&EPA
United States
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
EPA-560/5-83-006
September, 1983
Toxic Substances
Comprehensive Assessment of
the Specific Compounds Present
in Combustion Processes
Volume 3
National Survey of Organic
Emissions from Coal Fired
Utility Boiler Plants
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COMPREHENSIVE ASSESSMENT OF THE SPECIFIC COMPOUNDS
PRESENT IN COMBUSTION PROCESSES
VOLUME 3
NATIONAL SURVEY OF ORGANIC EMISSIONS FROM
COAL FIRED UTILITY BOILER PLANTS
by
Clarence L. Haile
John S. Stanley
Thomas Walker
George R. Cobb
Bruce A. Boomer
TASK 52
FINAL REPORT
EPA Contract No. 68-01-5915
MRI Project No. 4901-A(52)
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Dr. Frederick Kutz, Project Officer
Mr. David Redford, Task Manager
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DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substancesj
U.S. Environmental Protection Agency. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does the mention of trade names or commercial
products constitute endorsement or recommendation for use.
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PREFACE
This draft final report was prepared for the Environmental Protection
Agency under EPA Contract No. 68-01-5915, Task 52. The report describes the
results of research conducted under Tasks 36 and 52. The tasks were directed
by Dr. Clarence L. Haile. This report was prepared by Drs. Clarence L. Haile
and John S. Stanley with substantial contributions from Mr. Thomas Walker,
Mr. George R. Cobb, and Mr. Bruce A. Boomer.
Technical support was also provided by A. M. Megan, R. V. Northcutt,
R. B. Blair, T. Costello, E. Hirsch, M. Valla, B. Mitchell, G. Scheil,
M. Hansen, R. Stultz, E. Olson, D. Lacy, M. Gabriel, C. Brown, K. Hall,
S. Cummins, T. Arnold, G. Radolovich, J. Onstot, and M. Wickham.
MID!
SEARCH, INSTITUTE
John E. Going
Program Manager
Approved:
James L. Spigarelli, Director
Analytical Chemistry Department
August 26, 1983
iii
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CONTENTS
Preface ...
Figures . . .
Tables. . . .
Abbreviations
1. Introduction . . .
2. Summary
3. Recommendations. .
4. Plant Descriptions
No.
No.
No.
No.
No.
No.
No.
1.
2.
3.
4.
5.
6.
7.
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Sampling Methods ......
Flue gas train evaluation
Sampling locations, Plant
Sampling locations, Plant
Sampling locations, Plant
Sampling locations,
Sampling locations,
Sampling locations, Plant
Sampling locations, Plant
Analysis Methods
General analytical scheme
Sampling compositing and extraction
HRCG/Hall-FID screen
Scanning HRGC/MS
Flue gas extract cleanup
HRGC/MS-SIM
Field Test Data
Plant
Plant
No
No
No.
No
No.
No
No.
1
2
3
4
5
6 .
7
Plant
Plant
Plant
Plant
Plant
Plant
Plant
No.
No.
No.
No.
No.
No.
No.
111
vii
x
xvii
1
2
3
4
4
5
6
6
7
8
8
9
11
16
19
26
31
39
46
52
56
56
56
59
60
63
65
71
71
78
78
88
88
100
100
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CONTENTS (continued)
8. Analytical Results 112
HGRC/Hall-FID screen . 112
Scanning HRGC/MS analysis 112
HRGC/MS-SIM analysis 112
9. Analytical Quality Assurance Results 135
Surrogate compound recoveries 135
Blank sample results 141
Capillary column performance 164
10. Emission Results 170
References 177
Appendix - Sampling and Analysis Methods Manual 178
VI
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FIGURES
Number Page
1 Flue gas sampling probe used at Plant No. 4 10
2 Flue gas train evaluation spiking probe . . . . 12
3 Schematic representation of the flue gas sampling location
from (A) plan as cross-sectional view; (B) port height;
and (C) with respect to stack elevation for Plant No. 1 . . 18
4 Locations of flue gas inlet and continuous monitoring
sampling sites, Plant No. 2 . 20
5 Side view of the ESP, Plant No. 2 21
6 Top view of the ESP and sampling ports, Plant No. 2 22
7 Traverse poiii_. at each sampling port for isokinetic
sampling, Plant No. 2 . ..23
8 , Top view of the fly ash hoppers, Plant No. 2. . . 24
9 Bottom ash hopper and water sampling sites, Plant No. 2 ... 25
10 Side view of the flue gas outlet duct and disturbance
points, Plant No. 3 - 27
11 Top view of the sampling platform above the vertical
ducts, Plant No. 3 28
12 Location of sampling ports and individual sampling points
for isokinetic sampling within the flue gas outlet duct,
Plant No. 3 ....... 29
13 ESP hopper arrangement, Plant No. 3 30
14 Schematic of the bottom ash hopper for Unit 3, Plant No. 3. . 32
15 Top view of the flue gas outlet duct and sampling points,
Plant No. 4 33
vii
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FIGURES (continued)
Number
16 Side view of flue gas outlet duct and sampling points,
Plant No. 4 34
17 Cross-sectional view of the flue gas outlet duct showing the
location of the sample points within the duct, Plant No. 4. 35
18 ESP hopper array, Plant No. 4 37
19 Coal feeder arrangement, Plant No. 4 38
20 General layout of Plant No. 5 40
21 Vertical cross section of stack, Plant No. 5 41
22 Horizontal stack cross section and traverse point locations,
Plant No. 5 42
23 Bottom ash sluice system, Plant No. 5 44
24 Coal sampling locations, Plant No. 5 45
25 General layout of Plant No. 6 47
26 Vertical cross section, Plant No. 6 48
27 Horizontal view, Plant No. 6. . 49
28 Duct dimensions and traverse point locations, Plant No. 6 . . 50
29 Coal sampling locations, Plant No. 6 51
30 General layout of Plant No. 7 / 53
31 Duct dimensions and traverse point locations, side B,
Plant No. 7 55
32 Analysis scheme for sample extracts . 57
33 HRGC/Hall-FID chromatogram of the capillary column
performance standard 61
34 Mixed Aroclor standard used to establish retention windows
for HRGC/MS-SIM analyses of PCBs 67
35 HRGC/Hall chromatograms of the flue gas extracts for
sampling days 1-5, Plant No. 1 113
viii
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FIGURES (continued)
Number
36 Average distribution (mean ± standard deviation) of chloro-
biphenyls in coal-fired power plant flue gas and plant
background air 131
37 SIM response to a 2.5 pg injection of 1,2,3,4-TCDD 134
38 Surrogate compound recoveries from flue gas samples 155
39 Surrogate compound recoveries from bottom ash samples .... 156
40 Surrogate compound recoveries from fly ash samples 157
41 Surrogate compound recoveries from Economizer ash samples . . 158
42 Surrogate compound recoveries from coal samples 159
43 Surrogate compound recoveries from plant background air
samples. Data for Plant No. 4 from HRGC/Hall-FID . . . . . 160
44 Surrogate compound recoveries from quench effluent water
samples 161
45 Surrogate compound recoveries from quench influent water
samples 162
46 Fused silica column pH versus time as calculated from the
response of equal quantities of 4-bromo-2,6-dimethyl-
phenol and 4-bromo-2,6-dimethylaniline 164
47 Number of theoretical plates (N) versus time for a fused
silica capillary column . . 165
48 • Calculated HETP versus time for a fused silica capillary
column ......' 166
49 Adsorption versus time for selected compounds on a fused
silica capillary column . . . 168
50 Asymmetry versus time for selected compounds on a fused
silica capillary column 169
IX
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TABLES
Number Page
1 Spiking Solution Selection Scheme for Flue Gas Train
Evaluation Tests .................... . . 13
2 Results of Flue Gas Train Evaluations
3 Samples Collected, Sampling Locations, and Collection
Frequencies ............ ............ 17
4 Modified Method 5 Train Sample Point Locations, Plant No. 1 . 19
5 Modified Method 5 Train Sample Point Locations, Plant No. 5 . 43
6 Estimated Percent Fly Ash Collected in Each Row of ESP
Hoppers, Plants Nos. 2-6 ......... ........ . 58
7 Instrument and Operating Parameters for HRGC/Hall-FID
Screening ............. . ........... 60
8 Target PAH and Phthalate Compounds .............. 62
9 Instrument and Operating Parameters for Scanning HRGC/MS
Analysis .......................... 62
10 . Recoveries for Compounds Chromatographed on Silica Gel by the
Procedure Used to Clean Flue Gas Extracts ......... 64
11 Instrumental Parameters and Mass Ranges Used for HRGC/MS-SIM
Analyses of PCBs .......... . ........... 66
12 PCB Compounds Used for Quantitation Standards ........ 68
13 Instrument and Operating Parameters for HRGC/MS-SIM Analyses
of PCBs in All Flue Gas and Plant Background Air Samples
and Grab Samples from Plants Nos. 4-7 ........... 68
14 Recovery of PCB Isomers from Sulfuric Acid Treated Extracts . 69
15 Instrument and Operating Parameters for HRGC/MS-SIM Analyses
of PCDDs/PCDFs ............. ' .......... 70
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TABLES (continued)
Number Page
16 Daily Data Summaries for Flue Gas Sampling, Plant No. 1 ... 72
17 Summary of Plant Background Air Volumes, Plant No. 1 73
18 Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 1. , 74
19 Electrostatic Precipitator Operating Information, Plant No. 1 75
20 Log of System Changes, Upsets and Breakdowns During Flue Gas
Testing, Plant No. 1. 76
21 Proximate and Ultimate Analysis Results for Coal, Plant No. 1 77
22 Daily Data Summaries for Flue Gas Sampling, Plant No. 2 ... 79
23 Summary of Plant Background Air Volumes, Plant No. 2 80
24 Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 2. 80
25 Summary of Electrostatic Precipitator Operating Conditions
During Flue Gas Testing, Plant No. 2. 81
26 Log of System Changes, Upsets, and Breakdowns During Flue
Gas Testing, Plant No. 2 81
27 Proximate and Ultimate Analysis Results for Coal, Plant No. 2 82
28 Daily Data Summaries for Flue Gas Sampling, Plant No. 3 ... 83
29 Summary of Plant Background Air Volumes, Plant No. 3 84
30 Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 3 85
31 ESP Operating Conditions, Plant No. 3 86
32 Proximate and Ultimate Analyses for Coal, Bottom Ash,
Fly Ash, and Economizer Ash, Plant No. 3 87
33 Daily Data Summaries for Flue Gas Sampling, Plant No. 4 ... 89
34 Summary of Plant Background Air Volumes, Plant No. 4 90
35 Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 4 91
xi
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TABLES (continued)
Number Page
36 Summary of Electrostatic Precipitator Operating Conditions
92
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
Log of System Changes, Upsets, and Breakdowns During Flue Gas
Testing, Plant No. 4
Proximate and Ultimate Analysis Results for Coal, Plant No. 4
Daily Data Summaries for Flue Gas Sampling, Plant No. 5 . . .
Summary of Plant Background Air Volumes, Plant No. 5. . . . .
Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 5
Summary of Electrostatic Precipitator Operating Conditions
During Flue Gas Testing, Plant No. 5.
Log of System Changes, Upsets, and Breakdowns During Flue Gas
Testing, Plant No. 5
Proximate and Ultimate Analysis Results for Coal, Bottom Ash,
and Fly Ash, Plant No. 5
Daily Data Summaries for Flue Gas Sampling, Plant No. 6 . . .
Summary of Plant Background Air Volumes, Plant No. 6. . . . .
Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 6
Summary of Electrostatic Precipitator Operating Conditions
During Flue Gas Testing, Plant No. 6
Log of System Changes, Upsets, and Breakdowns During Flue Gas
Testing, Plant No. 6
Proximate and Ultimate Analysis Results for Coal, Bottom Ash,
and Fly Ash, Plant No. 6
Daily Data Summaries for Flue Gas Sampling, Plant No. 7 . . .
Summary of Plant Background Air Volumes, Plant No. 7
Summary of Plant Operating Conditions During Flue Gas
Testing, Plant No. 7 .
.7*.
93
94
95
96
97
98
98
99
101
102
103
104
105
106
107
108
109
Xll
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TABLES (continued)
Number Page
54 Log of System Changes, Upsets, and Breakdowns During Flue Gas
Testing, Plant No. 7. . 110
55 Proximate and Ultimate Analyses for Coal, Bottom Ash,
Fly Ash, and Economizer Ash from Plant No. 7 Ill
56 Target Compounds Identified in Flue Gas Samples from the
Seven Coal-Fired Power Plants 115
57 Target Compounds Identified in Fly Ash Samples from the
Seven Coal-Fired Power Plants 118
58 Target Compounds Identified in Bottom Ash Samples from the
Seven Coal-Fired Power Plants 120
59 Target 'Compounds Identified in Economizer Ash Samples
from Plants Nos. 3 and 7 123
60 Target Compounds Identified in Coal Samples from the Seven
Coal-Fired Power Plants (124
61 Target Compounds Identified in Background Air Samples from
the Seven Coal-Fired Power Plants 127
62 Polychlorinated Biphenyl Isomers Identified in Flue Gas
Outlet Samples 129
63 PCB Isomers Identified in Plant Background Air Samples. . . . 132
64 Method Detection Limits for PCB Isomers in Grab Samples . . . 132
65 Method Detection Limits for PCDDs and PCDFs for 5-Day
Composite Flue Gas and Grab Samples 133
66 Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 1 136
67 Surrogate Compound Recoveries in Bottom Ash Samples,
Plant No. 1 . . 136
68 Surrogate Compound Recoveries in Fly Ash Samples,
Plant No. 1 137
69 Surrogate Compound Recoveries in Coal Samples, Plant No. 1. . 137
70 Surrogate Compound Recoveries in Plant Background Air
Samples, Plant No. 1 138
Kill
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TABLES (continued)
Number Page
71 Surrogate Compound Recoveries in Raw Water Samples,
Plant No. 1 138
72 Surrogate Compound Recoveries in Bottom Ash Quench Effluent
Water Samples, Plant No. 1 139
73 Surrogate Compound Recoveries in Bottom Ash Quench Influent
Water Samples, Plant No. 1 . 139
74 Average Recoveries of the Surrogate Compounds for Samples
from Plant No. 1. . 140
75 Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 2 142
76 Surrogate Compound Recoveries in Bottom Ash Samples,
Plant No. 2 142
77 Surrogate Compound Recoveries in Fly Ash Samples,
Plant No. 2 143
78 Surrogate Compound Recoveries in Coal Samples, Plant No. 2. . 143
79 Surrogate Compound Recoveries in Plant Background Air
Samples, Plant No. 2 144
80 Surrogate Compound Recoveries in Bottom Ash Quench Effluent
Water Samples, Plant No. 2 144
81 Average Recoveries of the Surrogate Compounds for Samples
from Plant No. 2 145
82 Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 3 145
83 Surrogate Compound Recoveries in Bottom Ash Samples,
Plant No. 3 146
84 Surrogate Compound Recoveries in Fly Ash Samples, Plant No. 3 146
85 Surrogate Compound Recoveries in Economizer Ash Samples,
Plant No. 3 147
86 Surrogate Compound Recoveries in Coal Samples, Plant No. 3. . 147
87 Surrogate Compound Recoveries in Plant Background Air
Samples, Plant No. 3. 148
xiv
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TABLES (continued)
Number
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
Surrogate Compound Recoveries in Lake Water, Plant No. 3. . .
Average Recoveries of the Surrogate Compounds for Samples
from Plant No 3 ' ••" ...
Surrogate1 Compound Recoveries in Flue Gas Samples,
Plant No 4 "... .
Recoveries of the Surrogate Compounds for Samples from
Plant No 4
Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 5
Surrogate Compound Recoveries in Plant Background
Air Samples, Plant No. 5
Average Recoveries of the Surrogate Compounds for Samples
from Plant No .5
Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 6
Surrogate Compound Recoveries in Plant Background Air
Samples, Plant No. 6
Average Recoveries of the Surrogate Compounds for Samples
from Plant No. 6
Surrogate Compound Recoveries in Flue Gas Samples,
Plant No. 7
Surrogate Compound Recoveries in Plant Background Air
Samples, Plant No. 7
Average Recoveries of the Surrogate Compounds for Samples
from Plant No. 7
Average Surrogate Compound Recovery (%) for All Sample
Media from All Seven Plants
Summary of Surrogate Compound Recovery for Flue Gas Samples
with Respect to the Sampling Train Component Spiked ....
Concentrations and Emission Rates for Target Compounds in
Flue Gases ((Jg/dscm) and Emission Rates (mg/hr) from the
Seven Coal-Fired Power Plants
Page
148
149
149
150
150
151
151
152
152
153
153
154
154
163
163
171
XV
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TABLES (continued)
Number Page
104 Average Emission Rates of Target PAH Compounds in Flue Gases. 173
105 Flue Gas Outlet Concentrations of Total Polychlorinated
Biphenyls (PCBs) and Emission Rates for Plants 1 Through 7. 174
106 Average PCB Inputs and Emissions (Plant Background Air and
Flue Gas Outlet) 176
xvi
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acfm
dscf
dscfm
dscm
dscmm
EICP
ESP
HETP
HRGC/Hall-FID
HRGC/MS
HRGC/MS-SIM
HRGC/HRMS-SIM
PAHs
PCBs
PCDDs
PCDFs
PFK
TFE
THC
LIST OF ABBREVIATIONS
Actual cubic feet per minute
Dry standard cubic feet
Dry standard cubic feet per minute
Dry standard cubic meter
Dry standard cubic meter per minute
Extracted ion current plots, constructed by computer from
scanning gas chromatography/mass spectrometry data
Electrostatic precipitator
Height equivalent to a theoretical plate
High resolution (fused silica capillary column) gas chroma-
tography with Hall electrolytic conductivity and flame
ionization detectors
High resolution (fused silica capillary column) gas chroma-
tography with low resolution mass spectrometry detection
HRGC/MS operating the spectrometer in a selection ion
monitoring mode
HRGC/MS-SIM with the spectrometer operated at higher than
unit resolution (e.g., 10,000 resolution)
Polynuclear aromatic hydrocarbons
Polychlorinated biphenyls
Polychlorinated dibenzo-£-dioxins
Polychlorinated dibenzofurans
Perfluorokerosene
Polytetrafluoroethylene, e.g., Teflon®
Total hydrocarbons
xvn
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SECTION 1
INTRODUCTION
This study was conducted1 as a part of a nation-wide survey to determine
organic emissions from major stationary combustion sources. The principal
compounds of interest are polynuclear aromatic hydrocarbons (PAHs) and chlo-
rinated aromatic compounds, including polychlorinated biphenyls (PCBs), poly-
chlorinated dibenzo-£-dioxins (PCDDs), and polychlorinated dibenzofurans
(PCDFs).
This report describes the methods and results of sampling and analysis
activities at the seven plants constituting the nationwide survey of coal-
fired utility boiler plants. The statistical design of these studies was con-
structed by Research Triangle Institute (RTI)1 based on the results of a two-
plant pilot study2 that was conducted by Midwest Research Institute (MRI)
with assistance from TRW, Inc., Southwest Research Institute, and Gulf South
Research Institute.
A summary of the results of this study is contained in Section 2 of this
report. Section 3 presents recommendations for future work. Brief descrip-
tions of the coal-fired power plants are contained in Section 4. The sampling
and analysis methods as applied to these plants are described in Sections 5
and 6. The field test data and analytical results are presented in Sections
7 and 8. Section 9 describes the analytical quality assurance results and
the emissions results are summarized in Section 10.
As a part of the sampling and analysis effort, a detailed sampling and
analysis methods manual3 was prepared for use in the current surveys and in
similar EPA/Exposure Evaluation Division studies. The methods manual is
attached to this report as Appendix A.
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SECTION 2
SUMMARY
This study was conducted as a part of a nationwide survey to determine
organic emissions from major stationary combustion sources. The principal
compounds of interest are polynuclear aromatic hydrocarbons (PAHs) and chlo-
rinated aromatic compounds, including polychlorinated biphenyls (PCBs), poly-
chlorinated dibenzo-£-dioxins (PCDDs), and polychlorinated dibenzofurans
(PCDFs). This report describes the methods and results of sampling and analy-
sis activities at the seven plants constituting the nationwide survey of coal-
fired utility boiler plants.
All inputs and outputs (including fuel, water, ash, and flue gas) that
were related to the combustion process were sampled during a 5-day period at
each plant. Daily flue gas samples (20 m3) were collected at the outlet of
the control devices using a modified Method 5 sampling train. The solid and
aqueous grab samples were collected six times per 24-hr period for the test;
durations. The samples were extracted and analyzed for phthalates, PAHs, PCBs,
PCDDs, and PCDFs using fused silica capillary gas chromatography with flame
ionization, halide specific, and mass spectrometric detectors.
The polycyclic organic compound emissions from the plant included PAHs
and PCBs. These compounds were detected in the flue gases from all four
plants studied. Naphthalene was the most abundant PAH compound identified.
Emission rates for naphthalene ranged from approximately 500 to 5,000 mg/hr.
Polychlorinated biphenyls were determined in flue gases from all seven plants.
PCB emission rates ranged from 10 to 8,500 mg/hr. PCBs were also identified
in the plant background air from all plants except Plant No. 3. Although the
average emission rates for each plant were all higher than the input rates
attributable to plant background air, the average input rates were within one
standard deviation of the mean emission rates for five of the seven plants.
Additionally, the homolog distributions of chlorobiphenyls identified in flue
gas and plant background air samples were similar, both between flue gases
and background air at the same plant and between, plants. The PCBs were com-
prised primarily of penta- and hexachlorobiphenyls with lesser contributions
from tetra- and heptachlorobiphenyls.
The PAHs and PCBs were not identified at significant levels in the solid
and aqueous emissions from the seven plants. The levels of extractable organic
compounds were low for these samples. Polychlorinated dibenzo-£-dioxins and
dibenzofurans were not identified in either the grab samples or flue gas sam-
ples from the different power plants. The method detection limits achieved
for sample analyses for PCDDs and PCDFs were in the range of 0.1 to 0.7 ng/dscm
for the flue gas and combustion air, 0.05 to 0.35 ng/g ash samples, and 1 to
7 ng/liter for aqueous influents and effluents.
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SECTION 3
RECOMMENDATIONS
1. Continue the combustion emissions program for other major source
categories. The study design principles that were used to assess emissions
from coal-fired power plants should be used to obtain emissions information
for other source categories. Residential wood combustion and municipal ref-
use incineration should be high priority categories because of their poten-
tials for emissions of polynuclear aromatic hydrocarbons and polychlorinated
aromatics, respectively.
2. Conduct additional analysis of the archived mass spectrometric data
from the coal-fired plant samples. The computerized gas chromatography/mass
spectrometry data from the present study should be examined to determine the
presence of specific compounds in addition to the targeted compounds discussed
in this report. It is likely that additional compounds could be identified
and semi-quantitated so as to provide a more complete characterization of
emissions from coal-fired utility plants.
3. Investigate relationships between emission rates for specific com-
pounds and key plant design and operating parameters. The emissions data
contained in this report, plus data generated from additional data interpre-
tation (Recommendation No. 2), should be evaluated with respect to key design
and operating parameters employed by the seven plants. Data evaluation via
multivariant statistical analysis may provide indications of relationships
between specific compound emissions and combustion characteristics.
4. Continue development and evaluation of flue gas sampling systems
for quantitative measurement of organic emissions. The modified EPA Method 5
train used for this study efficiently retains particulates and a wide range
of organics. However, additional research should be directed toward evaluation
and development of adsorbents applicable for a wider range of compounds and
with a lower potential for troublesome blanks. Since particulates retained
on a heated filter can scavenge or off-gas organics, particulate sampling
should be developed which removes the solids from exposure to the gas stream.
This would allow reliable determination of organics in both the vaporous and
particulate-associated fractions.
5. Develop analytical reference materials for organics in combustion
source samples. In particular, standard reference ash samples should be de-
veloped with certified concentrations of polynuclear aromatic hydrocarbons,
polychlorinated biphenyls, polychlorinated dibenzo-p_-dioxins, and polychlo-
rinated dibenzofurans.
-------
SECTION 4
PLANT DESCRIPTIONS
The descriptions of the seven plants and their operating characteristics
in this section were obtained from interviews with plant management and oper-
ation staff.
PLANT NO. 1
Plant No. 1 consisted of two essentially identical units with capacities
of 660 Mw each. The boiler tested, Unit 1, is a pulverized coal-fired furnace,
tangentially fired with radiant heat and a balanced draft, divided furnace
system. The maximum continuous guaranteed capacity is 5,268,000 Ib of steam
per hour at the superheater outlet. The boiler is operated in base load with
manual control of fuel feed and combustion air. Soot blowing is continuous.
Bottom ash removal is continuous during full load and intermittent ;during
partial load, depending on the ash content of the coal. ,
The coal burned at Plant No. 1 is classified as subbituminous C. The
boiler is supplied by eight pulverizer units, each with a rated capacity of
132,000 Ib/hr plus 10% overfeed. The design fineness of the coal from the
pulverizers is 65% through a No. 200 sieve. The design temperature in the
combustion zone is 2500°F (1370°C).
Particulate emissions are controlled by two sets of electrostatic pre-
cipitators (ESP) in series. The ESP system consists of primary and secondary
fields. The secondary units were added after the initial construction to
ensure compliance with federal particulate emission standards. A number of
fields in the primary ESP units were inoperable during the test. The flue
gases from the secondary ESP units on Boiler No. 1 are discharged via Stack
No. 1.
The two secondary ESP units are of the single pass four-field type. Each
field is split into six separate bus sections. A high voltage direct current
is supplied to the discharge electrodes while the collector electrodes are at
ground potential. The discharge electrodes are flattened top mast wire elec-
trodes with 4x8 gauge twisted wire elements per mast with four-point suspen-
sion. The catch-type collector electrodes are vertical plates fitted at in-
tervals with channel stiffeners.
A continuous chain belt, reducing gear, cam shaft rapping system is used
for both the discharge and collector electrode systems. The discharge elec-
trode has drop rod rapping four points per frame. Each collector has two drop
rod rapper hammers per plate.
-------
Fly ash is removed from both the primary and secondary precipitator units
by an integrated system using the same transport blowers, fly ash bins, and
exhausters. Interlocks and valving were installed for sequential loading and
unloading of fly ash from the two sets of precipitators connected to the same
air and ash piping headers.
PLANT NO. 2
Plant No. 2 consists of five units. Units 1 through 4 have capacities
near 250 Mw and are approximately 20 years old. They were originally ducted
through individual ESPs into individual stacks approximately 250 ft tall. In
recent years, four new ESPs have been installed, and the flue gases have been
ducted to a single, dual-flue stack approximately 650-ft tall. Unit 5 has a
capacity near 900 Mw and has been in operation for 2 years. It has ESPs and
is ducted to a 700-ft stack.
Unit 4 was tested at Plant No. 2. The boiler is a pulverized coal, ver-
tical fired, radiant boiler with a maximum continous high pressure steam out-
put of 1,700,000 Ib/hr. The turbine is rated at 250 Mw. The boiler is oper-
ated in base load with automatic fuel feed and combustion air control. Soot
blowing is intermittent, three times per day. Bottom ash is removed manually
about every 3 to 4 hr.
Plant No. 2 burns bituminous coal in 18 burners fed by six pulverizers.
Coal is batch weighed. Accurate coal feed data were not available during the
test due to a few nonfunctioning integrators in the control room.
Particulate emissions are controlled by electrostatic precipitation.
The ESP is operated on the "hot-side" to raise the collection efficiency. In
certain types of low sulfur coal, fly ash resistivity is extremely high for
the usual operating temperature range (around 250 to 300°F, 120 to 150°C).
Higher collection efficiency can be attained by treating the gas at higher
temperatures since the resistivity of the fly ash decreases sharply as the
temperature increases.
Plant No. 2's ESP system was designed to treat 1,250,000 cfm (cubic feet
per minute) of gas entering at 650°F (350°C). The collecting plates in each
section are arranged in five groups of six or seven plates each. Suspended
in each section are 396 discharge electrode wires. Each section is supplied
with power from two rectifier-transformer sets, making a total of eight sets
of power control panels for the ESP. The ESP is equipped with 32 ash collec-
tion hoppers configured as four rows of eight hoppers each.
The collecting plates are cleaned by 160 magnetic impulse, gravity impact
rappers. The discharge electrodes are cleaned by a total of 32 rappers. The
switching unit controlling the rappers in each section of the ESP rotates at
1/2 RPM and therefore energizes each rapper once every 2 min.
The bottom ash quenching and boiler seal waters are not recycled in the
plant, and the overflows go into a single sink-type drain. Boiler makeup
water is taken from a nearby river.
-------
PLANT NO. 3
Plant No. 3 is comprised of three essentially identical units rated at
125 Mw each. They are typically operated at 120 Mw, burning approximately
45 tons of coal per hour. The units are operated as low as 40 Mw each on
weekends.
Unit No. 3 was tested at Plant No. 3. This boiler was placed into oper-
ation during 1951-1952 using cyclone dust collectors to control particulate
emissions. The cyclones were taken out of service and replaced with dry elec-
trostatic precipitators in 1973-1974. The unit is front wall fired with east-
ern Kentucky coal which has a heating value of approximately 12,000 Btu/lb.
The coal typically contains 10 to 15% ash. The ash is distributed as approxi-
mately 90% fly ash and economizer ash and 10% bottom ash.
The boiler is operated at base load. Fuel feed and combustion air are
automatically controlled but can also be operated manually. Four pulverizers
serve each boiler. These crush the coal to powder consistency by rolling
large steel rollers over the coal. The pulverized coal is then fed to the
burners. Coal feed rate to the boiler is regulated by adjusting the amount
of coal fed to the pulverizers. This rate usually varies according to the
heat content of the coal and the quantity of output required from the turbine.
Coal loading is based on totals for a 24-hr day. The calibrators for each
pulverizer were not operating during the test.
Soot blowing occurs once per shift. Bottom ash is sluiced out of the
collection hoppers once per shift. Ash collected by the ESP is continuously
removed to a recovery station.
The ESP that serves Boiler No. 3 was constructed by American Standard
and placed in operation in 1973-1974. It is a high voltage, single-stage
system that replaced cyclone dust collectors. The ESP ash collection system
is comprised of two rows of four hoppers each. The first row removes 70 to
80% of the ash. Total collection efficiency was 99.96% during the latest
compliance test.
PLANT NO. 4
Plant No. 4 consists of five identical units rated at 217 Mw. They were
installed in 1954-1955 and were originally ducted into three stacks approxi-
mately 400 ft tall. During 1980, ESPs were installed and all boilers were
ducted into a single 1,000-ft stack.
Unit No. 2 was tested at Plant No. 4. The boiler is a pulverized coal-
fired, radiant, front wall fired system with a steam capacity of 1,336,000
Ib/hr. The turbine has a nameplate total net generation capacity of 207 Mw.
The boiler is operated in peak load with automatic fuel feed and manual com-
bustion air control. Soot blowing and bottom ash removal are intermittent
once per shift.
-------
The coal burned at Plant No. 4 is a bituminous coal. Seven pulverizers
are available for Unit No. 2. Specific coal feed weight values were not avail-
able.
An ESP with multiple sections single casing construction is located in
the gas duct between the air preheater and the common stack. The ESP is
designed to handle a gas volume of 925,000 CFM at an average bulk flue gas
temperature of 350°F (175°C) with inlet grain loading ranging from 0.5 to
3.5 g/ft3.
The ESP consists of five fields arranged in series in the direction of
gas flow. Each field has four bus sections, resulting in a total of 20 bus
sections, each a rigid boxlike structure. The discharge electrodes are stain-
less steel wires suspended vertically in 28 parallel rows. The collecting
plates are 16-gauge steel plates.
The rapping systems for both the discharge electrodes and the collecting
plates are "tumbling hammers" mounted on horizontal shafts in a staggered man-
ner. The operation of the gear motors for the rapper system is controlled by
a program relay which can be adjusted to optimize the performance of each bus
section. Fly ash is collected in 20 hoppers, each suspended below a bus sec-
tion structure.
PLANT NO. 5
Plant No. 5 consists of a single unit with a net operating capacity of
584 Mw. The unit is cyclone-fired with eastern bituminous coal supplied by
five pulverizer mills. The mills are rated at more than 70 tons/hr (63,500
kg/hr) and are designed for removal of pyrites. At full capacity, the boiler
delivers 4,000,000 Ib of steam per hour to a four flow, single reheat turbine.
The unit is operated at base load using automatic fuel feed and automatic com-
bustion air control. Soot blowing is continuous and bottom ash is typically
removed twice per 8-hr shift. The unit operates near capacity during the day.
The output is typically reduced to 450 to 480 Mw for a few hours each evening.
Approximately 40% of the power produced services industrial users.
Particulate emissions are controlled by two electrostatic precipitators
(ESPs). One ESP is located at each preheater gas outlet. Each ESP consists
of four units with three fields. The two ESPs were designed to treat 1,984,000
cfm (56,180 cmm) of gas at 270°F (130°C).
Each precipitator contains 360 collecting plates (30 x 9 ft, or 9.1 x
2.7 m) and 4,176 discharge electrodes (0.109 in., or 2.8 mm, copper Bessemer
wires supporting a 25-lb, or 11.3 kg, plumb bob). Power is supplied to each
ESP from six rectifier-transformers. Collected ash is removed from the plates
and discharge electrodes by magnetic impulse, gravity impact rappers (six per
section for plates and two per section for electrodes) energized at 2-min in-
tervals. Ash is collected in 12 hoppers and slurried for disposal.
-------
PLANT NO. 6
Plant No. 6 consists of three units with capacities of 180, 290, and 670
Mw. Unit 1 (180 Mw) was tested. Unit 1 (in operation ~ 15 years) is cyclone-
fired and is operated primarily in base load with automatic fuel feed and auto-
matic combustion air control. The unit burns bituminous coal. Soot blowing
is intermittent (approximately one cycle per shift). Bottom ash is typically
removed at 2- to 4-hr intervals.
