United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-79-206
September 1979
Research and Development
&EFA
Methods for
Analyzing Inorganic
Compounds in
Particles
Emitted from
Stationary Sources
Interim Report
Interagency
Energy/Environment
R&D Program
Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-79-206
September 1979
METHODS FOR ANALYZING INORGANIC COMPOUNDS IN PARTICLES
EMITTED FROM STATIONARY SOURCES
Interim Report
by
William M. Henry
Battelle, Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
Contract No. 68-02-2296
Project Officer
Kenneth T. Knapp
Emissions Measurement and Characterization Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U. S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U. S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
1i
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ABSTRACT
This research program was initiated with the objective of
developing methods to identify and measure inorganic compounds in par-
ticulate matter which emanate from sources using or processing fossil
fuels.
An extensive literature review was carried out to ascertain
prior knowledge on the possible compound forms and chemical species
present in these fly ash emissions and to review and evaluate analytical
methodologies applicable for use in the research program. Based on the
findings of the literature review, appropriate methodologies were selec-
ted for laboratory trial. Concurrent with the method trial work, large
masses, 20 to 100 grams, of field samples were collected representative
of a range of both coal and oil-fired fly ashes and the selected method-
ology development efforts were tested on these field samples as well as
on synthesized samples.
FT-IR, XRD, and chemical phase separations and analyses are
the methodologies which have provided the most definitive identification
of inorganic compounds. The structural findings by these methods are
complemented by complete cation-anion chemical determinations.
Notable in the methodology development work has been the novel
application of infrared spectrometry to inorganic compound identification
and, in the analytical data, the findings of relatively high water solu-
bilities of fly ashes, the presence of vanadium oxysulfate as a principal
emission form of vanadium from fuel oil combustion and the presence of
high sulfates in the fly ashes especially those emitted from fuel oil com-
bustion processes. These are described and documented in detail in the
Experimental section of this report.
This report is submitted as an interim report in fulfillment of
Contract No. 68-02-2296 under the sponsorship of the U. S. Environmental
Protection Agency. This report covers the period January 1, 1977, to July
31, 1978.
iii
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(Blank)
iv
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CONTENTS
Abstract ii:L
Figures/Tables vi
Acknowledgements vlii
Introduction 1
Conclusions 2
Recommendations 3
Literature Review 4
Chemical and Physical Characteristics of Fly
Ash from Coal-Fired Power Plants 4
Chemical and Physical Characteristics of Oil-Fired
Power Plant Fly Ash 9
Petroleum Refinery Emissions 13
Analytical Methodologies for Inorganic Compound
Identification 14
Experimental 24
Field Sample Collections 25
Analytical Methodology for Element Concent
of Fossil Fuel Particulate Emissions 31
Fossil Fuel Particulate Emissions 31
Results of Composition Analyses 34
Compound Methodology 34
References 57
Appendix A - Compositions of Crudes from Various Origins 65
Appendix B - Tabular Data on Coal Ash Compositions 94
v
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FIGURES
Number Page
1 Thermograms of Oil-Fired Fly Ash Composite Samples
in Air and Argon - l°C/Minute 26
2 Spectra of Computer Generated Spectrum (A), Mixture
Before Solution (B), and Mixture After Solution
and Air Dried (C) 51
3 Spectra of Mixtures Dissolved, Dired, and Baked
at 80 C (A), at 120 C (B), and 350 C (C) 52
4 Stored Reference Spectra 53
TABLES
1 Principal Mineral Forms Occurring in Coal Seams 6
2 Probable Distribution of Minor and Trace Elements
in Coal 7
3 Major Constituents of U.S. Coals by Rank 8
4 Approximate Contents of Trace Elements in U.S. Coals 8
5 Principal Ash-Forming Elements in Crude Oil 10
6 Possible Vanadate Compositions Formed During
Combustion of Residual Oil 12
7 Estimated Emissions from 262 Refineries (1969) 14
8 Emission Factors for Petroleum Refineries 15
9 Weight Losses of Fly Ash Samples on Slow Heating
in Air 25
10 Changes in S0| Contents of Fly Ash Samples Before
and After Ignition in Air at 750 C 27
11 Analyses of Fuel Oil and Additives Used During
Collection of No. 2 Oil-Fired Fly Ash 28
12 Semiquantitative Analyses of Additives Used
During Collection of No. 4 Oil-Fired Fly Ash 28
vi
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TABLES
Number Page
13 Analysis of Fuel Oils Used During Collection
of No. 4 Oil-Fired Fly Ash 29
14 Analysis of Fuel Oil Used During Collection
of No. 5 Oil-Fired Fly Ash 29
15 Analysis of Fuel Oil Used During Collection
of the No. 6 Oil Fired Fly Ash Sample and
Additive Compositions 30
16 Analyses of Coal Fuels Used During Collection
of Nos. 2, 3, 4, and 5 Fly Ash Emission Samples 31
17 Oil and Coal Fired Fly Ash Compositions - Major
Constituents 35
18 Oil and Coal-Fired Fly Ash Compositions - Trace
Constituents 37
19 Possible Compound Compositions of Oil-Fired Fly
Ash Samples Based on Chemical Analyses of Soluble
and Insoluble Phases 40
20 V in the Presence of Reduced Vanadium and Total
Vanadium Determinations (Oil-Fired Fly Ashes) 42
21 Reference Compound and Mixture Used for FT-IR
Analyses 46
22 Comparison of Calculated and Measured Fly Ash
Compositions 56
vii
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ACKNOWLEDGEMENTS
The support of Dr. Kenneth Knapp, Project Officer, is grate-
fully acknowledged, especially for his assistance in obtaining access to
appropriate field sampling sites and for his advice and suggestions.on
program direction stemming from his overall background and knowledge of
source emissions and sampling procedures.
Mr. Robert Jakobsen and Michael Gendreau, who pioneered in the
application of subtractive Fourier Transform infrared spectrometry,
C. T. Litsey, Susan Mancey, and P. M. Shumacher, who provided technical
support in the areas of chemical analyses and X-ray diffraction, and
Dr. Ralph Mitchell, who aided in the field sampling efforts, all contri-
buted in support on this program.
viii
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INTRODUCTION
Sources using or processing fossil fuels are among the major
contributors to atmospheric particulate pollution. Comparatively little
is known about the nature of these particulate emissions other than their
mass emission rate, some particle size information and elemental composi-
tions. Even elemental composition data are sparse and incomplete in
respect to emissions from sources using or processing fuel oils. Based
on the known elemental data, potentially hazardous substances are contained
in fossil fuel derived particulate emissions which are released in large
tonnages into the atmosphere. However, a full assessment of their health
hazards requires knowledge of their chemical form—i.e., how the chemical
contents are tied together. Since the major emission sources of fossil
fuel derived particulate matter are from combustion processes, it can be
assumed that the particulate matter are principally of an inorganic nature.
Very little prior analytical effort has been applied to inorganic identifi-
cation of fossil fuel derived particulate emissions. Identification of
inorganic forms of particulates is in certain ways more difficult than identi-
fication of organic forms since, although the number of inorganic species
may be less, the more commonly used inorganic analytical methods are based
on the breaking down of chemical bonds and compounds to ionic forms prior to
completing the analyses.
The candidate structural or chemical form determination methods
anticipated of being of most value in the identification and measurement of
particulate emissions from fossil fuel operations—coal and oil-fired power
plants and petroleum refineries—were X-ray and electron diffraction (XRD
and ED) and Fourier transform infrared (FT-IR) with supplemental information
by electron microprobe (EMP), scanning electron microscopy (SEM), thermo-
dynamic predictions, photoelectron spectroscopy (ESCA or XPS), and Knudsen
cell mass spectrometry. These latter two techniques were not investigated
in any detail. Obviously, chemical analyses—cation and anion determinations-
would be necessary to elucidate and aid in the quantifications of the struc-
tural method efforts. Separation techniques—solvent, specific gravity,
magnetic, etc.—would be useful to reduce complexity of the diffraction pat-
terns and IR spectra. Also valence state determinations, viz., V***, V*V,
VV, ratios in oil fly ash, were anticipated to be needed and utilized to
corroborate structural findings. Thermal analyses would be useful in noting
species changes during and after sample preparation treatments.
A literature search was carried out to ascertain what methodologies
had been developed for fossil fuel emission inorganic particulate compound
identification and/or could be modified for such identification. Simultane-
ously with the literature examination, relatively large masses (20 to 100
grams) of typical samples were obtained for realistic trials of the candidate
methods. These efforts, (1) review of methods, (2) obtaining reference
samples, and (3) trials of methodologies, have constituted the principal pro-
gram activities and are described in detail in the Experimental section.
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CONCLUSIONS
The extensive literature revealed that very little data are
available concerning the compositions of oil-fired fly ash petroleum re-
finery particulate emissions and, accordingly, less concerning the inorganic
forms of these. Considerably more information is known about coal-fired fly
ash compositions, derived secondarily from studies directed toward utiliza-
tion and waste disposal studies of the huge coal fly ash tonnages produced
annually. The analytical results given in this interim report and those
planned to be obtained during the remaining contract period, in part, fill
this information gap on the chemical nature of fossil fuel derived particu-
lates.
Oil-fired fly ashes are to a high degree water soluble, excepting
their inert soot-like carbon contents. This water-soluble fraction is com-
posed primarily of sulfates. For example, fly ash from fuel oil derived from
Venezuelan crude can contain up to 40 percent vanadium oxysulfate. Much
lesser but still significant water solubilities of coal-fired fly ashes have
been found with, again, sulfates being the principal anion present in the
water soluble fraction.
Health effects studies on potential hazards of fossil fuel fly ash
emissions should consider the considerable water solubilities of such emis-
sions and their high concentrations of sulfates. Attention should be focused
especially on power plants utilizing fuel oils with high sulfur and vanadium
contents. Ambient air measurement studies have shown strong linkage between
high vanadium concentrations and fuel oil combustion, with the highest levels
of vanadium occurring along the East Coast where fuel oil usage is predominant.
