
LC2
LC3
LC4
LC5
LC6
LC7
134-OUT-XR-LC1
LC2
LC3
LC4
LC5
LC6
LC7
C7
ND
ND
ND
ND
29
ND
IB
ND
ND
ND
ND
LB
ND
LB
ND
ND
ND
ND
ND
16
ND
C8
ND
ND
ND
ND
380
ND
37
ND
ND
ND
127
453
ND
15
ND
ND
ND
ND
330
ND
40
C9
ND
ND
ND
61
ND
ND
43
ND
ND
ND
ND
ND
ND
60
ND
ND
ND
ND
ND
ND
ND
J 1 I
Hydrocarbons in Fraction, yg
CIO
25
35
37
ND
ND
ND
88
ND
ND
ND
ND
1065
ND
ND
10
10
ND
ND
ND
ND
ND
Cll
158
ND
ND
34
20
ND
ND
ND
ND
ND
220
43
ND
ND
ND
ND
ND
49
20
ND
ND
C12
292
20
23
65
35
ND
ND
ND
ND
ND
ND
19
ND
ND
ND
ND
ND
108
34
ND
ND
C13
125
ND
ND
ND
126
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
29
132
ND
ND
C14
ND
20
21
ND
34
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
9
ND
ND
26
ND
ND
C15
ND
149
ND
ND
ND
ND
ND
24
ND
ND
ND
39
ND
ND
ND
16
ND
ND
ND
ND
ND
C16
88
182
11
ND
31
ND
ND
51
18
ND
ND
20
ND
ND
ND
ND
50
ND
19
ND
ND
Total
688
406
92
160
655
0
168
H69
75
18
ND
347
1639
ND
75
215T
10
35
50
186
561
16
40
S98~
Amount
Applied
to Column
3730
52742
1085
CO
-------
TABLE B-10. GRAVIMETRY OF LC FRACTIONS
GRAV. of
Material Applied
to Column
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Total
Blank Correction
Net Gravimetry
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Total
134-IN-XR
9.45 mg
1.60
0.56
0.33
0.43
3.18
2.41
0.99
9.50
0.46
9.04
BLANK
0.12 mg
0.03
0.04
0.03
0.04
0.13
0.07
0.46
134-IN-CYR
15.00 mg
0.14
0
0
0.09
3.22
2.78
1.49
7.72
0.39
7.33
134-OUT-XR
18.25 mg
0.29
0.05
0.15
0.32
10.79
3.80
1.01
16.41
0.46
15.95
135
-------
TABLE B-ll. INTERPRETATION OF INFRARED SPECTRA OF LC FRACTIONS
Sample
Identification
134-IN-XR-LC1
134-IN-XR-LC2
134-IN-XR-LC5
Band
Location,
cnrl
3000-2800
1450
1380
3020
3000-2900
1600
1490
1450
1110
1050
1030
890
830
800
750
700
3300
3060
3000-2800
1710
1610
1590
1460
1420
1370
Band
Intensity
S
M
W
M
S
Ml
M|
M
M
W)
wf
S, broad
W
S
S, broad
M
W
. S
W
W
Compound
Classification
Aliphatic HC
Aliphatic HC
Aliphatic HC
Indicates:
Aliphatic hydrocarbon
Unsaturated or
aromatic HC
Aliphatic HC
Aromatic
CH2 (aliphatic)
Unassigned
Aromatic substitution
Indicates: Aliphatic
& aromatic hydrocarbons
OH, NH
aromatic CH
Aliphatic CH
C=0 ester, ketone
aromatic
aromatic
methyl
methyl
methyl
136
-------
TABLE B-ll (Continued)
Sample
Identification
134-IN-XR-LC6
Band
Location
cm-1
1270
1180
1120
1070
1030
810
760
720
3350
3050
3000-2800
1700
1600
1550
1450
1400
1320
1260
Band
Intensity
S, broad
W
W
W
W \
W (
W j
S )
M
W
S
S, broad
S
S
M
S
W
M
Compound
Classification
C-0 of benzoate esters
C-0
aromatic substitution
Indicates:
aliphatic & aromatic
hydrocarbons, alcohols,
esters, ketones '
OH, NH
unsaturated or aromatic
CH
aliphatic CH
C=0 - acid, aryl/
unsaturated ester or
ketone
aromatic ring, skeletal
or amine
COO"
aliphatic CH2
COO", alkenes
sulfone
C-0, ester, carboxylic
acid
137
-------
TABLE B-ll (Continued)
Sample
Identification
134-IN-XR-LC7
134-OUT-XR-LC-5
Band
Location,
cm~l
1170
1120
715
3000-2800
1730
1550
1400
1270
3200-2500
1690
(1720-1680)
1600
1580
1490
1450
1420
1320
1290
1180
1120
1070
1020
Band
Intensity
W
M
M
S
M
M, broad
M, broad
M, broad
S, broad
S, broad
M|
Ml
W
M
M
M
S
M
M
Compound
Classification
sulfone, ether
C-0, alcohol
aromatic subst.
Indicates: aromatic &
aliphatic species: aryl
or unsaturated ester,
ketone, nitro compound,
carboxylate, carboxylic
acid; possible amine,
alcohol
aliphatic CH
C=0, broad, ester
coo-
coo-
C-0, ester
Indicates: aliphatic
ester, carboxylic acid
salt
acid OH
C=0, ester, ketone,
acid
aromatic ring
unassigned
-CH2
C-0, acid
C-0, acid, sulfone
C-0 of acid, phthalate
ester
sulfone
C-0 of ester, possibly
phthalate
138
-------
TABLE B-ll (Continued)
Sample
Identification
134-OUT-XR-LC-5
134-OUT-XR-LC6
134-OUT-XR-LC7
Band
Location
cm~l
920
800
710
3350
3050
3000-2800
1670
(1645-1720)
1600
1540
1450
1400
1260
(1230-1280)
1170
1060
710
3300
3050
3000-2800
1720
1600
Band
Intensity
X
1
S, broad
W
S
W, broad
S
W
S
S, broad
W
M
S
M
W
S
S
S
Compound
Classification
aromatic substitution
Indicates: carboxylic
acids, ester & nitro
aromatic
OH, NH
aromatic CH
aliphatic CH
C=C or amide (C=0
buried?)
aromatic
-C00~; amide
-CH2
-COO'
C-0 of aromatic ester,
acid, alcohol
phenol
C-N of amine
aromatic subst.
Indicates: aliphatic &
aromatic esters, alcohol,
carboxylic acid, car-
boxylate, nitro compound,
possible amine
OH, NH
aromatic C-H
aliphatic C-H
C=0 - ester, ketone
aromatic ring
139
-------
TABLE B-ll (Continued)
Sample
Identification
134-OUT-XR-LC7
(Con't)
134-IN-CYR-LC5
Band
Location
cm~l
1550
1450
1400
1370
1270
1100
710
3400
3050
3000-2800
1700
(1650-1720)
1450
1370
1260
1180
1130
730
710
Band
Intensity
S
M
S
M
S
M
M
S
W
S
S, broad
S
S
S, very
broad
W
W
W
W
Compound
Classification
COO", or nitro
compound
-CH2
COO"
CHg, nitro compound
C-O-C stretch, ester
C-0, alcohol, ester,
ether
aromatic substitution
Indicates: aliphatic &
aromatic ester, alcohol,
possible carboxylate,
nitro compound, ether
OH, NH
aromatic CH
aliphatic CH
-C=0, unsaturated
ester, ketone acid
possible amine
aliphatic HC
possible sulfonate
C-0, ester, ether, acid,
alcohol possible
sulfonate, amine
unassigned
Indicates: ester,
ketone ether, acid
alcohol some
unsaturation, possible
phenols, sulfonate
140
-------
TABLE B-ll (Continued)
Sample
Identification
134-IN-CYR-LC6
134-IN-CYR-LC7
Band
Location
cm"l
3300
3050
3000-2800
1720
1610
1465
1375
1150
(1050-1300)
t
3000-2800
1700
1110
Band
Intensity
M
W
S
S
S
M
W
M
W
W
W
Compound
Classification
OH or NH
unsaturated CH
aliphatic CH2
C=0 ester, ketone
C=C, amine
CH2
dimethyl, possible
sulfonate
C-0, alcohol ether,
ester, amine N-H
stretch
possible sulfonate
Indicates: aliphatic
ester, ketone, alcohol,
ether; possible phenol,
sulfonate .
aliphatic CH
C=0
no identifiable
activity
141
-------
National Bureau of Standards compound Horary. Acceptance of the search
results Involves judgemental factors. Some incorrect identifications may,
therefore, exist in the tables. A final confirmation by GC relative
retention time and spectral comparison with known standards was not per-
formed. However, not all samples were subjected to quantisation or
confirmation because the initial screening showed very low concentration
levels and budget and schedule considerations limited further efforts.
Several representative samples from the various sample groups e.g.,
probe rinses, resin extracts, condensates, etc. have undergone a procedure
to estimate compound concentrations. Each representative sample was
selected on the basis of the greatest number of compounds detected and the
highest apparent levels. The remaining samples have fewer detected compounds
and/or lower levels. The next step was to identify potentially hazardous
compounds which exceed minimum established levels (Figure B-3, Logic Flow
Chart for Level 2 Organic Analysis and Figure B-3, Analysis of Samples from
Sampling Train). The process water extracts have been analyzed to the
point prior to concentrations for LC fractionation (see Figure B-4).
Estimation of Concentration Level s--
The following is a summary of the procedure by which compound
concentrations in selected samples were estimated for comparison with DMEG
values. An internal standard solution of naphthalene and chloronapthalene
was prepared in methylene chloride at 10 ug/ml for each standard. One
hundred yl of this solution was blended with one hundred yl of a sample to
be reanalyzed by GC/MS for quantitative purposes. The result was a solu-
tion containing the internal standards at 5 yg/ml and the original sample
solution at one half of its original concentration. This solution was ana-
lyzed by GC/MS using the same conditions as with the original screening
analysis. A total ion chromatogram was obtained and the areas for all
chromatogram peaks of interest were obtained. One of the compounds in the
sample was selected as a secondary standard and its concentration estimated
on the basis of the known concentration of the internal standard and the
ratio of the peak areas of the secondary standard and the internal standard.
Then, having an estimated concentration of the compound used as a secondary
standard, the data from the original screening analysis was used to obtain
142
-------
DOES LEVEL 1 DATA
INDICATE ANY POTEN
TIALLY HAZARDOUS
MATERIAL IN EXCESS
OF ITS ESTABLISHED
MINIMUM?
IS IT COST EFFECTIVE
OR A PROGRAM REQUIRE
MENT TO ANALYZE THIS
SAMPLE FURTHER?