The ESP system consists of two fields with four collection hoppers each.
Because of their age, the ESP was not operating efficiently during the test.
Addition of a new system was in progress.
PLANT NO. 7
Plant No. 7 consists of five units. Units 1, 2, and 3 are natural-gas-
fired boilers used for peak load power. Units 4 and 5 are coal-fired boilers
operated in base load. Unit 5 was tested. Unit 5 has a maximum gross capac-
ity of 580 Mw. It is cyclone-fired and is operated at base load with auto- .
matic fuel feed and automatic combustion air control. The unit burns bitumi-
nous coal and is fed by six pulverizer mills rated at more than 35 tons/hr
(31,800 kg/hr) each. Soot blowing is continuous. Bottom ash is typically
removed once each shift. Particulate emissions are controlled by two electro-
static precipitator units in parallel.
-------
SECTION 5
SAMPLING METHODS
The general procedures for sampling the gaseous, solid, and aqueous emis-
sions from each of the four different coal-fired power plants are described
in the methods manual in Appendix A. Flue gas samples (20 m3) were collected
at each plant with two modified Method 5 organic sampling trains operating
simultaneously (see Figure 1; Appendix A). Plant background air was collected
using an XAD-2 resin cartridge. The solid and aqueous grab samples were col-
lected according to specific schedules provided by RTI for random sampling at
each plant. The sampling schedules were dependent on the number of available
sampling points, such as the number of ash hoppers, and the wasting schedules
of the normal plant operations. •• ,
The specific sampling procedures were modified as required by the design
of each plant and the accessibility of sampling.sites. For example, the flue
gas at Plant Nos. 1, 3, and 5 was sampled with the probe attached directly to
the sample box in a conventional horizontal sampling position. Plant Nos. 2
and 4 required vertical sampling and included a heated flexible line between
the sample probe and the modified Method 5 train. A heated flexible line was
also used to facilitate horizontal sampling at Plant Nos. 5 and 7. Flue gas
sampling at Plant No. 2 required the use of a tripod assembly to hold the probe
in the horizontal position. The sample probe used at Plant No. 4 (shown in
Figure 1) was 25 ft in length and was lined with polytetrafluoroethylene (TFE).
A special sampling scaffold and probe suspension device was constructed to pro-
vide safe access to the sample ports and to aid probe handling operations with
overhead pulley controls.
Other specific differences in sampling at the four plants involved minor
operational changes for the modified Method 5 sampling train. The ball joints
for the sampling train used at Plant No. 1 were sealed with glycerol. How-
ever, the sealant tended to evaporate from joints in the heated zones so that
frequent reapplication of the sealant was required to avoid leaks. Thereafter,
DC-200, a high temperature silicon phase, was used to seal the joints in Plant
Nos. 2, 3, and 4. Also, the high temperature silicon gaskets used in the fil-
ter housings for the sampling trains at Plants 1 and 2 were replaced with TFE
gaskets for Plants 3 and 4 to reduce possible contamination from gasket mate-
rials.
Also, Apiezon L was used to seal all spherical joints on trains used at
Plant Nos. 5, 6, and 7. The sealant was easily removed from the joints with
a clean tissue saturated with cyclohexane just prior to rinsing each component
during sample recovery.
-------
Ceramic Plugs
for Heaters
and Thermocouples
2-1/2 Angle Iron
Thermocoupl
Heated Flexible TFE Probe
with Pitot Lines
To Sample Box
Swage lock Union Between the Two Probe Halves
Quick Disconnects for Pitot Lines
Teflon Line
Clamp
Stainless Steel Sheath
Ie M *«
Pitot Tube
Nozzle
Figure 1. Flue gas sampling probe used at Plant No. 4.
10
-------
FLUE GAS TRAIN EVALUATION
The collection efficiency of the flue gas sampling train was evaluated
for several target compounds by sampling spiked laboratory air. Complete
trains (without pilot tubes and sampling probes) were assembled (using
Apiezon L sealant) and operated in the laboratory in a manner simulating ac-
tual flue gas sampling, i.e., operated for ^ 8 hr at sampling rates ranging
from 0.70 to 0.80 ft3/min with the filter box at 275°F and ice water cooling
of impingers, condenser, and resin cartridge.
Trains were spiked using a special spike probe. The spike probe,.shown
in Figure 2, was fitted to the train with the hole on top and the dimple on
the bottom. Small aliquots of spiking solutions were deposited in the dimple
by syringe via the hole. The spike probes were then heated with a heat gun
to volatilize the spike into the gas stream during sampling. At the conclu-
sion of each run, the sample was recovered from the train, excluding the spike
probe, and analyzed as described in Section 6. The spike probe was thoroughly
rinsed with acetone and cyclohexane and the combined rinses analyzed in the
same fashion.
A total of seven tests were conducted. These included a blank run and
six spiked runs. The spiked runs were spiked with aliquots of one solution
from each of three pairs of solutions. The total volume of solutions for
each test run was 250 (Jl. The solutions pairs contained low and high concen-
trations of PAH and miscellaneous compounds, PCBs (Aroclor 1254), and selected
PCDDs. The selection scheme for the train test runs is shown -in Table 1.
The results of the train evaluation tests are summarized in Table 2.
The total recoveries were generally good for all compounds except 1,2,4-tri-
chlorobenzene and 2,4,6-trichlorophenol. Total recoveries in excess of 100%
were found from the low level spikes for some compounds, notably chrysene,
2-chlorodibenzo-p_-dioxin, and 2,7-dichlorodibenzo-p_-dioxin.
In general, a larger fraction of the total recovery for less volatile
compounds was found on'the spike probe. This trend was observed before
analysis for tetra- through hexachlorobiphenyls and 1,2,3,4-tetrachlorodi-
benzo-p_-dioxin was completed. In order to reduce the analytical effort,
those compounds were not determined in the train extracts.
The precisions of the total recovery determinations were also generally
good. The much larger variability observed for recoveries for several com-
pounds from the spike probes and trains likely reflect run-to-run variations
in the fraction of the spike volatilized into the gas stream. Nonetheless,
the results of the collection efficiency tests demonstrate the applicability
of the modified EPA Method 5 train for organics sampling.
11
-------
12 cm
J 28/15
Figure 2. Flue gas train evaluation spiking probe.
12
-------
TABLE I. SPIKING SOLUTION SELECTION SCHEME FOR
FLUE GAS TRAIN EVALUATION TESTS
PAH and misc. PCBs PCDDs
Spike Low High Low .High Low High
test no. cone. cone. cone. cone. cone. cone.
IX X X
2 XX X
3 X XX
4 X XX
5 XX X
6 X X X
13
-------
TABLE 2. RESULTS OF FLUE GAS TRAIN EVALUATIONS
Compound
Naphthalene
1 ,2,4-Trichlorobenzene
2 , 4 , 6-Trichlorophenol
Di-n-butylphthalate
Di-n-octylphthalate
Chrysene
Aroclor 1254
n
Trichlorobiphenyls (4)
Tetrachlorobiphenyls (5)
Pentachlorobiphenyls (3)
Hexachlorobiphenyls (4)
Trichlorobiphenyls (4)
Tetrachlorobiphenyls (5)
Pentachlorobiphenyls (3)
Hexachlorobiphenyls (4)
2-Chlorodibenzo-£-dioxin
2 , 7-Dichlorodibenzo-£-dioxin
Spike
level
(M8)
100
1,000
273
2,730
252
2,520
250
2,500
265
2,650
115
1,150
110.6
1,106
1.0
10
1.0
10
Recovery (%)
Probe
ND3
ND
ND
ND
ND
0.1 ± 0.2
19 ± 22
47 ± 8
72 79d
' d
96, 75d
140 ± 18
81 ± 19
75 ± 15
89 ± 24
87 ± 19
99 ± 25
51 ± 28
93 + 17
68 ± 10
71 ± 8
ND
9 ± 12
13 + 23
36 ± 33
Train
76 ± 5b
61 ± 6
26 + 4
51 ± 6
10 ± 4
33 + 7
35, 42d
30 + 10
5 ± 9
ND
15 ± 16
ND
24 ±21
NA
NA
NA
39 ± 29
NA
NA
NA
210 ± 21
95 + 42
140 + 40
61 + 41
Total
76 ± 5C
61 + 6
26 + 4
si + 6
10 + 4
33 + 7
35, 85d
11 ±1
72, 95d
n
96^ 75
150 + 8
81 ± 19
98 ± 22
89 + 24
87 + 19
99 ± 25
90 + 12
93 + 17
68 ± 10
71 + 8
210 + 21
100 + 30
150 + 50
97 ± 9
(continued)
14
-------
TABLE 2 (continued)
Compound
l,2,7-Dichlorodibenzo-j>Tdioxin
1,2,3 , 4-Tetrachlorodibenzo-p_-dioxin
Spike
level
(MR)
1.0
id
1.0
10
; Recovery (%)
Probe
63 ± 18
43 ± 36
100 ± 18
61, 81d
Train
66 ± 31
45 ± 40
NA
NA
Total
130 ± 17
88 ± 5
100 ± 18
61, 81d
a ND = not detected. > „ . .
b Mean ± standard deviation for three tests.
c Since mean total recoveries were calculated from total recoveries of
individual tests, mean total recoveries may not equal sum of the mean
components recoveries due to rounding.
d Results for two determinations. One analysis was an obvious outlier.
e Pooled recovery results for number of chromatographic peaks in parenthesis,
f NA = not analyzed. Total recovery represents amount in spike probe only.
15
-------
SAMPLING LOCATIONS, PLANT NO. 1
The samples collected from each plant are summarized in Table 3 with the
corresponding collection frequencies and descriptions of typical sampling points,
A more detailed discusson of the specific sampling locations and grab sampling
methods used at each plant is given below.
Flue Gas Outlet
Four ports were located on the stack at the 220-ft level. Figure 3
shows a schematic representation of the traverse point locations on the stack.
A heated, flexible, TFE line was used to connect the glass-lined probe to the
sample box to allow maneuverability in the limited space between the concrete
shell and the steel stack. Table 4 lists the sampling points relative to the
distance from the inside wall and fraction of the stack internal diameter.
Figure 3 also shows the exact location of the sample ports on the stack and
the position of the continuous monitoring equipment.
ESP Ash
ESP ash from both units at Plant No. 1 was conveyed to a storage bin
prior to loading into trucks for disposal. A portion of the ash was removed
from the bin to a size classifier prior to sale as a cement aggregate. Since
no access was available for sampling ash between the ash collection hoppers
and the storage bin, samples were taken from the air slide that conveys ash
from the bin to the classifier. Hence, the ESP ash samples from Plant No. 1
contain ash from both units.
Bottom Ash
Bottom ash was sluiced from Unit No. 1 to two holding bins (designated
11 and 12). The ash was dewatered by sedimentation prior to loading into
trucks for disposal. The dewatered ash was sampled with a scoop as it was
dumped into the trucks.
Waters
Bottom ash hopper quench water was sampled from an overflow tank adjacent
to the bottom ash hopper. Influent water was sampled from a tap near the hop-
per. Raw plant makeup water was sampled from a tap in the pump house.
Coal
Coal was sampled from conveyers feeding bunkers for both units at Plant
No. 1. Samples were taken at 2-hr intervals, ground, and combined into daily
composites by the plant staff.
16
-------
TABLE 3. SAMPLES COLLECTED, SAMPLING LOCATIONS, AND COLLECTION FREQUENCIES
Sample type
Gaseous samples
Typical location
Collection
frequency
Gaseous samples
1. Flue gas
2. Plant background
air
Solid samples
1. Coal
2. Bottom ash
3. Fly ash
Aqueous samples .
1. Quench water
effluent
2. Quench water
Ports on stack or duct downstream I/day (20 m3)
of ESP
Near forced draft fans
Feed streams between bunker(s)
and pulverizer mills
Collection hopper or sluice line
Individual hoppers or pneumatic
waste line
Overflow from bottom ash hopper
or sluice line
Tap near bottom ash hopper
I/day (10 m3)
6/day
6/day
6/day
3-6/day
1-3/day
17
-------
Airplane Light1 on
Hinged Steel Panel
Grating
Port '2
Sampling-
Points
Outer
Concrete
Shell
Transmissometer &
NOX - SO2 Analyzer
"Steel Stack (3/81 Plate) with Insulation
(~2" Total Stack + Insulation Thickness)
A. PLAN VIEW
In-Situ NOX - SO2
Analyzer
SAMPLING
PORT
Stee Stack
with Insulation
470 Ft.
Sampling
Platform
•SAMPLING
PORT COVER
^— 3-12"
3-1/2" Coupling
~ 220 Ft.
] _ Inlet
Breeching
24' ID at
*— Sampl
Level
ing-*^
x*
.
Samoling
Ports
Outer
• Concrete
Shell
NOX-SO2
•Analyzer
• Transmissometer
Elevator
B. PORT HEIGHT
C. ELEVATION
Figure 3. Schematic representation of the flue gas sampling location from:
(A) plan as cross-sectional view; (B) port height; and
(C) with respect to stack elevation for Plant No. 1.
18
-------
TABLE 4. MODIFIED METHOD 5 TRAIN SAMPLE POINT LOCATIONS, PLANT NO. 1
Fraction of duct Distance from inside wall
Radius point ID (%) (in.)
1
2
3
4.4
14.6
29.6
12.6
42.0
85.3
Plant Background Air ,
Plant background air was sampled on the ground floor near the forced-
draft fans. •'..,-
Continuous Monitoring
A port'for continuous monitoring was available on the duct inlet to the
primary ESP system.
SAMPLING LOCATIONS, PLANT NO. 2
Flue Gas Outlet
Sixteen ports were located on the duct outlet to the ESP under eight deck
plates between the first two rows of ESP hoppers. The ports were approximately
2 ft below the floor level and were canted approximately 10 degrees from ver-
tical. The duct was approximately 5 ft deep at the ports. The location..of..
the sampling ports for Plant No. 2 are shown in Figures 4 to 6. Figure 7
shows the locations of the traverse points.
ESP Ash
The ESP hopper array, consisting of four rows of eight hoppers, is illus-
trated in Figure 8. Ash was removed via a valve at the bottom of each hopper.
RTI constructed a hopper selection and sampling schedule to obtain six samples
per day. Each sample consisted of fly ash from one hopper from each row.
Extreme caution was exercised in taking these samples. The ESPs were "hot-
side" so that the ash was typically 400-500°F (200-260°C).
Bottom Ash
Bottom ash was wasted twice per shift. Just prior to wasting, the oper-
ator drew down the quench water and opened a hatch to allow removal of a sam-
ple with a long handle shovel. Samples were taken from specific sectors from
the two ends of the hopper according to a selection scheme provided by RTI.
Figure 9 shows the sector locations.
19
-------
To
Stock"
Trailer
•
Electrostatic .
Precipitator
Row Row Row Row
4321
\ A A A /
\AAA/
II
J
*" /
/
Sampling
Ports
Old
— Electrostatic
Precipitator
\
\
\
^s.
^^
t
t
t
t
t
t
t
t
t
t
f
f
t
t
t
f
t
t
t
t
t
* Contmous
/ Monitoring -y
' ^^^^^S^^sJ^X^
/ ^S*^^^^VNS
t ^^v^
; ^
t
t
t
t
Furnace
SIDE VIEW
Figure 4. Locations of flue gas inlet and continuous monitoring
sampling sites, Plant No. 2.
20
-------
Electrostatic Precipitator
(Side View)
/v32'-8"
8-1/2"
Figure 5. Side view of the ESP, Plant No. 2.
21
-------
onsole
["I fj f3 —7] rs 6~| ^""8!
|C 0, |0 0| lO 0| |0 0|
West Duct
and Ports
1
. in- ' *
N
1
r ~
r ~
L _
•"
l_ _
TS " 7"| r°~ 5"1
|c o| !c o
L. _J L_ _
East
and
Electrostatic
(Top V
|T" I] T2 "1 }
0 Cj JC Oj
Lm — .w J 1
Duct
Ports
,•
'
Precipitator
tew)
"^ """"
Consoli
Figure 6. Top view of the ESP and sampling ports, Plant No. 2.
22
-------
Port Nos. (West)
'
12345678
Port Nos. (East)
8 7 6 .5 4 3 2: 1
22-1/2"-*
J
6"
12" -
-i
12"
-|
"1911
1 L
4-
12"
T
6"
i 4
5"_^45"_^45»_HL_45»_
-------
• w
Col.4 1~ Col.5
Col. 8
V.OI. 1
[j
1 — 1
LJ
1 — 1
IQI.<
LJ
•
r — i
LJ
L j
LJ
•
. . .^ uu, -
r 1
a
UOI.J
h ^
L J
r— 1
LJ
rn
i — i
...
~
' nil 1
LJ
h, ,_.
G
r 1
r— i
LJ
n
j
ePnrti -!».«•«»
n
.....,_
T
["]
"""
r
r-i
"~
r— i
LJ
.
[I!
.
i — j
i
q
1.01. /
r-T
U.-J
_
[7]
.
r-i
LJ
•
r •
'"J
i — i
LJ
'
.
•a
r
LJ
r - • -
[I]
'
I
FigureS. Top view of the fly ash hoppers, Plant No. 2.
24
-------
to
Ln
East Door
to Bottom
Ash
•
*••***-
1
2
1
3
J
4
5
I nput Wate
River Wqt«
« 5' - »-
6
— 7-i
J
" 8
9
1
10.
1
il
>r or—'
sr
-
.
.
.
.
•
N
'
:.
'
\ /
- 5' >
5 . "
10
9—
_ j
r 8
r
7
•
.*- •
*— Inpu
or Ri
-* 5' »
5
4—
|_
3
r^
2
1
1
t Water
ver Water
West Door
to Bottom
JAsh
Bottom Ash
Water Overflow
and Bottom Seal
Figure 9. Bottom ash hopper and water sampling sites, Plant No. 2.
-------
Waters
The bottom ash quenching and boiler seal waters were not recycled. The
quench overflow and boiler seal overflowed into a single sink-type drain and
were sampled by simple bottle immersion. The quench overflow cascaded from a
6-8 in. pipe and was warm to the touch. The boiler seal water flowed from a
2-3 in. pipe and was cool. Makeup water was drawn from a nearby river and
was taken from a tap near the overflow basin. The sampling locations for
waters are also indicated on Figure 9.
Coal
The boilers were fired with pulverized coal. The coal was sampled from
the six weighing tables just above each pulverizer. The coal was typically
about 1/4 in. (6 mm) at this point with a few pieces as large as 3/4 in (20 mm)
Plant Background Air
Plant background air was sampled near the forced draft fans on an upper
level in the plant building.
Continuous Monitoring
A port for continuous monitoring was available on the duct just ahead of
the ESP. The port location is indicated in Figure 4.
SAMPLING LOCATIONS, PLANT NO. 3
Flue Gas
Eight horizontal ports were located on the duct between the ESP and the
stack. Figures 10 and 11 show side and top views of the ducts and the port
locations. The sampling platform was directly accessible from the top floor
of the plant building. The flue gas was sampled isokinetically such that ap-
proximately 20 m3 of flue gas was collected between two modified Method 5 sam-
pling trains. Figure 12 shows the locations of the traverse points on a hori-
zontal cross-section of the outlet duct.
ESP Ash
The ESP ash collection system was comprised of two rows of four hoppers
each. The first row removed 70 to 80% of the ash. The total efficiency of
the ESP system was 99.96% at the last compliance test. Ash was sampled di-
rectly from the valves on the hoppers. A pipe fitting and adaptor were used
to collect hot fly ash from the valve. RTI constructed a hopper selection
schedule to obtain a sample from each of the two rows of hoppers six times
per day. Figure 13 illustrates the ESP hopper arrangement for Unit No. 3 at
Plant No. 3.
26
-------
Room for Housing ->
Opacity Monitor \
14'
130' .
To Ground
/ * /
.. -X/7
\
.'
/
\
—
17'
3- i-Outlet Ports Inlet Ports -£
5> .
| Walkway
^/Disturbance Diiturbanc*^
ESP Building
r-Fr,
•1
^^
xn Boiler
17'
__i
14'
Boiler
Building
Figure 10. Side view of the flue gas outlet duct and disturbance points,
Plant No. 3.
27
-------
14'
Outlet
4'-M
I I
i;Flue Gas Outlet Sampling Ports! :£:!
20'
Continuous:
: Monitor
Sampling
: Ports
IT n n n
Inlet
— 2'-9"
-23'-6"-
-21'
Unit 3
~T
6'-6"
lO'-lO"
2'-6"
14'
N-
Walkwayi
Continuous!
Monitor
Sampling
Ports
n.n:.n..n.
Inlet
51
1
Units 2 & 1
Figure 11. Top view of the sampling platform above the
vertical ducts, Plant No. 3.
28
-------
N-
106-3/8"
87-3/8"
68"
48-3/4"
29-3/8"
10"
1 • • ••••• •
2 • • ••• • • •
3* • • • • • • •
4* • ••••• •
5 • • • •• • • •
6 • • • •• • • •
i
11
\
6"
1 H I2 1 I3 1 I4 1 5 6I I7 8 ii"
22" [*-
Figure 12. Location of sampling ports and individual sampling
points for isokinetic sampling within the flue gas
outlet duct, Plant No. 3.
*NOTE: These measurements are taken from the inside wall,
excluding the length of the nipple.
29
-------
Exterior
Door
Row 2
Row 1
N
Unit 3 Fly Ash Hoppers
Units 2 & 1
Fly Ash Hoppers
Figure 13. ESP hopper arrangement, Plant No. 3.
-------
Economizer Ash
Economizer ash was sampled directly from valves on the two collection
hoppers for Unit No. 3. The economizers were located ahead of the ESP array.
The economizer ash was sampled six times per day, and sampling was alternated
between the two hoppers, as required by the RTI scheme.
Bottom Ash
The bottom ash accumulated in six collection hoppers. The ash was
quenched and sluiced out once per shift. Dry ash was sampled by opening one
of the six ports (6 in.) and withdrawing hot'ash with a scoop on a 12- to
15-ft handle. The sampler was required to wear a full face shield. The plant
operator in that area opened and closed the ports. RTI prepared a sampling
schedule based on the configuration and wasting procedures for the bottom ash
hoppers. Figure 14 shows a schematic representation of the bottom ash hopper
system.
Coal , :
The plant personnel collected coal samples from the feed streams to each
of the four pulverizers every 4 hr and prepared a daily composite.
Plant Background Air
Plant background air was sampled near the forced draft fans on the top
floor of the plant building. ,
Continuous Monitoring :
Ports similar to those on the outlet duct were located on both ducts in-
let to the.ESP. The inlet and outlet ports were on the same level with a walk-
way between the platforms (see Figures 10 and 11). The heated sampling line
was dropped nearly vertically to the ground from the ports (130 ft) to the
lab trailer.
SAMPLING LOCATIONS, PLANT NO. 4
Flue Gas Outlet
Eight ports were located on the top of the duct between the ESP and the
stack breeching. The duct was 10 ft wide and 20 ft deep at this point. The
ports were approximately 1 ft below removable deck grates. Figures 15 and 16
show top and side views of the duct and give approximate dimensions and dis-
tances to disturbances. Figure 17 is a cross sectional view of the flue gas
outlet duct showing the location of the sample points within the duct. The
outlet flue gas temperature was 320-350°F with a velocity of approximately
60 ft/sec. The flue gas was sampled until approximately 20 m3 of flue gas
was collected between two modified Method 5 sampling trains.
31
-------
-~3'
~12'
rL_n_JT_r
A B C D E
Entry
Hatch
Figure 14. Schematic of the bottom ash hopper for Unit 3, Plant No. 3
32
-------
98'
13
u u
64'
-Ports for Unit 1
T
Sampling Ports
Unit 2
Walkway Based
~ 1' From Top
of Duct
•25'
•33'
Stack
Fan
20.5'
-57'
ESP
Unit 2
Figure 15. Top view of the flue gas outlet duct and
sampling points, Plant No.:4.
33
-------
Sampling
Ports
N
n
• 3
• 4
• 5
• 6
• 7
• 8
60'
33'
Duct Is ~ 25' Deep'
on Outside
Ground
ESP
Fly Ash Hoppers
Figure 16. Side view of flue gas outlet duct and sampling points, Plant No. 4.
-------
Ports
«*^
1
V*.
o
-8
'5
O
it.
o
S
(Measurements
i
1 i
49-3/4"
83*3/4 "'
117-3/4"
151-3/4"
185-3/4"
219-3/4"
253-3/4"
287-3/4"
R ' R R R FM
i • • • • • •
2 • • '•••'• • •
3 • • • • • •
4* • • • • •
5 • • • • • •
6« • • • • •
7 • • . • • • • • ..
*8 • • • • • •
i 11M" i
i
22
i
/4
•8'
* Point No. 8 was actually sampled at a point 282-3/4" inside the duct.
This was due to a miscalculation in the design of the probe.
Figure 17. Cross-sectional view of the flue gas outlet duct
showing the location of the sample points
within the duct, Plant No. 4.
35
-------
ESP Ash
The ESP hopper array consisted of five rows of four hoppers each.
Figure 18 is an illustration of the ESP hopper array. Ash was removed from a
port on the side of each hopper using a dipper. RTI constructed a hopper selec-
tion schedule to obtain a sample from each row six times per day.
Bottom Ash
Bottom ash was collected in four quench hoppers and was wasted once per
shift. Ash was sluiced out of the hoppers, through a clinker grinder, out to
the bottom ash pond approximately 2,000 ft from the plant building.. Since
the hoppers were not directly accessible for sample collection, samples were
taken from the outlet pipe at the pond. Sampling personnel maintained close
contact with the plant operators so that collection was conducted only when
ash was sluiced from Unit No. 2. Three or four pint jars of ash-water slurry
were taken three times per day.
Water
There was no effluent from the bottom ash wasting system other than the
sluice water. Hence, the river water used to quench and sluice the ash was
the only water sample to be collected. River water was used for the boiler
seal with the overflow feeding the ash hopper. The raw river water was taken
in duplicate from the screen intake house once per day.
Coal
The boilers were face-fired with pulverized coal. The coal was supplied
via seven pulverizer mills. Samples were taken from the feed pipes above the
mills according to a selection scheme provided by RTI. Three of the seven
hoppers were not sampled due to obstructions and the inability to remove port
caps. Figure 19 illustrates the feed pipe arrangement and indicates the six
sampling points that were accessible. The plant burned primarily West Virginia
coal with a fuel value of 12,000 Btu/lb and 11 to 12% ash.
Plant Background Air
Plant background air was sampled near the air intakes on the top floor
of the plant building.
Continuous Monitoring
Ports for continuous monitoring were located on the duct between the
boiler and the ESP.
36
-------
N
4 EC
DW-EC
DW EC
3W EC
DW EC
3 c
3 C
3 C
2 C
3 C
D C
3 C
1 C
3 C
3 C
3 C
B
Direction of Flow
Figure 18. ESP hopper array, Plant No. 4.
37
-------
Seven Hoppers Per Unit
543
oo
To Pulverizer
(Typical)
Sampling Ports
Obstructed Port,
Could Not Obtain Sample
Unobstructed, Could
Obtain Sample
Figure 19. Coal feeder arrangement, Plant No. 4.
-------
SAMPLING LOCATIONS, PLANT NO. 5
The general layout of Plant No. 5 is shown in Figure 20.
Flue Gas Outlet
Four ports were located on the stack at the 96-ft level. The stack inner
diameter was 21 ft at the sampling level. A vertical cross sectional view of
the stack, shown in Figure 21, indicates elevations and distances to distur-
bances. Figure 22 is a hofizontaT"cross sectional view of the stack at the
sampling platform level showing the positions of the ports, the locations of
the plant's continuous monitoring equipment, and the sampling traverse point
locations. The distances of the traverse points from the inside stack wall
are listed in Table 5.
ESP Ash
The two ESP units, shown in Figure 20, each consisted of three rows of.
four collection hoppers. The middle hoppers on each row of each ESP unit,
labeled Al-3 and Bl-3 on Figure 20, were fitted with valves for ash sampling.
Samples were taken from all six of these hoppers six times per day.
Bottom Ash
Bottom ash was sluiced twice per' shift from the three collection hoppers
through two sluice lines^per. hopper, into ,a common sump (see Figure 23). Bot-
tom ash samples were taken using a long-handled dipper from the'effluent of
one of the sluice lines, i.e., at-the sump, six times per day. .The selection
scheme for sampling ash from the three hoppers was provided by RTI.. The
sluiced ash was allowed to settle in a bucket for 30 min and the supernatant
decanted prior to transferring the sample to a jar for storage and shipment.
A portion of the supernatant was transferred to a water bottle as the corres-
ponding quench water effluent sample.
Water ' • '"'" • •, . '!',..-.
Quench water effluent samples were taken six times per day as described
above. Quench water influent samples were taken once per day from a tap on
the quench water supply line near the bottom ash hoppers.
Coal
Coal samples were taken six times per day from one of the feed streams
to the five pulverizer mills. The sampling locations and stream identifica-
tion system are shown in Figure 24. The feed stream selection scheme was pro-
vided by RTI.
Plant Background Air
Plant background air was sampled from the forced draft fan room on the
ground floor of the plant building.
39
-------
-p-
o
Stack
Lab Trailer
Cooling
Towers
Figure 20. General layout of Plant No. 5
-------
Fan
Top 750'
96' »
~54'
Ash
Evacuation
\
3/8" Steel Liner
Plus Insulation
Concrete Shell
Second Platform .(Test Site)
First Platform
Fan
Figure 21. Vertical cross section of stack, Plant No. 5.
41
-------
3/8" Steel with ~ 2" Insulation
Outer Concrete Shell
Stairs
Grating
Ladder
Figure 22. Horizontal stack cross section and traverse
point locations, Plant No. 5.
42
-------
TABLE 5. MODIFIED METHOD 5 TRAIN SAMPLE POINT LOCATIONS,
PLANT NO. 5
Fraction of Distance from
Traverse point no. stack ID (%) inside wall (in.)
1 1.6 4.0
2 4.9 12.4
3 -8,5 21.4
4 12.5 31.5
5 16.9 42.6
6 22.0 55.4
7 28.3 71.3
8 37.5 94.5
43
-------
Bottom Ash Hoppers
Figure 23. Bottom ash sluice system, Plant No. 5.
-------
Hopper
(Typical)
N
Ul
E
0
1
' 1
D
0
r i
c
o
' 1
B
O
A
O
Coal Feeder
1 (Typical)
Pulverize Mill
Figure 24, Coal sampling locations, Plant No. 5.
-------
Continuous Monitoring
Ports for continuous monitoring were located on the ducts between the
boiler and the two ESP units. A port on the B side duct was sampled (see
Figure 20).
SAMPLING LOCATIONS, PLANT NO. 6
The general layout of Plant No. 6 is shown in Figure 25.
Flue Gas Outlet
Eight ports were located in a vertical row 4 ft upstream from the stack.
The location of the ports is shown in the verical cross sectional view in
Figure 26 and the horizontal view in Figure 27. The very close proximity of
the ports to flow disturbances necessitated use of the maximum number of
traverse points. The duct dimensions and locations of the 48 traverse points
are shown in Figure 28.
ESP Ash
The ESP array, shown in Figure 27, consisted of two rows of four hoppers.
Ash samples were taken 6 times per day from ports on one hopper from each row
according to a selection scheme provided by RTI. Since samples could not be
taken from hoppers 1A and 2A because the ports were obstructed, alternate hop-
pers in row A were selected by RTI for these two points.
Bottom Ash
Bottom ash samples were taken six times per day from the sluice line ef-
fluent at the ash pond. Samples were collected, allowed to settle, and de-
canted prior to transferring to the sample container.
Waters
Quench water effluent was taken from the bottom ash sample decantate six
times per day. Quench water influent was sampled once per day from a tap on
the supply line to the bottom ash quench system.
Coal
Coal samples were collected six times per day from one of the four hop-
pers located above the pulverizer mills. The sampling locations are identified
in Figure 29.
Plant Background Air
Plant background air was sampled near the forced draft fans located di-
rectly beneath the ESP unit.
46
-------
Stack
N
Modified Method 5
Sampling Site
Laboratory Trailer
Unit 1
Coal Conveyor (
Parking
Lot
Coal
Entrance Road
Settling Pond
(Bottom Ash
Sampling Site )
Figure 25. General layout of Plant No. 6.
47
-------
Unit 1
ESP
N
Modified Method 5
Sampling Ports
~50'
Stack
_J
Figure 26. Vertical cross section, Plant No. 6.
48
-------
N
4B j 3B ] 2B ] IB
4A 3A 2A 1A
ESP
Continuous
Monitor
Lab Trailer
Figure 27. Horizontal view, Plant No. 6.
49
-------
21-1/2'
I.D.
- 10' I.D. -
118" 98" 78" 58" 38" 18"
• •••••
65432 1
•KM
_
Flow »•
Expansion Joint'
-
2
I
25" (To Outside Surface )
^— fc. 1
32"
32"
28"
3' 29-1/2"
30"
SO-
SO"
o 4-
42" (To Outside Surface)
1
48"
Stack Outside
Wall
Figure 28. Duct dimensions and traverse,point locations, Plant No. 6.
-------
4" Sampling Port
Figure 29. Coal sampling locations, Plant No. 6.
-------
Continuous Monitoring
Ports for continuous monitoring were located on the duct immediately up-
stream from the ESP unit (see Figure 27).
SAMPLING LOCATIONS, PLANT NO. 7
The general layout for Plant No. 7 is shown in Figure 30.