The much lower ambient levels of vanadium occurring in the Midwest urban
areas, where coal is the major fuel source, indicate that coal usage is not
a large factor affecting ambient air vanadium concentrations. This is under-
standable in the light that, while coals contain 10 to 150 ppm vanadium, an
average ash content of 10 percent gives a concentrational factor of ash of
only about 10X with much of the ash residing in bottoms or collected by pre-
cipitators. Thus coal fly ash, which is emitted as particulates, generally
contains 100 to 1500 ppm vanadium. Fuel oils can contain from 50 to 400 ppm
vanadium, but with an ash of 0.05 to 0.1 percent, a concentrational factor of
1000X is attained giving oil fly ash values of up to 100,000 ppm. Since most
fuel oil combustion units do not utilize control systems, much of this higher
concentrational level vanadium is emitted to the atmosphere.
X-ray diffraction, infrared spectroraetry, and chemical phase work
have proven to be the most useful structural identification mehtods for the
fossil fuel derived particulates especially when coupled with complete
elemental analyses to provide better quantifications of identified species.
The use of the subtractive capability of Fourier Transform with
infrared to identify inorganic sulfate forms is believed^ to be novel and has
proved to be very useful in this methodology development program.
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RECOMMENDATIONS
Fly ash samples from petroleum refinery operations should be
obtained and analyzed in order to provide a greater representation on
which to apply and test the developed methodologies and so as to increase
the limited analytical data bank on fossil fuel derived particulate
emissions.
Consideration should be given to expanding the program scope to
examining particulate matter emitted from nonconventional fossil fuel com-
bustion sources.
A more complete library of reference spectra should be prepared
for the Fourier Transform infrared spectrometry work. A replacement of
the presently used FTS-14, which has limited storage (^20 low resolution
files), by an FTS-10 of increased storage capacity will permit permanent
cataloging for storage and retrieval of the needed metal sulfate and oxide
reference spectra to facilitate identifications in the samples.
Additional studies should be carried out at a microscopic level
to examine single particles for compositions in order to ascertain the
chemical forms of trace constituents in the particulate emissions.
More emphasis should be placed on the development of methodologies
to obtain more quantitative XRD and FT-IR data.
Finally, particles should be examined for compositions as functions
of their surfaces versus depths.
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LITERATURE REVIEW
A comprehensive literature review was carried out of prior and
ongoing identification studies utilizing computer search of the Chemical
Abstracts, APTIC, and Smithsonian Science Information Exchange. Off-the-
shelf personal Battelle literature holdings and those contained in specific
journals, notably Analytical Chemistry, Analyst. Talanta. Atmospheric
Environment. Staub, Fuel, Science, Environmental Science & Technology.
JAPCA, and the Industrial Hygiene Association Journal, were searched speci-
fically. Findings have been grouped under the general classifications of
coal-fired fly ash constituents, oil-fired fly ash constituents, petroleum
refinery emissions, and analytical identification methodologies. The latter
includes methods which have not been used for fossil fuel particulate
emission analyses but are deemed applicable.
Overall, the literature review revealed that little prior work has
been done on the development and application of methods for the determination
of the coal ash chemical forms of inorganic particulate emissions from
fossil fuel sources as compared to the extensive work done on compositional
analyses and organic compound analyses methodology. The paucity of the
information on the compositions of oil fly ash emissions and trace elements
in fuel oils as contrasted to comparable data on coal fly ash and coals is
surprising. However, when the relative ash contents of fuel oils and coals
(0.05 and 10 percent, respectively) are considered, this is understandable.
Approximately 40 million tons of coal fly ash are produced annually in the
United States alone by the burning of some 400 million tons of coal by the
utilities. This high ash mass has given rise to usage, control measures,
and disposal studies which in turn have required study both of the composi-
tional and the chemical and structural form of the ash. On the other hand,
particulate emissions to the atmosphere from oil-fired sources, up to recently
at least, have largely not been controlled and the oil-fired fly ash,does not
pose a solids waste disposal problem.
CHEMICAL AND PHYSICAL CHARACTERISTICS OF
FLY ASH FROM COAL-FIRED POWER PLANTS
Coals
The nature and identity of inorganic compounds (mineral species)
occurring in coals have been studied extensively over the past 30 years and,
although chemical reactions and changes which occur during coal combustion
are complex and vary with the fuel and combustion conditions, an examination
of the various minerals and chemical combinations of elements found in coals
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can give useful insight into the inorganic compounds and chemical phases
found in coal-fired power plant fly ash emissions. Coals contain elements,
other than carbon, hydrogen, and oxygen, which may be present both as part
of the organic structure and as inorganic material from plants or minerals.
The principal mineral phases present in coals have been summarized by
O'Gorman and Walker(l), Nelson(2), Pringle^)^ and many others. The princi-
pal forms are listed in Table 1. The banded components of coal—vitrain,
clarain, durain, and fusain—which are the end-products of different coali-
fication routes, differ also in the manner in which they reacted to the
infiltration of contaminants during the formative period. Vitrain generally
is low in impurities, while durain often contains finely disseminated clay
minerals, and fusain with its open fibrous structure frequently is rich in
many minerals.
The modes of occurrence of minor and trace elements and sulfur and
their associations have been discussed by Bethel'^', O1Gorman^ ', Zubovic,
et al.' » ' A compilation of these is given for many elements in Table 2.
Many minor and trace elements are closely associated with and/or organically
bound with the coal substrates, especially the vitrain rather than with
minerals or other inorganic constituents. Zubovic, et al.,^' showed certain
elements to have organic affinity of the following order:
Ge>Be>(Ba Ti B V) > Ni>(Co Y)>Mo>Cu>Sn>Lu>Zn
Compositions of coals have been listed by many. ^ »">•*-"' These vary
widely with geographic locality and rank. Typical limits of the major inor-
ganic metals and sulfur present in various coal ranks are given in Table 3.
These are arbitrarily given as oxides, but are of the chemical forms given in
Table 1.
As can be seen, the variations even within rank are large. Trace
metals, as expected, also vary widely in coals. Typical contents for U.S.
eastern and western coals have been given in the literature^, 11) an
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TABLE 1. PRINCIPAL MINERAL FORMS OCCURRING
IN COAL SEAMS
Form
Silicates
Sulfides
Oxides
Sulfates
Carbonates
Chlorides
Minerals
Montmorillonite
Feldspar
Kao Unite
Muscovite
Chlorite
Pyrite
Marcasite
Quartz
Hematite
Magnetite
Gypsum
Jarosite
Calcite
Siderite
Ankerite
Halite
Silvine
Formula
(Mg Ca)0'Al203'5S102XH20
(Na'K)AlSi308
Al203-2Si02'2H20
H2KA13 (SiOi03
(MgFe)s(Al Fe)2Si3010(OH)8
FeS2
FeS2
S102
Fe203
^6304
CaSOit'2H20
KFe 3 (OH) 6 (80^)2
CaC03
FeC03
(Ca Mg Fe Mn) C03
NaCl
KC1
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TABLE 2. PROBABLE DISTRIBUTION OF MINOR
AND TRACE ELEMENTS IN COALS
Periodic Table
Grouping
Mineral Association
Coal Association
LI. Rb. Cs
L1
Cu. Ag. Au
tu
Ag, Au
Be
5r. Ba. Ra
5r
Ba
Ra
Zn. Cd. Hg
Si
Cd
Hg
Sc, V. Rare Earths
6a. In. T1
Cr
Most likely with mica
Chalcopyrlte Cu-Fe-S
Argentiferous and auriferous pyrites
Little
Barlte - BaSO,,. wltMrate - BaC03
Sphalerite - ZnS
Probably with minerals of sulflde type
Probably with minerals since poorly d strlbuted
Possibly tourmaline (a boroslHcate) and/or
1n mite
Probably extrinsic with clays or shales
Intrinsic with vitrafn, dura In
Intrinsic - vltraln, duraln
Intrinsic - vltriln
Possibly because well distributed
In low concentrations
Probably Intrinsic - mstly from
plant life
Probably Intrinsic with coal substance
With coal substance
6e, Sn. Pb
5e
Sn
T1. Zr. Th
T1
Zr
Th
P. As. Sb. B1
f
As
Sb
B1
Nb. Ta
Se. Te
Cr. Mo^ w. U
Tr
Ho
W
U
£1
Co. HI
Co
N1
Galena - PbS also PbO
ZrSIO,, - rlrcon
FluorapatHe
H1th misplckels (FeS2-FeAs2)
CarnotUe
Pyr1te/«arcas1te
ttoS3 presence correlates with S
Like No
Like V In camotile, also uranlnlte, coffinite
CaF2 fluorlte also with phosphorus fluorapatUe
CaF2-3Ca3(PO,,)2
Had partly
Llnnaelte (Co,N1)3SH
Pyr1te/mar1os1te, Ml with nllltrlte N1S
Intrinsic - vltraln
Also with coal substance
Intrinsic - vltraln
Also In the vltraln
Primarily with coal substance
Bonded to H2 ttam In coal substance
Intrinsic with coal substance
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TABLE 3. MAJOR CONSTITUENTS OF U.S. COALS BY
RANK (IN PERCENT)
Constituent
Fixed Carbon
Volatile Matter
Ash
S03
Si02
A12C-3
FezOs
Ti02
CaO
MgO
Na20
K20
Anthracite
75-90
1-10
5-20
1-5
1-10
3-15
2-10
0.1-1.0
1-5
0.2-2.0
0.1-1.0
0.2-2.0
Bituminous
40-70
20-45
5-25
2-12
2-12
1-10
0.5-0.5
0.1-1.0
0.3-3.0
0.1-1.0
0.05-0.5
0.1-1.0
Subbituminous
30-60
15-40
3-15
5-15
3-15
1-10
2-10
0.2-2.0
1-5
0.2-2.0
0.05-0.5
0.2-2.0
Lignite
20-50
20-50
5-20
4-16
3-15
3-15
1-5
0.2-2.0
1-5
0.2-2.0
0.1-1.0
0.2-2.0
TABLE 4. APPROXIMATE CONTENTS OF TRACE ELEMENTS
IN U.S. COALS (RESULTS IN PPM)
Element
As
Be
Cd
Co
Cr
Cu
F
Ge
Hg
Mn
Eastern
15
2
3
10
14
14
60
10
0.2
53
Western
2
1
0.1
7
8
20
60
3
0.06
45
Element
Mo
Ni
Pb
Sb
Se
Sn
V
Zn
Eastern
8
22
40
1.5
2
5
33
315
Western
5
5
17
0.6
1.5
5
20
11
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scanning, electron), thermal, and to a lesser extent infrared. Extensive
data are available on the compositions of coal ashes, variations in com-
positions as a function of particle sizes and on pathways of selected
elements from the fuel to residences in various ash beds to escape to the
atmosphere. Changes in phase of minerals in coal have been followed via
low temperature electronic (plasma) and higher temperature ashing techni-
ques. (26-29) The electronic ashing process, is lengthy, taking up to 200
hours to come to a relatively steady state weight change, but does provide
a useful means of predicting phase changes during coal combustion processes.