IDENTIFY COMPOUNDS
USING ORGANIC
ANALYSIS FLOWCHART
IS THERE SUFFICIENT
MATERIAL FOR
ANALYSIS?
ESTIMATE QUANTITY
OF EACH COMPOUND
DO ANY POTENTIALLY
HAZARDOUS COMPOUNDS
EXCEED OR APPROXIMATE
MINIMUM ESTABLISHED
LEVELS?
QUANTITATE POTENTIALLY
HAZARDOUS COMPOUNDS
QUANTITATE THOSE
COMPOUNDS FOR
WHICH IT IS COST
EFFECTIVE TO DO SO
IS FURTHER
QUANTITATION
COST EFFECTIVE?
LEVEL 2
ANALYSIS
COMPLETE
Figure B-3. Logic flow chart for Level 2 organic analysis
143
-------
HCW WASH
SAMPLE
FILIEU
t<3")
CYCtONt
<>lK>
XAD-J
KSIN
EXT RAO
M.0j
EXTRACT
M.O,
EXTRACT
M.CI2
EXTRACT
I/N EXTRACT
PH >n
.
^
OC/MS ©
ALIQUOT
CONCtNTIIATE
X100
ACID EXTRACT
PH < 2
OC/MS (T)
TINAX OC ^
H,P04/CARIOWAX
ALIQUOT
0 QMAYMUSEFUITOEASE
SPeaHAL INTKPKTATION
@ NITIOSOAMINES Att EXPtCTEO ONIY
AT LOW CONCENTRATIONS, IF PKSENT
SPECIAL PREPARATION Will K KQUIHED ,,
FOLLOWED IV GC/MS ANALYSIS USING '
CAKIOWAX 20 M AND SELECTED ION
MONITOMNC (SIM)
OC/MS <33
FFAPOR
SP-2I4-PS
-
DERIVITIZE
t
OC/MS
OV-»
Figure B-4. Analysis of samples for organic content
-------
peak areas for all compounds of interest. Concentration estimates were
obtained for all significant compounds on the basis of peak areas relative
to the secondary standard. Using total ion chromatogram peak areas for
different types of compounds is only useful for estimates because of several
variable factors affecting the recorded ion output per unit amount of any
group of compounds. The levels presented in the tables are believed to be
accurate to plus or minus a factor of 10. Should the need arise for more
accurate concentrations for any given compound, then special mixtures con-
taining known amounts of internal standard and the compounds of interest
will have to be prepared and run on the GC/MS to determine relative response
factors. These relative response factors can then be applied to the ori-
ginal sample data. Alternatively the original samples solutions can be
spiked with known added amounts of specific compounds and reanalyzed. This
generally is called the method of standard additions.
GC/MS Analysis of Gas Bag Samples-
Handling of these samples proceeded as follows. Two liters of gas bag
sample was passed through a pre-conditioned Tenax column. The Tenax column
was then heated and the absorbed species transferred to a liquid nitrogen
cooled trap. The LNg trap was then allowed to come to room temperature
while isolated from the system with closed valves. The contents of the
trap were then injected onto a GC column. The GC separation was accomplished
using the following conditions:
Column - 6 ft stainless steel containing
Poparak Q 60-80 mesh
Carrier - Helium at 30 cc per minute
Temperature - Programmed from 50°C to 230°C at 8°C per
minute and held at 230°C for 15 to 30 minutes
The mass spectrometer was used as the GC detector in a mode which
scanned the mass range in continuous cyclic recordings. Quantification of
the compounds was performed using peak areas. Determination of instrument
response to the detected compounds (i.e., calibration) was done directly
using a synthetic gas blend.
145
-------
A summary of the organic compounds found in the gas bag samples and
their calculations is presented in Table B-12. Units of concentration are
expressed in milligrams per cubic meter of gas sample at 1 atmosphere and
21°C.
The results generally indicate that the levels found in the samples
do not significantly exceed the levels found in the blank. The background
levels for these compounds in the blank sample appear to be rather high.
There are scattered instances where six compounds have consistently
higher concentrations than those found in the blank sample. The six com-
pounds are methyl methacrylate, a 67 hydrocarbon, an additional hydrocarbon
of similar but not accurately known molecular weight, trichloroethylene,
methylisobutyl ketone, and xylene. It is believed that these higher levels
result from variation in blank levels but this cannot be statistically con-
firmed because several blanks would be required to determine a range of
variation and these multiple blanks were not obtained.
GC/MS Analysis of SASS Train Sample Catches—
This section presents the results of the GC/MS analysis on the
extracts and rinses taken from the SASS train components. These samples
are reported in the following groups:
• Probe rinses, cyclone catch extracts, particulate filter extracts,
and cyclone rinses.
• Sorbent resin extracts.
0 Resin module rinses and condensate extracts.
These groupings were made to report samples most likely to contain
similar compounds.
Analysis of Probe Rinse, Particulate Catch and Cyclone Rinse Samples--
This section describes the results of the analysis of the probe and
cyclone rinses as well as the extracts from the particulate matter which
was found in the cyclones and filters. These samples as a unit repre-
sent the organic compounds found in the train upstream of the resin module.
No compounds of any significance were found in any of the unconcentrated
extracts. The following discussion deals with the analysis of the samples
146
-------
TABLE B-12. RESULTS OF GAS BAG ANALYSIS
Compound
Dichlorofluoromethane
Vinyl Chloride
Methyl Formate
Methyl ene Chloride
Diethyl Ether
Tetrahydrofuran
Unsaturated Hydrocarbon
Carbontetrachloride
Methyl Methacrylate
Hydrocarbon (Cy)
Toluene
Hydrocarbon
Trichloroethylene
Methyl i sobutyl ketone
Xylene
Concentration, mg/m^
132
(Blank)
0.13
0.05
0.18
11.9
5.9
1.8
1.2
12.7
1
ND *
6.9
0.17
ND *
ND *
ND *
132
In
0.13
0.05
0.15
11.2
5.5
2.4
0.4
5.1
2
0.8
4.6
0.33
4.
0.3
ND*
132
Out
0.39
0.08
0.25
11.9
5.9
3.0
1.2
5.7
2
0.4
6.5
ND*
5.
0.3
ND*
134
In
0.04
0.02
0.15
11.2
7.0
3.6
1.7
8.2
4
0.04
8.0
0.83
4.
2.5
ND*
134
Out
0.26
0.13
0.28
11.2
5.1
3.6
1.7
10.8
2
0.04
5.8
ND*
ND*
0.4
ND*
135
In
0.08
0.05
0.20
13.0
7.0
3.0
1.7
7.0
2
0.13
8.4
ND*
4.
1.7
3.5
135
Out
0.85
0.18
0.18
13.0
6.3
3.9
0.4
11.4
2
0.4
8.0
ND*
ND*
1.2
ND*
136
In
0.30
0.08
0.07
11.6
5.9
3.9
1.7
7.6
3
ND*
9.6
ND*
4.
ND*
0.4
136
Out
0.08
0.08
0.25
13.6
7.0
4.5
2.1
12.7
3
0.4
10.0
ND*
ND*
1.2
4.4
-p.
•-J
ND = Not detected - limit of detection is 0.02 mg/m3.
-------
which were concentrated by sample evaporation. Separation by liquid chro-
matography was not necessary. Identified compounds are summarized in
Table B-13. Estimated concentrations are presented for the major components.
Both probe rinse samples contain large quantities of 3-methylene-2-
pentanone. This is an acetone condensation product. The acetone is part
of the rinse solvent and it is likely that this compound has its origin
in the rinse solvent. The probe rinse from the SASS train at the scrubber
inlet contained only the diacetone condensation product at significant
levels. The concentrated probe rinse from the sample train at the scrubber
outlet contained additional compounds. Table B-13 shows additional ketones,
a possible 65 tertiary amine and a naphthalene substituted si lane. The
concentrated extracts from the particulate material caught in the cyclones
and on the filter of the scrubber Inlet sample train contained very little
organic material. A freon, either C^Cl.Fg or C,C13F7 was common to all
these samples. The 1 micron cyclone catch had three peaks which could not
be confidently identified using the computerized library search. They cur-
rently remain unknown and are not believed to be present at levels greater
than the other reported species.
The combined cyclone rinse concentrate was found to contain an exten-
sive number of compounds as shown in Table B-14. Ketones, substituted naphtha-
lenes and benzenes predominated. Several small condensed aromatics were also
believed to be present. These include acridine, and a possible acenaphtha-
lene. Concentration levels for the compounds found in the cyclone rinse were
estimated using total ion GC peak areas.
The estimated concentrations of compounds found in the cyclone rinse
were compared to the appropriate DMEG values as shown in Table B-14. In
most cases, compounds in the sample could not be found in the DMEG charts;
in those cases, the DMEG value for the most similar compound listed was used.
All DMEG values were at least 1000 times larger than the concentrations of
corresponding compounds found in the cyclone rinse.
Sorbent Resin Extracts—The compounds which were extracted from the
sorbent resin and are believed to have been present in the sample effluent
gas are presented in Table B-15. The concentrated extracts were analyzed
148
-------
TABLE B-13. PROBE RINSES, PARTICULATE EXTRACTS, CYCLONE RINSES
134 Scrubber Inlet
Sample
Probe
rinse
1 Micron
Cyclone
Catch
Extract
3 Micron
Cyclone
10 Micron
Cyclone
Catch
Extract
Partlcu-
late
Filter
Extract
Extract Gas
Concentration Concentration
Compound vg/ml ug/m3
3-Methylene-2-pentanone
Freon, C4C13F7 or CaC^Fe 2 0.6
Unknown, apparent molec. wt. 4 1
529
Unknown, apparent molec. wt. 7 2
470
Freon, [C4C13F7 or C4C14F6]
0-Methyl-benzaide-oxlme
3-Methylene-2-pentanone
Unknown.
Freon, C.Cl.Fy or C^Cl.F,
134 Scrubber Outlet
Extract Gas
Concentration Concentration
Compound wg/ml vg/m3
3-Methylene-2-pentanone
3-Methylene-3-pentanone
Possible N,N-D1methyl butanamlne
2-Methyl-2-octen-4-one
2,5-D1methyl-2,5-hepad1ene-4-one
Trlmethylnaphthalenyl Sllane
No cyclones used on scrubber
outlet SASS train.
No cyclones used on scrubber
outlet SASS train.
No cyclones used on scrubber
outlet SASS train.
Freon, [C4Cl3Fy or C4C14F6]
MW 154: Dihydroacenaphthalene
or Biphenyl .