Flue Gas Outlet
Ten ports were located on each of two ducts entering opposite side of
the stacks (see Figure 30). The ports were accessed by four platforms on each
duct. As in the case of Plant No. 6, the proximity of the ports to disturbances
necessitated use of a large number of traverse points (50 points on each duct).
Figure 31 shows the locations of traverse points on a cross section of the
side B duct. The side A duct differed only in the position of the platforms
relative to the duct.
ESP Ash
The two ESP units consisted of arrays of three rows of eight hoppers.
Samples were taken from the pneumatic waste lines of both units six times per
day. The ESP arrays and ash sampling points are shown in Figure 30.
Bottom Ash
Bottom ash was sluiced from the boiler once each operations shift. Sam-
ples of the sluiced ash were collected from the sluice line effluent at the
ash pond three time per day. Samples were allowed to settle and were decanted
prior to transferring to the sample container.
Economizer Ash
Economizer ash was sampled six time per day from one of the five hoppers.
The locations and identifications of the hoppers are shown in Figure 30. The
hoppers were selected according to a scheme provided by RTI.
Waters
Quench water effluent was taken from the bottom ash sample decantate three
time per day. Quench water influent was sampled three times per day from a
tap on the quench water supply line near the main pump.
Coal
Coal samples were taken six times per day from one of six feed streams
to the pulverizer mills. The stream selection scheme was provided by RTI.
52
-------
Fly Ash-/
Sampling Site
Continuous
Monitoring
Sampling Site
Modified Method 5
Sampling Sites
N
^ Ports
Electrostatic
Precipitators
-Fly Ash
Sampling Site
•Economizers
Figure 30. General layout of Plant No. 7.
-------
,10" 11"
Boort...
T
16-1/2
27-1/2
5-1/2
25
32
26-1/4
27-1/2
33
(12-l/B)
—11-1/8 33-3/S 55-5/S-
-100"
Figure 31. Duct dimensions and traverse point locations, side B, Plant No. 7.
54
-------
Plant Background Air
Plant background air was sampled near the forced draft fans located un-
der the main ducts between the plant building and the ESP units.
Continuous Monitoring
Ports for continuous monitoring were located on the duct immediately adja-
cent to the plant building and upstream of the ESP units. The location of
the port used is noted on Figure 30.
55
-------
SECTION 6
ANALYSIS METHODS
The general procedures for the preparation and analysis of samples from
the power plants are described in the methods manual in Appendix A. This sec-
tion provides descriptions of specific procedures used for sample compositing
(e.g., solid and aqueous grab samples), extract compositing, and extract
cleanup as well as other details related to the analyses of samples from the
four plants.
GENERAL ANALYTICAL SCHEME
Sample preparation and analysis followed the general analytical scheme
presented in Figure 32. The samples were spiked with surrogate compounds just
prior to extraction. A representative fraction of the extracts for each sam-
ple type from Plants Nos. 1-4 was screened by fused silica capillary gas chro-
matography using Hall and flame ionization detectors (HRGC/Hall-FID) to pro-
vide preliminary information on the presence of chlorinated compounds. The
extracts were then analyzed by fused silica capillary gas chromatography/mass
spectrometry (HRGC/MS) to provide information on the recovery of surrogate
compounds and quantitation of polynuclear aromatic hydrocarbons, phthalates,
and other major components of the sample extracts. The extracts were combined
as necessary to provide 5-day composites for HRGC/MS-SIM (selected ion moni-
toring) analyses of PCBs, PCDDs and PCDFs. If any tentative identifications
of PCDDs or PCDFs were made by HRGC/MS-SIM, HRGC with high resolution mass
spectrometry (HRGC/HRMS-SIM) was used to confirm the identification and to
quantitate.
SAMPLE COMPOSITING AND EXTRACTION
Ash, coal, and aqueous samples (excluding water samples collected once
per day or less) were combined to form daily composite samples prior to analy-
sis. These composites were prepared by combining equal weights for the sam-
ples (usually six) collected during that 24-hr period. Since compounds of
interest were not identified in grab samples from the first three plants, the
daily composites prepared for Plants Nos. 4-7 were further combined into 5-day
composites prior to extraction. Hence, the number of extracts for subsequent
analysis was decreased.
56
-------
ANALYSIS SCHEME
Sample Extract
HRGC/Hall - FID
Screen
Add Internal Standard
Anthracene - d]Q
Scanning HRGC/MS
Surrogates + Pol/cyclic
Organic Compounds
Add Internal Standard
2,3,7,8 - Tetrachlorodibenzo-p-dioxin-3?Cl4 or
HRGC/MS - SIM
Chlorinated Pol/cyclic Organic
Compounds (Biphenyls, Dioxins, Furans)
Hold
HRGC/HRMS - SIM
Confirmation
Hold
Interlaboratory
Verification
HRGC/HRMS - SIM
Figure 32. Analysis scheme for sample extracts.
57
-------
The ESP ash samples for Plants Nos. 2-6 were collected from multiple hop-
pers for each time period. The ESP ash samples for each collection time were
composited to form a representative ash for each collection time. The daily
composites were prepared from the time period composites as described in the
preceding paragraph. The compositing schemes were developed from the esti-
mated fractions of total ESP ash collected in each row of hoppers as provided
by the plant management. The estimated fractions of the total ESP ash col-
lected in each row of hoppers at Plants Nos. 2-6 are shown in Table 6. The
composite samples for each collection time were prepared by mixing weights of
the samples from each hopper row proportional to the fraction of ash collected
in the row.
TABLE 6. ESTIMATED PERCENT FLY ASH COLLECTED IN
EACH ROW OF ESP HOPPERS, PLANTS NOS. 2-6a
Plant No. Row 1 Row 2 Row 3 Row 4 Row 5
2b
p
3
4d
5e
6f
75
95
75
85
75
19
5
19
13
19
5
™
5
2
-
1
— ' —
1 < 1
-
. _
a Data provided by plant managements.
b Four rows of ESPs with eight hoppers each.
c Two rows of ESPs with four hoppers each.
d Five rows of ESPs with eight hoppers each.
e Two ESPs with three rows of four hoppers on each unit.
f Two rows with four hoppers each.
58
-------
Immediately prior to extraction, all composite and other grab samples
prepared for extraction were spiked with 50 [Jg of each of the surrogate spik-
ing compounds. These were naphthalene-dg, chrysene-d12, 1,2,4,5-tetrachloro-
benzene-13Ce, pentachlorophenol-13C6, and 3,4,3',4'-tetrachlorobiphenyl-d4.
All daily grab composites from Plants Nos. 1, 2, and 3 and the 5-day grab
composites from Plants Nos. 4-7 were analyzed in duplicate as described in
Appendix A.
The surrogate spiking compounds were selected from commercially available
stable labeled compounds to represent specific classes, of the target analytes.
Naphthalene-dg and chrysene-d12 were selected to represent small and large
PAH compounds. Naphthalene is the most volatile of the target analytes.
Hence, naphthalene-dg recoveries may provide an indication of maximum losses
attributable to volatilization during extraction and extract concentration.
Chrysene-d12 is the least volatile of the surrogate compounds. Chlorinated
benzenes and biphenyls were represented by l,2,4,5-tetrachlorobenzene-13C6
and 3,4,3',4'-tetrachlorobiphenyl-d4. Pentachlorophenol-13Ce was selected to
represent the most polar of chlorinated phenols.
The flue gas samples consisted of the cyclone catch, filter, adsorbent
resin, and probe rinse. Each media was extracted separately and the extracts
were combined to prepare a composite flue gas sample. Two modified method 5
sampling trains were used to collect 20 m3 of flue gas for each day. Hence,
the two composite flue gas samples were combined to make a daily composite
unless there was some question as to the validity of the sampling procedure
for a particular sampling train. The surrogate compounds (50 pg each) were
added to different train components for different sampling days as a means to
check the recovery efficiencies of individual components. The surrogate com-
pounds were spiked in the adsorbent resin for sampling days 1 and 4, the train
rinses for days 2 and 5, and the filter for day 3 for each plant. The first
impinger contents for each of the sampling trains were extracted but the ex-
tract was not combined with the flue gas sample extracts. This sample was'
used to test for breakthrough of analytes from the resin.
Field sample blanks and laboratory method blanks were prepared and ex-
tracted as described in Appendix A. .
HRGC/HALL-FID SCREEN
A representative fraction of the extracts for each sample type from
Plants Nos. 1-4 were screened by HRGC/Hall-FID to determine if chlorinated
cpmpounds were present in the samples prior to HRGC/MS analyses. The analyses
were .completed using the instrument and parameters designated in Table 7.
Although extract screening provided useful information on the compositions of
samples frpm the first four plants, the results did not justify the labor ex-
pended. Hence, screening was discontinued for samples from Plant Nos. 5 to 7.
59
-------
TABLE 7. INSTRUMENT AND OPERATING PARAMETERS
FOR HRGC/HALL-FID SCREENING
Instrument Tracor 550
Detectors Model 700A Hall electrolytic conductivity
(halogen mode) and hydrogen flame
ionization 1:1 split
Column 15 m fused silica, wall-coated with DB-5
Column temperature 60° - 325°C at 8°C/min
Carrier gas helium at 18 psi
Injector J & W on-column (1 (jl injection)
The column performance and Hall detector sensitivity were evaluated at
least once per week using a performance standard developed for this study.
The standard contained 11 halogenated compounds representing nonpolar, acidic,
and basic classes. Figure 33 is a representative chromatogram of the column
performance standard mixture. This mixture provided information regarding
separation efficiency, adsorption of specific classes of compounds and pH of
the column. The five-component surrogate compound mixture was also run at
least twice per day to check the sensitivity of the flame ionization and Hall
electrolytic conductivity detectors.
SCANNING HRGC/MS
The sample extracts were analyzed by scanning HRGC/MS to identify and
quantitate polynuclear aromatic hydrocarbons (PAH), phthalates, and any chlo-
rinated compounds that might be present. Table 8 lists the target PAH and
phthalate compounds. The gas chromatography parameters for the separation of
the sample extracts were essentially the same as that used for HRGC/Hall-FID
screening. The gas chromatography and mass spectrometer instrumental param-
eters for the scanning HRGC/MS analyses are given in Table 9. Anthracene-djo
(20 (jg) was added to sample extracts and standards prior to scanning HRGC/MS
to serve as an internal standard for quantitation. The five-component surro-
gate compound standard (25 ng/pl each) and a 20 or 25 ng/pl PAH-phthalate
standard were analyzed at least once per day with the sample extracts.
60
-------
II
Riiinllon TIoi* (MlnuHt)
1
I,
Figure 33. HGRC/Hall-FID chromatogram of the capillary
column performance standard.
61
-------
TABLE 8. TARGET PAH AND PHTHALATE COMPOUNDS
PAHs
Phthalates
naphthalene
acenaphthylene
acenaphthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
chrysene
benzo[k]fluoranthene
benzo[a]pyrene
dibenz[a,h]anthracene
benzo[g,h,i]perylene
dimethylphthalate
diethylphthalate
di-n-butylphthalate
butylbenzylphthalate
bis(2-ethylhexyl)phthalate
di-n-octylphthalate
TABLE 9. INSTRUMENT AND OPERATING PARAMETERS FOR
SCANNING HRGC/MS ANALYSIS
Instrument
Column
Column temperature
Carrier gas
Injector
Scan range
Scan rate
Finnigan MAT 311-A/Incos
15-m fused silica, wall-coated with SE-54
or DB-5
80°C for 2 min, then to 325°C at 10°C/min
helium at 2.5 psi
J & W on-column (1 fJl injection)
m/e 32-425
1.5 sec/scan
62
-------
The PAHs, phthalates and surrogate compounds were identified using three
extracted ion current plots (EICPs) for each specific compound. The criteria
for compound identification were coincident peaks in all EICPs at the appropri-
ate retention time with the characteristic response ratios. Compounds identi-
fied were quantitated by comparing the EICP response for the most abundant
ion with the most abundant ion of the internal standard (anthracene-djo) and
using the response factor for these two ions determined.from the standard so-
lutions.
FLUE GAS EXTRACT CLEANUP
All flue gas extracts were cleaned by adsorption chromatography prior to
scanning HRGC/MS analysis. The results of HRGC/Hall-FID screening of extracts
from Plants Nos. 1-4 and preliminary scanning HRGC/MS analysis of representa-
tive extracts from all plants indicated the need for cleanup. This was based
on observations of high levels of background levels in chromatograms, poor
chromatographic peak shapes characteristic of column overloading, and Tow
recoveries of surrogates likely attributable to background interferences.
The adsorption column chromatographic procedure subsequently used for
the flue gas extracts was adapted from methods developed by MRI for cleanup
of sludge extracts.4 Twenty-gram aliquots of freshly prepared silica gel (70
to 230 mesh, Soxhlet extracted with dichloromethane dried at 110°C and deac-
tivated with 1% water) were placed in 14.5 x 250 mm chromatography columns con-
taining hexane. The individual flue gas extracts were added to 2-g aliquots
of silica gel and evaporated to dryness. The extracts were then placed at
the top of the columns and eluted according to the following scheme.
Fraction 1 = 20 ml hexane
Fraction 2 = 80 ml hexane
Fraction 3 = 50 ml 10% benzene in hexane
Fraction 4 = 50 ml 50% benzene in hexane
Fraction 5 = 150 ml 10% acetone in benzene
Fraction 6 = 40 ml methanol
Fraction 1 from each column was discarded. The remaining fractions were
screened by HRGC/Hall-FID to estimate the degree of cleanup and recovery of
the surrogate compounds. Fractions 3-6 for flue gas extracts from Plant Nos.
1 and 2 were composited prior to scanning HRGC/MS analysis. Fraction 2 from
these extracts were analyzed individually since HRGC/Hall-FID screening indi-
cated the presence of significant interferences. Fractions 2-6 were compos-
ited for extracts from Plants Nos. 3-7 prior to scanning HRGC/MS analysis.
Table 10 shows the recoveries observed for the surrogate compounds, the target
PAH compounds, and selected PCDD and PCDF isomers spiked into hexane.
63
-------
TABLE 10. RECOVERIES FOR COMPOUNDS CHROMATOGRAPHED
ON SILICA GEL BY THE PROCEDURE USED
TO CLEAN FLUE GAS EXTRACTS
Q
Compound % Recovery
Naphthalene-d8 71
l,2,4,5-Tetrachlorobenzene-13C6 83
Acenaphthylene 55
Acenaphthene 69
Fluorene 76
Pentachlorophenol-13C6 37
Phenanthrene 87
Anthracene 81
Fluoranthene 87
Pyrene 91
3,4,3,4'-Tetrachlorobiphenyl-de 88
Chrysene-d12 . 57
Benzo[a]pyrene 95
Dibenz[£,h]anthracene 88
2-Chlorodibenzo-£-dioxin 80
2,7-Dichlorodibenzo-p_-dioxin 89
1,2,4-Trichlorodibenzo-£-dioxin 88
1,2,3,4-Tetrachlorodibenzo-£-dioxin 104
Octachlorodibenzofuran 104
a Spike level was 50 pg.
64
-------
HRGC/MS-SIM
PCBs
Extracts of grab samples from Plants Nos. 1, 2, and 3 were analyzed for
PCBs using a specialized HRGC/MS-SIM procedure, selected mass range scan
HRGC/MS. That is, the mass spectrometer was scanned over the m/e range of
the molecular cluster for each of the chlorobiphenyls. The specific operat-
ing parameters are listed in Table 11. In order to improve sensitivity, scan
ranges were switched according to a pre-set program during the course of the
HRGC/MS run so that only two sets of chlorobiphenyl compounds were analyzed
simultaneously. The specific time points for switching the ion sets were se-
lected based on the elution times for chlorobiphenyl compounds in a mixture
of Aroclor® 1248, 1254, and 1260. A chromatogram of this mixture analyzed by
scanning KRGC/MS is shown in Figure 34.' Ions for monochloro- and dichlorobi-
phenyl were monitored from the initiation of the run until a time after the
elution of monochlorobiphenyl but before the elution of trichlorobiphenyl.
At that time, the ion set was switched to monitor for dichloro- and trichloro-
biphenyl. This sequence was continued throughout each run. Hence, the last
set of ions monitored were for nonachlorobiphenyls and decachlorobiphenyl.
Positive responses to any of the PCB isomers in the composite extracts were
confirmed when the peaks for the ion plots for two ions were coincident with
responses in the proper ratios. PCB isomers identified were quantitated using
area response factors for specific isomers with the same chlorine number.
Standard solutions containing the isomers listed in Table 12 were analyzed
daily at concentrations of 10, 100, and 250 pg/JJl for each specific isomer.
Aliqubts .of the grab sample extracts from Plants Nos. 1, 2, and 3 were
combined to form 5-day composites prior to PCB analysis to reduce the number
of extracts analyzed. If PCBs had been detected in any of the 5-day compos-
ites, the extracts from which those composites were prepared would have been
analyzed individually.
The extracts of grab samples from Plants Nos. 4-7 and the flue gas and
plant background air samples from all plants were analyzed by HRGC/MS-SIM
using conventional SIM procedures. The instrument and operating parameters
are listed in Table 13. The analyses were completed in two runs. Mono-
through trichlorobiphenyls were determined in the first run and tetra- through
decachlorobiphenyls were analyzed in a second run.
The mixed Aroclor standard was used to identify the characteristic re-
tention windows for PCB isomers. At least two different levels of specific
PCB isomers were analyzed each day to determine area response factors for
quantitation.
65
-------
TABLE 11. INSTRUMENTAL PARAMETERS AND MASS RANGES USED
FOR HRGC/MS-SIM ANALYSES OF PCBs
Instrument
Column
Column temperature
Carrier gas
Injector
Scan rate
Scan ranges
No. chlorines
Finnigan 4024
15 m fused silica, wall-coated with DB-5
80°C for 2 min, then to 325°C at 8°C/min
helium at 2.5 psi
J&W on-column (1 pi injection)
1 sec/scan
Mass range scan (amu)
Retention time
monitored (min)'
1
2
3
4
5
6
7
8
9
10
187.5
221.5
255.5
289.5
323.5
357.5
391.5
425.5
459.5
493.5
- 188.5
- 226.5
- 262.5
- 298.5
- 334.5
- 366.5
- 400.5
- 434.5
- 468.5
- 502.5
13.0
13.0
13.0
14.5
16.9
18.2
20.0
22.2
23.1
25.0
- 14.5
- 14.5
- 16.9
-18.2
-20.0
-22.2
-23.1
-25.0
- 26.6
- 26.6
Determined by analyzing a mixed Aroclor standard and scanning
HRGC/MS.
66
-------
Sample: Combined Aroclor 1248,1254,1260
250ng/^tl & DCB 100ng//il, 1/il Injection
800 1000 1200 1400 1600 1800 2000 2200 SCAN
20:00 25:00 30:00 35:00 40:00 45:00 50:00 55:00 TIME
Figure 34. Mixed Aroclor standard used to establish retention
windows for HRGC/MS-SIM analyses of PCBs.
67
-------
TABLE 12. PCB COMPOUNDS USED FOR QUANTITATION STANDARDS
4,4'-Dichlorobiphenyl
2,3,5'-Trichlorobiphenyl
2,4,2',4'-Tetrachlorobiphenyl
2,3,4,5,6-Pentachlorobiphenyl
2,3,4,2',3',4'-Hexachlorobiphenyl
2,3,4,5,6,2',5'-Heptachlorobiphenyl
2,3,4,5,2',3',4',5'-Octachlorobiphenyl
Decachlorobiphenyl
TABLE 13. INSTRUMENT AND OPERATING PARAMETERS FOR HRGC/MS-SIM ANALYSES
OF PCBs IN ALL FLUE GAS AND PLANT BACKGROUND AIR SAMPLES
AND GRAB SAMPLES FROM PLANTS NOS. 4-7
Instrument
Column
Column temperature
Carrier gas
Injector
Ions
Chlorine No,
1
2
3
4
5
6
7
8
9
10
Finnigan MAT 311-A Incos
15 m fused silica, wall-coated with DB-5
80°C hold 2 min, then to 325°C at
10°C/min
helium at 2.5 psi
J&W on-column (1 [jl injection)
Ions (m/e)
188.0/190.0
222.0/224.0
255.9/257.9
291.9/293.9
325.9/327.9
357.9/359.8
393.8/395.8
427.7/429.7
461.7/463.7
497.7/499.7
68
-------
The flue gas extracts required additional cleanup prior to HRGC/MS-SIM
analysis for PCBs. Each individual extract was diluted to 5 ml with cyclo-
hexane and washed with 5 ml of concentrated sulfuric acid for approximately
30 sec. The phases were allowed to separate and the organic layer was removed.
The H2S04 layer was extracted with 5 ml of fresh cyclohexane. The cyclohexane
was separated, combined with the original cyclohexane fraction and concentrated
to 1.0 ml. The recoveries for specific PCB isomers spiked into cyclohexane
and treated by the acid wash procedures are shown in Table 14.
TABLE 14. RECOVERY OF PCB ISOMERS FROM SULFURIC
ACID TREATED EXTRACTS
Compound Recovery (%)
a
2,4,2',4'-tetrachlofobiphenyl 74,: 70
2,3,4,5,6-pentachlorobiphenyl 97, 92
2,3,4,2',3',4'-hexachlorobiphenyl 86, 91
2,3,4,5,6,2',5'-heptachlorobiphenyl 85, 85
2,3,4,5,2',3',4',5'-octachlorobiphenyl 78, 94
decachlorobiphenyl . 85, 86
a Duplicate determinations.
PCDDs/PCDFs
Sample extracts were also analyzed by HRGC/MS-SIM for PCDDs and PCDFs.
The instrument and operating parameters are listed in Table 15. Perfluoro-
kerosene (PFK) was used to obtain stable mass assignments during PCDD and PCDF
analyses. Analyses for the entire range of PCDDs and PCDFs required four in-
jections of each extract. Mono- through tri- PCDDs and PGDFs were determined
in the first run. Three subsequent runs were used to determine tetrachloro
compounds, penta- and hexachloro compounds, and hepta- and.octachloro com-
pounds, respectively. •• • ' .
69
-------
TABLE 15. INSTRUMENT AND OPERATING PARAMETERS FOR HRGC/MS-SIM ANALYSES
OF PCDDs/PCDFs
Instrument
Column
Column temperature
Carrier gas
Injector
Finnigan MAT 311-A/Incos
15-m fused silica, wall-coated with DB-5
80°C hold 2 min, then to 325°C at
10°C/min
helium at 2.5 psi
J&W on-column (1 (Jl injection)
Chlorine No.
1
2
3
5
6
7
8
Dioxins (m/e)
218.0/220.0
252.0/254.0
285.9/287.9
319.9/321.9
353.9/355.9
389.8/391.8
423.8/425.8
457.7/459.7
Furans (m/e)
202.0/204.0
242.0/244.0
269.9/271.,9
303.9/305.9
337.9/339.9
373.8/375.8
407.8/409.8
441.7/443.7
PFK (reference)
242.9
331.0
380.8
430.7
Five-day composites of grab sample and flue gas sample extracts were pre-
pared for each plant for PCDD and PCDF analyses. Potential PCB interferences
were removed from the composite flue gas samples by fractionation on alumina
columns (8 x 1.4 cm) according to the procedure outlined in the U.S. EPA
Method 613. The alumina was activated at 130°C for at least 24 hr before use.
The columns were packed, and eluted with 50 ml of hexane before the sample
was added to the top of the column. Each column was then eluted with 50 ml
of 3% dichloromethane in hexane and the eluent was discarded. The column was
then eluted with 50 ml of 20% dichloromethane in hexane which was collected
and concentrated to 1.0 ml for analyses. The recoveries of duplicate blanks
spiked with 50 ng of l,2,3,4-tetrachlorodibenzo-£-dioxin were 100 and 99%.
70
-------
SECTION 7
FIELD TEST DATA
This section presents summaries of the flue gas sampling data, unit
operating parameters, and particulate control device operating data for the
seven coal-fired utility boilers. •
PLANT NO. 1
A summary of the daily data for flue gas sampling as calculated from the
field data sheets is presented in Table 16. The data listed are corrected
to standard conditions, i.e., 20°C and a barometric pressure of 29.92 in.
(1.0 atm.) of mercury. Events that may have created uncertainties are noted.
Table 17 is a summary of the plant background air sampling data.
Table 18 summarizes the boiler process data monitored hourly during the
flue gas sampling periods. The parameters recorded include the turbine steam
flow (Ib/hr), flue gas temperatures from the two preheaters in °F, gross out-
put (Mw), opacity in the combined stack (%), and coal usage (tons/hr). All
information was collected in the control room from meters or the computer out-
put. Table 19 lists the inoperable fields in each of the ESP stages during
the test period and also notes the average ESP operating conditions. ESP per-
formance was monitored from the meters on the ESP control boards.
Table 20 summarizes the major variations in operating conditions during
the test periods. For the most part, operating conditions were very stable.
Slight variations in steam flow and gross output were related to variations
in the Btu value of the coal feed.
The average performance and ultimate fuel contents of the coal used to
operate this plant during the 5-day test period are shown in Table 21.
71
-------
TABLE 16. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, PLANT NO. 1
Test Sampling
No. Location
A
1
B
A
2
B
A
3
B
A
4
B
^i
ro Ad
5
B
Sample
dscf
344 . 50
339.27
359.19
364.11
372.22
326.74
354.76
293.11
_
374.67
volume
dscm
9.80
9.61
10.17
10.31
10.54
9.25
10.05
8.30
_
10.61
Gas composition
02 (%)
5.2
5.2
5.3
5.3
5.3
5.3
5.6
5.6
_
5.7
C02 (*)
14.0
14.0
14.4
14.4
13.2
13.2
13.7
13.7
_
13.8
CO (ppm)
NDC
ND
ND
ND
6.9
6.9
6.5
6.5
_
7.4
THC (ppm)
0.
0.
2.
2.
1.
1.
1.
1.
,
4,
.4
.4
3
,3
,7
.7
1
p i
.9
Stack
Temperature
(°F
322.
304.
311.
317.
310.
310.
293.
295.
_
299.
)
9
2
6
3
4
0
9
7
6
Molecular
weight
30 . 5 1
30.57
30.35
30.35
30.59
30.59
30.43
30.43
_
30.31
Moisture
Velocity Flue gas flow
(%) (ft/sec) acfm dscfm dscmm
10.74
10.59
10.49
10.30
10.09
10.97
10.32
11.81
_
10.36
101.
98.
96.
96.
77.
99.
88.
87.
_
99.87
9
5,428,000 3,266,000 92,500
05
22
5,238,000 3,166,000 89,650
77
81
5,364,000 3,257,000 92,200
78
98
4,796,000 2,990,000 84,680
72
2,711,000 1,688,000 47,800
Isokinetic
rate (%)
95.1
94.9
103.0
104.3
104.3
90.6
105.9
90.5
-
100.7
a Average values for duration of test.
b Sum of the flow through the total outlet.
c ND = not detected.
d Gasket slippage created a post leak rate of 0.7 cfm. This test was not valid.
-------
TABLE 17. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 1
Test
1
2
3
4
5
6a
:,. . • •
dscf
387.71
387.31
435.26
443.46
388.23
. - 521.47
Volume
dscm
10.98
. 10.97
12.33
12.56
10.99
14.77
a Test No. 6 was a lab background sample collected
in the same manner as the intake air for Test
Nos. 1 through 5.
73
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TABLE 18. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING, PLANT NO. 1
Test
1 -
2 -
3 -
4 -
5 -
average
range
average
range
average
range
average
range
average
range
Gross
output
(Mw)
611
598-628
612
580-635
615
553-636
555
533-573
610
584-623
Steam flow
(10,000 Ib/hr)
445
437-464
445
425-457
452
401-466
404
391-418
450
477-461
Gas temperature
from preheaters (°F)
Unit 11
340
340-352
338
330-352
330
328-347
322
319-322
331
327-333
Unit 12
327
325-338
— 330
326-350
331
325-339
316
314-321
323
320-324
Opacity
(%)
4.1
3.9-5.1
4.9
4.6-5.9
4.3
3.7-5.1
4.9
4.3-5.8
4.7
4.6-5.2
Coal usage
(tons/hr)
353
N/A
422
N/A
400
N/A
364
N/A
400
N/A
-------
TABLE.19. ELECTROSTATIC PRECIPITATQR OPERATING INFORMATION, PLANT NO. 1
A. Number of fields inoperable during flue gas test periods
Q "' , •
Primary unit 9-10
Secondary unit 1-2
B. Average operating conditions , .
Primary unit Secondary unit
Primary voltage 300-320 AC-v " 360-380 AC-v
Primary amperes ' N/A 140-160 AC-amp
Bushing-1 MA . N/A 240-260 DC-amp
DC kilovolts " N/A 36-40 DC-kv
Bushing-2 MA N/A 280-320 DC-amp
a 9 Fields inoperable day 1 and day 2.
10 Fields inoperable day 3 through day 5
b 1 Field inoperable day 1 to day 5.
2 Fields in operable day 4 and day 5.
75
-------
TABLE 20. LOG OF SYSTEM CHANGES, UPSETS AND BREAKDOWNS
DURING FLUE GAS TESTING, PLANT NO. 1
Test Day 1 - Relatively constant operating conditions.
Test Day 2 - Pulverizer no. 15 was removed from service causing a lower
output level in the final minutes of the test period.
Test Day 3 - At the beginning of the test period the system was gradually
normalizing after a load drop anticipator problem had earlier
caused a sudden drop in the output level. Later, a temporary
power reduction was caused by a maintenance check of turbine
valves. Later in the period, pulverizer no. 15 was removed
from operation causing a lower output level for the remainder
of day 3 and day 4.
Test Day 4 - A brief output reduction was caused by the temporary cut off
and of anpulverizer unit, otherwise, both days were relatively
m «. rv <- stable. '
Test Day 5
76
-------
TABLE 21. PROXIMATE AND ULTIMATE ANALYSIS RESULTS
FOR COAL, PLANT NO. 1
Standard
o
Average deviation
Proximate analysis
As received
Moisture (%) 22.69 1.65
Ash (%) 13.91 1.18
Volatile (%) 31.41 1.56
Fixed carbon (%) 31.98 0.48
Sulfur (%) 0.45 0.12
Heat of combustion (Btu/lb) 7,842 383
Dry basis
Ash (%) ; 18.00 1.56
Volatile (%) 40.62 1.43
Fixed carbon (%) 4li38 0.54
Sulfur (%)' 0.58 0.16
Heat of combustion (Btu/lb) 10,142 381
A and M free Btu (Btu/lb) 12,367 363
Ultimate analysis • ' '
Hydrogen (%) 3.00 0.17
Carbon (%) 59.47 2.37
Nitrogen (%) 0.72 0.23
Oxygen (%) : 18.20 1.64
Total chlorine (ppm) 269 187
a .Results for five daily composite coal samples.
77
-------
PLANT NO. 2
The daily data summaries for flue gas sampling at Plant No. 2 are shown
in Table 22. Table 23 is a summary of the volumes for plant background air
samples taken during the flue gas testing.
Table 24 is a summary of the process data monitored during the flue gas
test period. The parameters monitored include gross output (Mw), steam flow
(Ib/hr), outlet gas temperature from preheaters 4A and 4B (°F), and opacity
percentage (from a meter in the stack). All data were obtained from meters
and recorders in the control room or from the shift operator.
i
Table 25 is a summary of the ESP operating conditions during the five
flue gas test runs. Primary voltage (AC-v), primary current (AC-amp), pre-
cipitator current (DC-amp), and spark rate were read directly from the ESP
control panels. All sections of the ESP were operable during the test
periods.
Table 26 is a log of system changes, upsets, and breakdowns during the
flue gas test periods. In general, operations were quite stable except for
variations in power output and excess oxygen caused by variations in coal
quality. Power cutbacks due to reduced demand were made on days 1, 3, and 5.
An excesive spark rate and a drop in precipitator and primary current were
noted in the ESP on day 5.
Table 27 is a summary of the average proximate and ultimate fuels con-
tent of the coal used at Plant No. 2 during the 5-day testing period.
PLANT NO. 3
Table 28 presents the daily data summaries for the flue gas sampling at
Plant No. 3. A summary of the volumes for plant background air samples are
shown in Table 29.
Table 30 summarizes boiler operating conditions during the test period.
Continuous process monitors were available in the boiler room. These included
steam flow, pressure, temperature, megawatt output, feedwater temperatures,
pulverizer operation, ESP data, opacity (based on a continuous and 6-min aver-
age transmissometer in the ESP outlet), and flue gas temperatures.
Boiler operation remained steady and relatively unchanged throughout the
5 days of testing. Only minor adjustments occurred due to events such as one
high opacity episode, changes in coal properties, and regular adjustments
required when returning the boiler to typical operating parameters.
Table 31 summarizes the ESP operating conditions during the test for Plant
No. 3. During the test period, the ESP performed according to specifications.
No breakdowns or disruptions occurred.
78
-------
TABLE 22. DAILY DATA SUMMARIES FOR FLUE CAS SAMPLING, PLANT NO. 2
Test Sampling
No. Location
North
1
South
North
2
South
North
3
South
North
4
South
North
5
South
Sample
dscf
329.
240.
251.
242.
318.
317.
315,
326.
319,
323.
41
.53
.52
.11
.86
.15
.50
.63
.74
.04
volume
dscm
9.33
6.81
7.12
6.86
9.03
8.98
8.93
9.25
9.05
9.15
Gas composition
02 (%)
4.5
4.5
2.6
2.6
3.7
3.7
3.4
3.4
3.0
3.0
C02 (%)
17.1
17.1
17.5
17.5
15.4
15.4
15.7
15.7
15.8
15.8
CO (ppm)
119.9
119.9
143.8
143.8
19.4
19.4
31.7
31.7
71.7
71.7
THC (ppm)
0.4
0.4
0.6
0.6
_
Stack
Temperature
Molecular
Moisture
(°F) weight (%)
663.