Although wide variations exist in fly ashes derived from conven-
tional coal-fired power processes, th^y have been characterized generally as
consisting of heterogeneous finely divided, highly siliceous, spherical-
shaped particles containing residual unburned carbon, magnetic and nonmag-
netic iron compounds, some alkali and water-soluble components. Most coal
fly ashes are described as 5 to 15 percent of crystalline material and 70 to
90 percent glass, plus unburned carbon. The crystalline components princi-
pally have been identified as quartz, 1 to 5 percent; mullite, 5 to 15
percent; hematite, 1 to 3 percent; and magnetite, 1 to 10 percent. The re-
maining glass has a composition range generally given as: SiC>2, 50 to 60
percent; A^OS, 20 to 35 percent; Fe203, 5 to 12 percent; CaO, 1 to 10
percent; MgO, 2 to 5 percent; Na20, 0.5 to 1 percent; 1^0, 2 to 5 percent;
and TiC>2, 1 to 2 percent. (In the work described later in this report, it
is shown that certain coal fly ashes contain high concentrations of metal
sulfates and substantial water-soluble components.)
Studies of mineral phases or inorganic compounds largely have
been confined to the higher metal concentrational contents of fly ashes with
only very limited examinations of the possible states or chemical combina-
tions of the lower concentrations Ni, Co, V, Cr species, etc. Some work has
been done on these lower concentrational metals using techniques such as
electron microprobe and scanning electron microscopy equipped with X-ray
readout to ascertain elemental interrelations or empirical formulas. Addi-
tionally, studies of fly ash particle surfaces have been carried out by
surface techniques including ESCA, Auger, and EMMA. However, these latter
techniques are relatively insensitive for metallic components due in part to
their presence in the bulk rather than the surface of particles. These
techniques are well summarized by Keyser, Natusch, Evans, and Linton.(30)
CHEMICAL AND PHYSICAL CHARACTERISTICS
OF OIL-FIRED POWER PLANT FLY ASH
Fuel Oil
Fuel compositions used in power production vary depending on the
origins of the crude (see Appendix Tables A-10 to A-15), the minerals and
metals picked up as the crudes are transported to the refineries, the con-
tamination (or loss—desulfurization, etc.) occurring in the refining pro-
cess, and on the compositions of fuel additives, if used. Several metal
contaminants such as iron, nickel, and vanadium occur in crude oil as organo-
metallic compounds generally of the porphyrin type. Sulfur contents of fuel
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oils vary depending on the source of the originating crude and the subse-
quent refining process. While the concentration of sulfur varies widely
even in a given geographic area or oil field, most crudes contain from 1.0
to 2.5 percent sulfur present mostly as complex organic sulfides, some
elemental sulfur, and possibly as sulfates. Generally residual fuel oils
contain about twice the sulfur of the originating crude, but this is de-
pendent on the refining process. Ash-forming constituents in the crudes
go through the refining process practically unchanged and are concentrated
in the bottom, with residual fuel oil No.6 or Bunker C comprising the
residual or bottoms from distillation of crudes. The principal ash-forming
elements found in crude oil as given by Bowden, et al.,'31) are nsted in
Table 5. Vanadium, which occurs mostly in asphaltic-base crudes is present
principally as an oil-soluble porphyrin complex. These are very temperature
stable and so are retained in the residual during the refining process.
Thermal ashing of heavy residual fuels results in an ash percentage varying
generally from 0.01 to 0.1 percent. Fuel additives containing inorganic
metals such as Mg, Mn, Al, etc., when used, of course increse this thermal
ash percentage.
TABLE 5. PRINCIPAL ASH-FORMING ELEMENTS IN CRUDE OIL
Element
Type
Solubility
in Oil
Probable Chemical Form
Aluminum
Calcium
Inorganic
Organic
Inorganic
Insoluble
Soluble
Insoluble
Iron
Magnesium
Organic
Inorganic
Organic
Inorganic
Soluble
Insoluble
Soluble
Insoluble
Nickel
Silicon
Sodium
Vanadium
Zinc
Organic
Inorganic
Inorganic
Organic
Organic
Soluble
Insoluble
Insoluble
Soluble
Soluble
Complex alumino-sillcates in suspension
Not identified
Calcium minerals in suspension; calcium
salts in suspension or dissolved in
emulsified water
Possible iron porphyrin complexes
Finely sized iron oxides in suspension
Not identified
Magnesium salts dissolved in emulsified
water or in suspension in microcrystal-
line state
Probable porphyrin complexes
Complex silicates and sand in suspension
Largely sodium chloride dissolved in
emulsified water or in suspension in
mlcrocrystalline state
Vanadium porphyrin complexes
Not identified
10
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Fuel Oil Fly Ash
The above mineralogical or thermal ash content compositions and
percentages of fuel oils do not represent the total particulate contents
of oil-fired fly ashes. These include carbonaceous material (partially
combusted carbon) and nitrogen and sulfur compounds. The metallic salts,
sulfur and nitrogen compounds, which have as their sources the crudes
from which the fuel oils were derived plus impurities occurring during the
handling, transport, and refining of the crudes, constitute the basis for
inorganic compounds found in fly ash. The carbonaceous products are princi-
pally of a soot-like substance consisting largely of amorphous or partially
graphitic carbon and can constitute up to 70 percent of the mass of the fly
ash. Table 6 taken from Miller, et al.,(32) lists many possible metal ash
constitutents formed during fuel oil combustion and the melting points of
their oxide or sulfate forms.
The ash constituents of course are not simply oxide or sulfate
metal salts. For instance, vanadium complexes in the fuel oil droplets
decompose during combustion and oxidize in steps, possibly to V205. However,
the vanadium may react with other metal oxides (Ni, Fe, Na, Ca, Mg, and sul-
fur) present in the oil or oil additive to form a variety of vanadate salts.
Vanadium compounds in fly ash from oil-fired units have in several instances
been found to be water soluble to a large extent—see Experimental section.
Fly ash constituents vary from surface to bulk and surface compositions have
been studied by several techniques.(30) This can be important in characteriz
ing the porous, high surface area ashes commonly encountered in oil-fired
fly ashes.
Factors other than fuel composition which affect the nature and
quantities of fly ash emitted from oil-fired power plant burners include the
manner in which the fuel is sprayed and vaporized, the air-to-fuel ratio,
the residence time in the combustion zone, fuel additives, and the flame or
combustion zone temperature. McGarry and Gregory(33) in a study of particu-
late emissions from oil fired boilers for power generation found that an
important factor governing the size, quantity, and nature of the particles is
the degree of atomization. Their study showed that poor atomization results
in large fly ash particles and a high particulate loading since the droplets
of fuel may be large and difficult to combust completely. Conversely, with
small droplets more complete combustion is attained and usually the particle
size of the fly ash emissions is small as well. Goldstein and Siegmund'34) ±
their study of the influence of heavy oil composition and boiler combustion
conditions on particulate emissions showed, in their tests using convention-
al high-sulfur and low (0.3 percent) sulfur oils, that there was an optimum
level of excess air which corresponded to minimum particulate emissions.
Above and below that level particulate emissions increase. Their study
showed that 60 percent excess air was optimum for particulate burnout, but
this was not optimum for boiler efficiency. Normal practice is to operate
the boiler with the minimum of excess air. Combustion chamber residence
time also is an important factor in governing the quantities and character-
istics of particulate emissions from boilers—the longer the period in the
combustion zone, the less emissions and the smaller the size of the particu-
late emissions. With longer residence pariods the carbonaceous particles
11
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TABLE 6. POSSIBLE VANADATE COMPOSITIONS FORMED
DURING COMBUSTION OF RESIDUAL OIL*
Compound
V205
3Na20-V205
2Na20'V205
10Na20'7V205
Na20-V205
2Na20-3V205
Na20-2V205
5Na20'V2(VllV205
Na20«3V205
Na20 •V20i+ • 5V2Og
Na20-6V205
Melting Point, F
1274
1562
1184
1065
1166
1049
1137
995
1150
1157
1215
Compound
2N10'V205
3NiO-V205
Fe203-V205
Fe203-2V205
MgO'V205
2MgO-V205
3MgO-V205
CaO«V205
2CaO-V205
3CaO-V205
Melting Point, F
>1652
>1652
1580
1571
1240
1535
2175
1145
1432
1860
*Compiled from a number of sources.
are burned with a greater efficiency resulting in lesser amounts of particu-
late emissions and in smaller size particles.
All of these factors, fuel composition, air-to-fuel ratio, combus-
tion zone temperature, time of residence in the combustion zone, plus use of
additives, affect the nature, quantity, and size distribution of particulate
emissions from utility boilers. For these reasons methodologies to determine
inorganic compounds in oil-fired power plant emissions should take into
account the varying nature of these substances. For example, under a given
operating condition and with a certain fuel type, a highly oxidized form ot
vanadium might be found present in the emissions, while under other operating
conditions the vanadium can occur in a more reduced form.
Certain physical differences can be applied to oil-fired power
plant ash particulate emissions which distinguish them from coal-fired power
plant emissions. Some of these are pointed out by Cheng, et al.,^ *> who
described oil fly ash particles as black, rough, honeycomb-like structures
generally of irregular spherical shape, while coal fly ash particulates are
characterized as having smooth ball-like surfaces of a regular spherical
shape. Cheng, et al., go into further detail on their descriptions, but it
seems apparent that many of the finer details they describe are unique to
the sample or sample types being examined. While Cheng, et al., describe the
oil-fired fly ashes as rough, porous, opague spheres, Goldstein and
Siegmund(34) characterize them as cenospheres. The cenospheres are formed
from the residues of spray droplets from which, on passing through the flame,
12
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their volatile compounds vaporize and fragments crack from nonvolatile
compounds with both of these burning in the vapor phase around the droplet.
The nonvolatile carbonaceous residues, roughly the size of the original
droplet, which forms a solid skeletal particle and can be full of void
spaces, they call cenospheres.