-------
TABLE B-14. ANALYSIS OF CYCLONE RINSE TEST 134, SCRUBBER INLET SAMPLING TRAIN
en
O
Compound
3-Methylene-2-pentanone
THmethyl benzene
2,6-Piperiden-d1one-4,4-dimethyl
2,6-D1methyl-2,5-heptad1en-4-one
4(2-buteny1 )-l ,2-d1methyl benzene
Decahydronaphthal ene
Phenyl (2,2,3-trlmethyl cyclopentilidene
methane)
Trlmethyl naphtha! enylsllane
5-Methyl-benz-c-acrldine
2,6-bis (1,1 -Dimethyl ethyl) naphthalene
Hexamethylhexahydrolndacene
Long Chain Acid; Methyl ester (> C,4)
D1 Tert-butyl naphthalene
Dimethyl 1 sopropyl naphtha! ene
Hexamethyl bl phenyl
Cycl ohexy 1 benzene
Concentration
In Extract
yg/ml
4 x 102
2
6 x 101
4 x 101
1
0.3
5
4
0.7
0.9
1
0.6
1
1
2
0.8
Emission
Concentration
In Gas Stream
yg/m3
1 x 102
0.6
2 x 101
1 x 101
0.3
0.1
2
1
0.2
0.3
0.3
0.2
0.3
0.3
0.6
0.3
Representative
DMEG Value
pg/m3
2.5
1.2
4
2.5
2
2
6
1
5
5
2
2
2
1
2
x 104
x 105
x 104
x 104
x 105
x 105
x 104
x 106
x 104
x TO4
x 105
N
N
5
X 10°
x 105
x 103
x 105
N = No DMEG value given: either compound structure Is unclear or no biological toxicity data
Is available in the literature.
-------
TABLE B-15. ABSORBENT RESIN EXTRACTS
Compound
mcfRlJBRFR
2,3-Dimethyldecahydronaphthalene
1 ,3-Diethyl benzene
Cg substituted Benzene
1 ,2,3,4-Tetrahydronaphthalene
Di hydronaphthal ene
1 , 3, 5-Tri ethyl benzene
CIQ substituted Naphthalene
C,Q substituted Decahydronaphthalene
Ethyl benzal dehyde
Dimethyl benzal dehyde
Methyl naphtha! ene
Unknown: possible substituted
Anthracene p_r Phenanthrene
Methyl naphtha! ene
1 ,1 '-Biphenyl
9,10-Dihydrophenanthrene p_r
1-1 '-Diphenylethene
Unknown - Apparent mole wt. 242
1,1-Bis (p-ethylphenyl )-ethane or
Tetramethylbiphenyl. Three
isomers present
Another Tetramethylbiphenyl
2-Phenyl naphthalene
C3 substituted Benzene
Ethyl benza 1 dehyde
Tetramethyl benzene
2,4-Dimethylacetophenone
Trimethylcychexenone
Nitric acid decy Tester
yg/ml
INI FT
7
3
<0.1
1
1
0.2
4
11
2
4
1
I
2
12
0.6
5
25
4
1
nilTI FT
1
10
<0.1
2
4
1
ug/m
<0.03
2
1
<0.03
0.03
0.3
0.06
1
4
0.6
1
n ^
U .
-------
by GC/MS using an OV-17 column with a temperature program from 50°C to
280°C. (See Reference B-l for details.)
Both extracts from the trains at the scrubber inlet and outlet had
extensive amounts of the many compounds that were also extracted from the
blank resin sample. The relative amounts of materials common to both samples
and the blank vary somewhat between the two resin extract samples, and the
following general observations can be made. Of the compounds common to the
blank and the outlet resin samples, the amounts found in the outlet sample
generally were 1/4 to 1/2 the amount found in the blank. Ten to 15 times
greater amounts were found at the scrubber inlet than in the resin blank.
All of these resins had been precleaned in the same lot, therefore, lot to
lot variation is not suspect.
The cause of these variations is the resin cleaning specification. The
program specifications for clean XAD-2 resin is as follows:
• Acceptable - TCO and Grav. < 5 mg/150 g
- TCO < 1.5 mg/150 g
- Grav. < 3.75 mg/150 g
0 Marginal - TCO and Grav. 5-7 mg/150 g
• Unacceptable - TCO and Grav. > 7 mg/150 g
The SASS train resin module contains 150 g of resin. These specifications
were developed at the beginning of the EACCS program, and they are compatible
with the latest revision of the Level 1 manual. The total of TCO compounds
3 3
found at the scrubber inlet (Table B-15) was 26.3 yg/m or 789 yg in 30 m
or 789 yg in 150 g of resin. Similarly, the total of compounds found at the
3 3
scrubber outlet (Table B-15) was 5.2 yg/m or 156 yg in 30 m or 156 yg in
3
150 g of resin. The TCO requirement for resin acceptability was < 50 yg/m
(1500 yg per 150 g) which was greater than the levels of compounds being
sought. Thus, the blank ranged from 1.9 to 9.6 times greater than the levels
being sampled.
This shows that resin cleaned For Level 1 is not suitable for Level 2
sampling and analysis. The problem described above will occur whenever
Level 2 analyses are performed on resin samples acquired by Level 1 procedures,
152
-------
A computerized data manipulation and compound search technique was used
to increase the level of confidence in the reported compounds presented in
Table B-15. The procedure was required because of the presence of resin
artifact background interference. The blank resin extract data were searched
for the presence of every compound found in the two sample resin extracts.
The technique consisted of selecting a peak which was present in the inlet
or outlet sample resin extracts. A mass spectrum was obtained for the peak
and several characteristic masses specific to the compound were noted.
The blank resin data was searched for a peak caused by the selected charac-
teristic masses. If a peak occurred in the appropriate retention time
window the entire mass spectrum was searched for compound identification.
If the Library search results or the spectra were the same the compound was
deemed to be a resin artifact. If no peak was observed in the blank resin
chromatogram, the compound was deemed to be not from the resin but rather
from the sample effluent gas. This selected mass search technique was
performed for each peak where any doubt existed as to origin. The compounds
which passed this test and are believed to originate in the sample effluent
gas are the ones presented in Table B-15.
The compounds seen in the scrubber inlet resin extract generally con-
sist of substituted benzenes, naphthalenes, and biphenyls. A few benzal-
dehydes were also found. A few possible condensed aromatics such as sub-
stituted phenanthrenes were tentatively identified but further confirmation
would be required for certainty. The scrubber outlet resin extract contains
substituted benzenes and ketones. It is important to note that one of the
major classes of compounds extracted from the blank resin are also sub-
stituted benzenes, naphthalenes, and biphenyls. Thus, some of the reported
substituted benzene compounds may still be artifacts, i.e., compounds
remaining in the resin after pre-cleam'ng and blank extraction but which
become extractable after being used in the sample train.
The resin extract samples from both the scrubber inlet and scrubber
outlet sample trains were subjected to the concentration estimation pro-
cedures and these estimates were compared with DMEG values (Table B-15). In
nearly all cases, the ratio of the DMEG values to the estimated concen-
trations in the LaCygne effluent exceeded 10,000 to 1. Exceptions were
153
-------
biphenyl and four compounds believed to be alkyl substituted biphenyls.
The ratios of DMEG values to effluent gas concentration estimates for these
exceptions ranged between 100 to 1 and 1000 to 1. These effluent compounds
are believed to be present in the resin extracts at concentration levels
much lower than those levels at which further analysis would be recommended.
Analysis of Resin Module Rinsings and Aqueous Condensate Extracts—
This section summarizes the results of the analysis on the module rinses
and module condensates from the scrubber inlet and scrubber outlet sample
trains. These two sample groups are discussed together as they are
intended to contain materials which do not advance as far as the resin
canister or which pass through the resin module without being trapped on
the resin. The condensates were extracted after sequential pH adjustment
to acidic, neutral and alkaline conditions. The module rinses in acetone/
methylene chloride required no such extraction. These extracts were ana-
lyzed in both concentrated and non-concentrated forms. The details of
these procedures are presented in Reference B-l.
The unconcentrated extract solutions and rinses were analyzed to check
for volatile species present in a sample effluent which could be lost as
a result of evaporation during solvent removal. No volatile compounds
were seen in the unconcentrated extracts or rinses at detectable levels
other than solvent species. Instrument detection levels, calculated to
reflect gaseous effluent concentration levels, are 0.03 pg/rn^.
The results of these module rinses and condensate analyses are sum-
marized in Table B-16. The module rinse from the scrubber inlet train con-
tained only a diacetone condensation product and one unknown. The diacetone
is believed to be from the acetone/methylene chloride rinse solution. The
module rinse from the scrubber outlet train has four carboxylic esters,
a €4 Freon and one GS ketone. This sample was reanalyzed by GC/MS with
an internal standard to estimate concentration levels. The species were
estimated to be present at gaseous effluent levels all below 1 yg/m3.
The concentrated extract of the acidified condensate from the scrubber
inlet train was found to contain no reportable levels of material. The
154
-------
TABLE B-16. MODULE RINSES AND CONDENSATE EXTRACTS
Sample
Module
Rinse
Acidified
Condensate
Extract;
pH < 2
Neutral
Condensate
Extract;
pH 7
Daelr
Condensate
Extract;
pH 11
134- Scrubber Inlet
Compound
3-Methylene-2-pentanone
Unknown
No Compounds Detected
Possible Methyl Isopropyl phenol
Freon: C4C13F7 or C4d4Fg
Possible 5,7-D1hydro-6H-
d1 benzo/A ,C/cyc loheptene-6-
one
Concen- Concen-
tration tratlon Typical
In sample 1n flue gas DMEG
pg/ml pg/m^ Value
134-Scrubber Outlet
Compound
Butylacetate
l-{2^methyl) cyclopropylethanone
Freon
Methyl ester of carboxyllc Acid
(3 Separate Compounds)
5-Ethy1-2-methyl-t-heptene-3-one
1 Butanol-3-methylbenzoate
Possible 5,7-D1hydro-6H-
d\ benzo/A ,C/cycloheptene-6-one
Possible 5,7-D1hydro-6H-
dl benzo/A ,C/cycl oheptene-6-one
Concen-
tration
in sample
wg/ml
1
0.3
0.4
1
7
2
Concen-
tration
1n flue-gas
ug/mj
0.3
0.1
0.1
0.3
Quantlfled-
Quantlfled-
2
0.6
Typical
DMEG
Value
1 x 105
6 x 106
N
N
N
4 x 10*
tn
N - No DMEG value given: No biological toxldty data 1n literature.