657.
657.
668.
657.
5
4
0
0
2
648.9
0.4
0.4
0.2
0.2
654.
652.
651.
651.
9
3
9
9
31.
31.
30
30.
30.
30.
.34
.34
.93
.93
.76
.76
30.65
30
30.
30
.66
.81
.81
6.86
7.64
8.44
8.62
7.33
7.09
7.33
7.30
7.45
7.00
Velocity
(ft/sec)
66.25
66.23
68.48
69.17
70.25
67.0
67.95
70.53
67.25
69.33
Gas flow Isokinetic
acfm dscfm dscmm rate (%)
101.6
1,192,000 504,400 14,280
105.1
109.4
1,259,000 513,100 14,530
104.0
102.5 '
1,235,000 525,000 14,870
104.2
104.1
1,246,000 531,700 15,060
102.0
106.3
1,229,000 526,300 14,900
102.1
a Average values for duration of test.
b Sum of flow through the total outlet.
-------
TABLE 23. SUMMARY OF PLANT BACKGROUND AIR VOLUMES, PLANT NO. 2
Test
1
2
3
4
5
dscf
368.33
379.77
403.31
407.89
378.58
Volume
dscm
10.43
10.76
11.42
11.55
10.72
TABLE 24. SUMMARY OF PLANT OPERATING CONDITIONS
DURING FLUE GAS TESTING, PLANT NO. 2
Test
1 -
2 -
3 -
4 -
5 -
average
range
average
range
average
range
average
range
average
range
Gross
output
(Mw)
268
221-270
268
262-271
260
200-265
265
232-268
260
235-270
Steam flow
(10,000 Ib/hr)
188
150-190
192
190-195
190
135-192
175
168-196
191
160-195
Preheater outlet
gas temperatures (°F)
Unit 4A
300
290-305
300
295-305
277
275-280
285
280-290
285
275-290
Unit 4B
300
280-315
305
300-310
280
265-285
287
285-290
290
275-300
Opacity
(%)
40
20-60
50
20-90
45
25-80
45
25-80
40
25-80
80
-------
TABLE 25. SUMMARY OF ELECTROSTATIC'-PRECIPITATOR OPERATING
CONDITIONS DURING FLUE: GAS TESTING, PLANT NO. 2
... - . .
Test
1 _
2 -
3 -
4 -
5 -
average
range
average
range
average
range
average
range
average
range
Primary
voltage
(AC-v)
200
160-260
200
160-260
200
160-270
200
120-270
200
150-250
Primary
' current
(AC-amp)
140
110-220
160
90-220
160
-90-220
170
110-220
110
50-210
Precipitator
current .
(DC -amp)
0.9
0.5-1.4
0.9
0.5-1.2
0.9
0.4-1.3
0.9
0.5-1.4
0.5
0.3-1.0
Spark
rate
(sparks/min)
90
0-175
80
0-150
60
0-120
70
0-120
150
0-250
TABLE 26. LOG OF SYSTEM CHANGES, UPSETS, AND BREAKDOWNS
.' . . DURING FLUE GAS TESTING, PLANT NO. 2
Test Day 1 -
Test Day 2 -
Test Day 3 -
Test Day 4 -
Test Day 5 -
(Sunday)
Operating conditions were very stable except for two cutbacks
in power generation due to reduced demand. Excess oxygen
varied widely when the .cutbacks were made.
Operating conditions were very stable.
A brief upset was caused by a pulverizer outage. The power
output was reduced during the last 2 hr of the test period.
Power output varied somewhat due to changes in coal character-
istics. One brief upset was caused by a pulverizer outage.
ESP operating conditions changed significantly about 4 hr into
the test period. The spark rate was excessive and the precipi-
tator current and primary current decreased. Other operating
conditions were relatively stable except for a power decrease
later in the test period.
81
-------
TABLE 27. PROXIMATE AND ULTIMATE ANALYSIS RESULTS
FOR COAL, PLANT NO. 2
Standard
Average deviation
Proximate analysis
As received
Moisture (%) 7.05 0.36
Ash (%) 13.55 1.34
Volatile (%) 29.42 1.04
Fixed carbon (%) 49.98 0.99
Sulfur (%) 1.89 0.22
Heat of combustion (Btu/lb) 11,576 259
Dry basis
Ash (%) 14.58 1.45
Volatile (%) 31.64 1.15
Fixed carbon (%) 53.77 0.98
Sulfur (%) 2.03 0.23
Heat of combustion (Btu/lb) 12,492 305
A and M free Btu (Btu/lb) 14,624 116
Ultimate analysis
Hydrogen (%) 4.53 0.25
Carbon (%) 66.14 1.82
Nitrogen (%) 1.21 0.05
Oxygen (%) 11.48 2.85
Total chlorine (ppm) 225 268
a Results for five daily composite coal samples.
82
-------
TABLE 28. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, PLANT NO. 3
oo
Test Sampling Sample
No. Location dscf
A
1
B
A
2
B
A
3
B
A
4
B
A
5
B
320.92
345.90
341.32
350.96
340.21
347.01
347.75
356.59
337.44
343.36
volume Gas composition
Stack
Temperature
dscm 02 (%) C02 (%) CO (ppm) TIIC (ppm) (°F)
9
9
9
9
9
9
9
10
9
9
.09
4.9 13.8 17.7 1.6
.80
.67
5.2 13.7 14.6 0.3
.94
.63
5.0 14.1 11.7 1.6
.83
.85
4.9 14.1 8.8 0.2
.10
.56
5.0 13.8 10.3 0.5
.72
300
300
297.
300
294
300.
290
297
287
294
.7
.6
.6
.5
.3
.5
.0
.9
.0
.9
Molecular
weight
30.33
30.37
30.28
30.28
30.33
30.33
30.38
30.38
30.25
30.25
Moisture
Velocity
(%) (ft/sec)
6.46
6.49
6.99
6.98
7.42
7.57
7.88
7.69
7.90
7.81
54
55
54.
55
56
55.
56
56.
54
55
.68
.88
.95
.23
.10
.45
.03
.03
.85
.98
Gas flow Isokinetic
acfm dscfm dscmm rate
96
919,300 576,400 16,320
100
101
916,000 571,500 16,180
104
99
927,400 573,700 16,240
104
101
931,500 576,100 16,310
106
100
921,400 573,000 16,230
101
(%)
.1
.5
.2
.8
.4
.4
.8
.1.
.3-
.7
a Average values for duration of test.
b Sum of the flow through the total outlet.
-------
TABLE 29. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 3
Test
1
2
3
4
5
6a
7a
Volume
dscf
308.66
328.67
309.43
329.83
312.96
300.22
320.10
dscm
8.74
9.31
8.76
9.34
8.86
8.50
9.10
a Lab background samples.
84
-------
TABLE 30. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING, PLANT NO. 3
oo
Test
1 - average
range
2 - average
range
3 - average
range
4 - average
range
5 - average
range
Gross
output
(Mw)
121
120-122
123
151-125
121
120-123
121
120-122
121
100-123
Steam flow
(10,000 Ib/hr)
87
. 86-88
87
86-88
87
86-88
88
88-89
87
72-88
Gas temperature
from preheaters (°F)
308
300-310
307
300-310
310
305-312
308
300-312
304
292-310
Opacity
(%)
14
11-26
10.5
9-18
9.9
5-19
15
12-17
11
6-20
Coal usage
(tons/hr)
46
N/A3
42
N/A
: 46
N/A
'47
N/A
46
N/A
a NA = not available.
-------
TABLE 31. ESP OPERATING CONDITIONS, PLANT NO. 3
oo
1
2
3
4
5
Test
- average
range
- average
range
- average
range
- average
range
- average
range
•a
Spark rate
(sparks/min)
100
88-112
88
92-112
87
92-112
99
90-112
87
84-112
Primary current
(AC -amp)
134
80-175
136
80-185
129
70-180
134
80-185
140
80-185
Primary voltage
(AC-v)
258
215-300
256
220-300
258
220-295
269
240-300
264
250-300
All fields were operational during the test. Each field was periodically shut off about
each half-hour. Only one field was off at a time.
Manufacturer: American Standard
Design volume, acfm: 475,000
Design temperature, °F: 300
Design inlet concentration: 3.88 g/acf
Cells per chamber: 4
Fields deep: 4/precipitator
Gas passages/field: 74
Collecting surfaces: 75
Collecting surface spacing: 9 in.
Face area/precipitator, ft?: 1,665
Total surface, ft2: 153,290
Gas velocity, fps: 4.75
Retention time, sec: 7.29
-------
The results of proximate and ultimate fuels analysis on coal and ashes
from Plant No. 3 are shown in Table 32. Since bottom ash, ESP ash, and econo-
mizer ash were all sampled at Plant No. 3 as dry ash prior" to quenching', fuels
analyses were conducted to allow examination of possible 'correlation of spe-
cific compounds with gross characteristics.
TABLE 32. PROXIMATE AND ULTIMATE ANALYSES FOR COAL, BOTTOM ASH,
FLY ASH, AND ECONOMIZER ASH, PLANT NO. 3
•
s
Proximate Analysis
Reported as received
Moisture (%)
Ash .(%) . ..
Volatile (%)
Fixed carbon (%)
Sulfur (%)
Heat of combustion
(Btu/lb)
Dry basis
Ash .(%.)
Volatile (%)
Fixed carbon (%)
Sulfur (%)
Heat of combustion
(Btu/lb)
A. and M free Btu (Btu/lb)
Ultimate Analysis
Dry basis
Hydrogen '(%)
Carbon (%)
Nitrogen (%)
Oxygen (%)
Total chlorine (ppm)
Coal*
6.34 + 2,16
13.40 ± 1.08
31.91 ± 1.11
48.75 ± 1.85
0.88 ± 0.09
11,660 ± 430
*
14.32 ± 1.35
34.05 ± 0.75
51.63 ± 0.86
0.94 ± 0.09
12,446 ± 228
14,526 ± 77
4.63 ± 0.25
70.04 ± 0.87
0.55 ± 0.38
9.53 ± 0.47
528 ± 260 :
Bottom
Ashb
c.
14.01
81.54
0.33
4.13
0.09
66
94.82
0.38
4.80
0.11 •
77
1,492
0.01
3.60
0.68
0.79
NAC
Fly
Ashb
0.02
90.14
1.61
8.23
0.22
1,304 .
90.15
1.61
8.23
0.23
1,304
13,241
0.01
9.47
0.26
0.00
NA
Economizer
Ashb
0.10
74.60
0.01
25.30
0.12
. ,1,405
,
74.67 '
0.01
- 25.32
0.12
.1,407
5,553
.. 0 . 34
12.42
0.61
11.84
NA
a Results from five daily composite samples.
b Results from a single 5-day composite sample.
c Not analyzed.
87
-------
PLANT NO. 4 .
Table 33 presents the daily data summaries for the flue gas sampling at
Plant No. 4. The air volumes sampled for plant background air are shown in
Table 34.
Table 35 summarizes the process data monitored during the flue gas test
period. The parameters monitored include gross output (Mw), steam flow
(Ib/hr), the gas temperature from the heaters (east, middle, and west in °F),
and opacity percentage (from a meter in the stack). All data were obtained
from meters and recorders in the control room.
The ESP operating conditions during the five flue gas test runs are sum-
marized in Table 36. Primary current (AC-amp), primary voltage (AC-v), pre-
cipitator current (DC-mA), and precipitator voltage (DC-kv) were read directly
from meters in the ESP control room. The spark rates were calculated from
reading on the total sparks counter for each bus section. All sections were
operable during the test periods except one section during Day Nos. 3, 4,
and 5. Table 34 also identifies the individual bus sections having a signif-
icant sparking rate during the test periods. The sections not listed (most
notably the various sections in the D and E fields) had sparking rates of
approximately zero sparks per minute.
Table 37 is a log of system changes, upsets, and breakdowns during the
flue gas test periods. During test days 2 and 3, operating conditions were
very constant. On days 1 and 4 a change in pulverizer units caused a period
of variation. During day 5 the power output was changed several times due to
varying demand, producing a number of changes in operating parameters.
Table 38 is a summary of the average proximate and ultimate fuels content
of the coal used at Plant No. 4 during the testing period.
PLANT NO. 5
The daily data summaries for flue gas sampling at Plant No. 5 are shown
in Table 39. The volumes sampled for plant background air are shown in Table
40.
Table 41 lists the process data monitored during the flue gas test period.
Parameters observed included gross output (mw), steam flow (Ib/hr), preheater
outlet temperature, opacity, oxygen, coal usage and S02 and NO emissions.
All information was obtained from meters in the control room.
Electrostatic precipitator operating conditions during the test period
are summarized in Table 42. Parameters observed were primary voltage (AC-V),
primary current (AC-amp) and spare rate. Values were obtained from meters on
the ESP control units.
88
-------
TABLE 33. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, PLANT NO. 4
00
VO
Test Sampling
No
1
2
3
4
5
a
b
c
d
Location
AC
A
Bd
Ae
B
A
B
A
B
A
Bf
Average values
Sample volume Gas composition3
dscf
346.10
296.88
341.10
300.03
344.43
307.37
336.66
307.90
280.90
269.58
Stack
Temperature Molecular
dscm 02 (%) C02 (%) CO (ppm) T1IC (ppm) («F)
9.80
6.6 12.2 9.2 1.3
8.41
9.66
6.5 12.4 17.0 2.7
8.50
9.76
6.5 12.3 20.1 1.9
8.70
9.53
6.4 12.3 24.4 1.2
8.72
7.95
8.6 11.1 12.2 0.7
7.63
336.0
334.
342.
338.
335.
334.
342.
336.
336.
328.
3
1
2
3
8
2
5
1
7
weight
30.33
30.33
29.36
30.34
30.71
30.78
30.43
30.43
30.16
30.16
Moisture
('
7
6
7
7
7
8
8
8
7
7
X)
.71
.50
.93
.57
.88
.01
.40
.10
.31
.56
Velocity
(ft/sec)
57.38
54.18
58.08
52.95
56.27
52.22
56.90
54.62
47.47
46.62
Gas flowb Isokinetic
acfm dscfm dscmm rate
102
1,720,000 1,037,00 29,360
92,
101
1,711,000 1,020,000 28,890
96
104
1,672,000 1,002,000 28,370
100
102
1,719,000 1,012,000 28,665
97
101
1,450,000 867,100 24,550
98
(%)
.6
.6
.6
.4
.9
.1
.9
.8
.9
.2
for duration of test.
Sum of the flow through
Flexible line
Post leak rate
the total outlet.
was discovered to be disconnected during the change
from Port 1
to 2. The test
! to EPA Method 5
is
or
likely
ocedure
valid.
;s. The vi
ilidity of the test is questionable.
e Port change error sampled 3.5 of lowest points in Port 1 instead of Port 3. The test is likely valid.
f The flexible line was found to be kinked twice during the test. However, the test is considered valid based on close agreement of sample moisture.
g Post leak rate was 0.023 cfm, presenting a potential error of approximately 3%. The test is considered valid.
-------
TABLE 34. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 4
Test
1
2
3
4
5
6a
7a
Volume
dscf
277.821
264.785
261.126
202.408
284.516
309.131
337.028
dscm
7.868
7.499
7.395
5.732
8.058
8.755
9.545
a Lab background samples.
90
-------
TABLE 35. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING, PLANT NO. 4
VO
Test
1 -
2 -
3 -
4 -
5 -
average
range
average
range
average
range
average
range
average
range
Gross
output
(Mw)
209
182-209
212
212-213
214
213-215
213
212-215
152
125-155
Gas temperature
from heaters
Steam flow
(10,000 Ib/hr)
148
126-149
147
146-147
146
145-148
148
145-151
105
88-108
east
345
340-350
348
340-350
345
340-345
350
340-360
330
315-340
(°F)
middle
345
340-345
350
345-355
345
345-350
350
345-360
345
320-345
west
320
315-320
320
320
320
315-320
325
310-330
310
295-315
Opacity
12
7-12
10
8-13
11
5-14
10
8-12
9
3-12
-------
TABLE 36. SUMMARY OF ELECTROSTATIC PRECIPITATOR OPERATING CONDITIONS
DURING FLUE GAS TESTING, PLANT NO. 4
VD
Test
1
2
3
4
5
- average
range
- average
range
- average
range
- average
range
- average
range
Sections Sections with
operating active sparking
all
all
all except
1 unit
all except
1 unit
all except
1 unit
7
6
5
4
3
Spark rate of
active sparking Primary
sections current
(sparks/min) (AC-amp)
12
6-19
13
8-19
14
9-16
15
10-19
10
3-18
120
46-124
120
58-124
120
50-124
120
55-124
120
118-124
Primary
voltage
(AC-v)
350
300-500
350
280-520
350
320-540
350
320-500
340
330-500
Precipi-
tator
current
(DC-mA)
720
200-740
730
340-740
730
220-750
730
280-740
730
600-740
Precipi-
tator
voltage
(DC-kv)
43
38-60
43
38-62
43
38-66
43
38-62
44
32-56
-------
TABLE 37.-'-LOG-OF SYSTEM CHANGES, UPSETS, AND BREAKDOWNS
DURING FLUE GAS TESTING, PLANT-NO.1-4,.. .
Test Day 1 - Almost constant operating conditions until a pulverizer burned
out aout 45 min before the end of the sampling time. Operations
were erratic during the last 45 min.
Test Day 2 - No upsets—very constant operating conditions.
Test Day 3 - No upsets—very constant operating conditions.
Test Day 4 - Three hours into the test an additional pulverizer was placed
into service, causing temporary variations in operating parameters
Otherwise, operating conditions were very constant.
Test Day 5 - Operating parameters varied throughout the test period. The gross
output changed several times due to varying demand. Excess air
values varied significantly throughout the test.
93
-------
TABLE 38. PROXIMATE AND ULTIMATE ANALYSIS RESULTS
FOR COAL, PLANT NO. 4
Standard
Average deviation
Proximate fuel analysis
As received
Moisture (%) 5.90 0.76
Ash (%) 11.78 2.17
Volatile (%) 37.76 2.93
Fixed carbon (%) 44.56 2.39
Sulfur (%) 3.77 0.33
Heat of combustion (Btu/lb) 11,920 162
Dry basis
Ash (%) 12.51 2.21
Volatile (%) 40.14 2.30
Fixed carbon (%) 47.35 2.49
Sulfur (%) 3.90 0.30
Heat of combustion (Btu/lb) 12,669 244
A and M free Btu (Btu/lb) 14,483 112
Ultimate analysis
Hydrogen (%) 4.25 • 0.28
Carbon (%) 60.44 0.84
Nitrogen (%) 1.33 0.10
Oxygen (%) 9.52 2.07
Total chlorine (ppm) 359 29
a Results for five daily composite coal samples.
94
-------
TABLE 39. DAILY DATA SUMMARIES FOR FLUE CAS SAMPLING, PLANT NO. 5
vO
Test
No.
1
2
3
4
5
Sampling Sample
location dscf
A
B
A
B
A
B
A
B
A
B
334.62
336.91
337.98
340.95
333.51
344.48
340.90
341.00
296.48
289 . 95
volume Gas composition
Stack
Temperature Molecular
dscro 02 (%) C02 (%) CO (ppm) THC (ppro) (°F)
9
9
9
9
9
9
9
9
8
8
.48
6.0 13.3 12.9 0.9
.54
.57
5.0 12.6 8.0 0.8
.65
.44
4.9 13.1 7.3 NDC
.75
.65
5.4 12.2 9.4 0.3
.66
.40
6.1 11.2 23.6 0.1
.21
300
297
300
298
303
296
282
274
278
269
Moisture
weight (%)
30.
30.
30.
30.
30.
30.
30.
30.
30,
30.
53
53
55
.55
.64
.64
,52
.52
.48
.48
5.5
5.9
5.6
6.0
5.6
6.1
5.7
6.2
5.6
6.1
Velocity
(ft/sec)
98.
99,
97.
98
97
99.
80
79
69
67
.95
.53
.42
.40
.00
.08
.68
.87
.92
.70
Flue gas flow Isokinetic
acfm dscfm dscrran rate (%)
98.0
4,125,000 2,618,000 74,100
98.1
100.2
4,069,000 2,592,000 73,400 _
;.. 100.1
99.8
4,075,000 2,590,000 73,300
100.4
99.9
3,336,000 2,169,000 61,400
100.4
99.7
2,880,000 1,872,000 53,000
100.0
a Average values for duration of test.
b Sum of the flow through the total outlet.
c NO = not detected.
-------
TABLE 40. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 5
Volume
Test dscf dscm
1 331.24 9.38
2 349.64 9.90
3 351.21 9.95
4 350.58 9.93
5 338.30 9.58
96
-------
TABLE 41. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING; PLANT NO. 5
vO
Test
1 - Average
Range
2 - Average
Range
3 - Average
Range
4 - Average
Range
5 - Average
Range
Gross
output
(mw)
590
510-595
586
580-590
590
589-591
460
418-501
370
318-400
Steam flow
(1,000,000
Ib/hr)
3.8
3.3-3.8
3.8
3.80-3.84
3.9
N/A
3.0
-2.7-3.2
2.5
2.0-2.6
Gas temperature
from preheaters
(°F) Opacity" (%)
A
"320
310-328
320
302-330
328 .
310-330
300
295-305
305
395-310
B
320
310-325
320
302-328
325
308-328
295
290-300
290 . .
280-300
Stack
7
4-12
7 .
3-16
7
4-20
6
3-8
5
3-8
A
14
9-19
14
7-19
15
10-17
14
11-21
14
8-18
B
2
0-8
1
0-7
1
0-5
1
0.4
1
0-2
Oxygen" (%)
Stack
8.0
7-8.5
8.0
7.2-9.0
7.5'
7-8
6.5
6-7
7.5
6.5-8.5
A
4.0
3.8-4.2
3.8
-3.5-4.5
3.7
:3. 5-4.0
3.5
2.9-3.7
3.5
3.1-4.4
B
3.2
2.3-3.2
2.9
2.7-3.2
2.8
2.5-3.1
3.0
2.6-3.4
3.4
2.7-4.5
S02 (ppm)
840
800-840
950
9,010-1,050
980
840-1,000
900
810-960
950
880-1000
NO (ppm)
280
250-360
340
250-360
390
350-410
340
315-390
350
280-360
- Coal
usage
(tons/hr)
289
N/Ab
223
N/A
N/A
. N/A.
. 176
N/A
149
N/A
a Sections A and B are inlets to electrostatic precipitators.
b NA = not available. .
-------
TABLE 42. SUMMARY OF ELECTROSTATIC PRECIPITATOR OPERATING CONDITIONS
DURING FLUE GAS TESTING, PLANT NO. 5
Test
1
2
3
4
5
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
Primary
voltage (AC-v)
200
160-300
200
180-300
200
160-300
250
200-320
250
190-310
Primary
current (AC-amp)
100
40-230
100
35-240
90
40-240
140
60-240
160
80-250
Spark rate
(sparks/min)
25
5-50 .
20
1-50
20
5-45
15
1-40
15
1-50
NOTE - All units were functioning during all test runs.
A summary of system changes, upsets and breakdowns is listed in Table 43.
Other than a brief coal feeder breakdown on day 1, the only variations in
operation were due to variations in load demand.
TABLE 43. LOG OF SYSTEM CHANGES, UPSETS, AND BREAKDOWNS
DURING FLUE GAS TESTING, PLANT NO. 5
Test Day 1 - One coal feed unit stopped for about 10 min due to a
stoppage 5 hr into the test. This caused a temporary
reduction in output. Output was brought down during
the final half hour of testing due to reduced demand.
Test Days 2 and 3 - Very stable operating conditions during the test period.
Test Days 4 and 5 - Variable output due to variations in the weekend load
demand.
The results of proximate and ultimate fuels analyses of 5-day composites
of coal, bottom ash, and fly ash from Plant No. 5 are summarized in Table 44.
98
-------
TABLE 44. PROXIMATE AND ULTIMATE ANALYSIS RESULTS FOR COAL,
•' BOTTOM ASH, AND FLY ASH, PLANT NO. 5 . .
. Coal
Bottom
ash
Fly
ash
Proximate analysis
Reported as received.
Moisture (%)
Ash '(%)
Volatile (%) .
Fixed carbon (%)
Sulfur (%)
Heat of combustion (Btu/lb)
Dry basis
Ash (%)
' . Volatile (%)
Fixed carbon (%)
Sulfur (%),
Heat of combustion (Btu/lb)
A and M free Btu (Btu/lb)
6.13
13.81
33.30
46.76
1.81
12,121
14.71
35.47
49.82
1.93
12,912
15,140
36.73
46.31
1.95
15.01
0.21
799
73.19
3.08
23.73
0.33
1,262
4,708
0.22
96.59
0.28
2.92
0.10
432
96.80
0.28
2.92
0.10
433
13,529
Ultimate analysis
Dry Basis
Hydrogen (%)
./• .Carbon (%)
'.', ,. -Nitrogen (%).
. . Oxygen (%)'
Q .
Total chlorine (ppm)
-
4.15
67.17
1.37
10.67
780,
650
0.21
25.63
0.56
0.10
390,
500
0.06
4.10
0.28
0.00
940,
1,000
a Duplicate determinations.
99
-------
PLANT NO. 6
The daily data summaries for flue gas sampling at Plant No. 6 are shown
in Table 45. The volumes of plant background air sampled are shown in Table
46. . . ,
Table 47 lists the process data monitored during the flue gas test period.
Parameters observed included gross output (raw), steam flow (Ib/hr), tempera-
ture at the superheater outlets, and excess oxygen. Other parameters moni-
tored for plants tested previously, e.g., opacity, were not measured in Plant
No. 6. Due to defective meters or lack of measurement capacity, coal usage
was estimated by measuring the depth change in the coal feed bunkers one day
during a 6-hr period when new coal was not being loaded into the bunkers. All
other information was obtained from meters in the control room.
Electrostatic precipitator operating conditions during the test period
are summarized in Table 48. Parameters observed were primary voltage (AC-v),
precipitator average current (DC-amp), primary current (AC-amp), and spark
rate. Values were read from meters on the ESP control units.
A summary of system changes, upsets and breakdowns is listed in Table 49.
Other than a brief coal feeder breakdown on day 1, the only variations in
operation were due to variations in load demand.
The results of fuels analysis for 5-day composites of coal, bottom ash,,
and fly ash from Plant No. 6 are shown in Table 50.
PLANT NO. 7
Table 51 shows the daily data summaries for flue gas sampling at Plant
No. 7. The volumes sampled for plant background air are shown in Table 52.
Table 53 lists the process data monitored during the flue gas sampling
period. Parameters observed included gross output (mw), steam flow (Ib/hr),
% 02 in the flue gas (from right and left heaters), primary air heater output
temperature (°F from right and left heaters), opacity, and coal loading rate
(Ib/hr). All information was obtained from meters in the control room.
The control meters for each of 20 ESP sections showed little variation
with time. The ranges of values were as follows:
DC-kv DC-mA
Normal Range 25-40 400 - 1,500
Extremes 5-42 50-1,700
100
-------
TABLE 45. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, PLANT NO. 6
Test
No.
I
2
3
4
5
Sampling
location
A
B
A
B
A
B
A
B
A
B
Sample
dscf
475.20
488.38
375.59
395.15
314.65
329.22
355.55
277.62
312.71
337.14
volume Gas composition3
dscm 02 (%) C02 (%) CO (ppm) THC (ppm)
13.46
5.7 12.5 28.3 NDC
13.83
10.64
5.9 12.5 12.1 0.6
11.19
8.91
5.0 12.6 17.9 ND
9.32
10.07
5.6 12.8 36.4 ND
7.86
8.86
5.5 12.9 15.1 ND
9.55
Stack
Temperature
(°F)
372
341
373
336
376
344
365
343
364
338
Molecular
weight
30.49
30.49
30.21
30.21
30.31
30.31
30.44
30.44
30.45
30.45
Moisture
U)
7.9
7.7
8.0
8.0
8.2
8.3
8.5
8.8
8.0
8.4
Velocity
(ft/sec)
56.05
55.60
56.63
56.47
56.80
57.27
52.90
55.05
56.30
58.37
Flue gas flow Isokinetic
acfm dscfm dscmm rate (%)
101.7
1,440,000 832,000 23,600
100.4
99.7
1,459,000 843,000 23,900
99.8
100.3
1,471,000 843,000 23,900
99.6
100.6
1,393,000 799,000 22,600.
100.3
99.4
1,479,000 854,000 . 24,200
99.7
a Average values for duration of test.
b Sum of the flow through the total outlet.
c ND = not detected.
-------
TABLE 46. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 6
Volume
Test dscf dscm
1 349.65 9.90
2 346.96 9.83
3 329.39 9.33
4 322.02 9.12
5 325.78 9.23
102
-------
TABLE 47. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING, PLANT NO. 6
Test
1 -
2 -
3 -
4 -
5 -
Average
Range
Average
Range
Average
Range
Average
"Range
Average
Range
Gross output
(mw)
180
176-185
184
182-186
185
185-187
170
109-185
176
175-177
o
Steam flow
(106 Ib/hr)
1.118
N/A-
1.145
N/A
1.155
N/A
1.060
N/A
1.120
N/A
Temperature at
superheater outlets
(°F)
A
980
960-990
980
970-990
970 •
950-980
960 -
940-990
960
950-980
B
1,005
1,000-1,010
1,000
990-1,020
1,005
1,000-1,010
1,000
980-1,010
1,000
990-1,010
Excess 02 (%)
3.2
3.0-3.5
3.1
2.9-3.5
3.3
3.0-3.4
3.2
2.8-3.5
3.2
3.0-3.5
Coal usage
(tons/hr)
105b
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
;N/A
a Value is calculated from an integrator during the test period.
b Coal usage could only be estimated by measuring the depth change in the coal feed bunkers
when new coal was not being loaded intp the bunkers.
-------
TABLE 48. SUMMARY OF ELECTROSTATIC PRECIPITATOR OPERATING CONDITIONS DURING FLUE GAS TESTING,
PLANT NO. 6
Test
1
2
3
4
5
- Unit A
Unit B
- Unit A
Unit B
- Unit A
Unit B
- Unit A
Unit B
- Unit A
Unit B
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
- Average
Range
Primary voltage
(AC-v)
440
430-460
400
400-410
450
450-460
415
410-420
445
440-450
415
410-420
440
440-450
420
400-420
440
430-450
420
420
Precipitator
average current
(DC -amp)
0.75
0.75
0.95
0.95
0.75
0.75
0.95
0.95
0.7
0.7-0.8
0.9
0.9
0.8
0.6-0.9
0.9
0.9
0.7
0.7
0.9
0.9
Primary current
(AC-amp)
100
100
124
120-128
100
100
122
120-126
100
100
120
120
95
90-112
122
120-128
90
90
120
120
Spark rate
(sparks/rain)
90
70-100
70
20-100
80
60-100
40
10-60
95
90-100
80
60-100
90
50-100
50
10-90
100
100
35
30-40
NOTE: Both units were functioning during all test runs.
-------
TABLE 49. LOG OF SYSTEM CHANGES, UPSETS, AND BREAKDOWNS
"DURING FLUE GAS TESTING, PLANT NO. 6
Test Day 1 - A coal feeder was out briefly about 8 hr into the test
period. The: load was up slightly for the rest of the
test following recovery.
Test Days 2 and 3 - Very stable operating conditions during the test period.
Test Day 4 - Variations in output load due to varying demand on Sunday.
Test Day 5 - Very stable operating conditions during the test period.
105
-------
TABLE 50. PROXIMATE AND ULTIMATE ANALYSIS RESULTS FOR COAL,
BOTTOM ASH, AND FLY ASH, PLANT NO. 6
Coal
Bottom
ash'
Fly
ash
Proximate analysis
Reported as received
Moisture (%)
Ash (%)
Volatile (%)
Fixed carbon (%)
Sulfur (%)
Heat of combustion (Btu/lb)
Dry basis
Ash (.%)
Volatile (%) !
Fixed carbon (%)
Sulfur (%)
Heat of combustion (Btu/lb)
A and M free Btu (Btu/lb)
15.97
11.06
32.90
40.07
3.99
8,895
13.16
39.15
47.69
4.75
10,586
12,190
3.70
96.10
NDa
1.06
0.14
23
99.79
ND
1.10
0.15
24
11,339
0.00
97.09
1.26
1.65
0.64
105
97.09
1.26
1.65
0.64
105
3,615
Ultimate analysis
Dry Basis
Hydrogen (%)
Carbon (%)
Nitrogen (%)
Oxygen (%)
Total chlorine (ppm)
4.62
61.83
5.76
10.07
255,
341
0.12
0.87
0.00
0.00
151,
150
0.00
0.02
0.00
2.25
276,
331
a ND = not detected.
b Duplicate determinations.
106
-------
TABLE 51. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, PLANT NO. 7
Test Sampling Sample volume Gas composition3
No. location dscf
A
1
B
A
2
B
A
3
B
A
4
B
A
5
B
360.95
351
326
333
292
320
299
318
319
327
.71
.18
.42
.94
.31
.1.7
.92
.35
.26
Stack
Temperature Molecular
dscm 02 (*) C02 (%) CO (ppra) THC (ppm) (°F)
10
9
9
9
8
9
8.
9
9.
9,
.22
3.8 14.3 13.6 NDC
.96
.24
4.2 13.9 11.5 ND
.44
.30
4.8 13.6 13.6 ND
.07
.47
5.2 13.1 13.2 ND
.03
.04
5.2 13.8 12.2 ND
.27
303
298
298
292
284
280
268
259
277
265
Moisture
weight (%)
30
30
.42
.32
30.45
30.
30
30.
30.
30.
30.
30.