In contrast to most coal fly ash particles which generally are
smooth-surfaced, glassy spheres or cenospheres, oil-fired fly ashes general-
ly are more porous, roughly spherical in shape, and can vary quite widely in
overall chemical compositions, but to a large extent the carbon in oil-fired
fly ash is of a soot-like form. Due to the high combustion process organic
compounds are essentially absent in oil and coal-fired fly ashes.
PETROLEUM REFINERY EMISSIONS
The petroleum refining industry is a major fuel consumer, using
about 10 percent of the energy in the crude for the myriad separations,
fractionations, and other processes which result in their intended end
products. The principal origin of emissions from petroleum refineries is
the crude oil which represents over 90 percent of the material input to the
operations. The raw crude oil as received by a refinery is a mixture of
mostly hydrocarbons of varying molecular structure but also contains water,
brine, sludge, sulfur compounds, some metals and nitrogen compounds.
It is difficult to generalize about refinery operations and
resultant emissions since no two refineries are alike, with extreme variances
in the complexity of the processing utilized and the end-products produced.
Further variances are introduced by the crudes—what is done to refine one
type crude may not be practical for others. In general the older refineries
are less complex and produce the fewest petroleum products. However, many
of these refineries are being remodeled and reequipped to produce a larger
range of products and devices are being added to control pollutant emissions.
The principal products of oil refining are gasoline and fuel oils and, since
the needs for these are increasing rapidly, refineries will continue to grow
as a major energy consumer and as a potentially even larger source of
atmospheric emissions.
The exact nature and quantities of these emissions are difficult
to pinpoint because of the aforementioned variances in raw materials compo-
sitions (mostly crudes), complexity of operations and refining processes,
age, and technological sophistication of the plants and lack of data in the
literature on specific emissions measurements.
The compositions of crudes, the principal sources of pollutants,
are given in Tables A-l and A-2. An indication of the quantities of emissions
by pollutant is given in Table 7 and by process in Table 8.
Petroleum refinery emissions arise from a diverse number of process
operations as well as from a wide array of miscellaneous operations such as
storage, handling, spillage, incineration of wastes, leaks, flares, treating
13
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TABLE 7. ESTIMATED EMISSIONS FROM 262 REFINERIES (1969)
Pollutant Emissions, 1000 tons
Sulfur oxides 2200
Nitrogen oxides 61
Hydrocarbons 2300
Particulates 55
Carbon monoxide 2420
and blending operations. Smoke (unburned HC), particulate matter, hydro-
carbons, and other gaseous substances, mostly oxides of sulfar and nitro-
gen, constitute the major types of emissions released by oil refineries.
Although refineries vary greatly in the relative complexities of processes
employed, the major operations are: separation, conversion, treating, and
blending. The catalytic cracking unit is one of the principal sources of
pollutant emissions in refineries with the regenerator being the largest
offender. Particulate emissions can be reduced by control measures such
as use of electrostatic precipitators or cyclones, but efforts to control
particulate emissions generally have not received the emphasis as efforts
to reduce sulfur compound and hydrocarbon emissions.
Contrary to finding fairly extensive data on coal-fired fly ash
emissions and to a lesser extent on oil-fired fly ash emissions, no data were
obtained from the literature on the specific compositions of particulate
species emitted from refinery operations. Since the catalytic cracking
operation has been cited as being a major source of particulate emissions,
initial sampling possibly should be done there to obtain samples for use in
developing and establishing inorganic compound methodologies.
ANALYTICAL METHODOLOGIES FOR INORGANIC
COMPOUND IDENTIFICATION
The literature abounds with analytical methodology descriptions
and applications to inorganic particulate pollutant analyses. The great
majority of these publications and references describe and/or are applied to
the elemental and anionic contents of pollutant samples. No attempt has been
made to list these here since they have been reviewed in detail elsewhere in
the literature and in EPA reports(36-48)f and since their applications to
inorganic particulate compound methodology are mostly of a support role, i.e.,
to provide data on the overall elemental, cation, and anion groupings present
in samples and sample fractions.
Comparatively, methods applicable to inorganic compound or chemical
form identification and analysis are few, and descriptions of these applied to
pollutant samples are quite limited in the literature and in ongoing research
and development activities. This lack of attention given to inorganic com-
pound identification in pollutants is um sual in view of frequently declared
14
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TABLE 8. EMISSION FACTORS FOR PETROLEUM REFINERIES
Emission Factor
A. Boilers and process heaters
B. Fluid catalytic units
C. Moving bed catalytic cracking
D.
Compressor Internal combustion
engines
Miscellaneous process equip;
1
ent
4.
5.
6.
7.
8.
9.
Slowdown system
a. with control
b. Without control
Process drains
a. With control
b. Without control
Vacuum jets
a. With control
b. Without control
Cooling towers
Pipeline valves and flanges
Vessel relief valves
Pump seals
Compressor seals
Others (air blowing, blend
changing and sampling)
#Hydrocarbon/1000 bbl oil burned
/Hydrocarbon/1000 ft3 gas burned
/Particulate/1000 bbl oil burned
*Partlculate/1000 ft? gas burned
*N02/1000 bbl oil burned
»N02/1000 ft3 gas burned
/CO/1000 bbl oil burned
/CO/1000 ft3 gas burned
/HCHO/1000 bbl oil burned
/HCHO/1000 ft3 gas burned
lHydrocarbon/1000 bbl of fresh feed
JParticulate/ton of catalyst circulation
/N02/1000 bbl of fresh feed
SCO/1000 bbl of fresh feed
(PHCHO/1000 bbl of fresh feed
/NH3/1000 bbl of fresh feed
/Hydrocarbons/1000 bbl of fresh feed
/Particulate/ton of catalyst circulation
/N02/1000 bbl of fresh feed
ICO/1000 bbl of fresh feed
fHCHO/1000 bbl of fresh feed
*NH3/1000 bbl of fresh feed
/Hydrocarbons/1000 ft* of fuel gas burned
/N02/1000 ft3 of fuel gas burned
/CO/1000 ft3 of fuel gas burned
/HCHO/1000 ft3 of fuel gas burned
/NH3/1000 ft3 of fuel gas burned
/Hydrocarbon/ 1000 bbl refinery capacity
/Hydrocarbon/1000 bbl wastewater
/Hydrocarbon/ 1000 bbl vacuum distillation capacity
/Hydrocarbon/ 1,000. 000 gal cooling water capacity
/Hydrocarbon/1000 bbl refinery capacity
/Hydrocarbon/1000 bbl refinery capacity
/Hydrocarbon/1000 bbl refinery capacity
/Hydrocarbon/ 1000 bbl refinery capacity
/Hydrocarbon/1000 bbl refinery capacity
140
0.026
800
0.02
2,900
0.23
negligible
negligible
25
0.0031
220
1.8<*>
63
13,700
19
54
87
5
3,800
12
5
1.2
0.86
negligible
0.11
0.2
5
300
210
negligible
130
6
28
11
17
5
10
(a) With electrostatic preclpltator.
(b) With high efficiency centrifugal separator.
-------
needs for such information in health and toxicity assessment studies.
Several reasons can be cited for this anomaly, but the principal cause is
the relative difficulty of inorganic compound identification of samples
as complex and heterogeneous as are pollutant emission particulates. The
commonly and readily used techniques for analysis of inorganic constituents
consist of initially breaking samples down to their ionic forms and/or
utilizing the atomic characteristics of the samples' constituents and then
isolating individual elements, cation, or anions, chemically or spectrally,
for identification and quantification. This is in contrast with the more
commonly used organic species analysis methods which utilize the molecular
or molecular-fragment properties of the samples for organic constituent
identification. These of course are generalizations; since with selected
sample dissolution the valence state of certain elements can be retained and
quantified, and many inorganic species have unique molecular spectral charac-
teristics and specific crystalline forms. However, the use of these ele-
mental and compound specific techniques for inorganic species identification
have not been exploited to any great degree on complex pollutant emission
samples. Inorganic compound identification and analyses of pollutant emission
samples, what little has been done, has relied mostly on XRD techniques plus
morphological characterization of sample component recognition, from the
microscopy-instrumented tools of SEM, STEM, and BMP wherein microscopic viewing
can be aided by elemental analyses of the viewed particle or particle groupings,
and recently the surface identification techniques of ESCA, etc.
The review of literature, search of ongoing R&D efforts, and dis-
cussions with leaders in the field of pollutant analyses reveal the following
list of techniques and methodologies as most useful for identification of
inorganic compounds in particulates emitted from fossil fuel sources:
(1) X-ray diffraction
(2) Infrared spectrometry
(3) Microscopy - optical, electron, petrographic,
scanning electron, scanning electron transmission,
electron microprobe, and chemical
(4) Surface techniques - ESCA, Auger, SIMS, and IMA
(5) Chemical phase - valance state, separations
(6) X-ray fluorescence
These are discussed in some detail below and their applications to coal and
oil-fired power plant particulate and refinery emissions are described. How-
ever, as stated elsewhere, very little information is available on oil-fired
power plant particulate emissions chemical characterizations, even including
compositions.
16
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X-Ray Diffraction
X-ray diffraction methodologies have been used extensively to de-
termine the chemical structure of fossil fuel fly ashes with the referenced
publications being among the more thorough studies reported.^ '^'•'»^'' No
XRD studies of oil-fired fly ash emissions were found, although selected
studies have been made of oil ash boiler corrosion deposits. The coal ash
studies, principally of products of pulverized fuel, have shown fly ash to
be comprised of from 5 to 25 percent crystalline products and 75 to 95 per-
cent glass. The crystalline components vary depending on the fuel origin—
for instance, a range of British and U.S. fly ashes studied by Simons and
Jeffrey(49) were found by XRD analysis to have the following principal com-
ponents:
British Coal Ashes U.S. Coal Ashss
Quartz 1-6.5% 0-4%
Mullite 9-35% 0-16%
Magnetite ^5% 0-30%
Hematite ^5% 1-8%
Lime (CaO), anhydrite (CaSO^), gypsum (CaSO^-2H20), and dicalcium ferrite
(ZCaOFeaOs) also were found in lesser amounts. Using magnetic separations
and chemical solution techniques to further examine the iron-containing
fly ash components the following distributions were found in several coal
fly ash samples:
Magnetic iron (mostly magnetite and lower
amounts of hematite) ^20%
Nonmagnetic iron (dicalcium ferrite)
Soluble iron (FeSOiJ
Silicate iron
Several investigators used density (float-sink) techniques to examine various
fractions of fly ashes. However, as judged by compositional analyses, little
enrichment of chemical species were attained, attributable to the very hetero
geneous nature of coal fly ash particles and to the presence of cenospheres
which contain light and heavy phases. Several investigators used synthetical
ly prepared standards to aid in interpreting the XRD patterns of coal fly ash
samples. These were made up of the principal minerals found in coal (see
Table 1) and were fired at elevated temperatures or passed through an oxygen-
coal gas flame. The standards prepared this way were found to correspond
closely in appearance with those found in commercial glasses.