-------
lower limit of detection expressed in terms of concentration in a gaseous
effluent is estimated to be 0.03 yg/m^. The acidified condensate extract
from the scrubber outlet train contained what is believed to be a branched
CIQ ketone and a butyl ester of methyl benzoate. No repeat analysis was
made to quantify these compounds but inspection of the total ion chroma-
tograph data indicated their presence at gaseous effluent levels of much
less than 1 yg/m3. The condensate extracts after adjustment to neutral and
alkaline pH also showed very little material. Table B-16 shows one ketone,
one phenyl substituted hydrocarbon, a Freon and a possible 64 substituted
phenol. The possible presence of the phenol in a neutral fraction is
unexplained except for the possibility that the compound identification on
the basis of mass spectral data is in error. No reanalysis of this sample
was made to resolve this anomaly because of the apparently Insignificant
concentrations.
The basic condensate extract from Run 134 was rerun with an internal
standard to estimate concentration levels of the two species that were
identified. Table B-16 shows mlcrogram and submlcrogram per cubic meter
levels. Again these levels are at least a factor of a thousand below
typical DMEG values.
Process Water and Slurry Extracts—•
This section summarizes the results of the GC/MS analyses on the
process water and slurry extracts. Two GC column systems were used for
effective separation of the acid species and the basic species as separate
entities. Refer to Reference B-l for procedural details. Additional chro-
matography, i.e., the OV-17 screening GC/MS was also employed to analyze
the acidic fractions for neutral species as well as to provide backup data
for reporting confidence in observed species. The order of presentation
in Tables B-l7 and B-l8 1s acidified extracts followed by the neutral and
basic extracts.
The procedure used for the extraction of the aqueous samples such as
the process waters, the slurries and the aqueous SASS train condensates
156
-------
TABLE B-17. ACIDIFIED PROCESS WATER AND SLURRY SAMPLES
132/6-1 132/6-2 132/6-3 132/6-4 132/6-5 1 32/6-6L 132/6-7L
4-Hydroxy-4-methyl-2-pentanone X XX
2,2,4-Trlmethyl cyclohexene-1-methanol _
2-Ethyl hexanolc Acid _
2H-Pyran-2-one or_ 2-cyclohexene-l-one X X
4-Chloro-trsns cyclohexanol X _
Acetophenone X _ _
Possible Cg 01ol X _
Possible Propyl ether. X
C,.j SL^-it Acldt Methylestep
Phenol
Possible Dlmethoxy propane
fllodomethane (AKA Hethylene Iodide)
2-Cyclohexen-l-Ol
B1cyclo/3.1.O/hexane-3-one
l-Bromo-2-chloro-cls-cyclohexane
2-Chloro-trans-cyclohexanol
2,5-Dtethyl-tetra hydrofuran
Dlmethoxy methane or Trlmethoxy methane
e.g. l-chloro-2-l-buten-3-yne
2-Ethoxy-l-methoxy-ethoxy ethane
5-Hethyl-1,2-hexad1ene
1-(2-Methy1-2-eyclopenten-l-yl)-ethanone
ketone
Butyl oxyrane
2-Im1dazol1d1none
Vinyl Acetate
C4H3C1 (e.g.) Chloro butatrlene
-------
TABLE B-18. ANALYSIS OF SELECTED ACIDIFIED PROCESS
WATER EXTRACTS ON OV-17 GC COLUMN
Sample Extract
132/6-3-LEA-KD
(settling pond
overf 1 ow)
132/6-5-LEA-KD
(water to
slag pond)
132/6-6L-LEA-KD
(acidified
extract of liquid
portion of inlet
scrubber slurry)
Identified Species
(Estimated Concentrations pg/1 water)
• Butyl naphthalene (4)
(Plus possible an (1)
Alkyl substituted
naphthalene)
• l-Chloro-2,4-hexadine (0.5)
• Unknown (3)
• Freon Cmpd; C^Cl^Fg (1)
0 Olefin or Ketone; CS-GH
t Tetrachloropropane (possible)
• 6-Chloro-n-ethyl-n'-(l-methyl ethyl -1 ,3,5-
tr1azine-2,4-diamine
• Octyldipheny Tester of phosphoric acid.
t Freon; C.CKFg
158
-------
represents a deviation from established Level 2 procedures outlined in
Reference B-l. These samples were first acidified to pH 2 and extracted
with methylene chloride. The samples were then adjusted to pH 7 and re-
extracted with methylene chloride. A final extraction was made at pH 11.
This reversal in pH adjustment order results in the possibility that some
neutral compounds were extracted into the acid extract solution for analysis
on the Carbowax/H3P04 column. These neutrals are more suitably screened on
the OV-17 column. As a result, the acid pH extracts were also screened on
the OV-17 column to search for neutral compounds. The discussion below
discusses the results of these additional analyses.
Acidified Process Water Extracts—The results of the GC/MS screening
analysis of extracts from the acidified process water samples are presented
in Table B-l7. These results were obtained using the Carbowax 20M-
phosphoric acid column. In general, the detected compounds consist of
oxygenates such as ketones, alcohols, ethers, and cyclic ethers. Some of
these are lightly halogenated. One carboxylic acid, 2-ethyl hexanoic acid,
and phenol were seen in these samples. Some unsaturated hydrocarbons were
also identified.
Each of the acidified process water samples was generally found to
contain compounds not found in any of the other acidified water extracts.
However, two compounds were common to two or more samples. They were
2-cyclohexenol and a dt- or tri-methoxy methane.
The mixture of compounds from extracts of the acidified process water and
slurry liquid samples were not well resolved using the Carbowax 20M/phosphoric
acid column. The resulting chromatograms had high backgrounds and broad
peaks indicative of complex mixtures. Estimates of concentration levels
of the individual compounds believed to exist in these extracts proved too
unrealistic because of the high degree of background interference. Figure
B-5 is a GC/MS total ion chromatogram for the acidified extract of the
132/6-3 process water stream. The incomplete peak separation is evident.
If one makes a worst case assumption that some of the biggest peaks in these
chromatograms are single compounds, then the highest concentrations for any
159
-------
O1
o
100.01
RIC_
DATA: 13263LEAO II1894
CALI: C0627 13
BIG
86/27/78 13:24:9%
SAMPLE: 10 UL
RANGE. C 1.2080 LABEL: H 0. 46 f'UAN: A 0. 1.0 BASE: U 20. 3
1038
SCANS 160 TO 28»8
33:2«
15*8
50:88
1893
462848.
2800 SCAN
66:48 TIME
Figure B-5. Total 1on chromatogram of concentrated extract of acidified process water sample
-------
one compound in these process waters would not exceed 10 to 15 micrograms
per liter of water (vg/i).
Three acidified water extracts were selected for additional GC/MS
analysis on the OV-17 GC column intended for analysis of base/neutral com-
pounds. The three selected samples are identified in Table B-18 along with
compound identifications. It is interesting to note that there is no agree-
ment in the qualitative identifications between the data for the same sample
run under different GC conditions. The computerized data enhancement and
library search results on the acidified extracts run on the Carbowax 20M/
Phosphoric acid column should be considered more suspect. This is because
of the high backgrounds and compound interferences are causes of incorrect
background subtraction. No additional analysis have been carried out on
the acidified process water extracts at this time due to budget and schedule
limitations as well as the relatively insignificant estimated concentrations
being observed.
Neutral and Basic Process Water Extracts—The results of the GC/MS
analysis of the neutralized and basic process water extracts are presented
in Table B-19. The six or seven compounds for which reasonable identifi-
cations exist are ketones, a di-acid ester, an aliphatic hydrocarbon and
an aromatic hydrocarbon. Three ketones are common to at least two samples.
The remaining compounds are found in individual samples.
Several of the samples did not contain compounds at detectable or
identifiable levels. They are:
• 132/6-1-LEN
• 132/6-1-LEB
• 132/6-2-LEB
• 132/6-3-LEN
t 132/6-3-LEB
• 132/6-6L-LEN
• 132/6-7L-LEN
161
-------
TABLE B-19.
NEUTRAL AND BASIC PROCESS WATER EXTRACTS
(CONCENTRATION, yg/1 OF WATER SAMPLE)
ro
132/6-2-Neut U?/6-4-l»«ut 132/6-4-Baslc 132/6-5-Nfut 132/6-5-8as1c 132/6-6L-Ba$1c !32/6-7L-tas1c 132/6-6S
3-Hethyt-2-cyc1ohexen- 1-one X 1 n X X
(Also called Dlacetone)
R-Nethyl-M-dlhydro
naphthalene-one
3«,7A Dtltydro-S-iiethyl
1ndene-1,7(4H)-d1l ester of
Nonene dlolc acid
Possible l-(4-Chlorophenyl)-
1,4-D1hydro-2.3-b1phen>l
Qulnollne
Unkno.it
Z ,2 .5 ,5-Tetn»ethylhe«in«
A freon. e.g., 1,1.3,4-
Hcuf lucre tuttnc
Dlphtnyl Heptane (Possible)
Mixture of Trlchtoro propenes
DtMthylhe»ne
4-H«thyl-2-propyl pcntino!
C9 or Clo Drinched hydro-
carbon
TMnethylhexanft
Clo Hydroxylanlne
Dl-tert-butyl-mthylphenol
(»KT)
Freon: C^CljF, or C4Cl4Fj
1 ,1-Olpheny1-3-MtliylbuUn»
1 (1 ,6 ^"Tetraphtnylhexane
I
I
X
X
X
X
X
X
X
X
X
X
X
X
X • Compound Detected In Swiple Extract.
* DME6 Value for tutanoni It 6 K 10* ug/1.
t OKG Value for Indene t« 4 x 104 ug/1.
* No ONES Value It given for Acid Esters.
-------
Part of the reason why these samples did not contain any significant
material may be due, at least in part to the reversed extraction sequence
(acidified first) in which compounds normally found in the neutral extracts
were found in the acidified estracts. This appears to be borne out by the
results shown in Table B-16 for the acidified extracts. Many apparent neutral
compounds are found there. The concentration in the final concentrated
water extracts at which a compound would have to be present in a sample
in order to be detected is estimated to be 3 yg/ml. This corresponds to a
water concentration of 3 yg/£.
The neutral extract of process water sample 4 was additionally analyzed
with an internal standard to estimate the concentration of the detected
species. The concentrations for the three compounds identified in the
sample are shown in Table B-19. The presence of compounds found in the
remaining samples are indicated by an X.
The solids portion of the 132/6-6 and 132/6-7 slurry samples were also
extracted with methylene chloride after separation from the slurry.
These extracts were also screened on the GC/MS using the OV-17 column.
The extract of the solids from the process slurry sample 6 had a mixture
of hydrocarbons, 2 halogenated species, an ajcohol, a hydroxylamine and BHT,
a common antioxidant (Table B-19). The slurry solids extract from process
stream 7 had three compounds at levels too low to identify above sample
background. These levels were not specifically determined but inspection
of peak areas for the 3 unknowns are estimated to be very much less than a
water concentration of 1 yg/£.