18
.30
21
23
,26
16
.22
8.6
8.3
8.6
7.9
7.8
7.9
7.7
7.6
8.7
8.4
Velocity Flue gas flow Isokinetic
(ft/sec) acfro dscfm ' dscmm
46
46,
42
43
36
40,
33
35
36
36
.72
1,374,000 875,000 24,800
.13
.37
1,270,000 814,000 23,000
.47
.63
1,147,000 749,000 21,200
.87 . .:. .
.85
1,027,000 690,000 19,600
.57
.65
1,087,000 715,000 20,300
.80
rate (%)
99.3
99.5
98.6
99.3
100.0
100.0
99.6
99.. 7, „
100.6
100.7
a Average values for duration of test.
b Sura of the flow through the total outlet.
c ND = not detected.
-------
TABLE 52. SUMMARY OF PLANT BACKGROUND AIR VOLUMES,
PLANT NO. 7
Volume
Test dscf dscm
1 466.07 13.20
2 387.58 10.98
3 383.48 10.86
4 363.33 10.29
5 360.18 10.20
108
-------
TABLE 53. SUMMARY OF PLANT OPERATING CONDITIONS DURING FLUE GAS TESTING, PLANT NO. 7
h-1
O
VO
Test
1 - Average
Range
2 - Average
Range
3 - Average
Range
4 - Average
Range
5 - Average
Range
Gross
output
(Mw)
360
343-370
340
220-376
290
216-368
250
216-313
260
215-370
Steam flow
(106 Ib/hr)
2.4
2..2-2.4
2.2
1.4-2.4
1 .8
1.3-2.4
1.5
1.3-2.0
1.8
1..3-2.4
Flue
02
Right
2.2
2.0-2.2
2.5
2 . 0-5 . 2
3.5
2.8-4.8
3.9
3. 0-4". 2
2.9
2.2-4.2
gas
°/
la
Left
4.0 -
3.8-4.1
. 4.0
2.8-5.5
4.6
3.0-6.0
5.6
4.6-6.0
5.0
3.8-6.0
Primary air
heater outlet
temperature
(°F)
Right
302
294-305 ;
303
268-308
289
261-317
260
250-271
262
252-305
Left
306
298-311
303
264-313
286
262-314
270
252-280
268
254-319
Opacity
(%)
9
5-13
10
9-11
10
8-12
9
9-10.
10
9-15
Coal loading
rate (Ib/hr)
280,000
260,000-288,000
260,000
224,000-294,000
220,000
188,000-254,000
190,000
164,000-214,000
196,000
160,000-278,000
-------
Most of the time during all test runs, the spark rate was zero on 19 sec-
tion panels, and was pegging the meter (> 250 sparks per minute) on the other
section meters. However, around 1200 to 1500 hr daily, as many as six addi-
tional panel meters indicated spark rates between 10 to 250 sparks per minute
before returning to zero later in the day.
It is likely that the ESP was working due to the almost constant opacity
level of 10% (which agreed with casual visual observation). Possibly, the
panel spark meters were not properly calibrated or suffered from another mal-
function. However, the difficulties in collecting fly ash samples might in-
dicate an actual malfunction of the ESP.
A summary of system changes, upsets and breakdowns is listed in Table 54.
Other than a brief coal mill outage during Run 5, all variations in operation
were due to variations in load demand.
TABLE 54. LOG OF SYSTEM CHANGES,'UPSETS, AND BREAKDOWNS
DURING FLUE GAS TESTING, PLANT NO. 7
Test Day 1 - Very stable operating conditions during the entire test
period. j
i
Test Day 2 - Stable operating conditions for about 7 hr followed by
reduction in load due to reduced demand.
Test Days 3 and 4 - Constant variation in operations due to variable load
demand.
Test Day 5 - Very low load for 8 hr followed by high load level for the
final 4 hr. There was a very brief drop in load due to a
coal mill outage.
The results of fuels analysis on 5-day composites of coal, bottom ash,
fly ash, and economizer ash from Plant No. 7 are shown in Table 55.
110
-------
TABLE 55. PROXIMATE AND ULTIMATE ANALYSES FOR COAL, BOTTOM ASH,
FLY ASH, AND ECONOMIZER ASH FROM PLANT NO. 7
Coal
Bottom
ash
Fly
ash
Economizer
ash
Proximate analysis
Reported as received
Moisture (%) 6.27
Ash (%) 9.32
Volatile (%) 28.43
Fixed carbon (%) 55.98
Sulfur (%) 1.99
Heat of combustion 12,546
(Btu/lb)
:,D,ry basis
Ash (%) . .. 9.95
Volatile (%) 30.33
Fixed carbon (%) . . 59.73
Sulfur (%) 2.12
Heat of combustion 13,385
(Btu/lb)
A and M free Btii (Btu/lb) 14,863
12.07
61.74
13.39
12.80
0.90
3,751
70.22
15.23
14.55
1.02
4,266
14,322
0.02
97.74
1.36
0.88
0.39
44
97.76
1.36
0.88
0.39
44
1,952
0.02
98.44
0.73
0.81
0.17
53
98.46
, 0.73
0.81
0.17
53
3,468
Ultimate analysis
Dry basis
Hydrogen (%)
Carbon (%)
Nitrogen (%)
Oxygen (%)
Total chlorine (ppm)
4.97
• 72.24
0.82
9.90
700 ± 290
1.81
26.77
0.59
0.00
700,
900
0.07
i:21
0.00
0.58
100,
100
0:04'
';:' "1;27'<
'^O:il ;
0.06
. '' '•' ' .';•' i
100,
100
Mean ± standard deviation for four determinations on coal. Duplicate
determinations fo.r ashes.
Ill
-------
SECTION 8
ANALYTICAL RESULTS
The analytical results generated from this program include data from HRGC/
Hall-FID screening, scanning HRGC/MS for target compounds, and HRGC/MS-SIM
analysis of the sample extracts for PCBs, PCDDs and PCDFs.
HRGC/HALL-FID SCREEN
The HRGC/Hall-FID screening procedure used for Plant Nos. 1 to 4, was
useful in identifying the sample extracts that contained halogenated organic
compounds. The Hall chromatograms for grab and plant background air samples
from Plant Nos. 1 to 4 and the flue gas samples from Plant No. 3 did not. con-
tain significant peaks other than the chlorinated surrogate spiking compounds.
Halogenated compounds were indicated in flue gas samples from Plant Nos. 1,
2, and 4. The Hall chromatograms for the five flue gas samples from each
plant were quite similar. Figure 35 shows the Hall chromatograms for flue
gas extracts from Plant No. 1.
SCANNING HRGC/MS ANALYSIS
The results for the target PAH and phthalate compounds identified in the
flue gas, fly ash, bottom ash, economizer ash, coal, and background air samples
from the seven coal-fired power plants are shown in Tables 56to 61. These
data and all other analytical results reported in this document are presented
without correction for recoveries. The levels of extractable organics from
samples other than flue gas and coal were low. Most of the target compounds
determined in the ash and background air samples were present at levels near
the detection limits. No significant levels of the target compounds were
identified in the water samples.
HRGC/MS-SIM ANALYSIS
PCBs
The concentrations of PCB isomers identified in flue gas samples from
the seven coal-fired power plants are shown in Table 62. PCBs were identified
in flue gases from all plants. However, the concentrations found in samples
from Plant No. 3 were frequently at or near the method detection limit. Al-
though the mean total PCB concentrations varied 0.01 to 1.8 (Jg/dscm, the dis-
tributions of PCB isomers identified in flue gases from all plants were similar.
The isomer distributions were also similar, to that found in the pilot study
for flue gases from a utility boiler plant co-fired with coal and a refuse-
derived fuel.2 The similarity of isomer distribution for flue gas samples
from seven plants is illustrated by Figure 36. The PCBs were comprised pri-
marily of penta- and hexachlorobiphenyls with lesser contribution from tetra-
and heptachlorobiphenyls.
112
-------
Do, 1
Doy2
10 15 20
Retention Time (Minutes)
Day 3
10 15 20
Retention Time (Minutei)
25 0
10 15 20
Retention Time (Minwlcs)
Figure 35. HRGC/Hall chromatograms of the flue gas extracts for sampling days 1-5, Plant No. 1
-------
10 15 20
Retention Time (Minute*)
5 10 15
Retention Time (Minute* )
Figure 35 (concluded)
-------
TABLE 56. TARGET COMPOUNDS IDENTIFIED IN FLUE GAS SAMPLES FROM THE SEVEN COAL-FIRED POWER PLANTS
Compound
Naphthalene
Acenaphthylene
t-1 Acenaphthene
K^
Ul
Fluorene
Phenanthrene
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
0.37
0.28
0.32
0.17
0.34
0.66
0.018
0.015
0.21
0.22
0.14
0.33
Plant
No. 2
0.57
1.7
3.8
2.5
tra
54
0.67
0.42
7.8
1.4
0.26
Concentration (pg/dscm)
Plant Plant Plant
No. 3 No. 4 No. 5
0.43 1.2
0.10 0.51 1.1
0.53 1.5 0.86
1.4 2.0 2.2
0.33 0.78 0.83
0.32
tr
0.033
0.070
0.06 0.071
0.083
0.14
0.10 0.24
0.07 0.21
Plant
No. 6
1.0
0.45
1.3
6.0
1.1
0.95
0.056
0.12
0.13
0.26
Plant
No. 7
0.48
0.14
0.57
0.44
0.65
0.012
0.045
0.0064
0.078
0.037
0.072
(continued)
-------
TABLE 56 (continued)
Compound
Fluoranthene
Pyrene
Chrysene
Benzo [ a ] pyrene
Dime thy Iphthalate
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Concentration (|jg/dscm)
Plant Plant Plant Plant Plant Plant Plant
No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7
0.088
0.044
1.15
0.044 0.088
0.058
0.057
0.024
0.32
0.031
tr 0.070
0.75 0.048
0.14 tr 0.12 0.007
tr 0.18 0.045
0.006
0.15
0.13 0.54 0.060
0.071 tr
(continued)
-------
TABLE 56 (continued)
Concentration (pg/dscm) .
Compound
Diethylphthalate
Di-n-butylphthalate
Butyl benzylphthalate
Bis (2-ethylhexyl)phthalate
Di-n-octylphthalate
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
6.0
4.1
1.9
5.8
10.5
9.1
4.0
0.98
3.1
6.7
1.1
0.64
0.44
1.8
12.3
9.1
13.5
7.4
1.1
4.9
0.23
2.5
1.7
Plant
No. 2
8.7
6.5
6.8
4.1
28.3
41.6
2.2
1.8
4.0
1.3
5.0
Plant
No. 3
0.42
2.3
0.49
0.10
0.35
0.29
tr
0.46
2.7
5.2
25
24
6.8
0.93
Plant Plant Plant Plant
No. 4 No. 5 No. 6 No. 7
0.79
5.0
12.3
11.7
1.7
0.45
0.50
0.64
tr
21 34 0.53
3.4 0.93 0.82
15.3 9.2 11 1.4
3.4 30 8.3 6.7
31.2 8.6 0.55 18.
0.63 2.0
0.31
0.54 0.50
1.2
a tr = ^ 0.025 pg/dscm.
-------
TABLE 57. TARGET COMPOUNDS IDENTIFIED IN FLY ASH SAMPLES FROM THE SEVEN COAL-FIRED POWER PLANTS
00
Compound
Naphthalene ,
Phenanthrene
Chrysene
Dimethylphthalate
Diethylphthalate
Sampling Plant Plant
day3 No. 1 No. 2
1
2
3 15
4 10
5 10
1
2
3
4
5
1
2
3
4
5
1
2
3 10
4 5.0
5 7.5
1
2
3
4
5
Concentration (ng/g)
Plant Plant Plant Plant Plant
No. 3 No. 4 No. 5 No. 6 No. 7
6.5 10
10 30
18
23
4.3 15
6.0 10
2.3
4.6 0.80
10.7
22 10 40 36
14 30 22
14
13
(continued)
-------
TABLE 57 (continued)
Compound
Di-n-butylphthalate
Butyl benzylphthalate
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Sampling Plant
day No . 1
1
2
3
4
5
1
2
3
4
5
1 38
2 48
3 20
4 15
5 25
1
2
3
4
5
Plant
No. 2
120
28
78
18
15
13
15
30
73
48
78
Concentration (ng/g)
Plant Plant Plant Plant Plant
No. 3 No. 4 No. 5 No. 6 No. 7
21 10
30 20
11
29
8.0 15 15
22 45 230
7.3
3.5
14
36 160 2,800 1,100
190 230 620
36
18
46
390
a Results for duplicate 5-day plant composites from Plant Nos. 4-7 are listed on days 1 and 2.
-------
TABLE 58. TARGET COMPOUNDS IDENTIFIED IN BOTTOM ASH SAMPLES FROM THE SEVEN COAL-FIRED POWER PLANTS
[S3
O
Compound
Naphthalane
Acenaphthylene
Fluorene
Phenanthrene
Fluoranthene
Sampling Plant Plant
day3 No. 1 No. 2
1 65
2 18
3 20
4 40
5 13
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Concentration
Plant Plant
No. 3 No. 4
8.3 21
39 1
28
55
7.8
1.5
2.5 12
11
14
33
2.0
2.0
(ng/g)
Plant Plant
No. 5 No. 6
80
27
12
5.1
4.4
33
11
14
5.9
Plant
No. 7
220
210
8.7
63
65
8.2
(continued)
-------
TABLE 58 (continued)
Compound
Pyrene
Chrysene
Benzo [ a ] py rene
•
Dibenzof a, h] anthracene
Benzo [£,h,ijperylene
Concentration (ng/g)
Sampling Plant Plant Plant Plant Plant
day No. 1 No. 2 No. 3 No. 4 No. 5
1 1.5 11
2 4.2
3
4
5
1 9.5 7.8
2
3 7.5
4 18
5
1
2
3 1.5
4 11
5
1
2
3 10
4 3.5
5
1
2
3
4 3.1
5
Plant Plant
No. 6 No. 7
7.2
16
16
3.9
(continued)
-------
TABLE 58 (continued)
ro
hO
Compound
Diethylphthalate
Di-n-butylphthalate
Butyl benzylphthalate
Bis (2-ethylhexyl)phthalate
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
88
55
73
43
88
73
70
63
60
Plant
No. 2
53
15
13
~
43
18
33
20
Concentration (ng/g)
Plant Plant Plant Plant Plant
No. 3 No. 4 No. 5 No. 6 No. 7
24 4.5
9.0 5.5
10
3.0
9.0
7.0
5.0
6.8
11
6.0 26
1.8 13 480
3.3
5.8
3.3
47 12 560
37 7 250
21
49
26
a Results for duplicate 5-day plant composites from Plant Nos. 4-7 are listed as days 1 and 2.
-------
TABLE 59. TARGET COMPOUNDS IDENTIFIED IN ECONOMIZER ASH SAMPLES
FROM PLANTS NOS. 3 AND 7
Compound
Naphthalene
Acenaphthene
Phenanthrene
Dime thy Iphthalate
Diethylphthalate
Di-n-butyl phthalate
Butyl benzylphthalate
Bis(2-ethylhexyl)-
phthalate
Sampling Concentration (ng/g)
daya Plant No. 3 Plant No. 7
1 8.3 1.4
2 1.2
3
4
5
1 8.7
2 11
3
4
5
1 1.3
2
3 4.0
4
4
1
2
3
4 1.8
5
1 • ' 5.5
2
3
4
5
1 20
2 7.8
3
4 17
5
1 270
2
3
4 '
5
1 20
2 26
3 40
4 31
5 20
a Results for duplicate 5-day plant composites from Plant No. 7 are listed
as days 1 and 2.
123
-------
TABLE 60. TARGET COMPOUNDS IDENTIFIED IN COAL SAMPLES FROM THE SEVEN COAL-FIRED POWER PLANTS
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Sampling Plant
day3 No. 1
1
2 0 . 06
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4 0.019
5
1
2 0.10
3 0.053
4 0.25
5 0.33
Plant
No. 2
0.61
0.30
0.38
0.33
0.37
0.074
0.020
0.022
0.017
0.055
0.038
0.023
0.023
0.016
0.35
0.32
0.20
0.20
0.14
Concentration
Plant Plant
No. 3 No. 4
2.7
1.6
1.7
2.5
1.7
0.16
0.07
0.23
0.18
0.11
0.01
0.095 0.16
0.055 0.53
0.11
0.09
0.06
0.82 1.5
0 . 45 3.2
0.65
0.76
0.55
(MR/R)
Plant Plant
No. 5 No. 6
1.9 0.11
0.072
0.029
0.46
0.25
0.12 0.72
0.41
1.0 3.2
2.5
Plant
No. 7
3.5
2.7
0.025
0.098
0.061
0.18
0.15
1.2
1.0
(continued)
-------
TABLE 60 (continued)
Ul
Compound
Pyrene
Chrysene
Benzo [ a ] pyrene
Dibenz [ a , h ] anthracene
Benzo [g,h,i]perylene
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
0.10
0.20
0.16
0.19
0.054
0.034
0.040
0.20
0.19
0.17
0.40
0.54
0.057
0.11
Plant
No. 2
0.11
0.082
0.059
0.056
0.033
0.19
0.18
0.078
0.086
0.055
0.091
0.088
0.048
0.029
0.027
0.015
0.020
0.013
0.086
0.10
0.071
0.061
Concentration
Plant Plant
No. 3 No. 4
0.13
0.07
0.15
0.11
0.10
0.19 0.35
0.15 0.36
0.18
0.23
0.16
0.12
0.06 0.28
0.095
0.070
0.08
0.02
0.02
0.21
0.07
0.16
0.21
0,13
(Mg/g)
Plant Plant
No. 5 No. 6
0.20 0.64
0.50
7.6
0.53
0.70
0.080
0.009
0.56
0.066
Plant
No. 7
0.20
0.16
0.51
0.55
0.85
0.70
0.062
0.053
(continued)
-------
TABLE 60 (continued)
Compound
Fluoranthene
Benzof luoranthene
Butyl benzylphthalate
Bis (2-ethylhexyl)phthalate
Sampling Plant Plant
day No. 1 No. 2
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Concentration (pg/g)
Plant Plant Plant Plant Plant
No. 3 No. 4 No. 5 No . 6 No. 7
0.12 0.065 0.60 0.22
0.31 0.19
0.13
0.11
0.05
0.24 0.10
0.096 0.086
0.12
0.58 0.75
0.23
a Results for duplicate 5-day plant composites from Plant Nos. 4-7 are listed as days 1 and 2.
-------
TABLE 61. TARGET COMPOUNDS IDENTIFIED IN BACKGROUND AIR SAMPLES FROM THE SEVEN COAL-FIRED POWER PLANTS
Compound
Naphthalene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Concentration (ng/dscm)
Sampling Plant Plant Plant Plant Plant
day No. 1 No. 2 No. 3 No. 4a No. 5
1 1,300 1,100 1,000
2 1,200 2,800 2,200
3 1,800 2,100
4 1,700 2,800
5 2,000 2,100 2,600 690
1 78
2
3
4
5 20
1
2
3
4
5
1
2 190
3
4
5 490
1
2
3
4
5 '
1
2
3 - - •"•••'•
4
5 170
Plant Plant
No. 6 No. 7
1,000
1,600
1,200
4.8 31
8.6
11 27
15 34
59
96
120
18
27
18
180
16
(continued)
-------
TABLE 61 (continued)
NJ
00
Compound
Chrysene
Diethylphthalate
Di-n-butylphthalate
Butyl benzylphthalate
Bis (2-ethylhexyl)phthalate
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
450
370
550
580
360
390
480
940
550
91
91
120
380
430
320
390
1,300
Concentration (ng/dscm)
Plant Plant Plant Plant Plant Plant
No. 2 No. 3 No. 4a No . 5 No. 6 No. 7
18 8.6
350
480
720
960
970 2,400
120
260
140
710
210 2,500
310 3,000
250
270
1,500 3,600
a Extract aliquots prepared for scanning HRGC/MS were lost.
-------
TABLE 62. POLYCHLORINATED BIPHENYL ISOMERS IDENTIFIED IN FLUE GAS OUTLET SAMPLES
Concentration (|Jg/dscm)
Compound
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Sampling
day
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Plant
No. 1
0.15
0.11
0.01
0.13
0.08
1.86
1.15
0.11
1.31
0.29
0.93
0.58
0.06
0.74
0.11
0.18
0.14
0.02
0.25
0.06
0.004
0.003
Plant
No. 2
0.17
0.10
0.22
0.05
0.002
0.32
0.08
0.60
0.06
0.01
0.15
0.02
0.32
0.04
0.06
0.07
0.002
Plant Plant
No. 3 No. 4
0.59
0.20
0.28
0.28
0.06
0.015 1.60
0.003 0.32
tr 0.35
tr 0.15
tr
0.033 1.09
tr 0.15
0.0012 0.26
tr 0.48
tr 0.11
1.13
0.13
0.54
0.87
0.37
0.17
Plant
No. 5
tra
tr
tr
tr
tr
0.013
0.006
0.009
0.009
tr
0.007
0.002
0.005
0.003
tr
Plant
No. 6
tr
tr
tr
0.26
0.095
0.010
0.032
0.18
0.12
0.047
0.004
0.015
0.18
0.045
0.028
0.013
0.076
0.002
0.002
Plant
No. 7
tr
tr
tr
tr
0.009
0.010
0.046
0.005
0.004
0.048
(continued)
-------
TABLE 62 (continued)
Concentration (|Jg/dscm)
Compound
Total chlorobiphenyl
Mean
Standard deviation
Sampling
day
1
2
3
4
5
Plant
No. 1
3.1
2.0
0.2
2.4
0.5
1.6
1.3
Plant
No. 2
0.18
0.63
0.32
1.04
0.10
0.45
0.38
Plant
No. 3
0.048
0.0026
0.0012
tr
tr
0.010
0.021
Plant
No. 4
4.6
0.8
1.4
1.8
0.5
1.8
1.6
Plant
No. 5
0.020
0.008
0.014
0.012
g 0.004
0.012
0.006
Plant
No. 6
0.43
0.17
0.014
0.074
0.44
0.22
0.20
Plant
No. 7
0.014
^ 0.002
S 0.002
0.014
0.094
0.025
0.039
a tr = ^ 0.00005 |jg/dscm.
OJ
o
-------
70
60
Flue Gas
CO
U
f:
p
o
50
40
"5 30
#
20
10
0
70
60
50
ca
Q.
- 40
D
O
I—
'o 30
20
10
Plant
Background
Air
456789
Chlorobiphenyls
Figure 36. Average distribution (mean + standard deviation) of chlorobiphenyls
in coal-fired power plant flue gas and plant background air.
131
-------
The concentrations of PCB isomers identified in plant background air
samples are shown in Table 63. These results are for analyses of 5-day com-
posite samples. PCBs were not identified in the composite sample from Plant
No. 3. The PCB isomer distributions observed for these samples are similar
to those for the flue gas samples.
TABLE 63. PCB ISOMERS IDENTIFIED IN PLANT BACKGROUND AIR SAMPLES
Concentration (|jg/dscm)
Compound
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Total chlorobiphenyl
Plant
No. 1
0.081
0.12
0.022
0.009
0.23
Plant
No. 2
0.096
0.12
0.022
0.007
0.25
Plant
No. 4
0.15
0.37
0.17
0.32
0.027
1.04
Plant
No
0.
0.
0.
0.
. 5
004
002
001
007
Plant
No. 6
0.001
0.002
0.0004
0.0034
Plant
No. 7
0.001
0.002
0.003
PCBs were not identified in any of the grab samples from the four coal-fired
power plants. Table 64 shows the method detection limits for PCBs in the grab
samples and plant background air samples.
TABLE 64. METHOD DETECTION LIMITS FOR
PCB ISOMERS IN GRAB SAMPLES
Sample type Detection limit
Bottom ash 1 ng/g
Fly ash3 1 ng/g
Q
Economizer ash 1 ng/g
Aqueous samples 20 ng/£
Q
Plant background air 2 ng/dscm
a Five-day composite equivalent to a 100-g sample.
b Five-day composite equivalent to a 5-£ sample.
c Five-day composite equivalent to 50 dscm.
132
-------
PCDDs and PCDFs
PCDD and PCDF isomers were riot identified in any sample from the seven
coal-fired power plants. All samples were analyzed using 5-day composites to
maximize the method sensitivity. The method detection limits for each sample
type are shown in Table 65. Figure 37 shows the SIM ion plots for a 2.5 pg
injection of 1,2,3,4-TCDD.
TABLE 65. METHOD DETECTION LIMITS FOR PCDDs AND PCDFs FOR
5-DAY COMPOSITE FLUE GAS AND GRAB SAMPLES
Dioxin and
Sample type
Flue gas
Bottom ash
Fly ashb
Economizer ash
Plant background air
Aqueous samples
Units
pg/dscm
P8/8
P8/8
P8/8
pg/dscm
P8/L
a PI
1 LJ-3
250
25
25
25
50
500
C14
100
10
10
10
20
200
furan isomers
C15, C16
500
50
50
50
100
1,000
C17, C18
700
70
70
70
140
1,400
a All flue gas samples were diluted 1:10 for HRGC/MS-SIM analysis.
The 5-day composite was calculated as equivalent to 10 dscm.
b The 5-day composite is equivalent to a 100-g sample.
c The 5-day composite is equivalent to a 50-dscm sample.
d The 5-day composite is equivalent to a 5-£ sample.
133
-------
80.6-1
320
100.0-1
322
94.0n
324
DATA: 4901L22S2 «816
CALIi MID308L22 il
MID MASS CHROMATOGRAMS
12/22/81 11:34:00
SAMPLE: TCDD 2.5 PG/UL 1UL IHJ.
RANGE: G 1,1378 LABEL: N 0, 4.0 QUAN: A 8, 1.0 BASE: U 20, 3
1.023
SCANS 721 TO 912
0.913
1.013
563 '•'Vv^
84736
319.84:
1.872 '-j?89 1.193 * 0'501
0.984 0.923
105088
321.84:
± 0.50)
98816
323.84:
± 0.501
750
15:37
800
16:40
850
17:42
900
13:45
SCAN
TIME
Figure 37. SIM response to a 2.5 pg injection of 1,2,3,4-TCDD.
-------
SECTION 9
ANALYTICAL QUALITY ASSURANCE RESULTS
The primary indicators of the performance of the analytical procedures
for this study were the recoveries of surrogate spiking compounds. These re-
sults are presented and discussed in this section. Another key aspect of the
quality assurance procedures used in this study was the performance of the
fused silica capillary columns used for HRGC and HRGC/MS analyses. This sec-
tion also discusses the column performance checks and presents the results of
the development of a performance evaluation solution used for HRGC/Hall-FID.
SURROGATE COMPOUND RECOVERIES
The surrogate compound recoveries for samples from Plant No. 1 are shown
in Tables 66 to 73. These tables also show the means and standard deviations
for recoveries from samples from the five sampling days. The ash, water, and
coal samples were analyzed in duplicate. The average percent deviation for
the duplicate determinations are shown in the appropriate tables. Table 74
is a summary of the average recoveries for the Plant No. 1 samples. The re-
coveries and standard deviations generally indicate that the precision and
accuracy were good for all compounds except pentachlorophenol-13C6. Penta-
chlorophenol (PCP) is very polar and acidic, more polar than the target ana-
lytes. This characteristic is manifested in a gas chromatographic peak shape
for PCP that is generally broad and very susceptible to changes in the activ-
ity of the column. Hence, the recovery of pentachlorophenol-13Ce provides an
indication of the maximum apparent losses due to adsorption on the fused silica
capillary column.
The average percent deviations for duplicate determinations were gener-
ally good. Excluding pentachlorophenol-13C6, the average value for all com-
pounds in all sample types was 18%.
.The surrogate recoveries for the flue gas samples are generally lower
than for all other sample types. This is likely caused by the high levels of
extractable materials in the flue gas extracts. Even after cleanup on silica
gel, the flue gas extracts required dilution prior to scanning HRGC/MS analysis.
The dilution reduced the maximum concentrations of the surrogate compounds to
just above their detection limits so that accurate and precise determination
was difficult.
135
-------
TABLE 66. SURROGATE COMPOUND RECOVERIES IN FLUE CAS SAMPLES, PLANT NO. 1
Day
1
2
3
4
5
Mean
Standard deviation
% Recovery
1,2,4,5-Tetrachloro-
Napthalene-dg Chrysene-dI2 benzene-13Ce
56 16 11
56 30 6
19 14 7
9 14 28
35 32 74
35 21 25
21 9 29
3,4,3' ,4'-Tetrachloro-
biphenyl-d6
18
22
10
13
30
19
4
Pentachloro-
phenol-'3C6
46
100
82
97
70
79
22
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
TABLE 67. SURROGATE COMPOUND RECOVERIES IN BOTTOM ASH
% Recovery
1,2,4,5-Tetrachloro-
Napthalene-dg Chrysene-di2 benzene-l3Ce
60, 67 71, 74 60, 77
55,. 52 68, 66 58, 48
53 60 57
46, 39 72, 68 45, 27
47, 44 89, 53 59, 50
52 68 54
8 5 12
58 12
SAMPLES, PLANT NO. 1
3,4,3' ,"4' -Tetrachloro-
biphenyl-dg
120, 150
140, 110
76
65, 85
61, 70
95
32
12
Pentachloro-
phenol-13C6
68, 81
57, 42
8
70, 66
62, 44
51
26
10
for duplicates
-------
TABLE 68. SURROGATE COMPOUND RECOVERIES IN FLY ASH SAMPLES, PLANT NO. 1
CO
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
Napthalene-dg
30, 31
27, 27
32, 31
26, 27
46, 47.
32
8
1
TABLE 69.
Napthalene-dg
50
100
76, 100
100, 130
130
98
31
11
I Recovery
1 ,2,4,5-Tetrachloro-
Chrysene-d12 benzene- I3C8
88, 123 55, 69
73, 10! 29, 39
83, 32 33, 29
100, 110 32, 52
43, 43 33, 40
80 41
28 12
16 13
SURROGATE COMPOUND RECOVERIES IN COAL SAMPLES
% Recovery
1,2,4,5-Tetrachloro-
Chrysene-dtjj benzene-13C6
59 42
110 83
54, 130 46, 57
130, 130 67, 74
110 78
100 65
27 18
17 7
3,4,3' ,4'-TetrachIoro-
biphenyl-d6
9B, 210
79, 100
46, 64
98, 110
50, 47
90
42
18
FROM PLANT NO. 1
3,4,3" ,4'-Tetrachloro-
biphenyl-d6
48
71
39, 98
97, 88
99
76
20
21
Pentachloro-
phenol-13C6
230, 570
210, 180
82, 180
120, 180
44, 29
183
135
30
Pentachloro-
phenol-l3C6
25
NDa
29, 76
89, 95
94
65
31
18
a ND = Not determined.
-------
TABLE 70. SURROGATE COMPOUND RECOVERIES IN PLANT BACKGROUND AIR SAMPLES, PLANT NO. 1
U>
00
Day
1
2
3
4
5
Mean
Standard deviation
Napthalene-dg
36
30
50
48
51
'43
9
Chrysene-d|2
99
21
79
78
82
72
30
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-13Ce
32
17
68
60
81
52
26
3,4,3' ,4' -Tetrachloro-
biphenyl-dg
70
29
98
75
110
76
31
Pentachloro-
phenol-13C,5
2
2
1
2
0
1
1
Day
2
3
4
5
Mean
Standard deviation
Average 1 deviation
TABLE 71.
Napthalene-dg
39
25
64, 58
55, 37
43
15
11
SURROGATE COMPOUND
Chrysene-di2
55
45
90, 82
110, 71
69
22
13
RECOVERIES IN RAW WATER
% Recovery
1,2,4,5-Tetrachloro-
benzene-l3C6
93
32
130
62, 100
84
40
—
SAMPLES, PLANT NO. 1
3,4,3' ,4'-Tetrachloro-
biphenyl-de
110
68
140, 140
96, 130
108
30
7
Pentachloro-
phenol-13C6
7
5
4, 2
9, 79
15
20
80
for duplicates
-------
TABLE 72. SURROGATE COMPOUND RECOVERIES IN BOTTOM ASH QUENCH EFFLUENT WATER SAMPLES, PLANT NO.
VO
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
TABLE
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
It Recovery
1,2,4,5-Tetrachloro- 3
Napthalene-dg Chrysene-d|2 benzene- I3C6
48, 48 53, 76 84, 76
16, 16 30, 33 26, 20
11, 24 19, 41 15, 38
1, 1 61, 60 11, 7
33, 73 41, 89 35, 70
27 50 38
22 18 28
20 11 20
73. SURROGATE COMPOUND RECOVERIES IN BOTTOM ASH QUENCH INFLUENT
% Recovery
1,2,4,5-Tetrachloro- 3
Napthalene-dg Chrysene-di2 benzene- I3C6
37 50 50
1, 36 51, 46 12, 40
48, 27 88, 53 87, 60
1, 29 50, 55 3, 61
48, 70 88, 94 100, 100
33 63 56
18 18 31
40 10 25
,4,3' ,4'-Tetrachloro-
biphenyl-de
110, 100
26, 35
17, 38
60, 69
54, 97
61
32
15
WATER SAMPLES, PLANT NO.