Based on the work reviewed, the principal crystalline phases in
coal ash—quartz, mullite, magnetite, and hematite—can be identified by XRD
aided by the use of synthetic standards. Most of the iron present in coal
ash occurs in separate iron-rich particles and these too can be separated and
identified. The glassy particles of coal ash, largely Si02, A1203, and Fe2C>3,
may be chemically extracted, as has been done with ceramic materials, and the
composition cf the glass phase determined by chemical means. No XRD work has
17
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been reported on fly ash emissions from oil-fired power plants. However, as
can be seen later in the Experimental work section of this report, the chemical
nature of these are quite different from the coal ashes. XRD studies of the
oil-fired fly ashes should be of considerable value in showing the chemical
forms of the important vanadium, iron, and nickel species.
Other than as described above and specialized applications such as
free-silica analysis and asbestos identification, X-ray diffraction has not
been used extensively in particulate analysis. However, with increasing con-
cern regarding the form of toxic compounds, XRD may play an increasingly
active role. One limitation to XRD identifications is the lack of a simpli-
fied and valid reference. Ubrary. There are some 30,000 materials cataloged
in the JCPDS-International Center for Diffraction Data. This represents
a difficult search problem to identify unknown patterns based on d-spacings
and line intensities. Further, some of the data given in the reference file
was obtained using impure materials and/or materials in a hydration or
crystalline state other than listed. This leads to improper identifications.
Despite these problems, X-ray diffraction remains a key technique
for the identification of inorganic compounds in particulate pollutant sample
catches and development work, as described by later workers(50-54)f indicates
that XRD analyses can provide good compound identification.
Infrared Spectroscopy
Infrared techniques have been explored to some extent for use in
pollutant analyses, but have not been utilized widely for detailed character-
ization of fly ashes. Blanco(55) examined dust particulates by infrared
spectrometry and found them to consist mostly of the mineral species present
in soils and outcroppings. O1 Gorman'-*-) used infrared analysis coupled with
X-ray diffraction to follow the mineralogy of coals through low temperature
ashing processes. Again, the IR identification consisted principally of the
minerals and mineral groupings found naturally in coals and higher oxidation
products of these. Both Blanco and 0'Gorman point out problems of spectral
overlap and inadequate sensitivty. These problems are alleviated considerably
by the use of a Fourier transform spectrometer. Cunningham, et al.,(56)
using a Digilab Model FTS-14 spectrometer over the spectral range of 400 to
3600 cm"1 with an 8 cm"1 resolution, measured many of the major chemical con-
stituents of ambient samples. From known reference spectra, assignments
of 28 species were made. However, in this work no accounting was taken for
spectral alterations due to waters of hydration, mixed sulfates, band
splittings due to crystal structure and other factors which complex the
identifications. The importance of these factors is discussed in more detail
later.
Fourier Transform infrared systems differ from conventional dis-
persive infrared spectrophotometers in that conventional infrared spectroscopy
uses a monochromator to generate the spectral information, whereas an inter-
ferometer is used for this purpose in Fourier Transform infrared spectroscopy.
The use of an interferometer to generate spectral information in the form of
an interferogram (light intensity versus time) necessitates a second
18
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difference between the two types of infrared spectroscopy. This difference
is that FT-IR systems use a dedicated digital computer to obtain the Fourier
Transform of the interferogram, converting it to a conventional infrared
spectrum (light intensity versus wavelength or frequency). These two dif-
ferences lead to the following two major advantages of FT-IR over conven-
tional infrared spectroscopy:
• An interferometer results in a substantial gain in
energy or light throughput as compared to a mono-
chromotor. This gain in energy results from the elim-
ination of the dispersive device since all wavelengths
of light are examined simultaneously in an interferometer
and no energy is lost (as in a dispersive instrument
by examining the light one wavelength at a time). This
additional energy can be used in one of several ways:
(2) for faster scan speeds (as fast as 0.6 sec), (b) for
up to a 30-fold increase in signal-to-noise ratio, and
(c) for 102-103 greater sensitivity.
• The availability of a dedicated computer offers several
major data-handling advantages. Not only can spectra be
ratioed against each other to remove absorption bands due
to background materials, but the computer can be used to
perform spectral arithmetic. Thus, spectra can be added
or subtracted from each other and also multiplied or divided.
In this way, the spectra can be adjusted in size, and
unwanted components can be removed from the spectra with
out the necessity of chemical separations. This ability
to utilize a computer is not unique to Fourier Transform
spectroscopy, i.e., in theory a computer could be attached
to a conventional dispersive infrared spectrophotometer.
However, in practice, this is rarely done, whereas all
Fourier Transform systems use -a computer. Thus, from a '
practical standpoint, the use of a computer is a major
advantage in FT-IR systems.
The applications of FT-IR to inorganic compound identifications
have been described by Henry, Mitchell and Knapp(57) aruj Jakobsen, Gendreau,
Henry, and Knapp(58) and are detailed later in the Experimental section.
Microscopy Instrumental Methods
The instrumental techniques of microscopy, scanning electro micro-
scopy (SEM), electron microprobe (EMP)., scanning transmission electron micro-
scopy (STEM), electron microscopy microanalyzer (EMMA), and IMA (ion micro-
analyzer) all have in common a capability to focus on or "see" a very small
area of a sample and, in addition to giving a morphological view of the area
under the beam, provide elemental compositional data usually via an energy
dispersive X-ray analyzer (EDXA). (The IMA gives a mass-sorted signal.)
19
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Several investigators have used one or a combination of these
Instruments to examine various types of particulate pollutants including
coal fly ashes£24,59-67) since pollutant samples, especially fly ashes,
are highly heterogeneous in size and in composition within a given size
distribution, the use of the techniques Is tedious even with computer con-
trolled readout. The analytical responses obtained are subject to variation
due to such factors as interelement, bacAground, matrix, particle mass, and
geometry effects and require fairly complex corrections for quantitative
analyses.
Despite these problems, since the focusing beam is highly localized
a very good detectability can be obtained for many elements. (With EMP for
example, if 100 ppm is detected in a 10 um^ volume, this equates to a detec-
tion of 1 x 10~ grams in a material of average density.) Of course the
analytical data obtained are elemental, not species nor compound in nature.
However, when all elements are scanned in a given area, as on a single parti-
cle or particle group, a stoichiometric relationship can be derived and
related to compound form. This approach may well be the best technique for
determining the chemical association of low concentrations of key metal
impurities such as Ni in coal ash at 200 ppm, etc.
ESCA
ESCA has been given increasing attention in examining the composi-
tion and chemical states of pollutant species, principally in ambient
atmospheric particulate samples. (68-78) For the exciting X-ray photon
energies in common use, the outer 10 to 20 A of a sample are probed, and
this can represent both an advantage and a disadvantage. There are many
problems associated with the use of ESCA techniques, but since both the
chemical state and chemical composition are determined, it can provide in-
valuable (although not always easily int erpretable) information regarding
particulate pollution composition.
Linton, et al.,"°' using ESCA plus other surface analysis tech-
niques including IMA, Auger, ISS, and even EMP, compared surface compositions
with compositions at depths up to 1000 A and bulk compositions and showed
conclusively that many elements are concentrated on the surface of particles
of coal ash. This has been shown also more indirectly by analyzing various
particle size fraction of samples. Linton further concluded that since coal
ash is predominantly mac e up of an insoluble aluminum silicate glass the
analysis obtained by a T ater OT dimethyl sulfoxide extraction might be more "
meaningful in terms of health effects than bulk composition analyses. Craig,
et al.,(°9) U8e(j ESCA to examine the chemical states of sulfur in ambient
pollutants and found seven species — 863, SOf, SO*, S02, S° , and two kinds
of sulfides. Several workers cross-compared ESCA results with wet chemical
and other methods and found variations of a factor of 2, with much higher
discrepancies on volatile species.
As stated earlier, many problems are encountered in the applica-
tion of ESCA to pollutant analyses. These include poor resolution of peaks
20
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resulting from different elements in the same oxidation state; poor quanti-
tative data even with the use of standards; requirement for a hard vacuum
which with localized heating from X-ray bombardment can result in loss of
NHi+NC^, HNC>3, ^SO^ acid species, and others; difficulty in suitably mount-
ing samples, and of course the problem that ESCA is a surface technique
method which makes data interpretation more difficult. However, since ESCA
is a surface analysis technique (and this is advantageous in many respects)
it is difficult to standardize and to intercompare results with those
obtained by other methods. The complexity and heterogeneity of pollutant
particles enhances the difficulties of carrying out ESCA analyses. Certain
elements or species are present on the surface of fly ash along with carbon.
Others such as iron compounds are bulk components. Ion etching can be used
to look beyond a particle surface, but this can further increase the
difficulty of interpretation. Much more work needs to be done in looking
between ESCA results and results from other methods before ESCA can be used
routinely in compound identification. Certainly the combination of ESCA
and Auger instrumentation (electron excitation) can provide considerable
data on surface species.
The general conclusion is that ESCA provides considerable insight
into compound species present in pollutant particulates and especially in
respect to surface composition, but correct interpretation of data quantita-
tively is difficult. This, coupled with problems of "presenting" the sample
and maintaining its integrity in the X-ray or electron beam, makes ESCA or
ESCA augmented by Auger still a development technique. In substance, this
abbreviated conclusion is apparently that obtained also by C. H. Lockmuller(79)
who recently evaluated ESCA and other techniques for their applications to
inorganic compound characterizations of emission species and by McAlister(80)
of the NBS laboratories who evaluated ESCA similarly for characterization of
St. Louis particulate matter.