163
-------
APPENDIX C
LA CY6NE INORGANIC ANALYSIS RESULTS
The comparative assessment tests conducted at the La Cygne Power Plant
were designed to study the effect of emission control devices on the flue
gas composition. As part of this program, Level 1 and comprehensive Level 2
sampling and analysis procedures were used to study the inorganic compounds
in the flue gas streams. The Level 2 sampling consisted of using a modified
Method 5 train for particulate matter in the flue gas and the controlled
condensation system for the H2SO. content of the flue gas.
After the Level 1 data was reviewed, specific analytical techniques
were used as part of the comprehensive Level 2 approach. These methods
included:
• Thermogravimetric Analysis (TGA) and Differential Scanning
Calorimeter (DSC) — Used to determine drying temperatures
or stability data.
• Polarized Light Microscopy (PLM) — Used visually to
identify materials present in the sample.
• Atomic Absorption Spectroscopy (AAS) — Used to determine
accurate inlet/outlet concentration of elements.
0 Particle Induced X-Ray Emission (PIXE) - Used to
determine elemental composition of individual
impactor stages.
a Fourier Transform IR (FTIR) - Used to identify inorganic
compounds from specific IR band correlations.
0 X-Ray Diffraction (XRD) - Used to directly identify
crystalline material in the solid samples.
0 Electron Spectroscopy for Chemical Analysis (ESCA) —
Used to study the surface and sub-surface sulfur
concentrations and oxidation state of bulk samples.
0 Secondary Ion Mass Spectrometry (SIMS) — Used to study
the surface and sub-surface composition of bulk samples.
0 Scanning Electron Microscope with Energy Dispersive X-Ray
Fluorescence (SEM-EDX) — Used to obtain high resolution
photographs and elemental composition of single particles.
164
-------
In addition to these Instrumental methods, specific anlon analyses for
Cl~, F~, and SO." were run on the CCS train samples.
The following sections will discuss the results from TGA/DSC, PLM,
SEM/EDX, SSMS, XRD and MRI Impactor analyses. PIXE, FTIR, and SIMS analyses
did not give meaningful results and are not reported here. The results of
other analytical techniques (AAS, ESCA, and specific anion analyses) have
been discussed in the text.
RESULTS OF ANALYSES
Complete sets of samples were available for the 135 run. Only this
sample set was analyzed. The following sections contain the data from each
of the methods employed for each sample analyzed. In some cases, two or
more methods will be discussed together for comparison purposes.
TGA/DSC Results
Differential Scanning Calorimeter (DSC) measures the energy required
to maintain a sample at the same temperature as a reference material as both
temperatures are raised. In this way the area under the peak is a direct
measure of the enthalpy of a physical or chemical change. Thermogravimetric
analysis (TGA) measures weight gain or loss as the temperature is steadily
increased. By comparing DSC and TGA results, phase changes can be differ-
entiated from chemical decomposition.
TGA and DSC's were run on: 133-18-BA (bottom ash), 135-6 (scrubber
slurry in), 135-7 (scrubber slurry out), 135-LF (lime feed), and 135-OUT-CYC
(SASS cyclone catch). In addition TGA's were run on 135-IN-PF (SASS filter
catch), 135-IN-PFa (SASS filter catch; "a" denotes second filter used during
run), 135-OUT-PF, and 135-IN-CYC. The analyses were run using DuPont 950
TGA/DSC system in a N2 atmosphere at temperatures up to 650°C.
Table C-l summarizes the results of the TGA and DSC results. The inlet
cyclone and filter catches show similar weight loss profiles. The inlet
filter samples show an additional feature on the TGA at 170°C which does not
appear in the cyclone TGA. While both inlet filter samples have the same
profile, the weight loss for 135-IN-PF is over twice as much than 135-IN-PFa.
Also the inlet filters have more of a weight loss than the inlet cyclone
catch.
165
-------
TABLE C-l. TGA/DSC RESULTS
Sample
DSC
TGA
135-IN-CYC No significant features
135-IN-PF
135-OUT-CYC
133-18-BA
135-6
135-7
135-LF
Not Run
135-IN-PFa Not Run
- Three large endothermic
peaks at 87°C, 120°C,
and 190°C. Small endo-
thermic peak at 220°C.
135-OUT-PF Not Run
No significant features
Small endothermic peak
at 113°C
Small endothermic peak
at 128°C and a large,
sharp endothermic peak
at 407°C
- Possible endothermic peak
at 33°C
- Slow loss of weight (1.3%)
up to 550°C. Slight
increase in weight loss up
to 650°C.
- 20% weight loss up to
175°C.
- An additional weight loss
of 8% until ^525°C.
- Sharp weight loss after
550°C.
- Loss of 9.7% weight up to
170°C.
- An additional 2.8% lost
up to 550°C.
- Sharp increase in weight
loss at up to 650°C limit
- Large weight loss (36.7%)
over a range of 50°C to
350°C.
- Sharp increase in weight
loss at 550°C.
- Loss of 6.3% weight up to
6QOC.
- Slow, consistent weight
loss (5%) from 60<>C to
475<>C.
- Loses no weight from 25°C
to 65QOC.
- Slight weight loss starts
at ^525°C.
- 0.8% weight loss up to
360°C.
- 2.1% lost from 395 to
420°C.
- Stable to 600°C.
- Weight loss of 1.9% at
500C.
- Slow weight loss from
400° to 650°C (<3%) -
possibly due to
instrument interference
166
-------
At the scrubber outlet the cyclone sample weight loss is far greater
than the filter. The DSC of the outlet cyclone shows three large endothermic
peaks at 87°C, 120°C, and 190°C with several smaller shoulders at 140°C and
230°C. The major peaks roughly correspond to the dehydration of CaSOj-
1/2 H20 (100°C), CaS04-2H20 (to the half hydrate - 128°C) and CaS04-l/2 HgO
(163°C). The profiles for the outlet samples may indicate that the outlet
material is modified with respect to the inlet particulate.
DSC can be influenced by the heating rate. At high heating rates the
sample temperature may tend to lag behind the temperature of the reference
material for endothermic reactions. The DSC spectra of the 135-OUT-CYC was
repeated at a heating rate of 2°C/min (original 10°C/min). The scan is
quite different, showing peaks at 47°C, 94°C, 160°C, and shoulders at 115°C
and 175°C. The 47°C peak is probably due to surface water and baseline
drift. The 94°C and the 160°C may correspond to the CaSCyl/2 H20 -»• CaS03
and the CaS04'l/2 H20 -»• CaS04 dehydrations. The shoulder at 115°C might be
due to the dehydration CaSO^ZHgO. The 175°C shoulder is unidentified, but
may represent a phase change of CaSO^ between o & B forms or a reaction of
an unidentified material.
PLM and SEM-EDX Results
Polarized light microscope analyses were completed on the following
samples:
133-18-BA 135-6
135-IN-CYC 135-7
135-IN-PF 135-OUT-CYC
135-IN-PFa 135-OUT-PF
135-IN-PFb 135-OUT-PFa
135-LF
Where SEM-EDX analysis emphasizes the PLM results, the photos are used
to illustrate the result.
Size Distributions
Where possible a size distribution of each sample was determined.
Materials which appeared to have crystallized on the filter or within
a sample after collection were not included in the size distribution.
167
-------
The outlet filter samples, 135-OUT-PF and 135-OUT-PFa were composed
almost exclusively of these crystallized materials. For this reason,
no size distribution of these samples was determined.
All of the particles in 133-18 are too large to be sized with
optical microscopy. The samples containing limestone as the major com-
ponent, 135-LF and 135-6 are composed of a large number of particles
which are too big to be sized with optical microscopy. With such a great
size range (
-------
TABLE C-2. OVERALL SIZE DISTRIBUTIONS
Size Ranges (urn)
<1.0
1.0-2.0
2.0-3.0
3.0-4.0
4.0-6.0
6.0-8.0
8.0-10.0
10.0-14.0
14.0-20.0
>20.0
Arithmetic Mean
Diameter
<3.2
3.2-6.4
6.4-12.8
12.8-19.2
19.2-32.0
32.0-48.0
>48.0
Arithmetic Mean
Diameter
135-IN-
CYC
16.2%
19.8%
21.6%
14.4%
14.4%
4.5%
4.5%
2.7%
1.8%
0
3.5 ym
135-7
32.5%
26.3%
23.0%
13.9%
3.8%
0.5%
0
7.7 ym
135-IN-
PF
54.9%
34.6%
9.3%
0.2%
0
0
0
0
0
0
1.0 ym
135-IN-
PFa
53.1%
34.9%
9.3%
2.7%
0
0
0
0
0
0
1.1 ym
135-IN-
PFb
62.2%
28.6%
7.6%
1.3%
0.4%
0
0
0
0
0
1.0 ym
135-OUT-
CYC
40.9%
28.8%
15.6%
8.6%
4.7%
1.2%
0.4%
0
0
0
1.5 ym
169
-------
TABLE C-3. COMPOSITION OF SAMPLES
COMPONENTS 133-18 135-IN-CYC 135-IN-PF 135-IN-PFa 135-TN-PFb 135-LF 135-6 135-7 135-OUT-CYC 135-OUT-PF 135-OUT-PFa
Limestone 95% + 98% + 45-60%
Flyash 80-95% 35-50% 35-50% 40-55% 5-10% 15-30%
Magnetite <2% 5-15% 5-10%
Partially Combusted
Coal <2% <2% <2% <2% <2% <2%
Crystallized Minerals 95% 95% +
Type I 50-65% 50-65% 40-60%
Type II 70-85%
Type III
CaS03'l/2 H20 30-45%
-------
Figure C-l - 135-OUT-PFa Showing the Three Types of Crystallized Minerals Found in
These Samples; Partially Uncrossed Polars (PUP), 131X
-------
Type 2: The second type of crystallized mineral is either in thin
plates or irregular round chunks. In the photomicrograph it is
the mottled angular plate upon which the spherulites are sitting.
It has a birefringence of approximately 0.01. The refractive
indices are difficult to determine since the plates are composed
of many tiny, independent crystals. This mineral type is found
in all three outlet samples but in none of the others.
Type 3: These are the brown nodules seen in the photomicrograph.
They are brown in transmitted light and white in reflected light.
Air bubbles within the nodules are probably responsible for the
white color. They also show a maltese cross on their surfaces
with crossed polars. The refractive indices of these particles
are between 1.515 and 1.600 (closer to the latter). They have
very low birefringence, probably less than 0.010 and show parallel
extinction. These nodules are only found in the filter outlet
samples, 135-OUT-PF and 135-OUT-PFa.
The above crystals will be refered to as Type 1, Type 2, and Type 3
in the text.