,4,3' ,4'-Tetrachloro-
biphenyl-de
55
51, 65
110, 86
53, 80
120, 130
80
29
11
Pentachloro-
phenol-*3C6
54, 33
50, 0
0, 0
48, 22
15, 41
26
16
47
1
Pentachloro-
phenol-13C6
0
0, 0
0, 4
0, 0
0, 2
1
1
for duplicates
-------
TABLE 74. AVERAGE RECOVERIES OF THE SURROGATE COMPOUNDS FOR SAMPLES FROM PLANT NO. 1
-O
O
Sample type
Flue gas
Bottom ash
Fly ash
Coal
Plant background air
Quench influent
Quench effluent
Napthalene-dg
35 ± 21a
52 ± 8
32 ± 8
98 ± 31
43 ± 9
33 ± 18
27 ± 22
Chrysene-di2
21 + 9
68 + 5
80 + 28
100 ± 27
72 + 30
63 + 18
50 + 18
% Recovery
1,2,4,5-Tetrachloro-
benzene-I3C6
25 ± 29
54 ± 12
41 ± 12
65 ± 18
52 + 26
56 ± 31
38 ± 28
3,4,3' ,4'-Tetrachloro- Pentachloro-
biphenyl-d6 phenol- 13C6
19 + 4
95 + 32
90 + 42
76 + 20
76 ± 31
80 + 29
61 + 15
79 ± 22
61 + 12
183 ± 135
65 + 31
1 + 1
1 + 1
26 ± 16
a Mean ± standard deviation.
-------
The surrogate compound recoveries for samples from Plant Nos. 2-7 are
shown in Tables 75 to 100. The plant data summaries are shown in Tables
81, 89, 91, 94, 97, and 100 for Plant Nos. 2, 3, 4, 5, 6, and 7, respectively.
The recoveries and recovery levels for samples from Plant Nos. 2 and 3
are very similar to those discussed for Plant No. 1. The average percent
deviation for duplicate analyses of grab samples for Plant Nos. 2 and 3 are
both 16% (excluding pentachlorophenol-13C6). The recoveries for economizer
ash from Plant No. 3 were consistently lower than those for bottom ash and
fly ash from the same plant. As shown in Table 32 (Section 7), the economizer
ash has a much higher fixed carbon content and is lower in volatiles than
bottom ash or fly ash. Hence, the economizer ash may have adsorption proper-
ties similar to that of activated charcoal.
Since grab samples from Plant Nos. 4 to 7 were analyzed as plant compo-
sites, surrogate recoveries for those samples are included only in the plant
summary tables. Separate tables show recovery results for daily flue gas
samples from each of Plant Nos. 4 to 7 and for daily plant background air
samples from each of Plant Nos. 5 to 7.
The mean recoveries of each surrogate compound for the seven plants are
also illustrated by bar plots for each sample shown in Figures 38 to 45.
Most of these plots show considerable differences in surrogate recoveries
from plant to plant, likely due, at least in part, to differences in the
characters of samples from the different plants. One of the most conspic-
uous observations from the bar plots are low recoveries of pentachlorophenol-
13Cg from water samples. Since the water samples were extracted witho.ut ad-
justment to acidic pH, much of the pentachlorophenol spike may have remained
ionized in the aqueous solution.
The surrogate recovery data for samples from all plants are summarized
in Table 101. As noted previously, the recoveries observed for the surrogate
compounds are generally lower for flue gas samples. The surrogate compounds
were spiked into the three components of the flue gas samples according to
the schedule described in Section 6. Table 102 summarizes the surrogate re-
covery data for all flue gas samples by the sample component spiked. These
results indicate that the recoveries were independent of the train component
spiked.
BLANK SAMPLE RESULTS
Solvent blanks, container blanks, and flue gas train component blanks
from Plant Nos. 1 to 4 were screened using HRGC/Hall-FID. All flue gas train
blanks, i.e., two complete trains for each plant, from all plants and all
other blank samples from Plant Nos. 5 to 7 were analyzed using HRGC/MS. All
flue gas blank samples were also analyzed for PCBs, PCDDs, and PCDFs by HRGC/
MS-SIM. In general, only low concentrations of phthalate esters were identi-
fied. All results from sample analyses were blank corrected. Analyte identi-
fications were reported only for concentrations greater than two times the
concentrations in the corresponding blanks. No PCB, PCDD, or PCDF compounds
were identified in any flue gas blank samples.
141
-------
TABLE 75. SURROGATE COMPOUND RECOVERIES IN FLUE GAS SAMPLES, PLANT NO. 2
Day
1
3
4
5
Mean
Standard deviation
a
NS = Not spiked.
Day
1
2
3
4
5
Mean
Standard deviation
Average X deviation
Napthalene-dg
14
3
41
30
22
17
TABLE 76.
Napthalene-dg
54, 56
49, 48
50, 67
92, 81
66, 71
63
15
6
Chrysene-d|2
43
47
61
43
49
9
SURROGATE COMPOUND
Chrysene-di2
82, 70
70, 69
64, 92
130, 82
84, 81
82
13
25
% Recovery
1,2,4,5-Tetrachloro-
bcn7.ene-13Ce
8
0
0
27
16
13
RECOVERIES IN BOTTOM ASH
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-13Cg
54, 79
56, 69
54, 94
110, 73
75
74
11
15
3,4,3" ,4'-Tetrachloro-
biphenyl-dg
14
29
8
23
19
9
SAMPLES, PLANT NO. 2
3,4,3' ,4'-Tetrachloro-
biphenyl-dg
110, 86
100, 78
81, 84
93, 130
71, 65
90 ,
16
22
Pentachloro-
phenol-13C6
75
NSa
87
60
56
39
Pentachloro-
phenol-»3C6
92, 71
73, 76
74, 120
160, 120
120, 170
107
33
14
for duplicates
-------
TABLE 77. SURROGATE COMPOUND RECOVERIES IN FlY ASH SAMPLES, PLANT NO. 2
•P-
CO
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
Napthalene-dg
34
49, 79
48, 64
57, 54
62, 76
56
13
13
TABLE 78.
Napthalene-dg
71, 73
130, 70
35, 49
73, 49
53, 53
66
22
15
% Recovery
1,2,4,5-Tetrachloro- 3
Chrysene-di2 benzene-l3Cg
41 37
51, 83 46, 82
50, 64 63, 74
64, 55 74, 52
66, 77 62, 63
59 59
12 13
13 13
SURROGATE COMPOUND RECOVERIES IN COAl SAMPLES
% Recovery
1,2,4,5-Tetrachloro- 3
Chrysene-dj2 benzene-'3Ce
88, 89 230, 280
190, 100 71, 270
75, 74 67, 120
73, 71 200, 110
61, 91 100, 100
91 155
31 65
14 25
,4,3' ,4'-Tetrachloro-
biphenyl-dg
52
66, 94
55, 84
65, 58
87, 103
72
17
13
, PLANT NO. 2
,4,3' ,4'-Tetrachloro-
biphenyl-dg
76, 87
110, 94
24, 60
77, 52
50, 50
68
24
13
Pentachloro-
phenol-13C8
0
0, 0
2, 2
29, 7
42, 23
11
14
39
Pentachloro-
pheno!-13C6
73, 76
99, 100
36, 50
87, 47
29, 36
64
27
11
for duplicates
-------
TABLE 79. SURROGATE COMPOUND RECOVERIES IN PLANT BACKGROUND AIR SAMPLES, PLANT NO. 2
Day
1
2
3
4
5
Mean
Standard deviation
TABLE
Day
1
2
3
4
5
Mean
Standard deviation
Napthalene-dg
43
63
54
70
46
55
11
Chrysene-df 2
46
46
39
54
37
44
7
80. SURROGATE COMPOUND RECOVERIES
Napthalene-dg
67
51
78
60
61
63
10
Chrysene-di2
74
59
85
59
65
68
11
% Recovery
1,2,4,5-Tetrachloro- 3,4,3' ,4' -Tetrarhloro-
benzene-'3C6 biphenyl-d6
52
52
42
53
40
48
6
IN BOTTOM ASH QUENCH EFFLUENT
% Recovery
1,2,4,5-Tetrachloro- 3,
benzene- 13Cg
64
72
84
52
53
65
13
51
44
44
46
29
43
8
WATER SAMPLES, PLANT NO.
4,3',4'-Tetrachloro-
biphenyl-dg
72
95
91
47
86
78
19
Pentachloro-
phenol-13C6
0
0
0
0
0
-
2
Pentachloro-
phenol-I3C6
7
11
24
23
16
16
7
-------
TABLE 81. AVERAGE RECOVERIES OF TIIE SURROGATE COMPOUHDS FOR SAMPLES FROM PLANT NO. 2
Sample type
Flue gas
Bottom ash
Fly ash
Coal
Plant background air
Aqueous effluent
Napthalene-dg
22 ± 17a
63 ± 6
56 ± 13
66 i 22
55 ± 11
63 ± 10
Chrysene-d|2
49 ± 9
82 ± 13
59 ± 12
91 ± 31
44 ± 7
68 ± 11
% Recovery
1,2,4,5-Tetrachloro-
benzene-'3C6
16 ± 13
74 ± 11
59 ± 13
160 ± 65
48 ± 6
65 ± 13
3,4,3' ,4'-Tetracliloro-
biphenyl-de •
19 ± 9
90 ± 16
72 ± 17
68 i 24
43 ± 8
78 ± 19
Pentachloro-
phenol-13C6
56 ± 39
110 ± 33
11 i 14
64 ± 27
0
16 t 7
a Mean ± standard deviation.
Day
1
2
3
4
5
Mean
Standard deviation
TABLE 82.
Napthalene-dg
18
22
36
46
49
34
14
SURROGATE COMPOUND
Chrysene-di2
22
40
69
74
63
54
22
RECOVERIES IN FLUE CAS
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-I3C6
23
42
9
52
53
36
19
SAMPLES, PLANT NO. 3
3,4,3" ,4'-Tetrachloro-
biphenyl-dg
37
25
9
52
74
39
25
Pentachloro-
phenol-13C6
75
44
37
64
153
75
46
-------
TABLE 83. SURROGATE COMPOUND RECOVERIES IN BOTTOM ASH SAMPLES, PLANT NO. 3
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
Napthalene-dg
50, 43
33, 43
36, 19
39, 41
33, 32
37
7
10
TABLE 84.
Napthalene-dg
33, 43
33, 41
37, 30
25, 59
49, 34
38
3
19
% Recovery^
1, 2,4,5 -Tetrachloro-
Chrysene-di2 benzene- I3C$
64, 54 76, 50
30, 62 53, 47
54, 42 45, 26
59, 61 76, 52
53, 53 53, 52
53 53
6 12
11 14
SURROGATE COMPOUND RECOVERIES IN FLY ASH
% Recovery
1,2,4,5-Tetrachloro-
Chrysene-dt2 benzene- 13C6
42, 57 41, 56
56, 62 80, 62
53, 64 61, 82
57, 65 42, 101
72, 74 66, 58
60 65
8 10
7 19
3,4,3' ,4'-Tetrachloro-
biphenyl-d6
83, 67
66, 82
55, 47
88, 61
81, 62
69
10
12
SAMPLES, PLANT NO. 3
3,4,3" ,4' -Tetrachloro-
biphenyl-d6
54, 69
93, 75
75, 80
88, 140
96, 88
86
19
11
Pentachloro-
phenol-13C6
0, 0
0, 0
0, 1
0, 29
17, 1
5
7
92
Pentachloro-
phenol-'3C6
12, 3
25, 42
2, 1
4, 0
12, 17
12
13
30
for duplicates
-------
TABLE 85. SURROGATE COMPOUND RECOVERIES IN ECONOMIZER ASH SAMPLES, PLANT NO. 3
Day
1
2
3
4
5
Mean
Standard deviation
Average % deviation
for duplicates
Day
1
2
3
4
5
Mean
Standard deviation
Average 1, deviation
Napthalene-dg
22, 22
20, 35
30, 51
27, 25
26, 31
29
7
15
TABLE 86.
Napthalene-dg
110, 72
82, 97
40, 91
89, 130
61, 74
85
18
19
% Recovery
1,2,4,5-Tetrachloro- 3
Chrysene-diz benzene- I3C6
6, 26 25, 49
35, 26 33, 42
4, 4 21, 37
46, 52 33, 43
19, 47 25, 39
27 - 34
17 4
23 21
SURROGATE COMPOUND RECOVERIES IN COAL SAMPLES
% Recovery
1,2,4,5-Tetrachloro- 3
Chrysene-dj2 benzene- I3Ce
120, 98 120, 99
110, 110 150, 86
66, 140 26, 120
110, 130 140, 140
81, 97 69, 260
106 121
11 34
13 31
,4,3' ,4' -Tetrachloro-
biphenyl-dfj
30, 55
69, 80
35, 33
57, 52
30, 84
53
15
18
, PLANT NO. 3
,4,3' ,4'-Tetrachloro-
biphenyl-d6
120, 130
120, 110
55, 140
100, 120
80, 83
106
17
12
Pentachloro-
phenol-'3C6
0, 2
0, 0
0, 0
0, 0
0, 0
-
. -
—
Pentachloro-
phenol-I3Ce
110, 88
110, 71
31, 110
94, 120
75, 95
90
14
21
for duplicates
-------
TABLE 87. SURROGATE COMPOUND RECOVERIES IN PLANT BACKGROUND AIR SAMPLES, PLANT NO. 3
00
Day
1
2
3
4
5
Mean
Standard deviation
Day
1
2
3
4
5
Mean
Standard deviation
Napthalene-dg
l>l>
41
37
32
44
40
5
TABLE 88.
Napthalene-dg
44
48
50
45
48
47
2
1
Chrysene-di2
51
58
57
64
65
59
6
SURROGATE COMPOUND
1
Chrysene-di2
53
63
60
59
62
59
4
% Recovery
,2,4,5-Tetrachloro- 3
benzene- I3Ce
47
44
55
30
46
44
9
RECOVERIES IN LAKE WATER,
% Recovery
,2,4,5-Tetrachloro- 3
benzene- 13C6
67
66
74
72
67
69
4
,4,3' ,4'-Tetrachloro-
biphenyl-dg
71
130
81
59
98
89
28
PLANT NO. 3
,4,J' ,4'-Tetrachloro-
biphenyl-dg
76
100
98
100
95
95
11
Pentachloro-
phenol-'3C6
60
82
87
41
94
73
22.
Pentachloro-
phenol-13C6
2
2
7
0
0
2
3
-------
TABLE 89. AVERAGE RECOVERIES OF THE SURROGATE COMPOUNDS FOR SAMPLES FROM PLANT NO. 3
Sample type
Flue gas
Bottom ash
Fly ash
Economizer ash
Coal
Napthalene-dg
34 ± 14a
37 ± 7
38 ± 3
29 ± 7 .
85 ± 18
Plant background air 40' i 5
Aqueous influent
a Mean ± standard
Day
1
2
3
4
5
Mean
Standard deviation
47 t 2
deviation.
TABLE 90.
Napthalene-dg
25
17
65
56
22
37
22
Chrysene-di2
54 ± 22
53 ± 6
60 ± 8
27 ± 17
106 i 11
59 ± 6
59 i 4
SURROGATE COMPOUND
Chrysene-di2
24
39
70
110
86
65
34
% Recovery
1,2,4,5-Tetrachloro-
benzene-13C6
36 ± 19
53 ± 12
65 ± 10
34 ± 4
121 ± 34
44 + 9
69 ± 4
RECOVERIES .IN FLUE GAS
% Recovery
1,2,4,5-Tetrachloro-
benzene-13C6
22
20
47
51
47
37
15
3,4,3' ,4'-Tetrachloro-
biphenyl-ds
39 ± 25
69 ± 10
86 ± 19
53 ± 15
106 ± 17
89 ± 28
95 ± 11
SAMPLES, PLANT NO. 4
3,4,3' ,4'-Tetrachloro-
biphenyl-dg
34
28
41
56
64
45
15
Pentachloro-
phenol-'3C6
75 ± 46
5 ± 7
12 ± 13
0
90 ± 14
• 73 4 22
2 ± 3
Pentachloro-
phenol-13C6
40
36
100
120
15
63
47
-------
TABLE 91. RECOVERIES OF THE SURROGATE COMPOUNDS FOR SAMPLES FROM PLANT NO. 4
Ul
o
Sample type
Flue gas
Bottom .ash
Fly ash
Coal
Plant background
Quench influent
Quench effluent
a Determined by
Napthalene-dg
37 ± 22
62, 110
50, 87
ft, 22
air NDa>b
77
76, 58
HRGC/FID.
Chrysene-di2
65 ± 34
79, 110
56, 90
53, 45
48a
37
83, 69
X Recovery
1,2,4,5-Tetrachloro-
benzene-l3C8
37 ± 15
51, 76
36, 86
0, 23
"C
78
80, 68
3,4,3' ,4'-Tetrachloro-
biphenyl-de
45 ± 15
70, 120
52, 101
40, 37
15C
94
91, 72
Pentachloro-
phenol-13C6
63 ± 47
51, 96
17, 56
0, 0
39C
0
0, 0
b Co-eluting interferences did not permit determination.
c Determined by
Day
1
2
3
4
5
Mean
HRGC/Hall .
TABLE 92.
Napthalene-dg
58
53
49
65
46
54
Standard deviation 8
SURROGATE COMPOUND RECOVERIES IN FLUE GAS
Chrysene-di2
71
55
62
58
70
63
7
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-'3C6
50
45
41
60
43
48
8
SAMPLES, PLANT NO. 5
3,4,3' ,4'-Tetrachloro-
biphenyl-dg
42
50
54
68
63
55
10
Pentachloro-
phenol-l3C6
49
40
34
49
54
45
8
-------
TABLE 93. SURROGATE COMPOUND RECOVERIES IN PLANT BACKGROUND AIR SAMPLES, PLANT NO. 5
% Recovery
Day
1
2
3
4
5
Mean
Standard deviation
TABLE
Sample type
Flue gas
Bottom ash
Fly ash
Coal
Plant background air
Quench influent
Quench effluent
Napthalene-dg
47.
59
35
9
7
31
22
Chrysene-dj2
80
68
95
41
56
68
21
94. AVERAGE RECOVERIES OF THE
Naphtha lene-dg
54 ± 8
25, 11
26, 65
73
31 ± 22
73
68, 64
Chrysene-d|2
63 ± 7
43, 27
68, 40
35
68 ± 21
83
51, 32
1,2,4,5-Tetrachloro- 3,4,3' ,4' -Tetrachloro- Pentachloro-
benzene-'3Cs biphenyl-d6 phenol-'3C6
44
64
43
13
10
35
23
SURROGATE COMPOUNDS FOR
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-13C6
48 ± 8
30, 17
40, 70
72
35 ± 23
84
71, 61
58 64
69 83
89 92
.38 37
52 48
.61 65
19 23
SAMPLES FROM PLANT NO. 5
3,4,3' ,4' -Tetrachloro- Pentachloro-
biphenyl-de phenol-13Ce
55 ± 10 45 ± 8
35, 24 10, 2
64, 83 0, 0
85 93
61 ±19 65 ± 23
94 7
82, 63 42, 26
-------
TABLE 95. SURROGATE COMPOUND RECOVERIES IN FLUE CAS SAMPLES, PLANT NO. 6
Ui
10
Day
1
2
3
4
5
Mean
Standard deviation
Day
1
2
3
4
5
Mean
Standard deviation
NapthaLene-dg
110
35
82
96
120
84
33
TABLE 96. SURROGATE
Napthalene-dg
0
0
42
19
42
20
21
1,2
Chrysene-di2
67
45
23
57
110
60
31
COMPOUND RECOVERIES
1,2
Chrysene-di2
64
63
79
78
60
69
9
X Recovery
,4,5-Tetrachloro-
benzene-*3C6
78
21
71
73
84
65
25
IN PLANT BACKGROUND
% Recovery
,4,5-Tetrachloro-
benzene-13C6
50
52
49
39
41
46
6
3,4,3' ,4'-Tetrachloro-
biphenyl-ds
96
45
82
88
100
82
22
AIR SAMPLES, PLANT NO. 6
3,4,3' ,4'-Tetrachloro-
biphenyl-d8
74
75
68
72
59
70
6
Pentachloro-
phenol-13C6
76
41
57
17
73
53
24
Pentachloro-
phenol-13C6
72
76
53
64
67
67
9
-------
TABLE 97. AVERAGE RECOVERIES OF TIIE SURROGATE COMPOUNDS FOR SAMPLES FROM PLANT NO. 6
U>
Sample type
Flue gas
Bottom ash
Fly ash
Coal
Plant background air
Quench influent
Quench effluent
Naphthalene-dg
88 ± 33
44, 56
0, 4
53, 82
20 ± 21
73, 84
66, 64
Chrysene-dij
60 ± 3!
73, 85
73, 64
150, 85
69 ± 9
75, 90
89, 65
TABLE 98. SURROGATE COMPOUND
Day
1
2
3
4
5
Mean
Standard deviation
Napthalene-dg
71
25
14
43
46
40
22
Chrysene-di2
67
41
28
70
58
53
18
% Recovery
1 ,2,4,5-Tctrachloro-
benzene-'3C6
65 ±,25
42, 58
28, 6
67, 76
46 ± 6
69, 65
55, 65
RECOVERIES IN FLUE GAS
% Recovery
1 ,2,4,5-Tetrachloro-
benzene-13Ce
43
25
13
41
47
34
14
3,4,3' ,4'-Tetrachloro-
biphenyl-dg
.82 ± 22
79, 81
72, 63
100, 150
70 ± 6
82, 92
83, 87
SAMPLES, PLANT NO. 7
Pentachloro-
phenol-13C6
53 ± 24
80, 82
50, 66
79, 130
67 ± 9
9, 11
2, 0
3,4,3' ,4'-Tetrachloro- Pentachloro-
biphenyl-d6 phenol-13Ce
63
34
20
72
74
53
24
83
32
17
49
78
52
29
-------
TABLE 99. SURROGATE COMPOUND RECOVERIES IN PLANT BACKGROUND AIR SAMPLES, PLANT NO. 7
(Ji
Day
1
2
3
4
5
Mean
Standard deviation
TABLE
Sample type
Flue gas
Bottom ash
Fly ash
Economizer ash
Coal
Plant background air
Quench influent
Quench effluent
Napthalene-dg
110
110
87
110
82
100
15
Chrysene-di2
71
83
48
76
77
71
14
100. AVERAGE RECOVERIES OF THE
Naphthalene-ds
40 ± 22
86, 66
76, 50
69, 66
64, 50
100 ± 15
69, 62
79, 74
Chrysene-di2
53 ± 18
77, 88
110, 76
83, 79
81, 69
71 i 14
110, 110
110, 110
% Recovery
1,2,4,5-Tetrachloro-
benzene-'*C6
73
93
64
37
67
67
20
SURROGATE COMPOUNDS FOR
% Recovery
1,2,4,5-Tetrachloro-
benzene-13C6
34 ± 14
72, 67
84, 64
76, 74
68, 55
67 ± 20
80, 69
82, 83
3,4,3* ,4'-Tetrachloro- Pentachloro-
biphenyl-d6 phenol- l3Ce
61
67
45
66
63
61
9
SAMPLES FROM PLANT NO. 7
3,4,3' ,4'-Tetrachloro-
biphenyl-de
53 ± 24
72, 92
100, 73
89, 84
74, 61
61 ± 9
87, 92
90, 86
53
83
59
27
76
59
22
Pentachloro-
phenol-13Ce
52 ± 29
79, 96
72, 72
38, 50
70, 60
59 ± 22
7, 8
11, 8
-------
100
90
80
70
60
50
40
30
20
10
n
-
-
-
-
-
'
-
-
-
6
5
4
3
2
7
1
5
3
2
6
7
;
6
5
3
2
1
1
4
7
1
6
5
4
3
2
1
2
7
3
4
7
5
Naphtha lene-dg Chrysene-d]2 1,2,4,5-Tefra- 3,4,3',4'-Tetra- Perrfachloro-
chlorobenzene- C^ chlorobiphenyl-d^ phenol- C
Figure 38. Surrogate compound recoveries from flue gas samples.
-------
100
90
80
70
60
8 50
40
30
20
10
0
4
-
-
2
-
1
-
-
-
_
2
6
3
5
7
1
4 1
6
3
5
7
2
1
4
3
6
5
7
;
'
7
(
3
4
t
>
1
6
4
3
5
7
Naphtha lene-dg Chrysene-d)2 1 ,2,4,5-Tetra- 3.4,3',4'-Tetra- Pentachloro-
chlorobenzene-'3C£ chlorobiphenyl-d^ phenol-'3C^
Figure 39. Surrogate compound recoveries from bottom ash samples.
-------
Ul
100
90
80
70
60
>v
§ 50
£
£
40
30
20
10
0
180
' ' t
7
-
1
t
-
-
-
1
~
-
-
2
3
.
7
5
6
1
i
2
1
\
6
5
i
3
1
2
'
•
5
6
7
7
2
3
t
\
5
6
1
(.
4
2
I
h
5
7
Naphrhalene-dg Chrysene-dj2 1 ,2,4,5-Tetra- 3,4,3',4'-Tetra- Pentachloror-
chlorobenzene-':'C6 chlorobiphenyl-d6 phenol-'3C6
Figure AO. Surrogate compound recoveries from fly ash samples.
-------
Ui
oo
100
90
80
70
60
X
§ 50
£
40
30
20
10
0
"
7
-
-
-
-
-
-
-
-
I
r
r
3
r
;
-
7
3
Naphthalene-do Chrysene-di2 1 ,2,4,5-Tetra- 3,4,3',4'-Tetra- Pentachloro-
* • • 1Tj-» 11 i • i ii i i IJ/—
Figure 41. Surrogate compound recoveries from Economizer ash samples.
-------
VO
100
90
80
70
60
X
oi
3 50
V
40
30
20
10
0
r- 1
-
-
-
"
-
-
-
-
2
3
C
4
1
<
7
2
3
5
16C
2
7
1
1
20 1C
3
C
4
1
(!
7
6 12
1
3
5
i
•
0 1C
6
7
1
2
5
3
4.
)5
6
7
Naphfhalene-dg Chrysene-d]2 1 ,2,4,5- Tetra- 3,4,3',4'-Tetra- Pentachloro-
chlorobenzene- C^ chlorobiphenyl-d^ phenol- C^
Figure 42. Surrogate compound recoveries from coal samples.
-------
100
90
80
70
60
50
40
30
20
10
0
~
-
.
-
_
2
1
~
-
_
i
5
6
3
2
i
\
i
C
\
)
'
7
7
1
f
'
3
i
4
i
2
3
i
5
4
i
i
i
i
i
i
5
7
12
1
5 7
4
i
i
i
i
i
i
i
i
i
NapMhalene-dg Chrysene-d]2 1 ,2,4,5- Tefra- 3,4,3',4'-Tetra- Pentachloro-
chlorobenzene- C^ chlorobiphenyl-d^ phenolr'JC^
Figure 43. Surrogate compound recoveries from plant background air samples.
Data for Plant No. A from HRGC/Hall-FID.
-------
100-
90
80
70
60
X.
0
§ 50
02
£
40
30
20
10
0
-
-
~
-
-
-
1
-
~
110
t
6
7
1
i
4
5
7
7
'
4
2
1
5
6
r
1
i
2
i
•
5
5
1
2
1 .1
Naphtha lene-dg Chrysene-d]2 1 ,2.4,5-Tetra- 3,4,3' ,4'-Tetra- Pentachloro-
chlorobenzene-'^C^ chlorobiphenyl-d^ phenol- C^
Figure 44. Surrogate compound recoveries from quench effluent water samples.
-------
100
90
80
70
60
X.
OJ
8 50
&
40
30
20
10
n
110 ,
! .
5
4
5
-
_
1
-
-
6
7
1
4
7
S
4
1
1
7
6
7
6
6
.ill
Naphtha lene-dg Chrysene-d]2
1,2,4,5-Tetra- _,.,-,. .
chlorobenzene-'^C^ chlorobiphenyl-d^ phenol- C
Figure 45. Surrogate compound recoveries from quench influent water samples.
-------
TABLE 101. AVERAGE SURROGATE COMPOUND RECOVERY (%) FOR ALL SAMPLE MEDIA FROM ALL SEVEN PLANTS
CO
Sample media
Flue gas
Bottom ash
Fly ash
Economizer asha
Coal
Plant background air
Aqueous influent
Aqueous effluent
a For Plant Nos. 3
b Results for Plant
Component3
XAD-resin
Probe rinse
Filter
Napthalene-dg
44 ± 21
55 ± 23
44 ± 23
29, 68
65 ± 27
b 48+28
65 ± 19
61 ± 17
and 7 only.
Chrysene-d|2
52 ± 15
71 ± 20
70 ± 14
27, 81
82 ± 31
64 ± 11
75 ± 27
70 ± 24
No. 4, determined by HRGC/Hall-FID,
TABLE 102
Napthalene-dg
50 ± 29
43 ± 27
38 ± 29
% Recovery
1,2,4,5-Tetrachloro-
benzene-13C6
37 ± 16
55 ± 17
53 ± 19
34, 75
80 t 46
49 ± 11
72 ± 11
64 ± 15
were not averaged.
. SUMMARY OF SURROGATE COMPOUND RECOVERY FOR
WITH RESPECT TO THE
Chrysene-d12
54 ± 27
55 ± 23
45 ± 23
SAMPLING TRAIN COMPONENT
% Recovery
1,2,4,5-Tetrachloro-
benzene-13Cs
39 ± 24
41 ± 22
27 ± 26
3,4,3' ,4'-Tetrachloro-
biphenyl-ds
45 ± 22
74 ± 22
79 ± 9
53, 87
82 ± 27
67 ± 16
89 ± 6
78 ± 10
FLUE GAS SAMPLES
SPIKED
3,4,3' ,4'-Tetrachloro-
biphenyl-d6
47 ± 28
49 ± 25
35 ± 26
Pentachloro-
phenol-13C6
60 ± 13
60 ± 40
53 ± 63
0, 44
69 ± 35
44 ± 34
5 ± 4
14 ± 14
Pentachloro-
phenol-13C6
67 ± 27
61 ± 36
55 ± 32
a A single component of each train was spiked with surrogate compounds according to the selection schedule
described in Section 6. Hence, each recovery shown here represents the recovery for the entire train.
-------
CAPILLARY COLUMN PERFORMANCE
The five component surrogate standard was analyzed daily by HRGC/Hall-FID
and scanning HRGC/MS. Peak shape and response data were recorded. When the
column performance was not satisfactory, remedial action was taken to improve
performance. Typically, this required breaking off several inches of the in-'
jection end of the column. If the remedial action did not result in satisfac-
tory performance, a new column was installed. A column performance mixture
was used to evaluate the columns used for HRGC/Hall screening at least once
per week during use. The mixture contained several halogenated, nonpolar and
polar compounds which were used to calculate acid-base character of the column
(pH), the number of theoretical plates, (N), the height equivalent to a theo-
retical plate (HETP), and the adsorption and asymmetry of the test mixture
compounds. Figures 46 to 50 show charts of the performance of the fused sil-
ica columns used for HRGC/Hall-FID screening during this study. The pH was
calculated as the ratio of responses for equal quantities of 4-bromo-2,6-
dimethylaniline versus 4-bromo-2,6-dimethylphenol. A neutral column should
give a value equal to 1.0. The plot of pH versus date (Figure 46) indicates
that the columns used were usually slightly acidic in character. The number
of theoretical plates, N (Figure 47) and the HETP value (Figure 48) reported
were calculated for 1-bromoundecane. The adsorption ratios (Figure 49) were
determined by comparing the peak height for test compounds susceptible to
adsorption with that of an inert compound, 1-bromo-undecane. The asymmetry
was calculated for each peak of the test mixture from the formula.
W
As = — x 100
Wf
where W, and W,. are the back and front baseline widths of the peak measured
b f
from a line bisecting the peak maximum. A perfectly symmetrical peak should
have an asymmetry value of 100. However, the Hall detector response created
tailing of the peaks in the test mixture and the optimum asymmetry for this
detector response is actually greater than 100 as indicated in Figure 50.
164
-------
8.Or
7.0 -
6.0
5.0
4.0
3.0
2.0
1.0
4/20 4/27 5/11 6/17 8/24 10/5
4/24 4/28 6/3 8/12 9/9
Date
Figure 46. Fused silica column pH versus time as calculated from the
response of equal quantities of 4-bromo-2,6-dimethylphenol
and 4-bromo-2,6-dimethylaniline
165
-------
20
18
16
14
12
10
8
6
4
2
0
4/20 4/27 5/11 6/3 8/12 9/9
4/24 4/28 5/27 6/17 8/24 10/5
Date
Figure 47. Number of theoretical plates (N) versus time
for a fused silica capillary column.
166
-------
LLJ
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
4/20 4/27 5/11 6/3 8/12 9/9
4/24 4/28 5/27 6/17 8/24 10/5
Date
Figure 48. Calculated HETP versus time for a
fused silica capillary column.
167
-------
2. 0.r
1.8
1.6
1.4
1.2
c
jo
e-
1.0
0.4
0.2
A
A
* A
2,6- Dichloroaniline
1 - Bromododecane
2 - Chloronaphthalene
0.8
0.6
1 l
4/20 4/27 5/11 6/3 8/12 9/9
4/24 4/28 5/27 6/17 8/24 10/5
Date
Figure 49. Adsorption versus time for selected compounds
on a fused silica capillary column.
168
-------
500
400
b 300
E
< 200
100
2,6- Dichloroaniline
1 - Bromododecane
2 - Chloronaphthalene
A A
I I
I I
4/20 4/27 5/11 6/3 8/12 9/9
4/24 4/28 5/27 6/17 8/24 10/5
Date
Figure 50. Asymmetry versus time for selected compounds
on a fused silica capillary column.
169
-------
SECTION 10
EMISSIONS RESULTS
The emission rates for the target PAH and phthalate compounds determined
in flue gases for the seven coal-fired power plants are shown in Table 103.
The emission rates were calculated from the concentrations of each compound
in the flue gases (presented in Section 8) and the flue gas volume flow rates
(presented in Section 7). Average emission rates for each compound identified
in flue gases for the 5-day sampling period at each plant are shown in Table
104. The emission rates for most compounds were generally similar for all
plants except Plant No. 3. In general, emission rates were lower for Plant
No. 3.