ISS (ion scattering spectrometry), SIMS (secondary ion mass
spectrometry) also are surface analysis techniques and suffer many of the
disadvantages of ESCA. Much more work needs to be carried out by the use
of standards and intercomparisons of results before ISS or SIMS ever approach
routine use in pollutant analyses.
Chemical Phase
Chemical phase analysis as defined by Steger in a review article™-^'
is the determination, by a chemical dissolution technique, of the distribution
of an element in an ore or rock with a goal of selective dissolution of one
or more minerals present. Since fly ash particulates do not contain natural
minerals, the techniques and uses of chemical phases analyses usually must be
modified from those given in the literature. However, since the goal remains
essentially the same, it appears useful to retain, and use of the term
"chemical phase analysis" for work on particulate pollutants which involve
valence determinations and other selective dissolution techniques which lead
toward identifying the presence and chemical states of elements and elemental
groupings. Possibly because of the lusser availability of sophisticated
instrumentation, chemical phase analysis is utilized most by the eastern
21
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European and U.S.S.R. countries, and this introduces difficulties because
translations are not readily available and access to the original work is
difficult.
Below are examples of chemical phase or preferential and controlled
chemical state determination of species Ln participate samples. Many other
similar techniques can be found and are adaptable for identification of other
species or chemical states.
Free I^SOit acid determination lias received considerable attention
in atmospheric aerosol analysis as well as fossil fuel emission, but the
various methodologies proposed still have not been totally adequate nor statis-
factory, Leahy, et al.,(°^) state that 1128014 acid can be extracted and de-
termined without interferences from other sulfate salts using a benzaldehyde
extraction. Barton and McAdie'"^) have described an isopropanol extraction
method which they found unique for H2SOif. Others, including Shafer(84)>
Scaringelli(85) , and WestC^o), described methods for sulfuric acid aerosols
in the presence of other sulfate salts. Estimates of 10 percent for ambient
to 65 percent for oil fly ash are given for the relative proportion of sul-
• furic aerosol to the total sulfate content.
Vanadium, a key pollutant found in high concentrations in oil-fired
power plant fly ash emissions using South American crudes, can be present in
several chemical combinations. Knowledge of the valence state (s) of vanadium
can be useful in determining its chemical form. Vanadium (V^ and VlV) have
been determined in the presence of each other by Shcherbakova, et al.(°7)
Working with catalyst samples they found optimal conditions for the sequential
determination of VV and V^ by use of an extraction-photometric method.
Rao (88) has described a potentiometric titration for determining V^I alone
and in mixture with
The several forms of carbon present in aerosols have been deter-
mined by several means! Grosjean(y9) usi:d a solvent extraction followed by
organic carbon analyzer analysis. Appel, et al.,'90) aiso working with
atmospheric samples, developed a technique for estimating elementary carbon,
and primary and secondary organics, while Mueller, et al.,(91) measured the
carbonate-noncarbonate content of particulates. In our own work, XRD has
shown carbon in oil fly ash to be largely amorphous but with some graphitic
structure. Low concentration of COf in fly ash and ambient particulate
amples have been analyzed by us using a gas chromatographic technique.
Sant and Brasant^"^' after a brief review of 21 methods for deter-
mining various forms of iron in mixtures, outline a simple and rapid method
of sequential determination of Fe°, ~Fe++, and Fe"*""*"1". The sample is treated
with brominol and filtered. Iron in the filtrate is titrated iodometrically.
The oxide residue is dissolved with HC1 under a C02 blanket with the Fe"4""1"
formed, equivalent to the FeO present, titrated with a standard vanadate
solution, and the total Fe(= FeO + Fe203) in the titrated solution is then
obtained iodometrically. Brimblecombe and Spedding'93) in their studies of
iron dissolution from pulverized fuel ash showed that the iron more likely
is present as finites. This is in agreement with Minnick(23) wno found that
22
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a large fraction of the iron in pulverized fuel ash residues is nonmagnetic
particles. If the iron were present as Fe304 a larger magnetic fraction
would be expected.
Hexavalent chromium CrVI can be determined in the presence of iron,
copper, nickel, and vanadium by the very sensitive s-diphenylcarbazide
method/94^
^ '
has shown that CaO can be differentiated from many other
calcium salts by its formation with a sucrose solution, a water-soluble
saccharate. This can be titrated with a standard oxalic acid solution,
Large quantities of the carbonate and oxide of magnesium have no effect on
the determination of CaO by the procedures.
Components of fossil fuel fly ash emissions can be separated and
determined by selective chemical means — e.g., the glassy constituents of
coal ashes have been quantitatively determined by extraction with cold 40
percent HF acid as developed by Konopicky and Kohler("6), Free silica in
environmental samples has been determined by XRD, IR, and chemical means.
These have been reviewed in detail by Anderson!' '' Free silica is a com-
ponent of the crystalline phases present in many coal fly ash samples.
X-Ray Fluorescence
X-ray fluorescence (XRF) has been used indirectly in compound
identification efforts to provide data on samples before and after chemical
and/or physical separation—e.g., analyses before and after water leach can
be used to identify soluble and insoluble species. In these applications
the very good reproducibility and rapid multielement capabilities of XRF
make the technique ideal for complex sample types such as fly ashes. Because
of the non-destructive nature of excitation, the XRF equipment can be auto-
mated and computerized to provide accurate multielement data rapidly.
Wagman, Bennett, and Knapp describe this application of XRF to particulate
pollutants.(98,99) XRF also has been used to identify the chemical forms of
elements in the atomic number range of 11 to 17 - Na to Cl. Gilfrich,
Pickerar and Birks^OO) have used a conventional single-crystal XRF analyzer
to measure K3 emission of sulfur to quantitatively discriminate sulfate
and sulfide forms. These authors project that similar identities can be
obtained on P and Cl. The Ko X-ray emission results from the transition of
valence electrons (from the M shell) to fill vacancies in the K shell and
as such displays structure associated with the chemical combination of
the element. Other workers(101>102) have used X-rav analyses to determine
the valancies of vanadium and manganese and Paris *•' applied the technique
to the direct determination of organic sulfur in coal.
23
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EXPERIMENTAL
The experimental efforts were directed toward the investigation
and application of well-established techniques since at the start of this
program very little information was found available on even the compositions
of oil-fired fly ash emissions. More recently, studies by EPA workers,
Knapp, Bennett, and Conner(1°4,105,106) have been useful in filling this
information gap. An exception to this technique selection process was the
exploration and use of FT-1R which hitherto had been applied mostly to
organic identification work.
FIELD SAMPLE COLLECTIONS
Samples of oil-fired and coal-fired fly ashes were collected from
several power plant sites which burn fossil fuels of various origins with
the objective of obtaining a range of fly ash sample compositions represen-
tative of present power production processes. Sampling was performed at the
port holes in the stacks or ducts beyond any emission control process opera-
tion. The fly ash samples were obtained by simply inserting a 2-cm-diameter
glass-lined probe into the center of the stack perpendicular to the stack
stream flow and, with a 1 hp blower, drawing a portion of the flow into a
fine mesh Teflon bag. A 24-hour sampling time period usually provided 50
to 75 grams of stack emission particulates. At the conclusion of the sam-
pling period the Teflon bag was removed from the Hi-Vol container, sealed in
a polyethylene bag, and returned to the laboratory for analyses of the
collected particulates.
Sample pretreatment was considered carefully in carrying out the
analyses of fossil fuel particulate emissions samples since unknown alter-
ations of their chemical forms must be avoided. Samples collected in the
way described from stack exit flues at temperatures of about 150 C contain
large amounts of water, and pretreatments such as desiccation and heating
can alter the sample weights and chemical forms. From the structural, cry-
stallographic and/or optical—XRD, IR, petrography—analytical aspects, it
is desirable to work with samples in a stable, moisture-free condition
since the presence of loose and even bound forms of water, "nonessential
and essential" hydrogen, complex the identification efforts. The practice
of drying samples at 105 C before bottling, weighing, and analysis is not
applicable to the wet particulate emissions since for many samples there is
no point where loose, unbound, capillary water only is removed by heating
in air atmosphere. This is illustrated by the data given in Table 9 for
samples collected at the stack exit ports of coal and oil-fired power
plants. Thermograms of a composite of four oil fly ash samples (equal
amounts of each mixed together) heated slowly at 1 degree per minute in air
and in argon are shown in Figure 1. The thermogram for the oil-fired fly
ash composite heated in air shows a cont nuous weight loss over a 15 hour
24
-------
TABLE 9. WEIGHT LOSSES OF FLY ASH SAMPLES ON
SLOW HEATING IN AIR (IN PERCENT)
105 C 200 C 400 C 750 C
Oil Fly Ash 1
Oil Fly Ash 2
Oil Fly Ash 4
Oil Fly Ash 5
Coal Fly Ash NBS
Coal Fly Ash 1
Coal Fly Ash 2
Coal Fly Ash 3
2.4
3.0
4.5
5.05
0.25
1.0
4.0
4.0
4.5
4.8
12.5
10.6
0.55
1.8
5.4
6.5
18.0
69.5
28.0
36.9
1.1
2.6
13.0
9.0
22.5
74.0
57.0
45.5
4.1
4.7
19.2
24.2
heating increase at a 1 C per minute change. The sequence of weight losses,
as shown by individual sample TGA and DTA plots in air, indicate capillary
or unbound water, hydrated or bound water, carbon, and then partial SOI^
losses. The partial and variable losses of SO^ are confirmed by the data
given in Table 10 for SO^ contents of samples before and after ignition at
750 C.
Thermograms based on heating the samples under argon show minor
incremental weight changes between 200 and 400 C, as illustrated by the com-
posite sample in Figure 1, indicating probable loss of most unbound water
contents. IR and XRD spectral and pattern images obtained on the samples
after heating under argon are much improved as are the microscopic appear-
ances of viewed sample particle fields. Based on these findings, heating
the samples under argon appears to be a reasonably satisfactory mode of re-
moving the unbound water without altering otherwise the integrity of the
sample structure, and based on individual thermograms for several samples,
heating samples at 300 C under argon was adapted as the general preparation
mode for IR, XRD, and microscopic examinations.