Other than the crystals, the most frequently encountered emissions
are flyash and magnetite. Partially combusted coal is seen in most samples
but always as a minor component. Calcium sulfite hemi-hydrate
(CaS03'l/2 H20) laths were found as a major component of the scrubber
cake. Limestone was also found in the scrubber cake.
Descriptions of the individual samples follow.
133-18-BOTTOM ASH
The particles in this sample were much too large to be analyzed with
optical microscopy. For this reason, a small portion of the sample was
crushed with a mortar and pestle for the analysis.
The slag is composed of glassy, isotropic particles which show con-
coidal fracture (Figure C-2). They have a refractive index of about
1.595 and are an olive-green color. The glassy nature of the slag indicates
that the temperatures reached were sufficient to vitrify the mineral con-
taminants of the coal.
172
-------
0,1
Figure C-2 - 133-18 Showing the Crushed Slag; Plane Polarized Light (PPL); 51X
-------
Incorporated within the slag is magnetite, most of which is less
than lym in diameter. These spheres are speckled throughout the glassy
slag. Irregularly shaped magnetic fragments are also associated with
the slag.
135-IN-CYC-INLET CYCLONE
Average
Components Concentration Diameter (urn)
Flyash 80-95% 4
-------
--4
on
Figure C-3 - 135-IN-CYC Showing Flyash, Magnetite, and Partially Combusted Coal
PPL, 51X.
-------
en
I
Figure C-4 - 135-IN-CYC Showing the Same Field of View as Figure C-3 but at a Higher
Magnification; PPL, 131X.
-------
Figure C-5 - SEM Photograph (1400X) of 135-IN-CYC Showing
Cenospheres and Air Pockets in Broken Cenosphere
177
-------
Figure C-6 - Closeup
(4000X) of Smaller Cenospheres that Fill
Into Fractured Cenosphere
17R
-------
The photomicrographs of this sample (Figure C-7) and of the other two
inlet filter samples (Figures C-8 and C-9) are of the undesiccated samples.
This is because after desiccation the particles agglomerated making dis-
persion impossible. After desiccating the samples, Type 1 spherulites
was the major sample component. Since the photos are of wet samples, the
particles shown do not include the soluble Type 1 spherulites.
By far the most numerous particulate found in this sample is flyash.
Almost all of the flyash is less than 4ym in diameter. The average flyash
diameter is about lym. The color of the glassy flyash spheres are primarily
golden brown with a few spheres which are colorless, red, or brown.
Partially combusted coal was the only other combustion product
detected. It is a minor sample component, not more than 2% of the sample
mass. Magnetite which was 5-15% of the 135-IN-CYC sample is not present
in this sample. This is probably because the magnetite spheres are too
large and heavy to pass the cyclone.
135-IN-PFa, 135-IN-PFb-Filter Samples
Average Size
Concentration Diameter (ym) Range (vim)
135-IN-PFa
Flyash 35-50% 1
-------
< •
-
Figure C-7 - 135-IN-PF Before Desiccation, Shows Flyash; PUP, 131X.
-------
*.
00
*•£* «e** * *
^^^k A A *
' ^rv • •**,%*« •. •
Figure C-8 - 135-IN-PFa Before Desiccation, Shows Flyash; PUP, 131X
-------
CX>
T*v**a'
• . *.
> *• .4
• \^,
€ .
; '-
•„
1»
Figure C-9 - 135-IN-PFb Before Desiccation, Shows Flyash; PUP, 131X.
-------
Figure C-10 - SEM Photograph of Section of 135-IN-PFa Filter Sample
With Type I Crystal in Upper Right Hand Corner
183
-------
Figure C-ll - 9000X Enlargement of Type I Crystal in Figure 3.
EDX Analysis: High, Fe, Si, S; Medium Zn; Low K, and Ca
184
-------
may only be the result of a possible difference in crystallizing conditions
between the samples. The elemental analysis showed Fe, Si and S to be
the major elements, Zn, K and Ca were also present. It could be possible
that H2S04 impinging on the flyash dissolved Fe and formed the crystals.
However, the strong (30 kV) beam strength probably excited the flyash
underneath the Type I crystals, which resulted in the apparent Fe line.
As in the 135-IN-PF sample, flyash is the most numerous particulate.
The colors and modal size of the flyash spheres are approximately the
same in all three samples. Even though spheres greater than 4ym in diam-
eter are present, 99% of the flyash is less than 4pm in diameter.
Partially combusted coal, (average diameter: 3ym) is <2% of both
samples. As in 135-IN-PF, no magnetite was seen.
135-LF-Limestone Feed
Probably greater than 95% of this sample is limestone. Other com-
ponents can be regarded as contaminants and the degree of contamination
is highly dependent upon which portion of the sample was used for the
analysis. Approximately 10 slides were made. Several were made of a
large crushed limestone "rock". The rest of the slides were prepared
of the fine limestone dust in the sample.
The samples prepared from the crushed rock were almost exclusively
composed of limestone (Figure C-12). Much less than 1% of these samples
was contaminants. These contaminants were primarily quartz and clays and
there was a very trace amount of coal or humus. These contaminants were
probably those which adhered to the outside of the rock and are not
incorporated within it.
The samples of dust or fine particles were much more heavily con-
taminated. Some samples contained as much as 10-25% contaminants. As
in the crushed rock, clays and quartz were the predominant contaminants.
Most of the quartz fragments were heavily speckled with clays and
humus and there are individual clay particles as well. Agglomerates of
clay and quartz (Figure C-13) were commonly seen. A trace of coal (or
humus) is present, too. In reflected light some of the limestone chunks
have a yellow surface coating. This is probably a thin coating of hydrated
iron oxide.
185
-------
CD
Figure C-12 - 135-LF Showing a General View of Crushed Limestone "Rock"; PUP, 51X.
-------
03
- I
Figure C-13 - 135-LF Showing Soil Agglomerates Which Contaminate the "Dust" Samples
PUP, 131X.
-------
Determination of the actual percent of contaminants is impossible
since they are so unevenly distributed within the sample received. By
far the greatest sample mass is involved in the limestone "rock" and its
purity would imply greater than 99% is limestone. However, if limestone
dust is a large sample component, then the sample may not be this pure.
135-6-SLURRY IN
This sample of limestone (Figure C-14) seems to be much cleaner than
the 135-LF sample. In no slide prepared of this sample were contaminants
greater than 2% of the sample mass. In most samples, the contaminants
were difficult to find and contributed considerably less than 1% of the
mass.
The major contaminants found in 135-6 were humus, coal fragments,
and quartz. Individual clay particles and soil agglomerates are much
lesser contaminants than in 135-LF sample. Some of the limestone chunks
have an iron oxide coating making them appear yellow in reflected light.
135-7-Scrubber Cake
Average Si ze
Components Concentration Diameter (ym) Range (pm)
CaS03-l/2 H20 30-45% 15 (length) 3-60 (length)
Limestone 45-60% 9 <1-200
Flyash 5-10% 5 <1-40
Magnetite 5-10% 20 5-80
The primary components are calcium sulflte hemi-hydrate (CaSO,*l/2 H^O
laths and limestone (Figures C-15 and C-16). Though the laths appear to
be more numerous, the limestone particles are generally larger and thereby
contribute a greater mass to the sample.
The CaSCL-1/2 tU) laths compose 30-45% of the overall sample mass.
These laths are transparent and have refractive indices: a=1.596, 0=1.598,
Y=1.634. The birefringence of the lath surface usually observed is about
0.028. The modal lath length is about 15ym though they range from 3-60ym
in length. Most have about a 3:1 aspect ratio (length: width). The
maximum thickness of a lath seen was only about 5ym - most were less than
2ym thick.
188
-------
•
Figure C-14 - 135-6 Showing Limestone; PUP, 51X
-------
1'..
< >
Figure C-15 - 135-7 Showing General View of This Sample at Low Magnification: PUP 51X.
-------
f
U i
*
J
Figure C-16 - 135-7 Showing CaSCL • 1/2HLO Laths, Limestone, Flyash, and Magnetite;
PUP, 131X.
-------
The limestone is present both as single crystals and as aggregates
of smaller crystals. They range in size from
-------
1C
0 '
7
V u"
Figure C-17 - 135-OUT-CYC Showing Type 2 Crystallized "Crust" With Flyash Embedded in it:
PUP, 51X.
-------
Figure C-18 - SEM Photograph of 135-OUT-CYC Showing
Flyash and Crystalline Material Aggregates
194
-------
Figure C-19 - SEM-EDX (2000X) Photograph of Crystalline Material in
135-OUT-CYC. EDX Analysis: High Fe & S; Low Si, Zn, Ca
195
-------
Flyash is 15-30% of this sample. There are some flyash spheres
which are 40pm in diameter though the average size is only about 2ym.
As in most samples, the flyash spheres are predominantly golden brown
and a small percentage are plerospheres.
Partially combusted coal accounts for less than 2% of the sample mass.
The average diameter is about 2ym and the diameters of these irregular
chunks range from
-------
ID
- i
o
Figure C-20 - 135-OUT-PF Showina the Crystal Types Present in This and the 135-OUT-
PFa Samples; PUP, 51X.
-------
Figure C-21 - SEM of 135-OUT-PFa Filter (500X)
Showing Donut-Shaped Particles
198
-------
Figure C-22 - SEM-EDX Enlargement (5500X) of Single Nodule from
135-OUT-PFa. Arrow 1 EDX: High S, Fe, Zn; Low Ca,
Si, K. Arrow 2 EDX: High S, Fe, Zn; Medium Si; Low K, Ca
199
-------
Figure C-23 - SEM-EDX of 135-OUT-PF Showing Cubic and Platelet Materials
Arrow 1 EDX: High S, Fe, Zn; Low K. Arrow 2 EDX: High
Fe, Si, Ca, Zn, S
200
-------
SSMS
Trace element analyses by SSMS of the following coal firing samples
are presented in Tables C-4 to C-20:
- Coal Feed (tests 132-136)
- Combined Flue Gas Particulates (test 135)
- Boiler Feedwater (test 132)
- Demister Inlet (test 132)
- Settling Pond Overflow (test 132)
- Inlet Scrubber Water (test 132)
- Water to Slag Pond (test 132)
- Lime Feed (test 135)
- Inlet Scrubber Slurry Liquid (test 135)
- Inlet Scrubber Slurry Solids (test 135)
- Outlet Scrubber Slurry Liquid (test 135)
- Outlet Scrubber Slurry Solids (test 135)
- Bottom Ash (test 133)
XRD
All samples, powders and filters, were analyzed on the Diano-8000
x-ray diffractometer with Cu,, radiation. Instrument parameters were
constant for all samples. Powder samples were ground to ca 40y size and
then packed in a sample holder. Filter samples were pressed to ensure a
smooth surface and were mounted on a flat surface with double-back Scotch
tape. A filter blank was run. No diffraction pattern was observed. Thus,
the glass fiber filters did not interfere in the analysis of filter
samples.