The emission rates for total PCBs in flue gases at the seven plants are
shown in Table 105. The average emission rates for each plant are shown in
Table 106 with the average PCB input rates determined for plant background
air. Although the average emission rates for each plant were all higher than
the input rates attributed to plant background air, the input rates were all
within one standard deviation of the 5-day average emission rates for five of
the seven plants.
The exact origin of the PCBs in the flue gas emissions from the coal-
fired power plants cannot be determined from the data presented from this in-
vestigation. However, some of the possible sources for PCBs suggested by
Richards and Junk5 include (a) degassing of fuel; (b) air used to support the
combustion; (c) contamination from components of the ducts leading to and from
the combustion zone; (d) chlorination of biphenyl in or after the combustion
zone; and (e) the formation in the combustion zone by a series of complex
reactions.
PCDDs and PCDFs were not identified in the flue gas samples. The method
detection limits were comparable to those achieved for the pilot study for
municipal incinerator flue gas samples that contained several PCDD and PCDF
isomers. An estimated worst case emission rate for TCDD or TCDF from the
coal-fired power plants based solely on the method detection limit (assuming
100%) recovery would be in the range of 100 to 500 |Jg/hr.
170
-------
TABLE 103.
CONCENTRATIONS AND EMISSION RATES FOR TARGET COMPOUNDS IN FLUE GASES (pg/dscm)
AND EMISSION RATES (mg/hr) FROM THE SEVEN COAL-FIRED POWER PLANTS
Composite
Compound day
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
1
2
3
ft
5
1
2
3
ft
5
1
2
3
ft
5
1
2
3
ft
5
1
2
3
ft
5
1
2
3
4
5
1
2
3
ft
5
1
2
3
Plant
Flue gas
cone .
(pg/dscm)
0.37
0.28
0.32
0.17
0.34
0.66
0.018
0.015
0.21
0.22
O.lft
0.33
0.088
O.Oftft
0.04ft
0.057
0.024
0.031
No. 1
Emis.
rate
(mg/hr)
2,040
1,500
1,800
980
970
190
100
79
1,170
1,210
720
950
490
240
220
310
130
170
Plant No
Flue gas
cone.
(pg/dscm)
0.57
1.7
3.8
2.5
0.32
tr3
tr
0.67
0.42
7.8
1.4
0.26
1.15
0.32
0.75
. 2
Emis.
rate
(mg/hr)
490
1,500
3,400
2,200
290
600
360
6,950
1,200
240
1,030
290
670
Plant No. 3 Plant
Flue gas Emis. Flue gas
cone. rate cone.
(pg/dscm) (mg/hr) (Mg/dscm)
0.43
0.10 99 0.51
0.53 520 1.5
1.4 1,400 2.0
0.33 320 0.78
tr
0.033
0.070
0.06 57 0.071
0.083
O.lft
0.10 98 0.24
0.07 71 0.21
0.088
0.058
tr
0.048
No. 4
Emis.
rate
(mR/hr)
750
890
2,500
3,500
1,100
57
120
130
140
240
410
310
150
85
82
Plant No. 5 Plant No. 6 Plant
Flue gas Emis. Flue gas Emis. Flue gas
cone. rate cone. rate cone.
(pg/dscm) (mg/hr) (pg/dscm) (mg/hr) (pg/dscm)
1.2 5,500 1.0 1,400 0.48
1.1 ft, 700 0.45 640 0.14
0.86 3,800 1.3 1,900 0.57
2.2 8,200 6.0 8,100 0.44
0.83 2,600 1.1 1,600 0.65
0.012
0.95 130 0.045
0.056 140 0.0064
0.12 170 0.078
0.13 180 0.037
0.26 380 0.072
0.070 100
No. 7
Emis .
rate
(mg/hr)
710
190
720
520
780
16
66
9
100
44
87
0.14
120
0.12
210
0.007
26
0.045
65
(continued)
-------
TABLE 103 (continued)
Plant No.
Flue gas
Composite cone.
Compound day (pg/dscm)
Benzo[a]-
pyrene
Dimethyl-
phthalate
Diethyl-
phthalate
Di-n-butyl-
phthalate
Butylbenzyl-
phthalate
Bis(2-ethyl-
hexyl)-
phthalate
Di-n-octyl-
phthalate
1
2
3
4
5
1
2
3
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
0.006
0.15
0.13
0.071
6.0
4.1
1.9
5.8
10.5
9.1
4.0
0.98
3.1
6.7
1.1
0.64
0.44
1.8
12.3
9.1
13.5
7.4
1.1
4.9
0.23
2.5
1.7
1 Plant
No. 2 Plant
No. 3
Emis. Flue gas Emis. Flue gas Emis.
rate cone. rate cone. rate
(mg/hr) (pg/dscm) (mg/hr) (ug/dscm) (mg/hr)
33
21
10
29
30
50
21
5
15
19
6
3
2
5
68
48
68
21
5
26
I
12
4
34
860
710
360 tr
,400 8.7
,900
,700 6.5
,400 6.8
,100 4.1
,600 28.3
,600
,400 41.6
,700 2.2
,200 1.8
,000
,500
4.0
,200
,200 1.3
,500 «5.0
, 900
,000
,200
,900
,200
,300
,600
,800
7,470 0
2
5,760
6,160
3,670 0
24,300
0
37,100
2,010
1,600
0
0
3,500
1,100 0
4,280 2
5
25
24
6
0
.42
.3
.49
.10
.35
.29
tr
.46
.7
.2
.8
.93
410
2,200
480
94
340
280
440
2,600
5,100
24,200
23,300
6,600
910
Plant
No. 4 Plant No. 5 Plant No. 6 Plant
Flue gas Emis. Flue gas Emis. Flue gas Emis. Flue gas
cone. rate cone. rate cone. rate cone.
_((Jg/dscm) (mg/hr) (pg/dscm) (mg/hr) (pg/dscm) (mg/hr) (pg/dscm)
0
5
12
11
1
0
0
0
15
3
31
0
0
0
1
.79
.0
.3
.7
.7
.45
.50
.64
tr
.3
.4
.2
.63
.31
.54
.2
0.54 780 0.060
1,400
8,400
21,100
17,300
3,000
780
860
1,100
21 93,000 34 48,000 0.53
3.4 15,000 0.93 1,300 0.82
26,100 9.2 40,000 11 16,000 1.4
5,800 30 110,000 8.3 11,000 6.7
46,000 8.6 27,000 0.55 800 18
1,100 2.0 8,800
540
910 0.50 2,200
2,000
No. 7
Emis.
rate
(mg/hr)
83
790
1,100
1,700
7,800
22,000
a tr = £ 0.025
-------
TABLE 104. AVERAGE EMISSION RATES OF TARGET PAH COMPOUNDS IN FLUE GASES
Compound
Naphthalene
Acenaphthylene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benzo [ a ] py rene
Dimethylphthalate
Diethylphthalate
Di-n-butylphthalate
Butylbenzylphthalate
Bis (2-ethylhexyl)phthalate
Di-n-octylphthalate
Plant
No. 1
1,400
38
36
810
190
88
34
7
390
25,000
23,000
3,400
41,000
10,000
Plant
No. 2
1,500
72
120
1,800
210
58
160
4,600
13,000
920
860
Emission rates (mg/hr)
Plant Plant Plant Plant
No. 3 No. 4 No. 5 No. 6
470 1,700 5,000 2,700
35
45 250 200
47
110 5 33
160
620 9,600
19 600
210 550
11,000 16,000 57,000 15,000
2,200
Plant
No. 7
580
3
61
170
6,700
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TABLE 105. FLUE GAS OUTLET CONCENTRATIONS
OF TOTAL POLYCHLORINATED BIPHENYLS
(PCBs) AND EMISSION RATES FOR
PLANTS 1 THROUGH 7
Concentration Emission rate
(|jg/dscm) (mg/hr)
Plant 1
Day 1
Day 2
Day 3
Day 4
Day 5
Plant 2
Day 1
Day 2
Day 3
Day 4
Day 5
Plant 3
Day 1
Day 2
Day 3
Day 4
Day 5
Plant 4
Day 1
Day 2
Day 3
Day 4
Day 5
3.1
2.0
0.2
2.4
0.5
0.18
0.63
0.32
1.04
0.10
0.0482
0.0026
0.0012
^ 0.0005
S 0.0005
4.6
0.8
1.4
1.8
0.5
17,200
10,700
1,100
12,200
1,400
Mean = 8,500
S.D. = 7,100
150
550
290
940
90
Mean = 400
S.D. = 350
47
2.5
1.2
^ 0.5
^ 0.5
Mean = 10
S.D. = 21
8,100
1,400
2,400
3,100
700
Mean = 3,100
S.D. = 2,900
(continued)
174
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TABLE 105 (continued)
Plant 5
Day 1
Day 2
Day 3
Day 4
Day 5
Plant 6
Day 1
Day 2
Day 3
Day 4
Day 5
Plant 7
Day 1
Day 2
Day 3
Day 4
Day 5
Concentration
(|jg/dscm)
0.020
0.008
0.014
0.012
< 0.004
0.43
0.17
0.014
0.074
0.44
0.014
g 0.002
S 0.002
0.014
0.094
Emission rate
(mg/hr)
89
35
62
44
^ 12
Mean = 48
S.D. = 29
610
250
20
81
640
Mean = 320
S.D. = 290
20
£ 3
S 3
17
114
Mean =31
S.D. = 47
175
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TABLE 106. AVERAGE PCB INPUTS AND EMISSIONS
(PLANT BACKGROUND AIR AND FLUE GAS OUTLET)
Plant No.
1
2
3
4
5
6
7
Q
Inputs - plant background
air (mg/hr)
1,130
220
NDb
1,740
28
4.5
5
Emissions - flue gas
(mg/hr)
8,500 ± 7,100
400 ± 356
^ 0.5
3,100 ± 2,900
48 ± 29
320 ± 290
} 15 31 ± 47
a PCB levels in combustion air samples were determined as
5-day composites.
b ND = not detected.
176
-------
REFERENCES
1, Lucas, R. M., D. K. Melroy, "A Survey Design for Refuse and Coal Combus-
tion Process," from Research Triangle Park to EPA/EED/OTS/Washingtbh,
DC, EPA Contract No. 68-01-5848, June 1981.
2. Haile, C. L., J. S. Stanley, R. M. Lucas, D. K. Melroy, C. P. Nulton,
and W. L. Yauger, Jr., "Pilot Study of Information of Specific Com-
pounds from Combustion Sources," Final Report from Midwest Research
Institute to EPA/EED/OTS/Washington, D.C., EPA Contract No. 68-01-5915,
March 23, 1982.
3. Stanley, J. S., C. L. Haile, A. M. Small, and E. P. Olson, "Sampling and
Analysis Procedures for Assessing Organic Emissions from Stationary Com-
bustion Sources in Exposure Evaluation Division Studies," from Midwest
Research Institute to EPA/OPTS/Washington, DC, under Contract No. 68-01-5915,
Report No. EPA-560/5-82-014, August 1981.
4. Haile, C. L, and V. Lopez-Avila, "Development of Analytical Test Procedures
for the Measurement of Organic Priority Pollutants in Sludge, Revised Draft
Final Report, from Midwest Research Institute to EPA/EMSL, Cincinnati, Ohio,
under EPA Contract No. 68-03-26-5, August 1981.
5. Richard, J. J., and G. A. Junk, "Polychlorinated Biphenyls and Effluents
from Combustion of Coal/Refuse," Environmental Science and Technology,
15, 1095 (1981).
177
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APPENDIX
SAMPLING AND ANALYSIS METHODS MANUAL
178
-------
SAMPLING AND ANALYSIS PROCEDURES FOR ASSESSING ORGANIC
EMISSIONS FROM STATIONARY COMBUSTION SOURCES IN
EXPOSURE EVALUATION DIVISION COMBUSTION STUDIES
by
John S. Stanley
Clarence L. Haile
Ann M. Small
Edward P. Olson
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
METHODS MANUAL
EPA Contract No. 68-01-5915
MRI Project No. 4901-A(36)
Prepared for:
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Dr. Frederick Kutz, Project Officer
Mr. David Redford, Task Manager
-------
DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substances,
U.S. Environmental Protection Agency. Approval does not signify that
the contents necessarily reflect the views and policies of the Environ-
mental Protection Agency, nor does the mention of trade names or com-
mercial products constitute endorsement or recommendation for use.
-------
PREFACE
This sampling and analysis document was prepared for the Environmental
Protection Agency under EPA Contract No. 68-01-5915. The methods described
in this document were designed for use by Midwest Research Institute in
assessments of stationary combustion source emissions. They may also be
used as guidelines by other researchers who wish to conduct comparable stud-
ies. This document was prepared by Dr. John S. Stanley, Dr. Clarence L.
Haile (MRI Task Manager), Ms. Ann M. Small, and Mr. Edward P. Olson.
MIDWEST RESEARCH .INSTITUTE
John E. Going
Program Manager
Approved:
-J ~L
James L. Spigarelli, Director
Analytical Chemistry Department
December 1, 1981
iii
-------
CONTENTS
Preface iii
Figures vi
Tables vi
1. Introduction 1
2. Sampling 2
Media selection 2
Presampling site visit 3
Flue gas sampling equipment and materials 5
Solid and liquid sampling 11
Combustion air sampling 11
Continuous monitoring 12
Process data collection 12
Quality assurance procedures 12
Sample control and shipping 13
3. Sample Analysis 19
General analytical procedures 19
Extraction 21
Extract fractionation/cleanup 22
Extract analysis 22
Quality assurance (QA) procedures 24
4. Data Reporting 28
Sample tracking (analytical) 28
Data management and reporting 28
5. References 33
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FIGURES
Number Page
1 Modified Method 5 train for organics sampling 6
2 Condensed and sorbent trap modification of the Method 5 sampling
train for collection of organic vapors from flue gas 7
3 Eight-digit label code for stationary combustion source samples. 14
4 Sixteen character sample code for stationary combustion source
samples 15
5 Sample custody transfer sheet used by MRI 18
6 Analysis scheme for sample extracts 20
TABLES
Number Page
1 Sample Capture Requirements 4
2 GC/MS-SIM Ions 24
3 Sampling and Analysis Quality Assurance 26
4 Sample Tracking Sheet. 29
5 Analytical Data Reporting Sheet 30
6 Total Inputs and Emissions 31
7 Daily Flue Gas Sampling Data 32
va.
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SECTION 1
INTRODUCTION
The sampling and analysis methods described in this report were specifi-
cally designed for use in an ongoing nationwide survey of emissions of organic
pollutants from stationary combustion sources. The primary focus of this sur-
vey is on polynuclear aromatic hydrocarbons (PAHs) and polychlorinated aromatic
hydrocarbons including polychlorinated biphenyls (PCBs), polychlorinated di-
benzo-£-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs). To date,
these procedures have been used by Midwest Research Institute (MRI) to survey
emissions from coal-fired utility boilers, a co-fired (coal + refuse-derived
fuel) utility boiler, and a municipal refuse incinerator. This document was
prepared by MRI solely as a guideline for other laboratories who may partici-
pate in the same study, and for other researchers who wish to use these methods.
-------
SECTION 2
SAMPLING
The procedures described in this section have been used by MRI in ob-
taining representative samples of the inputs and the emissions from station-
ary conventional combustion sources. These procedures encompass the specific
requirements for site surveys, pretest preparations, and actual sampling pro-
cedures. A quality assurance program and sample control and custody docu-
mentation procedures are also presented.
The precise sampling procedures used for a specific plant may vary some-
what depending on the specific configuration and operation of the facility.
The samples that should be collected include gaseous, solid, and liquid ma-
terials. Gaseous emissions should be collected by the EPA Method 5 pro-
cedures1 modified for the capture of trace organic compounds as described in
this section. The solid and liquid samples should be collected according to
a sound, statistically designed 24-hr schedule.
These methods were designed to provide both qualitative and quantitative
information on polycyclic and chlorinated organic compounds. Therefore, it
is imperative that the sampling procedures should be followed as closely as
possible to prevent contamination or compromise the integrity of the samples.
MEDIA SELECTION
The sample collection program should be designed to allow accurate as-
sessments of the organic pollutants in both input to and emissions from the
combustion process. Although the focus of this project is on organic com-
pounds that likely undergo considerable chemical changes in the combustion
process, the media selection criteria are the same as would be used to deter-
mine a mass balance for a conservative pollutant, e.g., a nonvolatile metal.
It is of paramount importance that the collection procedures provide the most
representative specimens of the media selected.
The specific media and sampling points for each plant will depend some-
what on the specific design of the plant. However, the media can be described
in three categories: inputs, emissions, and miscellaneous media. The princi-
pal inputs to the combustion process are fuels and combustion air. All pri-
mary fuels should be sampled. Fuels used only for unit startup should be ex-
cluded from the sampling program. Combustion air can be sampled near the air
intake for the unit. However, care should be taken to avoid collection of
fugitive dust that may be suspended by the activities of the sampling equip-
ment or personnel.
-------
The principal emission media are the bottom ash, i.e., the residue from
the combustion process, and the flue gases with associated fly ash. Flue gas
emissions may have the most widespread impact on the quality of the surround-
ing environment. Hence, flue gas samples must be collected at a point down-
stream of the unit's particulate emissions control systems. However, the
materials collected by air pollution control devices must also be sampled to
allow accurate characterization of the total plant emissions. For example,
many coal-fired utility boilers employ electrostatic precipitators (ESPs) to
control particulate emissions. The fly ash collected in the ESP hoppers of
these plants must be included in the sampling program. In addition, ash that
is removed from flue gases by economizers in many plants must also be sampled
where practical.
Miscellaneous sample media include other materals that may have direct
contact with the combustion products. Examples are the input and overflow
waters from a bottom ash wet quenching system. These secondary emission media
may pose environmental hazards depending on the plant disposal practices.
A list of typical sample capture requirements for several materials is
given in Table 1. Included are sample size, storage container type and size,
sampling frequency, and total samples obtained each day. No compositing
should b£ done in the field. All samples should be placed in the appropriate
containers prepared as outlined in the pretest preparation and setup proce-
dures .
PRESAMPLING SITE VISIT
Representatives from EPA and the sampling crew chief must consult with
the plant supervisor to determine where and how each type of sample may be
captured. The crew chief should obtain data on key parameters related to
flue gas sampling. These parameters include the stack dimensions, flue gas
temperatures, moisture content, static pressure, and flue gas velocities.
Sampling points for grab samples should be located as close as possible
to the actual combustion process to avoid sampling combined streams (e.g.,
from multiple units) or combined waste media (e.g., ash-water mixtures) and
to prevent dilution of the desired sample. These precautions should allow
simpler data assessments. It is also advantageous to centralize the sampling
locations if possible such that the sampling schedules can be followed accu-
rately by the sampling crew. Where possible, special aids for obtaining the
samples in a safe and efficient manner should also be considered. Plant staff-
operated equipment, limited access areas, special tools, electrical outlets,
and periodic safety calls are some possible considerations.
Once all possible sampling points are determined, a statistically sound,
random sampling scheme should be provided for solid/liquid sampling that cor-
responds with the flue gas sampling activities. The sampling schedule should
be constructed to provide the sampling team with the specific time and loca-
tion a sample will be taken. It may be necessary to follow an assigned grid
pattern or port selection scheme in order to effectively subsample large sur-
face areas. In addition, sampling schedules may be subject to change each day.
-------
TABLE 1. SAMPLE CAPTURE REQUIREMENTS
Material
Solid
Coal
Refuse or RDF3
Bottom ash
Fly ash
Other solid waste
Gaseous
Dry particulate
Reeve Angel 934 AH
filter
Nozzel, probe, cyclone
and flask combined
rinses
Sorbent trap
First impinger with
rinses
h
Control 934 AH filter
Combustion air
Storage
size/type
1 qt amber glass
1 qt amber glass
1 pt amber glass
1 pt amber glass
1 pt amber glass
1 pt amber glass
150 mm X 15mm glass
petri dish
1 qt amber glass (may
require additional
250 ml of same)
Traps capped with plugs.
950 ml amber glass (may
require additional
250 ml of same)
150 mm X 15 mm glass
petri dish
Sorbent trap capped with
plugs
Total
Sample samples
frequency (24 hr)
Twice per shift
Twice per shift
Twice per shift
Twice per shift
Twice per shift
c
One per train
Q
One per train
One per train
One per train
One per train
•
One per day
One per day
6
6
6
6
6
2
2
2
2
2
1
1
Liquid
Effluent water
Influent water
1 qt amber glass
1 qt amber glass
Twice per shift 12
(duplicates)
One per day 1
(duplicate)
a Refuse - derived fuel.
b Or equilvalent.
c Dry particulate will be collected only from trains using a cyclone trap.
This trap may not be necessary if particulate loading is light.
d Additional filters may be necessary if particulate loading is high.
-------
The presampling site visit should also allow the crew chief to determine
local sources for expendable sampling supplies. In addition, the most con-
venient accommodations for the sampling crew during the testing period should
be located.
FLUE GAS SAMPLING EQUIPMENT AND MATERIALS
The modified Method 5 train, shown schematically in Figure 1, is used to
collect samples for organic compounds from the stack. (See Note below.) Ad-
ditional empty impingers may be added just after the first impinger to retain
water from high moisture gases. This train should be operated according to
Method 5 specific procedures modified by the additional cleanup and recovery
procedures required for organic compounds.
The sampling probe liners must be glass or TFE, depending on the flue
gas temperature. A glass cyclone should be provided for high particulate
gases to avoid excessive filter loading. Vaporous organics are collected by
a sorbent trap (Figure 2). This trap is located in the sample line down-
stream of the heated oven and upstream of the first impinger. The trap is
packed with precleaned XAD-2. The module that houses the sorbent trap is
water-jacketed. Cold water from an ice bath surrounding the impingers is
pumped through the jacket to maintain an outlet temperature of ^ 16°C (60°F).
Because of the possible sensitivity of potential analytes to ultraviolet
light all sorbent traps should be kept wrapped in aluminum foil.
All solvents used for preparing the sampling train for testing and for
field laboratory cleaning of sample trains should be stored in glass or TFE
bottles. All solvents should be Burdick and Jackson Distilled-in-Glass or
equivalent grade. TFE or stainless steel forceps should be used for handling
filters. The train and train components that contact the sample should be
handled with clean, bare hands, i.e., without gloves.
Flue Gas Sampling Pretest Preparation
All train components that will contact the sample (probe, cyclone,
filter holder, resin cartridge, and connecting tubes) must be clean of all
potentially interfering materials. Component joints that have been previously
treated with a sealant, such as silicone grease, must be thoroughly cleaned
before use. The recommended procedure for removing Dow Corning High Vacuum
NOTE: The collection efficiencies for PCBs, PCDDs, PCDFs, and PAHs have not
been evaluated for this sampling train. However, the train design was based
on a validated particulate emissions collection system (EPA Method 5) with
the addition of an adsorbent cartridge (packed with XAD-2 resin) to collect
vaporous emissions of semivolatile organics. The collection efficiencies of
XAD-2 have been evaluated for a large number of compounds including PCBs and
PAHs, and XAD-2 was selected for use in the EPA source assessment sampling
system (SASS) train.2'3 XAD-2 was also evaluated for use in a train specially
designed for PCB sampling.4
-------
Cyclone
(Optional)
Probe
Thermocouple
Reverse-Type
Pilot Tube
Condenser
& Resin
Cartridge
Figure 1 - Modified EPA Method 5 Train for Organics Sampling
-------
Condenser
Sorbent Trap
Flue Gas Flow
8mm Glass Cooling Coil
28/15
/ /
Water Jacket Cooling Coil
Glass Wool Plug Water Jacket Pre-Purified Glass Sintered
XAD - 2 Disk
(75 Grams)
Figure 2. Condensate and sorbent trap modification of the Method 5 sampling
train for collection of organic vapors from flue gases.
-------
Silicone Grease involves several steps. Removal of excess grease is accom-
plished by wiping clean with a rag. The joint is then dipped in warm concen-
trated KOH for 10 min, rinsed with distilled water, and wiped dry. The last
traces of sealant are removed by dipping in chromic acid, followed by rinsing
with distilled water and drying. Subsequently, the entire component should
be washed in soap (such as Alconox®) and water, followed by at least three
liberal rinsings of tap water and then distilled water. All apparatus are
then rinsed with acetone (reagent grade) until all traces of water are re-
moved. Finally, the glassware is rinsed sequentially with acetone and cyclo-
hexane (Burdick and Jackson Distilled-in-Glass or equivalent), taking care to
contact all sampling surfaces with the solvent. The components should be al-
lowed to dry in a dust-free and organic-free area to minimize contamination
of cleaned surfaces. The dried glassware should be protected by covering all
open joints and exposed sample-contacting surfaces with solvent-rinsed alumi-
num foil and by subsequent storage in a closed airtight shipping container
until use.
The filter housing gaskets should be cleaned using the same basic proce-
dure with the following modifications. Do not allow non-TFE gaskets to soak
in the 15% HN03 solution. Following the air drying, place the gaskets in a
225°F oven for 30 min to remove any moisture/solvents. Remove gaskets from
the oven and, store in a clean, covered container.
It is highly recommended that TFE filter housing gaskets be used when-
ever possible as contact with silicon and rubber gaskets can cause significant
sample contamination. If non-TFE gaskets must be used, care must be taken to
avoid contact with the organic solvents, during sample recovery.
Sample storage containers must also be cleaned prior to use. All sample
containers must be amber glass (or wrapped with aluminum foil) with TFE-lined
caps. All bottles and sample recovery apparatus must be cleaned with soap
and water, water rinsings, acetone rinsing and cyclohexane rinsing as outlined
above.
Sorbent resin used in the sampling trains should be precleaned and its
cleanliness verified prior to use. The recommended protocol for XAD-2 resins
is outlined in the EPA Level 1 Procedures Manual.3
All aspects of sampling train assembly should be conducted under the
cleanest laboratory conditions possible. To accomplish this, a limited-access
field laboratory should be maintained at the site to minimize the possibility
of airborne dust problems. Similarly, activities not directly related to train
preparation or sample recovery should be done elsewhere. Finally, smoking
should not b_£ permitted in the laboratory.
Prior to assembly, all sample-contacting train surfaces should be rinsed
with cyclohexane (Burdick and Jackson, Distilled-in-Glass or equivalent).
Care must be taken to contact all surfaces with solvent. During assembly it
is of vital importance that sealants, such as silicone grease, are not applied
to any connecting joints. All train parts must be closely examined for any
visual signs of contamination or defects that might induce sample error or
downtime problems; corrections will be made if necessary. Leak sealing should
-------
be accomplished using a material that has a high boiling point and high
thermal stability, such as the gas chromatography phase, Dow Corning DC 200.
Sorbent cartridges must be protected from exposure to light during sampling,
sample recovery, and shipping by wrapping each cartridge with aluminum foil.
tlLt£:i!i Checkout of Sampling Apparatus
Briefly, the checkout involves assembling the entire sampling train as
shown in Figure 1 without the probe. The fitting at the inlet of the filter
box is sealed and the oven brought to operating temperature. The pump is
turned on, and the flow meter gauges are observed for the existence of any
appreciable flow. The train must pass the Method 5 standard leak test of
less than 0.02 cfm at 15 in. of mercury or 4% of the sampling rate, whichever
is less. If an unacceptable leak rate is observed, the operator should
(starting at the pump and moving in the direction of the probe) tighten each
fitting in order to assure that a loose fitting is not responsible for the
leak. If this action does not solve the leak, the system should be leak
checked on a modular basis until the problem is pinpointed. Under no condi-
tion should a sampling test be conducted with a leak rate in excess of 0.02
cfm at 15 in. Hg.
Flue Gas Sampling Procedures
Standard U.S. EPA methodology for particulate sampling, Method 5, as
specified in the Federal Register1 will be followed.
Two modified Method 5 sampling trains operating simultaneously should be
used to traverse points at the center of equal areas within the stack. The
number of traverse points and duration of sampling at each point should be
provided to the sampling crews. The sampling rates should be adjusted to ob-
tain samples at isokinetic conditions. The sum of flue gas collected each
day in the two trains should total 20 m3 ± 10%.
After the sampling trains are properly assembled and an acceptable pre-
test leak checkout has been made, preheat the probe and oven to 250°F. The
stack temperature, moisture content, and velocity profiles must be determined.
Compute the appropriate sampler flow rate and the proper nozzle size using
the procedures and calibration curves supplied by the equipment manufacturer.
During the course of the sampling run, scheduled parameter checks should
be made on flow rates, temperatures, and pressures. These data should be
logged in a sampling record book. Sufficient ice must be kept in the impinger
box to chill the condenser and resin trap to keep the impingers cool. At the
conclusion of the sampling run, a post leak rate check should be performed.
Sample Recovery
Proper cleanup procedure begins as soon as the probe is removed from the
stack at the end of the sampling period. During all rinsing, the approximate
volumes of glass-distilled water, acetone, and cyclohexane used should be re-
corded. This is necessary for the determination of background contributions
from the solvents. All organic solvents should be Burdick and Jackson
-------
Distilled-in-Glass or equivalent quality. The wash bottles used for all rins-
ings should be clean glass or TFE. Other plastic materials are unacceptable
due to their potential for sample contamination.
When the probe can be safely handled, wipe off all external particulate
matter near the tips of the probe nozzle. Remove the probe from the train
and cap off the mating joints of both the probe and the train with solvent-
rinsed aluminum foil. Also, cap the outlet of the train assembly after dis-
connection from the pump. Transfer the probe and train assemblies to the
field laboratory for cleanup. This area should be clean and protected to
minimize the chance of sample contamination or loss. Inspect the train prior
to and during disassembly and note any abnormal conditions. Remove the sor-
bent trap from the train and cap it off. The cartridge should be transferred
to the analytical laboratory intact for further sample recovery.
Rinse the probe with three portions each of water, acetone, and cyclo-
hexane. Brush the entire length of the probe with a natural bristle brush
during each rinse. The connecting tube between the sorbent module and the
filter housing should then be subjected to sequential rinsings using acetone
and cyclohexane, respectively. These rinses should be combined with the probe
and filter holder rinses.
The filter particulate is recovered by carefully removing the used filter
from the filter housing. Care must be taken to avoid tearing the filter or
losing particulate sample. The filter should be stored in a suitable sealed
glass container, such that the filter and its contents may be readily removed
for weighing in the lab. After removal of the filter, both halves of the fil-
ter housing should be subjected to sequential rinsing with acetone and cyclo-
hexane. These rinses should be combined with the preceding rinses. Non-TFE
filter housing gaskets should not be rinsed during sample recovery.
When cyclones are employed, the cyclone particulate catch should be re-
covered and stored in a separate sealed glass container. The cyclone should
be rinsed with water, acetone, and then cyclohexane. The rinses should be
combined with the other rinses. Similarly, all remaining interconnecting
tubing should be rinsed with acetone and cyclohexane. These rinses should
be combined with previous rinses.
The contents of the first impinger (aqueous condensate) should be poured
into a tared sample bottle. The bottle should be reweighed to ± 1 g and the
weight recorded in the sampling record book. The impinger jar should be rinsed
with acetone and cyclohexane and the rinses added to the sample bottle. Water
accumulated in the remaining impingers should also be determined gravimetrically
to ± 1 g.
Upon completion of the train recovery, at least four and possibly five
samples should be recovered: (a) the resin cartridge, (b) filter particulate,
(c) the first impinger contents, and (d) combined water, acetone, and cyclo-
hexane rinses of the entire train forward of the sorbent trap. A cyclone
catch will be the fifth sample if cyclones are employed.
10
-------
The importance of thorough rinsing cannot be overstressed. Care must be
taken to completely contact the interior surfaces of the train with each rinse
to quantitatively remove the analyte material. Approximate rinsing volumes
of each solvent used for each component should be recorded to allow the accu-
rate determination of solvent background contributions. After all rinsing is
completed, the sample bottle should be sealed and the volume of the contents
marked to identify possible losses during shipment. All samples should be
labeled and logged in the sampling record book as they are recovered. All
samples and rinses should be refrigerated at 4°C (or stored in an ice chest)
and exposure to light should be minimized during storage and shipment.
SOLID AND LIQUID SAMPLING
All sampling site locations should be clearly and appropriately labeled
for easy identification. Also posted at the sample site should be an expla-
nation of any subsample grid scheme to be followed. This serves as a reminder
of specific details in subsampling. The crew chief should tour the sampling
locations with the sampling personnel prior to the test to verify the collec-
tion procedure.
Crew chiefs should provide copies of all sampling schedules for the
plant supevisor to post with the plant operations staff. This should provide
for any necessary plant staff supervision or assistance in obtaining samples,
or in the event of an emergency.
The solid and liquid sampling schedule will start at 0000 hr on the
first day of flue gas sampling. Visits should to be made to sample sites as
scheduled, and samples taken and placed into prelabeled bottles. Sample and
container size required for typical media which should be sampled are given
in Table 1. Also included are the recommended number of samples to be col-
lected each day. All samples should be labeled and logged in the sampling
record book as they are collected.
Stainless steel trowels, cups, and tongs and glass bottles should be
used as necessary in sample capture. Long-handled extensions may be needed
to reach some specific areas. Sampling tools should be kept free from con-
taminants and cleaned with methodology described in this manual. Collection
of some samples may require special safety measures such as lab coat, work
suit, plant staff or assistance. Safety should be a primary consideration in
all sampling operations.
Solid and liquid sampling should continue through all three shifts each
day. Sampling staff will have to determine a suitable schedule so all shifts
are covered.
COMBUSTION AIR SAMPLING
Combustion air samples should be collected on 75 g of prepurified XAD-2
resin using vacuum pumps equipped with dry gas meters. A sampling rate of
0.75 cfm should be sustained until a total of 10-20 m3 has been sampled. The
resin should be placed in a cartridge similar to that in the sampling train,
but without the condensor. The resin cartridge should be wrapped in aluminum
11
-------
foil to prevent photodegradation of the adsorbed organic compounds. The sor-
bent cartridge should be capped immediately after sampling has been completed
to prevent contamination. This sample should be labeled and stored on ice as
soon as possible after collection.