Sample Descriptions
Six oil-fired and five coal-fired fly ash samples were obtained
for the methodology development work. These are:
Oil Fly Ash No.l—
This is an aged sample obtained during a 1973 research program
from a Connecticut power plant purportedly burning No.6 fuel oil of a domes-
tic origin. No sample of the fuel oil was available for analysis. As
judged by the particle size range of the fly ash, the ESP control probably
25
-------
ON
100
200
300
600
700
800
400 500
Temperature, °C
FIGURE 1. THERMOGRAMS OF OIL-FIRED FLY ASH COMPOSITE SAMPLES IN AIR AND ARGON - 1°C/MINUTE
900
-------
TABLE 10. CHANGES IN SOJj! CONTENTS OF FLY ASH SAMPLES
BEFORE AND AFTER IGNITION IN AIR AT
750 C (RESULTS IN PERCENT)
Total SO^ In
Collected Samples
Oil Fly Ash 1
Oil Fly Ash 2
Oil Fly Ash 4
Oil Fly Ash 5
Coal Fly Ash NBS
Coal Fly Ash 1
Coal Fly Ash 2
Coal Fly Ash 3
36.9
12.0
41. 2
57.6
0.98
5.0
7.26
22.0
S0£ After
Ignition
28.7
10.4
21.0
18.9
0.20
3.0
0.92
0.90
Loss of SO^
at 750 C
-8.2
-1.6
-20.2
-38.7
-0.78
-2.0
-6.34
-21.1
was not operating at the time of sampling, and as evidenced by the high
concentration of magnesium in the collected fly ash, a magnesium additive
was added to the fuel. The high SO^ value casts some doubt on the oil
being of domestic origin.
Oil Fly Ash No.2--
The No.2 oil fly ash sample was collected from a Florida utility
boiler which at the time of collection was burning a No.6 fuel oil derived
from a Venezuelan crude. Front-end magnesium additive was employed in the
combustion process. At the time of sampling, the plant was operated at a
minimal excess air. Analyses of the fuel oil and additives are given in
Table 11.
Oil Fly Ash No.3--
This sample was collected at the same location as the No.2 sample
with the sampler being allowed to operate unattended for about a week.
During that period the collected particulates became excessively wet— 36
percent free water. Compositionally the collected sample, on a dry basis,
was similar to the No.2 above.
Oil Fly Ash No.4--
This sample was collected from a South Carolina electric utility
boiler. At the time of sampling the plant was burning a No.6 fuel oil de-
rived from predominantly Venezuelan crude origin. Both a front-end (Chesco
22) and a back-end additive (Coaltrol) were being used and the plant was
operating at a normal air-to-fuel combustion ratio. Analyses of the addi-
tives and the fuel oil are given in Tables 12 and 13.
27
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TABLE 11. ANALYSES OF FUEL OIL AND ADDITIVES USED DURING
COLLECTION OF NO.2 OIL-FIRED FLY ASH - RESULTS
IN PPM EXCEPT WHERE PERCENT IS GIVEN
Mg
V
Ni
Fe
S
Al
Si
Ca
Mn
Pb
Ash
Na
K
Fuel Oil
(No Additive)
9
570
72
5
2.5%
1
2
5
1
1
0.11%
20
3
Fuel Oil
(With Additive)
137
540
69
5
2.47%
2
5
10
1
1
0.18%
20
4
Mg Additive
No. 1
25.8%
<5
<5
500
—
2%
500
0.2%
50
2000
52%
—
— —
Mg Additive
No. 2
33.5%
<5
<5
2000
—
0.2%
0.4%
1%
2000
<5
59.7%
—
— —
TABLE 12. SEMIQUANTITATIVE ANALYSES OF ADDITIVES USED DURING
COLLECTION OF NO.4 OIL-FIRED FLY ASH*
Ele-
ment
Mg
Ca
Si
Al
Na
K
Front-End
Additive
15
0.2
<0.05
2
0.05
<0.05
Back-End
Additive
30
0.3
2
0.3
3
0.5
Ele-
ment
Fe
Pb
B
V
Ash
Front-End
Additive
0.03
0.1
0.01
<0.01
33.4
Back-End
Additive
0.2
—
0.04
<0.01
93
*Results in percent
28
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TABLE 13. ANALYSES OF FUEL OILS USED DURING COLLECTION
OF NO.4 OIL-FIRED FLY ASH*
Element
No.6 Fuel Oil
(12/14/76)
No.6 Fuel Oil
(12/15/76)
"^Results in ppm except where percent is given.
No.6 Fuel Oil
(12/16/76)
Ash
S
Na
K
Mg
V
Ni
Fe
Al
Si
Ca
Mn
Pb
0.10%
2.15%
10
4
6
446
62
45
2
3
5
<1
<1
0.09%
2.2%
10
4
7
450
60
45
2
3
5
<1
<1
0.095%
2.1%
10
4
5
445
64
45
2
3
5
<1
<1
Oil Fly Ash No.5--
This fly ash was taken at the same site as was the No.2 sample
but about 6 months later. Reportedly the plant had switched to a fuel oil
derived from a Near East crude. The analysis of the fuel oil combusted
during the sampling period, given in Table 14, is lower in vanadium content.
TABLE 14. ANALYSIS OF FUEL OIL USED DURING
COLLECTION OF NO.5 OIL-FIRED FLY ASH
Element
No.5 Oil-Fired Fly Ash
(2/10/77)
Mg
V
Ni
Fe
S
Al
Si
Ca
Na
K
Mn
Pb
Ash at 550 C
114
292
50
17
2.65%
1
4
7
159
7
1
<1
0.14%
*Results in ppm except where; percent is given
29
-------
Oil Fly Ash No.6--
This sample was obtained from a Louisiana electric utility plant
allegedly burning a domestic derived fuel oil. Two additives were availa-
ble for combustion control. However, based on analysis of the collected
ash, the Mn additive was not used during the sampling period. The analyses
of the fuel oil and additives are given in Table 15.
TABLE 15. ANALYSIS OF FUEL OIL USED DURING COLLECTION
OF THE NO.6 OIL FIR.iD FLY ASH SAMPLE AND
ADDITIVE COMPOSITIONS
Fuel Apollo MC-7 Additive
Mg
V
Ni
Fe
S
Al
Si
Ca
Na
K
Mn
Pb
Ash at 550 C
1490
40
20
15
1.56%
60
10
5
8
6
<1
<1
0.5%
5000
100
400
2%
—
5%
3%
4000
—
—
35%
—
53%
Betz FS-62U Additive
25%
—
—
100
—
20%
2000
5000
—
—
—
—
56.5%
NBS Coal Ash—
This is the NBS Standard Reference Material 1633 which, according
to the certificate, is a blend of six ashes - five of which were collected
by electrostatic precipitators and one by a mechanical collector. These
were sieved and the portion passing through a 170 mesh sieve were taken and
blended to make up the SRM.
Coal Fly Ash No.l--
This is an aged sample collected in 1973 at an electric utility
plant operating in West Virginia. The sample was collected from the stack,
past the ESP. No coal fuel was available for analysis.
Coal Fly Ash No.2 and No.3—
The No.2 and No. 3 coal-fired fly ash samples were collected in
July, 1977, at an Ohio and a Kentucky power plant, respectively. The
operating capabilities of these power plants are between 100 to 200 mega-
watts and both use ESP controls in burning Ohio and Appalachian origin pul-
verized coals of compositions given in Table 16.
30
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TABLE 16. ANALYSES OF COAL FUELS USED DURING COLLECTION OF
NOS. 2, 3, 4, AND 5 FLY ASH EMISSION SAMPLES(a>
Coal Fuel CoaTl\iel Coal Fuel Coal Fuel
No. 2 No. 3 No. 4 No. 5
s
Fe
Al
Si
Ca
Mg
Ti
Ash at 700 C
Zn
3.87
1.0
1.3
1.0
0.2
0.02
0.02
8.2
<0.1
3.62
0.9
1.0
1.7
0.3
0.1
0.1
14.4
<0.1
5.14
2.0
2.0
3.0
1.5
0.2
0.1
27.7
0.30
0.49
—
—
—
—
—
—
7.03
0.03
(a) Results in percent.
Coal Fly Ash No. 4. This sample was collected in May, 1978, from
a utility power plant (rated at 875 megawatt capacity) burning a locally
mined subbituminous coal fuel of a composition given in Table 16. The con-
trol mechanism is a wet-lime scrubber process. The combination of a high-
ash, high-sulfur fuel with scrubber control resulted in a fly ash of con-
siderably different composition than other coal-fired fly ashes—see Table
17. The most striking differences are the considerable water-solubility of
the ash and high concentrations of SO^ and heavy metal compounds. The
latter appeared to be derived from a zinc-base mineral present in the coal.
The plume has a high visibility with particulate emissions estimated at
0.213 lb/106 Btu.
Coal Fly Ash No. 5. This sample was collected in May, 1978, at
a utility power plant (rated at 800 megawatts) burning a low ash, low sulfur
Wyoming coal of a composition given in Table 16. The emission control used
is an electrostatic precipitator. At a short distance the plume is barely
visible. Particulate emissions have been measured at 0.012 Ib/Btu.
These samples appear to be sufficiently representative of fly ashes
emitted from oil and coal-fired utilities which use fuels of various origins
and control processes to test the efficiencies of developed compound methodolo-
gies thoroughly. The effects of rapid "aging" or changes in sample composition
during and subsequent to sample collection were not studied in this program,
although it is believed that these effects can be of considerable significance.
ANALYTICAL METHODOLOGY FOR ELEMENT CONTENT
OF FOSSIL FUEL PARTICULATE EMISSIONS
Prior to inorganic compound identification, determinations were
made of the elemental contents of the sfmples, both as a guide to the
31
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selection and use of the inorganic compound techniques and quantification
and substantiation of the compound results obtained. The techniques used
are only briefly outlined below since they are well established and thorough
discussions on their applicability to fuel and fuel ashes are given in
numerous publications including references 107 to 110.
Atomic Absorption Spectrometry (AAS)
AAS is used for determining the metallic elements present in con-
centrations<0.01 percent in the samples with the exception of the determinations
of Si and Al in the coal-fired fly ashes. Elements of key interest such as
As, Se, Hg, Pb, Tl, and others also are determined by AAS at concentrational
levels down to about 0.001 percent when it is desired to obtain better quanti-
tative data than obtained by SSMS.
Equipment: Perkin-Elmer 305B with HGA 2000 high temperature
graphite furnace ar.d deuterium accessories.