Results of these analyses are summarized in Table C-21. Standard ASTM
d-spacings were used for matching compounds.
MRI Impactor Data
PLM analysis was performed on the inlet particulates for test 135.
MRI impactor data were gathered for tests 135 and 136 at the outlet. The
impactor data was reduced using the procedure developed by Ensor (Reference
C-l). In this approach the data is normalized so that a smooth curve can
be drawn through the limited number of data points obtained from the
impactor. In order to draw a smooth curve, the geometric mean of the D's
*
The DSQ of an impactor stage is the calculated aerodynamic particle
diameter for which the stage achieves 50% efficiency: one half of the
particles of that diameter are captured and one half are not.
201
-------
TABLE C-4. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF COAL FEED - TEST 132 (132-CF)
CONCENTRATION IN PPAA WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Indium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
CONC.
14
10
<0.2
*360
<1
NR
<0.9
2
.0.2
0.9
0.1
0.8
1
2
ELEMENT
. Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.4
1
0.5
4
10
5
52
41
320
5
4
iO.3
14
2
STD
0.7
2
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
20
9
160
29
140
77
2
11
62
4
13
59
96
37
17
MC
300
100
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron.
Beryllium
Lithium
Hydrogen
CONC.
90
MC
5
MC
MC
13
MC
150
MC
MC
MC
MC
=780
NR
NR
NR
21
0.7
6
NR
NR - Not Reported
AM elements not reported <0.1 ppm weight
MC - Major Component
*Hetcrogeneous
202
-------
TABLE C-5. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF COAL FEED - TEST 133 (133-CF)
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbi urn
Thul i urn
Erbium
Holmium
Dysprosium
CONC.
17
12
<0.2
340
<2
NR
<0.8
1
0.3
1
0.2
1
2
3
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium.
Cadmium
Silver
Palladium
Rhodi urn
CONC.
0.6
2
0.8
7
10
7
55
37
380
5
3
<0.5
11
1
STD
1
2
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromi urn
CONC.
32
7
91
21
180
81
2
43
39
6
16
185
84
10
14
MC
57
54
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryl 1 i urn
Lithium
Hydrogen
CONC.
47
MC
8
MC
MC
20
MC
970
MC
MC
MC
MC
=390
NR
NR
NR
5S
1
49
NR
NR - Not Reported
All elements not-reported <0-"2ppm weight
MC - Major Component
203
-------
TABLE C-6. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF COAL FEED - TEST 134 (134-CF)
CONCENTRATION IN PPAA WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thul i urn
Erbium
Hoi mi urn
Dysprosium
CONC.
*63
13
<0.1
200
<0.2
MR
<0.2
<2
1
0.2
1
0.1
0.8
1
2
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodi urn
CONC.
0.4
1
0.7
4
10
6
66
120
480
5
3
<0.3
16
2
STD
0.8
4
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromi urn
CONC.
13
6
73
*120
180
39
2
55
31
10
33
130
60
15
11
MC
57
34
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodi urn
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
45
MC
2
MC
MC
17
MC
170
MC
MC
MC
MC
=39
NR
NR
NR
17
0.6
6
NR
NR - Not Reported
All elements not-reported <0.l ppm weight
MC - M.JOT Component *Heter0geneOUS
204
-------
TABLE C-7. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF COAL FEED - TEST 135 (135-CF)
CONCENTRATION IN PPM WEIGHT
ElEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
CONC.
46
31
<0.1
470
0.3
NR
0.7
0.8
0.2
0.8
0.1
0.6
0.8
1
ELEMENT
Terbium
Gadolinium
Europi urn
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.3
0.8
0.4
5
9
7
38
34
770
4
3
<0.1
6
1
STD
0.5
0.5
ElEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Sel eni urn
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
16
7
47
14
100
70
1
10
68
16
5
95
19
18
10
MC
no
25
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
33
MC
2
MC
MC
18
MC
140
MC
MC
MC
MC
=76
NR
NR
NR
14
0.2
3
NR
NR - Not Reported
All elements not-reported <0.1 ppm weight
MC — M«|o' Component
205
-------
TABLE C-8. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF COAL FEED - TEST 136 (136-CF)
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thai 1 1 urn
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetlum
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
CONC.
22
16
<0.2
170
<1
NR
2
2
0.2
1
0.1
0.2
1
2
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodi urn
CONC.
0.8
2
1
5
10
11
36
42
440
5
11
29
2
STO
*3
2
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromi urn
CONC.
41
11
48
30
150
35
3
45
38
9
14
*150
55
38
18
MC
310
35
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
69
MC
2
MC
MC
52
MC
160
MC
MC
MC
MC
=130
NR
NR
NR
22
1
6
NR
NR - Not Reported
All elements not-reported <0.1 ppm weight
MC — Major Component
*Hetcrogeneous
206
-------
TABLE C-9. COMBINED SPARK SOURCE MASS SPECTROMETRY ANALYSES
OF FLUE GAS PARTICULATES - TEST 135
Element
Al
Ag
As
B
Ba
Be
Bi
Ca
Cd
Ce
Cl
Co
Cr
Cs
Cu
F
Fe
Ga
Ge
K
La
Li
Mg
Mn
Mo
Na
Nb
Nd
Ni
P
Pb
Rb
Sb
Se
Si
Sn
Sr
Ti
Tl
U
V
Y
Zn
Zr
Concentration,
Inlet
1.94
> 20.6
> 95.1
0.300
> 2.34
0.0034
0.012
179.6
0.862
0.688
> 0.524
0.088
0.975
0.106
1.958
0.27
>134.9
0.889
0.415
>101.0
0.670
0.108
> 49.0
> l'.62
0.994
> 49.0
0.233
0.136
> 1.03
>100.8
>100.4
0.557
0.888
0.376
> 1.92
0.160
> 1.658
>100.4
0.192
> 0.786
1.008
0.262
>134.9
0.833
mg/m
Outlet
> 0.139
0.036
> 9.00
0.039
0.320
0.001
0.002
>44.0
0.316
0.011
0.206
0.007
>26.0
0.003
>26.0
0.062
>62.6
0.020
0.070
10.4
0.003
0.011
> 0.122
0.02
0.155
> 0.372
0.004
0.001
0.036
62.6
>90.0
0.007
0.117
0.130
41.0
0.025
0.047
> 9.00
0.043
0.09
0.128
0.004
>76.00
0.005
207
-------
TABLE C-10. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF BOILER FEEDWATER - TEST 132 (132-6-1-1)
CONCENTRATION IN
vg/ml
ELEMENT CONC.
Uranium 0.07
Thorium 0.4
Bismuth 0.03
Lead 0.09
Thallium
Mercury NR
Gold
Platinum
Irldium
Osmium
Rhenium
Tungsten
-------
TABLE C-11. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF DEMISTER INLET - TEST 132 (132-6-2-1)
CONCENTRATION IN
ELEMENT CONC.
Uranium o.04
Thorium
Bismuth
Lead o.Ol
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium <0.005
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.001
0.003
0.003
0.5
0.3
10.004
0.01
STD
0.009
0.001
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
0.5
0.005
0.008
0.004
3
0.02
0.9
0.1
0.05
0.01
0.002
0.5
0.1
0.07
0.01
0.3
0.6
<0.03 -
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.004
0.04
<0.001
MC
MC
1
>8
0.09
1
0.04
MC
>3
=0.4
NR
NR
NR
2
0.02
NR
NR - Not Reported
All elements not reported <0.001 U9/IB.1
MC - Major Component
209
-------
TABLE C-12. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF SETTLING POND OVERFLOW - TEST 132 (132-6-3-1)
CONCENTRATION IN
ELEMENT CONC.
Uranium 0.02
Thorium
Bismuth
Lead 0.06
Thallium <0.002
Mercury NR
Gold
Platinum
Irldium
Osmium
Rhenium 0.004
Tungsten 0.003
Tantalum
Hafnium
Lutetian
Ytterbium
Thulium
Erbium
Holmlum
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC
<0.001
0.002
<0.001
<0.001
0.004
0.003
0.2
<0.001
0.2
<0.002
0.02
0.001
STD
0-.02
0.001
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
0.3
0.003
0.003
0.001
4
0.02
0.6
0.1
0.5
0.02
0.001
5
0.01
INT
0.01
0.3
>3
0.02
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.002
<.0.008
<0.001
MC
>4
MC
>2
0.04
0.5
0.1
MC
>1
=0.5
NR
NR
NR
&
<0.001
0.02
NR
NR - Not teportad
All tltmenu not reported <0. 001
«*c - M*ior component INT- Inte rference
210
-------
TABLE C-13. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF INLET SCRUBBER WATER - TEST 132 (132-6-4-1)
CONCENTRATION IN
ELEMENT CONC.
Uranium 0.01
Thorium
Bismuth
Lead 0.01
Thallium
Mercury NR
Gold
Platinum
Irldlum
Osmium
Rhenium <0.004
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmlum
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodynri um
CONC.
0.002
Praseodym1um<0.001
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
0.002
0.003
0.2
0.001
0.3
<0.002
0.02
0.002
STD
0/005
0.001
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
'Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
0.6
0.003
0.009
0.003
2
0.02
0.2
0.08
0.06
iO.Ol
0.001
0.6
0.009
0.07
0.01
0.3
1
0.08
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.004
0.4
<0.001
MC
>8
3
>4
0.05
2
0.03
MC
>2
~2
NR
NR
NR
1
0.02
NR
NR - Not Reported
All elements not reported < 0.001
MC - M*ior Component
211
-------
TABLE C-14. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF WATER TO SLAG POND - TEST 132 (132-6-5-1)
CONCENTRATION IN
ELEMENT CONC.
Uranium Q.05
Thoriun
Bismuth o.2
Lead Q.09
Thallium
Hercury NR
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetlum
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
NR - Not Rcporttd
All ftlftmcnts not rftporttc
MC - MtoiBr Camaanant
ELEMENT CONC.
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium 0.009
Lanthanum 0.009
Barium i
Cesium
Iodine 0.4
Tellurium 0.006
Antimony
Tin
Indium STD
Cadmium 0.006
Silver
Palladium
Rhodium
J <0.002 yg/nrt
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
0.1
0.004
0.005
2
0.004
0.4
0.01
0.04
0.003
0.5
0.05
0.08
<0.003
1
0.08
0.1
ELEMENT
Vanadium
Titanium
Scandi urn
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesi urn
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.01
0.06
<.0.002
MC
MC
9
MC
0.1
0.7
>2
7
>5
*0.3
NR
NR
NR
0.4
0.007
NR
212
-------
TABLE C-15. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF LIME FEED - TEST 135 (135-LF)
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Indium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thul i urn
Erbium
Hoi mi urn
Dysprosium
CONC.