CONTINUOUS MONITORING
Continuous monitoring of the flue gas should be conducted during the
period of flue gas sampling to aid in characterizing the efficiency of the
combustion process and to provide an indicator of dramatic changes in the
unit performance. The parameters monitored should include oxygen, carbon
monoxide, carbon dioxide, and total hydrocarbons. The continuous monitoring
probe should be inserted into the gas stream inlet to the air pollution con-
trol device to mitigate the influence of dilution by ambient air infiltration.
PROCESS DATA COLLECTION
In order to fully characterize the operation of the particular combus-
tion facility it is necessary to collect the engineering data during flue gas
sampling. A member of the sampling crew should be assigned to obtain perti-
nent information concerning the general description and design data and param-
eters for the power plant and air pollution control equipment that is not suf-
ficiently described from the presite visit. In addition, details and sched-
ules for soot blowing and ash removal during the actual testing period should
be recorded. A member of the sampling crew should document any plant break-
down, maintenance, or operating problem during each day's test period that
may have an impact on that day's test results. Process engineering data should
also be recorded for the megawatt output, steam flow rate, coal loading (rate
or total during each test period), and the operation of the electrostatic pre-
cipitators during each test period. The electrostatic precipitators should
be monitored for operating voltages and amperages, rapping frequency, spark
rate, and the number of inoperable units, if any. Information should also be
obtained concerning the electrostatic precipitator installed on the unit.
Specific parameters include the design volume, temperature, inlet concentra-
tion, number of precipitators, field array, gas passages per field, collecting
surfaces, collecting surface spacing, face area per precipitator (ft2), total
surface (ft2), gas velocity, and retention.
QUALITY ASSURANCE PROCEDURES
Calibrations
All sampling equipment should be calibrated prior to testing according
to the procedures outlined for Method 5 sampling trains.1 This should include
probe nozzle diameter measurements, pitot tube, and dry gas meter calibrations
as well as dial and liquid-filled thermometers and thermocouple-potentiometer
system calibrations.
12
-------
Field Blanks
The collection of field blanks is mandatory to indicate the cleanliness
of all sample handling phases. A complete flue gas sampling train should be
assembled in the field laboratory for use as a train blank at each plant.
The probe and filter oven should be maintained at operating temperatures for
a period equivalent to a typical sampling run. At the end of this period the
train should be disassembled and the sample components recovered in the same
manner as a flue gas sample.
Blanks of each rinsing solvent, as well as unused filters and resin car-
tridges, must be collected for blank determinations. The resin cartridges
and filter blanks should be exposed to the same laboratory environment for
the same time intervals as the sample filter and sorbent resin. Similarly,
individual samples of acetone and cyclohexane rinse solvents must be collected
from the wash bottles for each lot number solvent used. The volume of each
solvent blank collected should be approximately equal to the solvent volumes
used during the recovery of a sampling train. At least three unused sample
bottles of each type should be designated as bottle blanks. All blank materials
must be stored in clean sealed glass or TFE containers and treated as samples.
Liquid volumes should be marked on the containers to monitor possible shipping
losses.
SAMPLE CONTROL AND SHIPPING
An area designated for sample control and shipment preparation should be
close to the field laboratory. This area should also have limited personnel
traffic. Some stations may require lock and key access if outside of regular
plant surveillance. The following shipment preparations should be done by
staff on solid/liquid sampling duty.
Properly labeled bottles should be supplied to the sample train recovery
team. This team should then complete the label and return the full sample
bottle and any necessary sampling or recovery remarks to the sample control
and shipment operator.
Labels should be provided on computer printout paper and should be
grouped by date. Each date should be subgrouped into air sample labels and
solid and liquid sample labels. Extra labels should be provided at periodic
intervals of the label packet.
All labels should be provided in duplicate. One label should be placed
along the left column of a log book page each time a sample is labeled arid
secured in an ice chest. This will provide chronological entry of sample
codes in the log book. Any sampling remarks should be recorded along side
the label. Also to be included in this right margin is the sample cooler
number in which the corresponding labeled sample has been placed.
MRI's labeling system provides an 8-digit number on each label to be
used for primary sample tracking. The label number is defined in Figure 3.
The label will also contain a 16-character sample code which provides for
easy, accurate identification. This sample code is defined in Figure 4.
13
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LABEL CODE
Plant Number
e.g., 01-
Sample number
within sample
type, e.g., 01-10
Train Component-
see key
Sample type-
see key
Sampling Day
e.g., 01-05
or 90 for blanks
SAMPLE TYPE
0 - Flue Gas Outlet
1 - Bottom Ash
2 - Control Device Ash (Fly Ash)
3 - Combustion Air
4 - Coal
5 - Refuse-Derived Fuel
Water sources will be numbered and defined as they
are taken.
TRAIN COMPONENT
0 - No Component
1 - Probe Rinse
2 - Cyclone Catch
3 - Filter
4 - Resin
5 - Aqueous Condensate
Figure 3. Eight-digit label code for stationary combustion source samples.
14
-------
SAMPLE CODES
task
Plant Number -
e.g., 01-
j v
Sample type - See 1
ey to tables
Date-MMDD
Sample Type
BA - Bottom Ash
FA - Fly Ash
CA - Combustion Air
FO - Flue Gas Outlet
CO - Coal
RF - Refuse-Derived Fuel
OW - Overflow Water
SW - Sluice water
RW - River water
Train Component
P - Probe Rinse
C - Cyclone Catch
F - Filter
X - Resin
W - Aqueous Condensate
Time
Train
Compo
ent:
Duct Code
(Optional)
Figure 4. Sixteen character sample code for stationary
combustion source samples.
15
-------
All labels should be prepared so that minimum amount of additional in-
formation must be entered in the field. The time of sample capture, any sub-
sampling location designations, and the sampler's name are typically the only
entries. All entries must be made on the duplicate label as well.
Labels should be self-adhesive. In addition, 1-1/2 to 2 in. transparent
tape should be overlaid on the completed label placed on sample containers as
a precautionary measure.
All liquid samples should have the volume marked on the side of the ship-
ping container with a permanent marker. This should allow losses of sample
from handling and shipping to be noted.
Samples other than those in amber glass bottles will require special
packaging. These are given in the following two paragraphs.
Modified Method 5 Particulate
The particulate filters should be returned to their original containers
(petri dishes) when sampling is completed. Each petri dish should be taped
shut using masking tape. The identification label should be placed on the
top center of each dish. The filter and dish number should be included on
both labels. The dish should be wrapped in aluminum foil and sample ID number
(from label) copied onto top side. The petri dish should be carefully sealed
in a ziplock bag, with a minimum air space. Care must be taken to ensure that
filters are returned to the original containers since it is necessary to know
the predetermined weight of each specific filter.
Resin Cartridge
The sample identification label should be affixed to the aluminum foil
covering. The entire cartridge should be wrapped in an adequate amount of
bubble pack (bubbles to inside) with cartridge ends capped securely with
glass balls. A lab marker should be used to copy the label ID number on to
the outside of the wrap.
Sample Custody Documentation
A chain-of-custody record should be prepared for every sample. The
custody sheet should be initiated in duplicate immediately after the sample
has been labeled. It should include the sample label number and the sampler's
signature. At the time of sample shipment, the record should be signed and
the time and date should be noted. The original copy of the chain-of-custody
record should be enclosed in the sample container. The yellow copy should be
retained by the crew chief until the samples are received and logged in at
the analytical laboratory.
When the container arrives at the laboratory, the person who will be
preparing the samples should receive (take custody of) it. That person should
then open the shipping container and check each sample for damage or tamper-
ing. This person should then sign all the enclosed chain-of-custody records
and note any damage or indication of tampering.
16
-------
Whenever custody of the sample is transferred from one person to another,
the person relinquishing custody of the sample should sign the chain-of-custody
form and note the time and date. The person receiving the sample should do
the same. The person having custody of the sample should have sole control
of access to the sample.
Figure 5 is an example of a chain-of-custody record used by MRI.
17
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4900-A36
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
CHAIN OF CUSTODY RECORD
Label No.:
Samplers:
(Signature)
Relinquished by:
(Signature)
Date/Time
Received by:
(Signature)
Date/Time
Comments (Changes, Volume
Removed, Dilutions, etc.)
Figure 5. Sample custody transfer sheet used by MRI.
18
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SECTION 3
SAMPLE ANALYSIS
The analytical procedures described in this section were developed
during a pilot study of stationary combustion source facilities. The primary
objective of this section is to ensure that the extraction and analysis of
samples from other such facilities is coordinated and consistent for all labo-
ratories involved in possible future Exposure Evaluation Division programs.
Each of the different types of samples should be combined into daily
composites, extracted, and analyzed by capillary gas chromatography using
flame ionization and Hall (halide mode) electrolytic conductivity detectors
(HRGC/Hall-FID) and by capillary gas chromatography/mass spectrometry
(HRGC/MS) using fused silica columns. The analytical scheme presented in
Figure 6 should be followed to determine the presence of various compounds in
sample extracts. Both qualitative and quantitative results are expected for
the range of polycyclic and chlorinated organic compounds determined by these
procedures. A rigorous quality assurance/quality control program has been
outlined and should be considered by other laboratories participating in sim-
ilar analytical efforts. In addition, a procedure to determine total organic
chlorine (TOC1) is described. This technique may be beneficial for pilot
studies to provide a more sensitive means of identifying the presence of
chlorinated polycyclic compounds.
GENERAL ANALYTICAL PROCEDURES
All solvents should be Burdick and Jackson, Distilled-in Glass, pesti-
cide grade quality, or equivalent. Glass wool, boiling chips and anhydrous
sodium sulfate should be pre-extracted with a hexane-acetone mixture or ben-
zene. The anhydrous sodium sulfate should be extracted with the hexane-
acetone azeotropic mixture, air dried, heated at 110°C for several hours, and
finally baked at 650°C for at least 2 hr. It is important to allow the ex-
tracted Na2S04 to dry thoroughly before baking at high temperature to avoid
explosions in the high temperature oven.
All glassware that will be used in handling the samples and extracts
should be cleaned first with soap and hot water, rinsed thoroughly with hot
water, followed by distilled water. Acetone (reagent grade) should be used
to rinse glassware for removal of all traces of water and final rinses with
acetone and cyclohexane should be required. If blanks are a problem, the
glassware should be baked at 400°C for at least 8 hr prior to use.
19
-------
ANALYSIS SCHEME
Sample Extract
Capillary GC/HALL & FID
Screen
Add Internal Standard
Anthracene - djQ
Capillary GC/MS
( Scanning) Surrogates +
Polycyclic Organic Compounds
Add Internal Standard
37,
< 2,3,7,8 - Tetrachlorodibenzo-p-dioxin- C^or Co
Capillary GC/MS (SIM)
Chlorinated Polycyclic Organic
Compounds (Biphenyls, Dioxins, Furans)
«-Hold
Capillary GC/MS (SIM)
HIRES
Confirmation
Hold
Interlaboratory
Verification
Capillary GC/MS (SIM)
HIRES
Figure 6. Analysis scheme for sample extracts.
20
-------
EXTRACTION
The sample extraction methods described below have been developed to max-
imize recovery of a wide range of PAH compounds and polychlorinated aromatics.
Each sample should be spiked with labeled surrogate compounds prior to extrac-
tion for component recovery determinations.
Solid Samples
All solid samples should be Soxhlet extracted for 8 to 24 hr using ben-
zene (Burdick and Jackson, Distilled-in-Glass or equivalent) as the solvent.
Solid samples include XAD-2 resin, filters from the filter catch, and the
cyclone catch from the modified Method 5 train, control device ash (fly ash),
bottom ash, and fuel.
Samples from the Modified Method 5 sampling train should be extracted
simultaneously. For example, filters from the filter catch taken for a single
day's operation may be combined and extracted in the same Soxhlet apparatus.
However, sampling train materials should not be mixed (e.g., XAD-2 resin,
filters, cyclone material) since XAD-2 resins may be reclaimed. The filters
from the filter catch should be weighed prior to extraction. The weight of
the collected particulate matter should be calculated from measurements for
each filter made prior to sampling the field. No attempt should be made to
achieve constant weights for the filter samples. Also, the particulate ma-
terial obtained from the cyclone and probe rinses should be weighed prior to
extraction.
Control device ash and bottom ash should be individually composited for
each sampling day and 20 g each of these media Soxhlet extracted with benzene
for 8 to 24 hr. Prior to extraction, 10 ml of organic-free water should be
added to the control device ash. If the bottom ash is dry, 10 ml of water
should also be added to wet the material before beginning the extraction. An
inert material, such as Chromosorb W can be added to ash samples to promote
more efficient solvent flow through the sample.
Coal (10 g) should be Soxhlet extracted with benzene (8 to 16 hr). Large
mesh coal samples should first be ground to a powder using a ceramic mill with
stainless steel balls. Refuse-derived fuel will be evaluated when homogeneous
samples are available. This material (10 to 20 g) should also be milled and
Soxhlet extracted with benzene as the solvent for periods of 8 to 24 hr. This
extract should be washed three to four times with 100-ml aliquots of organic
free water.
All extracts should be dried by passage through short columns of an-
hydrous sodium sulfate. The dry extracts should be concentrated in Kuderna-
Danish appartus to approximately 5 ml. The extracts from the various com-
ponents of each day's flue gas sample should be combined and reduced to 5 ml
in a Kuderna-Danish evaporator. The extracts should be further concentrated
to 1 ml with a gentle stream of purified nitrogen. If solids precipitate from
extracts during concentration, slowly dilute and stir the extract to redissolve
the solids. Do not attempt to further concentrate the extract.
21
-------
Aqueous Samples
Aqueous samples may be obtained as plant influents and effluents, as well
as from the combined train rinses from flue gas sampling and the aqueous con-
densate from the first impinger. The combined train rinses should include
water, acetone, and cyclohexane. This sample should be shaken vigorously and
the organic layer removed using a separatory funnel. Two 60-ml aliquots of
cyclohexane should be used to extract the aqueous solution. The cyclohexane
extracts should be combined, dried by passing through a short column of an-
hydrous sodium sulfate, and finally combined and reduced with other extracts
from the modified Method 5 sampling train. If emulsions are formed during
the extraction, 2 to 3 g of sodium sulfate can be added to the mixture to pro-
mote adequate separation. The extracts should be dried and concentrated in
the same manner as extracts from solids.
EXTRACT FRACTIONATION/CLEANUP
Sample extracts, particularly the flue gas samples, may contain consider-
able interferences that may present problems in the effective analysis of such
compounds as polychlorinated dibenzo-£-dioxins and polychlorinated dibenzo-
furans or the surrogate compounds. These extracts should be cleaned by EPA
Method 613 to simplify the sample matrix prior to analysis for polychlorinated
dibenzo-£-dioxins and dibenzofurans. Since other polycyclic organic compounds
may be lost by this cleanup procedure, and it may be necessary to fractionate
a portion of sample by other techniques, such as silica or florisil adsorption
chromatography, prior to GC/MS analysis. Only half of a sample extract should
be submitted to any fractionation scheme. It is also important to measure
the exact volume of a sample extract subjected to cleanup to ensure valid
quantitation of specific compounds on the final aliquot.
EXTRACT ANALYSIS
HRGC/Hall-FID
Each extract should be screened first for the presence of halogenated
organic compounds by capillary gas chromatography separation with a Hall
electrolytic conductivity detector operated in the halogen specific mode.
Fused silica capillary columns, 30 m in length and coated with SE-54 [1% vinyl
in poly(methylphenylsiloxane) previously deactivated by silylation], 0.25 mm
ID, will be used for gas chromatography separations of all extracts.
On-column and direct injection techniques are preferred, but Grob-type
splitless injectors may be used, if necessary. The extracts should be chro-
matographed using the following temperature program: isothermal at 60°C for
2 min, increase temperature at 10°/min to 300°C and hold isothermally for 15
min. The qualitative results from these analysis should be useful in identi-
fying the presence of halogenated compounds by gas chromatography/mass spec-
trometry analyses. Large halogen responses at specific retention times should
identify the regions of the chromatograms where interpretation of the mass
spectra data may lead to the identification of halogenated compounds.
22
-------
HRGC/MS (Scanning)
The correlation of the mass spectral data with halogen responses from
the Hall electrolytic conductivity detector is necessary for positive identi-
fication of chlorinated organic compounds in the sample extract. Therefore,
it is necessary to duplicate gas chromatography conditions for the two methods.
Fused silica capillary columns coated with SE-54, 15 to 30 m in length, should
be used for all scanning HRGC/MS studies. On column, direct, or Grob-type
splitless injections should be used and the same temperature program used for
HRGC/Hall-FID should be followed.
Mass spectra should be acquired over the range of m/e 40 to 500 at a rate
of 1 to 1.2 sec/scan. The spectral data from these analyses should be used
for both qualitative and quantitative determinations. The compounds that are
positively identified and are of sufficient concentration should be quantitated
by peak area from the total ion chromatogram versus the peak area of the ap-
propriate internal standard.
HRGC/MS Selected Ion Monitoring (HRGC/MS-SIM)
The selected ion monitoring (SIM) technique should be used to determine
the presence of chlorinated dibenzodioxins or dibenzofurans. Preliminary in-
dications of the presence of these compounds may be evident from results of
the HRGC/Hall-FID and HRGC/MS (scanning) experiments. However, the HRGC/MS-
SIM technique has greater sensitivity for determination of these compounds in
the sample extracts. Selected ions characteristic of the mono- through octa-
chloro PCDDs, PCDFs, and PCBs should be monitored by this technique. The cri-
teria for the identification of these analytes in any extract will be dependent
on the coincidence of peaks in the extracted ion current plots of the char-
acteristic ions at the appropriate retention times and on the characteristic
relative intensity ratios of these selected ions. Table 2 lists the HRGC/MS-
SIM ions that should be used to identify the presence of the dibenzodioxins,
dibenzofurans, and biphenyls. Fused silica capillary columns coated with Car-
bowax 20M or other polar materials may be used for isomer specific SIM analyses
for polychlorinated dibenzodioxins and dibenzofurans.
HRGC/MS High Resolution Mass Spectrometry (HRGC/HRMS)
The tentative identification of dibenzodioxins and dibenzofurans by
HRGC/MS-SIM in any extract should be confirmed by HRGC/HRMS. This procedure
should be used to verify the presence of these compounds in any sample extract.
Positive identifications of chlorinated dibenzodioxins or chlorinated dibenzo-
furans by HRGC/HRMS should be supplemented by verification by other accredited
laboratories with HRGC/HRMS capabilities. All HRGC/HRMS studies should employ
fused silica capillary columns coated with either SE-54, Carbowax 20M, or
other materials capable of providing equivalent or better chromatographic
resolution.
23
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TABLE 2. GC/MS-SIM IONS
Number of chlorines Biphenyls Dibenzofurans Dibenzo-p_-dioxins
1
2
3
4
5
6
7
8
9
10
188/190
222/224
256/258
290/292
324/326
360/362
394/396
428/430
462/464
498/500
202/204
242/244
270/272
304/306
338/340
374/376
408/410
442/444
-
-
218/220
252/254
286/288
320/322
354/356
390/392
424/426
458/460
-
-
Total Organic Chlorine (TOC1) Measurements
TOC1 measurements may be used in a primary sensitive screen of the chro-
matographable organically bound halide contents of extracts prepared for GC/MS
analysis in tiered analytical schemes. The TOC1 procedure is a simplified
gas chromatographic method using a Hall electrolytic conductivity detector in
the halide mode. A short packed GC column (typically 1-2 in. x 1/4 in. ID)
and a rapid temperature program are used to elute all chromatographable com-
pounds with volatiles equal to or greater than dichlorobenzenes as a single
peak. The area of this peak constitutes the TOC1 response which is quanti-
tated as chloride against a mixture of chlorinated compounds (typically a PCB
mixture such as Aroclor 1254). The typical method senstivity is 0.25-2 ng
chloride.
QUALITY ASSURANCE (QA) PROCEDURES
The positive identification and quantitation of specific compounds in
this assessment of stationary conventional combustion sources is highly de-
pendent on the integrity of the samples received and the precision and accu-
racy of all analytical procedures employed. The QA procedures described in
this section were designed to monitor the performance of the analytical meth-
ods and to provide information to take corrective actions if problems are
observed. These procedures are summarized in Table 3.
Field Blanks
The field blanks should be submitted as part of the samples collected at
each particular testing site. These blanks should consist of materials that
are used for sample collection and storage and are expected to be handled with
exactly the same procedure as each sample medium.
24
-------
Method Blanks
A method blank should be prepared for each set of analytical operations.
This will evaluate contaminations and artifacts that are derived from glass-
ware, reagents and sample handling in the laboratory. Method blanks should
be evaluated by each laboratory for solid and aqueous sample extractions.
Recovery Spikes
Surrogate compounds should be added to all samples prior to extraction
to provide an accurate record of analyte recovery. Specific analytes should
be used for method development procedures. In either case, duplicate samples
should be prepared. The surrogate compounds should include napthalene-d8 and
chrysene-d12. The other compounds that will be used as surrogates include
pentachlorophenol-13C6, l,2,4,5-tetrachlorobenzene-13C6, and 3,4,3',V-tetra-
chlorobiphenyl-d6.
Internal Standards
Each concentrated extract should be spiked with anthracene-d10 prior to
analysis by HRGC/MS in the scanning mode. This should allow for adequate quan-
titation of specific analytes in the extracts once proper response ratios have
been established using standard solutions. This internal standard should be
added to the extracts to yield a concentration in the range of the analytes
and the surrogate compounds. This internal standard can also be used to de-
termine relative retention times in any particular chromatograms, and this
provides another means of analyte identification. Stable isotope labeled
isomers of tetrachlorodibenzo-g-dioxin and tetrachlorodibenzofuran should be
used for selected ion monitoring methods for these specific compounds. The
isotope label should provide sufficient distinction of the internal standard
and the actual isomers present in the sample extracts.
Reference Materials
A reference ash will be prepared by compositing ash from several facili-
ties by MRI. Portions of this ash may be sent to interested laboratories as
a means of evaluating interlaboratory performance. Two samples of spiked ref-
erence ash and two samples of unspiked reference ash will be submitted to all
laboratories. These samples will be extracted and analyzed with the same pro-
cedure used for all other samples.
Capillary Column Performance Tests
The optimum performance of the fused silica capillary columns coated with
SE-54 is an integral function of the separation and identification of specific
compounds in the sample extracts. Therefore, each laboratory should frequently
evaluate the performance of capillary columns used for extract analysis. Grob-
type test mixtures should be used to evaluate each column used for GC/Kall
and GC/MS studies. A test mixture prepared with halogenated compounds should
be used to test capillary columns with Hall electrolytic conductivity detectors.
25
-------
TABLE 3. SAMPLING AND ANALYSIS QUALITY ASSURANCE
Field blanks
Method blanks
Recovery spikes -
analytes
surrogates
dg-napthalene
d12-chrysene
13C6-1,2,4,5-tetrachlorobenzene
d6-3,4,3',4'-tetrachlorobiphenyl
13C6-pentachlorophenol
Internal standards - d10-anthracene
37C1-TCDD or 13C
37C1-TCDF
Reference materials
Capillary column performance checks
Interlaboratory verification
The parameters that should be monitored include separation number (Tz)
for a homologous series of compounds, the height equivalent for theoretical
plates (HETP), the number of theoretical plates (N), peak asymmetry, adsorp-
tion ratios, and pH of the column. Peak asymmetry is calculated for each peak
of the test mixture from the formula:
W
AS = ^ x 100
Where W, and Wf are the back and front baseline widths of the peak measured
from a line bisecting the peak maximum. Adsorption ratios are determined by
comparison of the peak height for a compound susceptible to adsorption with
that of an inert compound. The pH of a column can be determined from the
ratio of the peak heights of equivalent quantities of an acid and a base in
the test mixtures.
The capillary columns should be evaluated immediately upon installation
and at least once per week. The capillary columns should be rejected for poor
performance as related to separation number, adsorptivity, and pH. The columns
should be tested more frequently if drastic deterioration of the column is
noted in a 1-week time span.
26
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Interlaboratory Verification
All extracts in which polychlorinated dibenzodioxins and dibenzofurans
are identified by HRGC/MS or HRGC/HRMS should be submitted to other labora-
tories for confirmation of these identifications by HRGC/HRMS.
27
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SECTION 4
DATA REPORTING
The following section provides examples of the pertinent data that should
be reported for characterization of polycyclic organic matter from stationary
combustion sources. Examples are given for methods of sample tracking through
the entire organic compound analyses, reporting of analytical data for surro-
gate compounds and the inputs and emissions of particular analytes, and the
reporting of the engineering process data necessary for describing flue gas
sampling methods and the actual combustion process. It is highly recommended
that all laboratories involved in combustion facility characterizations for
polycyclic organic materials adhere as closely to these reporting guidelines
to facilitate comparision of data from several sources.
SAMPLE TRACKING (ANALYTICAL)
Sample tracking sheets should be used by all analytical laboratories to
monitor the status of sample analyses. An example of the tracking sheet is
shown in Table 4. The sample numbers illustrated are truncated when samples
for 1 day's operation are composited. The pertinent information presented in
this sample number includes the task number (36), plant number, and the date
sampled.
The sample tracking sheets should be initiated upon receipt of the sam-
ples from the field stations. The information on the sheets should include
dates samples were received and dates the samples were composited and ex-
tracted. The other designations should indicate the extent of analysis for
each composited sample, i.e., screening sample by HRGC/Hall-FID, HRGC/MS, and
HRGC/MS-SIM. Other remarks can be added as required. For example, PAH, PCDD,
or PCDF might be added to indicate that polynuclear aromatic hydrocarbons,
chlorinated dibenzodioxins, or chlorinated dibenzofurans have been tentatively
identified in particular extracts. Likewise, other abbreviations might be
added for identification of chlorinated benzenes or phenols. Target may be
used to indicate that analysis for specific compounds has been completed.
Major will be used to specify that the major components of a sample have been
investigated.
DATA MANAGEMENT AND REPORTING
The data generated for the target compounds and the major components of
each sample extract should be presented to MRI in two forms. Assessment of
the QA program should be accomplished by reporting percent recovery of the
surrogate compounds in a specific extract together with the concentrations of
the target and major compounds in the extracts. Concentrations for the target
28
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TABLE 4. SAMPLE TRACKING SHEET
Sample no .
36/03/FA/0330
36/03/BA/0330
36/03/CA/0330
36/03/FO/0330
36/03/CW/0330
Received
0415
0415
0415
0415
0415
Compos -
sited
0418
0418
0418
0419
0419
Ex-
tracted
0418
0418
0418
0419
0419
HRGC/
Hall-
FID
4-20
4-20
4-20
4-21
4-21
HRGC /MS
(Scanning)
4-23 Target
4-23 Major
Target
4-25
4-25
4-25
HRGC/
MS-SIM
4-27 Target
4-27
4-27
To MRI
HRGC/
HRMS
4-29
-------
compounds should be reported for all extracts. If a compound is present but
cannot be quantitated, it should be reported as less than the detection limit.
If a compound is not detected, it should be reported as not detected. The
data for QA will be reported as shown in Table 5. The percent recovery should
be reported for the surrogate compounds only.
TABLE 5. ANALYTICAL DATA REPORTING SHEET
Day 1 Bottom ash - Composite ID No.
Surrogate compounds Concentration % Recovery
d8-Naphthalene
c12-Chrysene
13C6-1,2,4,5-Tetrachlorobenzene
13C6-3,4,3',4'-Tetrachlorobiphenyl
13C6-Pentachlorophenol
Analyte Compounds
1.
2.
3.
4.
The other method for reporting the data should follow the concentration
of a particular compound in all sample matrices. Sample concentrations should
be grouped according to inputs and outputs of the plant. This data report
should be presented as shown in Table 6, representative for particular com-
pounds over five composited sampling days.
The data supplied by the engineering report will be used to determine
the mass flow inputs and emissions for the various sample media. The summary
of the flue gas sampling and the continuous monitoring data should be tabu-
lated as shown in Table 7.
30
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TABLE 6. TOTAL INPUTS AND EMISSIONS
Combustion
Inputs
Emissions
Coal
Flue gas
Bottom ash
Mass CA Feed Mass FO Mass BA
Composite input Cone. input rate Cone. Coal emissions Cone. emissions flow Cone, emissions
day (dscm/hr) (ng/g) (mg/hr) (kg/hr) (ng/g) input (dscm/hr) (ng/dscm) (rag/hr) (kg/hr) (ng/g) (mg/hr)
I
II
III
IV
V
Mean x
Standard deviation
Emissions
Fly ash
Composite
day
Mass FA
flow Cone, emissions
(kg/hr) (ng/g) (mg/hr)
Miscellaneous outputs (water)
Mass WO
flow Cone, emissions Total inputs Total outputs
(l/hr) (ng/l) (mg/hr) (mg/hr) (mg/hr)
I
II
III
IV
V
Mean x
Standard deviation
-------
TABLE 7. DAILY FLUE GAS SAMPLING DATA
w
Date
(1980)
Gas composition • Stack
Test Train Sample Volume Oz C02 CO THC temperature Molecular Moisture Velocity Gas flow
no. no. DSCF DSCM % % ppm ppm °F weight % ft/sec ACFM DSCFM DSCMM
Isokinetic
rate
1
2
3
4
5
a Average during test period.
-------
SECTION 5
REFERENCES
1. Federal Register, 41(111), 23060-23090 (1976).
2. Adams, J., K. Menzies, and P. Levins, "Selection and Evaluation of Sorbent
Resins for the Collection of Organic Compounds," EPA 600/7-77-044
(April 1977).
3. IERL-RTP Procedures Manual: Level 1 Environmental Assessment (Second
Edition), EPA 600/7-78-201 (October 1978).
4. Haile, C. L., and E. Baladi, "Methods for Determining the Total Poly-
chlorinated Biphenyl Emissions from Incinerator and Capicator- and
Transformer-Filling Plants," NTIS No. PB-276 745/761 (1977).
33
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Sample C, Technical Report Data Sheet, EPA Form 2220-1
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
560/5-82-OU
3. RECIPIENTS ACCESSION NO.
4. TITLE AND SUBTITLE
Sampling and Analysis Procedures for Assessing Organic
Emissions from Stationary Combustion Sources for EED
Studies. Methods Manual
5. REPORT DATE
12/1/.81 Preparation Date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J. Stanley, C. Haile, A. Small, and E. Olson
3. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME ANO AOORESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, MO 64110
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-5915
12. SPONSORING AGENCY NAME ANO AOORESS
Exposure Evaluation Division (TS-798)
Office of Pesticides and Toxic Substances
401 M Street, SW
Washington. DC 20460
13. TYPE OF REPORT ANO PERIOD COVERED
14. SPONSORING AGENCY CODE
1S. SUPPLEMENTARY NOTES
16. ABSTRACT
The sampling and analysis methods described in this report were specifically designed
for use in an ongoing nationwide survey of emissions of organic pollutants from
stationary combustion sources. The primary focus of this survey is on polynuclear
aromatic hydrocarbons (PAHs).and polychlorinated aromatic hydrocarbons including
polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and
polychlorinated dibenzofurans (PCDFs). To date, these procedures have been used by
Midwest Research Institute (MRI) to survey emissions from coal-fired utility boilers,
a co-fired (coal + refuse-derived fuel) utility boiler, and a municipal refuse in-
cinerator. This document was prepared by MRI as a guideline for laboratories who
may participate in this study, and for other researchers who wish to use these
methods.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b-IOENTIFIERS/OPEN ENDED TERMS C. COSATI Field/GfOUO
Sampling and Analysis
Methodology
Combustion
Emissions
PAH
PCDD
PCDF
POM
18. DISTRIBUTION STATEMENT
'Release to Public
19. SECURITY CLASS /This Report/
Unclassified
21. NO. OF PAGES
34
20. SECURITY CLASS fThii pagei
Unclassified
22. PRICE
EPA form 2220-1 (9-73)
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
560/5-83-006
3. Recipient's Accession No.
4. Title and Subtitle Comprehensive Assessment of the Specific Com-
pounds Present in Combustion Processes. Vol. 3 National Survey
of Organic Emissions for Coal Fired Utility Boiler Plants
5. Report Date
September 1983
6.
7. Author(s)
Clarence L. Haile, John S. Stanley, Thomas Walker,
George R. Cobb. Bruce A. Rnnmer
8- Performing Organization Kept.
No.
9. Performing Organization Name and Address
Midwest Research Institute
425 Volker Boulevard
Kansas City, MO 64110
10. Project/Task/Work Unit No.
Task 52 •
11. Contract/Grant No.
68-01-5915
12. Sponsoring Organization Name and Address
Field Studies Branch
USEPA
401 M Street, SW
Washington. DC 20460
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
F. W. Kutz, Project Officer
D. P. Redford, Task Manager
16. Abstracts
This study was conducted as a part of a nationwide survey to determine
organic emissions from major stationary combustion sources. The principal
compounds of interest are polynuclear aromatic hydrocarbons (PAHs) and
chlorinated aromatic compounds, including polychlorinated biphenyls (PCBs),
polychlorinated dibenzo-p_-dioxins (PCDDs), and polychlorinated dibenzofurans
(PCDFs). This report describes the methods and results of sampling and
analysis activities at the seven plants constituting the nationwide survey
of coal fired utility boiler plants.
17. Key Words and Document Analysis. 17o. Descriptors
Combustion, Emissions, Sampling and Analysis
17b. Identifiers/Open-Ended Terms
PAH, PCDD, PCDF
17c. COSATI Field/Group
18. Availability Statement
Release to public
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. oi Pj^es
231
22. Price
FORM NTIS-33 (10-701
USCOMM-DC 40329-P71
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