18
10
0.3
20
<0.2
NR
0.7
<0.3
0.3
<0.1
0.5
<0.1
0.5
0.6
1
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.4
1
0.7
5
5
5
30
23
220
1
11
10.4
1
1
STD
1
0.3
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Stronti urn
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromi urn
CONC.
6
5
65
7
MC
20
0.9
0.6
5
0.3
4
15
15
9
1
MC
>520
19
ELEMENT
Vanadium
Titanium
Scandi urn
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryl 1-ium
Lithium
Hydrogen
CONC
30
800
0.7
MC
MC
13
MC
870
MC
MC
MC
NR
=180
NR
NR
NR
3
0.2
7
NR
NR - Not Reported
All elements not reported
MC - Major Component
<0.1 ppm weight
213
-------
TABLE C-16. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF INLET SCRUBBER SLURRY LIQUID - TEST 135
(135-6-LIQUID)
CONCENTRATION IN pg/ml
ELEMENT . CONC.
Uranium 0.1
Thorium
Bismuth
Lead 0.02
Thallium
Mercury NR
Gold
Platinum
Irldlun
Osmium
Rhenium
Tungsten <0.03
Tantalum
Hafnium
Lutetlum
Ytterbium
Thulium
Erbium
Hoi ml urn
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymlum
Praseodyml urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.008
0.01
0.1
<0.001
0.2
<0.01
0.03
0.005
STD
0.01
0.002
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
1
0.01
0.02
<0.009
8
0.02
1
0.07
3
0.03
0.02
0.3
0.05
INT
0.02
0.1 '
0.04
0.04
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.008
<0.03
10.002
MC
MC
MC
>8
0.1
1
0.02
MC
>3
MC
NR
NR
NR
8
<0.1
NR
NR *~ Not
All •tantnts net reported
MC - M*ior Component
<0.002 vg/ml
INT-Interference
214
-------
TABLE C-17.
SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF INLET SCRUBBER SLURRY SOLIDS - TEST 135
(135-6-SOLID)
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
Uranium 11
Thorium 7
Bismuth
Lead 12
Thai 1 i urn
Mercury NR
Gold
Platinum
Indium
Osmi urn
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium <0.1
Ytterbium 0.7
Thulium 0.2
Erbium 0.6
Hoi mi urn 0.8
Dysprosium 1
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.6
2
0.8
4
2
4
40
31
320
4
7
1
2
STD
1
0.7
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromi ne
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
15
3
29
10
MC
13
0.8
2
4
1
6
45
4
12
1
MC
>690
19
ELEMENT
Vanadium
Titanium
Scandi urn
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
13
200
0.2
MC
MC
17
MC
230
MC
MC
MC
MC
=240
NR
NR
NR
3
<0.1
4
NR
NR - Not Reported
All elements not reported
MC ~~ MA jor
<0.1 ppm weight
215
-------
TABLE C-18. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF OUTLET SCRUBBER SLURRY LIQUID - TEST 135
(135-7-LIQUID)
CONCENTRATION IN yg/ml
ElEMENT CONC.
Uranium 0.01
Thoriun
Bismuth
Lead <0.004
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium <0.01
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodi urn
CONC.
0.001
0.001
0.009
0.2
<0.001
2
<0.007
0.07
0.003
STD
0.003
0.003
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromi urn
CONC.
4
0.01
0.02
<0.006
6
0.03
3
0.5
5
0.4
0.007
0.06
0.005
INT
<0.003
0.01
0.5
0.2
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
0.01
10.02
<0.001
MC
MC
HC
>6
0.06
MC
0.004
MC
>3
»8
NR
NR
NR
MC
0.1
NR
NR- Net Reported
All elements not reported
-------
TABLE C-19. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF OUTLET SCRUBBER SLURRY SOLIDS - TEST 135
(135-7-SOLID)
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osml urn
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thul 1 urn
Erbium
Hoi mi urn
Dysprosium
CONC.
44
11
0.2
820
6
NR
<0.3
0.6
0.3
1
0.2
1
2
3
ELEMENT
Terbi urn
Gadolinium
Europi urn
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.6
2
1
5
13
3
65
47
270
4
6
<0.4
44
5
STD
33
3
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
25
13
73
12
910
22
5
7
120
17
19
MC
50
23
9
MC
>580
16
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryll-ium
Lithium
Hydrogen
CONC.
19
880
2
MC
MC
130
MC
970
MC
MC
MC
MC
=260
NR
NR
NR
13
0.7
5
NR
NR - Not Reported
All elements not reported
MC - Major Component
<0.1 ppm weight
217
-------
TABLE C-20. SPARK SOURCE MASS SPECTROMETRY ANALYSIS
OF BOTTOM ASH - TEST 133 (133-18-BA)
CONCENTRATION IN
ELEAAENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Indium
Osmium
Rhenium
Tungsten
Tantalum
. Hafni urn
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
CONC.
1
0.4
MC
1
NR
0.01
<0.001
0.03
0.002
0.04
0.004
0.04
0.06
0.09
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
CONC.
0.04
0.1
0.1
0.2
1
0.2
2
2
MC
0.3
0.004
<0.007
0.04
0.004
STD
0.007
0.005
ELEAAENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
0.1
1
2
1
3
3
0.02
0.05
0.03
0.03
0.1
MC
0.3
0.8
0.3
MC
>5
0.4
ELEAAENT
Vanadium
Titanium
Scandi urn
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC. .
1
MC
0.03
MC
>6
0.2
>3
8
MC
>1
MC
>1
.0.1
NR
NR
NR
0.1
0.01
0.4
NR
NR - Not Reported
All elements not reported <0. 001
MC - Major Con*>on*n*
218
-------
TABLE C-21. SUMMARY OF XRD ANALYSES OF COAL-FIRED SAMPLES
Sample
Compound Definitely Present
Compounds Possibly Present
135-Out-PF
135-Out-PFa
CaS04; a-S102; CaS03'l/2
Kaolinite; Fe2Al4Si5018; Na2S12
Fe,,Si04; barium aluminosilicate
135-In-PF
135-In-PFa
CaSO/
ro
135-In-CYC
135-6 j
135-LF (
Fe3°4
CaC03; a-Si02
Li2B204-16H20; CagAlgO^
Ba3Ca2Ti2Og; Mg3Ca(C03)4
135-7
133-18-BA
135-PFB
CaC03; a-Si02; CaS03
-------
for stages n and n-1 is taken as the average diameter of the particles in
stage n. In this case two assumptions were made: (1) the upper limit of
the first stage was arbitrarily set at lOOy and (2) the final filter
absolute collection point was set at 0.2y. Figure C-24 shows the differential
mass loading at the outlet for tests 135 and 136 plotted against the geo-
metric mean D5Q for each stage. This method of data presentation allows
comparison of mass loadings for the individual Impactor stages, which is
difficult if the data are presented as cumulative mass loadings. There is
good agreement between tests 135 and 136 for outlet loadings on impactor
stages 2 to 7. Stage 8 for test 135 showed a weight loss and this data
point was discarded. The weight for stage 1 of test 135 was considerably
higher than for test 136. The high value was considered to be in error,
since this stage catch contains the coarse partlculate and most of the
coarse particulate is expected to be removed by scrubbing. The high weight
was probably due to some extraneous matter which was found on the Impactor
plate. Because the outlet impactor data agreed quite well for the two
tests, with the exception of the two points which could reasonably be dis-
carded, the data from test 136 was used to calculate the outlet weight
distribution data for comparison with the inlet PLM data from test 135.
This is presented in the text in Table 4-9.
220
-------
1000
o
o
i.o 10.0
GEOMETRIC AERODYNAMIC DIAMETER,
100.0
Figure C-24. Outlet MRI Weight Data for Runs 135 & 136
221
-------
REFERENCES FOR APPENDIX C
C-l. Ensor, D.S., et al. Evaluation of a Particulate Scrubber on a Coal
Fired Utility Boiler. Prepared by Meteorology Research, Inc. for
the U.S. Environmental Protection Agency. EPA 600/2-75-074.
November 1975.
222
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/7-80-086
2.
3. RECIPIENT'S ACCESSION-NO.
4, TITLE AND SUBTITLE
Environmental Assessment of a Coal-fired
Controlled Utility Boiler
5. REPORT DATE
April 1980
6. PERFORMING ORGANIZATION CODE
7.AUTHoms) c Leavitt,K.Ar ledge. C.Shih.R.Orsini,
A. Saur, W. Hamers ma, R. Maddalone, R. Beimer,
G. Richard, S. Unges. and M.Yamada
8. PERFORMING ORGANIZATION REPORT NO.
I. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW, Inc.
One Space Park
Redondo Beach, California 90278
10. PROGRAM ELEMENT NO.
EHE624A
11. CONTRACT/GRANT NO.
68-02-2613, Task 8
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD C
Task Final; 6/78-12/79
COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES ffiRL-RTP project officer is Michael C. Osborne, Mail Drop 62,
919/541-3996.
. ABSTRACT The repor|. giVQS results of a comprehensive multimedia emissions assess-
ment of the cyclone-fired La Cygne No. 1 boiler, equipped with SO2 and particulate
emission controls. Levels 1 and 2 procedures were used to characterize pollutant
emissions in gaseous, liquid, and solid process streams. Assessment results, in
conjunction with assumed typical and worst case meteorological conditions, were
used to estimate the environmental impact of emissions from this type of unit. Prin-
cipal conclusions were: (1) The risk of violating NAAQS for 24 hour and annual aver-
age levels is low; however, units using high sulfur fuel may exceed short term
NAAQS for SO2. (2) Little adverse health effect is anticipated as a result of SO2,
SO4 (—), and particulate emissions projected from widespread use of coal-fired
units of the type tested. (3) Increases in the concentrations of Cd and Pb in soil and
plant tissue as a result of trace element emissions could damage plants and adver-
sely affect the health of animals consuming vegetation in the affected areas. (4)
Plants may be damaged by NOx emissions since estimated NOx concentrations ap1-
proach or exceed threshold concentrations. (5) Sensitive plant species may be
damaged by predicted short-term SO2 concentrations which are in the damage
threshold range.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution
Assessments
Boilers
Coal
Combustion
Sulfur Oxides
Dust
Nitrogen Oxides
Cadmium
Lead
Pollution Control
Stationary Sources
Environmental Asses-
sment
Utility Boilers
Particulate
13B
14B
13A
21D
2 IB
07B
11G
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
233
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
223
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