Spark Source Mass Spectrography (SSMS)
Samples are mixed with high purity graphite to yield a 40 percent
graphite mixture and pressed into 7/64-inch-diameter by 5/16-inch conductive
electrodes. The sample electrodes are placed into the ion source and a series
of graded exposures are recorded on a photoplace with the heaviest exposure
providing sensitivities of 0.1 ppm, atomic basis. The photo plates are
interpreted visually using sensitivity factors derived from analyses of
reference standards. SSM data is used for the semiquantitative estimation
of concentrations of elements present in contents of <0.1 percent in the
samples.
Equipment: AEI MS-702 R using 2 x 12 inch
Ilford Q2 Plates
Carbon, Hydrogen, Nitrogen
Three mg of sample are weighed into a preweighed platinum boat,
reweighed, and combusted at ^950 C after a purge cycle with oxygen to remove
air. The instrument automatically controls the purge cycle, a helium sweep
cycle and the read-out cycle. C, H, and N contents are measured as C02 ,
H20, and N2 by thermal conductivity cells. The instrument is calibrated by
extensive use of standards.
Equipment: Perkin-Elmer Model 240 Elemental Analyzer
LEGO Carbon-Oxygen Determinator
Ion Chromatography — Cl~, F , NO^, SO^ Determinations
Typically a 1-ml portion of sample solution is introduced into an
ion exchange column containing a low-capacity resin, eluted with a weak
NaHC03-NaC03 solution and the anions are separated. The effluent stream is
passed through a second ion exchange colu m (a suppression column) to remove
32
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unwanted ions and then through a conductivity cell where the concentrations
of the separated anions are read as a series of peaks on a strip chart
recorder. Calibration is achieved by processing standard solutions similarly.
The ion chromatograph has seven electronic attenuations which allow coverage
of seven concentrational ranges from about 0.5 to 1000 ppm of the sample
solution.
Equipment: Dionex Ion Chroma tography
Nitrite (NO^) Determination
Colorimetric method through formation of azo dye formed by coupling
diazotized sulfanilic acid with N~(l-naphthyl)-ethylenediamine.
Sulfite (S0"5) Determination
Titration with standarized potassium iodide- iodate titrant
releasing free iodine giving, a. blue color with starch indicator.
Total Sulfide (S) Determination
Acidify sample in sulfur evolution apparatus, heat while passing
purging gas through system, collect any H2S released by passing gas stream
through ammoniacal zinc acetate solution, acidify, titrate with KI solution.
Ammonium (NHfr) Determination
Specific ion ammonia gas-sensing electrode.
Total Organics
Repetitive (5) methylene chloride extractions made on 0.5 g of
sample and the extracted phase carefully dried and weighed to obtain the
total organic mass content extracted.
Total Reduced Sulfur Species —
Treat samples with 0.1 N iodine solution, acidify and titrate
unreacted iodine with 0.1 N sodium thiosulfate.
Fe, Al, Si in Coal Ashes
Fusion of ash with NaOH, leach with water, acidify with HC1 and
determination of Si as silico-molybdenum blue and aluminum as the calcium
alizarin red-S complex. Decomposition of ash with HF, HN03, and I^SOit acids.
Fume off Si, dissolve residue in water, and spectrophotometric determination
of Fe as tiron complex.
33
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RESULTS OF COMPOSITION ANALYSES
The results obtained by use of the above techniques are given in
Tables 17 and 18. Included in Table 17 are the concentrations of certain
components on the bases of water solubility and insolubility—e.g., Oil Fly
Ash No. 1 contains 36.9 percent SO^ with 36.0 percent being water-soluble
and 0.9 percent insoluble, etc. The data given in Table 17 show that a
very large percentage of the oil-fired f]y ash samples are water soluble as
well as substantial percentages of certain coal-fired fly ash samples.
These data also show SO^ to be the only significant form of sulfur In the
fossil fuel particular.^ emission samples'. Although the method of determTn-
ation of SO^ might measure other sulfur forms, separate S= determinations
and total reduced sulfur species determinations have shown the presence of
other sulfur forms to be neglible. This has been confirmed by SO^ determined
values correlating closely with total sulfur values (determined by combus
tion) calculated as SOiJ. The SOJJ is nearly all in the water-soluble phase
of the samples and is essentially the only anion present in this phase.
These findings suggest a ready, simple mode of fractionating
fossil fuel particulate emissions into water-soluble metal (and ammonium)
sulfates and water-insoluble metal oxides (and silicates) plus inert carbon.
Any free ^SOi^ acid of course also is contained in the water-soluble phase
of the samples, but I^SOi^ acid has not been found to be present in large
percentages except in the No. 4 coal-fired fly ash which was collected at a
port behind the wet scrubber control mechanism.
The separations or fractionations of the samples into water-soluble/
insoluble phases has proved useful for structural identifications of specific
metal sulfate forms, principally by FT-IK, and of oxide forms by XRD.
COMPOUND METHODOLOGY
Chemical Phase Methods and Separations
Free t^SOit Acid—
A benzaldehyde extraction procedure was used similar to that
described in several recent literature references. The method used basically
followed the procedures described by Leahy, Tanner, et al.,(111,112) ,nd
Barrett, et al.UU) Both of these groups checked the specificity of
benzaldehyde as an extractant for H2S04 acid and the recovery of H2SOU acid
via spikes and/or generation of known quantities of H^O,. Recoveries were
found to be greater than 80 percent and experimental tests showed the extrac-
tion to be specific for H^SO,. However, the results obtained by us were very
s^'^.^^i'L^^:factor of 10'attriLtabie -
34
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TABLE 17. OIL AND COAL FIRED FLY ASH COMPOSITIONS - MA.IOR CONSTITUENTS (PERCENT)
CHS NH^ N0~ Nlli*~
so;
so-
s
Cl 1' Hi
Oil-Fired Fly Ashes
No. 1
No. 2
No. 4
No. 5
No. 6
Total Sample Content 12.4 0.9 0.1 0.005 <0.01 0.012
Water-Soluble Content
Water-Insoluble Content
Total Sample Content 69.0 0.7 0.9 0.013 0.005 0.13
Water-Soluble Content
Water-Insoluble Content
Total Sample Content 21.5 1.0 0.9 0.02 0.01 0.81
Water-Soluble Content
Water-Insoluble Content
Total Sample Content 1.5 1.2 0.1 0.02 <0.01 0.16
Water-Soluble Content
Water-Insoluble Content
Total Sample Content 14.5 2.4 6.5 <0.01 0.03 7.3
Water Soluble Content
Water-Insoluble Content
36.9
36.0
0.9
12.0
12.0
0.15
41.2
41 .1
0.1
57.6
58.6
0
49.2
48.4
0.8
'0.01
^0.01
-0.01
'0.01
0.01
• 0.01
'0.01
<0.01
'0.01
<0.01
<0.01
'O.oi
<0.01
<0.01
<0.01
• 0.01
• 0.01
<0.01
<0.01
••11.01
-0.01
'0.01
<0.01
-o.oi
<0.01
<0.01
-.0.01
<0.01
<0.0l
'0.01
0.05 D.008 0.31
0.01
0.31
0.1)2 0.002 0.2
0.01
0.2
0.02 0.004 0.2
0.01
0.2
0.05 0.001 0.05
0.01
0.05
0.06 0.05 0.22
0.01
0.22
Coal-Fired Fly Ashes
NBS
SRM 1633 Total Sample 3.3 0.1 <0.1 T <0.01 <0.01 <0.01
Water Soluble Content
0.98
0.60
<0.01
<0.01
'0.01
'0.01
0.005 0.12 20.9
Water-Insoluble Content
No. 1 Total Sample Content 1.7 0.3 <0.1 <0.01 <0.01 <0.01
Water Soluble Content
Water Insoluble Content
Ho. 2 Total Sample Content 7.0 0.5 0.1 <0.01 <0.01 0.06
Water Soluble Content
Water Insoluble Content
No. 3 Total Sample Content 0.5 0.7 <0.1 0.02 <0.01 0.01
Water Soluble Content
Water Insoluble Content
No. 4 Total Sample Content 0.1 1.2 <0.1 0.03 <0.01 0.15
Water Soluble Content
Water Insoluble Content
No. 5 Total Sample Content 0.1 <0.1 <0.1 <0.01 <0.01 0.01
Water Soluble Content
Water Insoluble Content
3.05 <0 01 <0.01 <0.003 0.14
2.13 <0.01 <0.01
6.9 <0.01 <0.01 0.007 0.02
5.75 <0.01 <0.01
22.1 <0.01 <0.01 0.05 0.08
19.6 <0.01 <0.01
50.6 <0.01 <0.01 0.06 0.2
50.2 <0.01 <0.01
5.23 <0.01 <0.01 <0.01 0.05
2.32 '0.01 '0.01
19.7
16.7
16.fi
6.2
<0.01
6.2
-------
TABLK 17. (CONTTNUF.n)
Al
Fe
Nl
V
Mg
C.T
Na
K
Total Uater
Ornanics Solubility
H?0 HjSOi, pH
Oil-Fired Fly Ashes
No. 1
No. 2
No. 4
No. 5
No. 6
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
1.25
0.5
0.75
0.05
0.02
0.03
0.40
0.23
0.17
0.01
<0.01
0.01
1.42
0.27
1.15
0.61
0.30
0.31
0.40
0.25
0.15
0.41
0.20
0.21
0.48
0.49
0
0.40
0.43
0
1.66
1.0
0.66
0.85
0.60
0.25
1.29
1.06
0.23
2.28
2.31
0
0.35
0.30
0.05
2.27
0.50
1.77
6.68
2.23
4.45
10.2
8.98
1.22
12.85
12.9
0
1.10
0.78
0.32
18.4
4.71
13.7
3.41
1.1".
:>.26
5.94
3.0
0.94
2.50
2.65
0
2.4
2.4
0
1 .0
0.6
0.4
0.31
0.1'i
0.16
0.1
0.07
0.03
0.20
0.19
0.01
0.32
0.16
0.16
3.91
3.9
O.OL
0.30
0.30
0
0.50
0.51
0
2.02
2.0
0
0.20
0.21
0
0.
0.
0
0.
I).
1)
0.
0.
0
0.
0.
0
0.
0.
0
13 '0.1 58.0
13
1 23.3
1
10 0.053 72.0
12
10 <0.1 98.5
09
12 --0.1 83.0
11
7.0 -0.1 3.9
5.0 0.2 2.7
4.5 0.04 2.42
5.5 1.0 2.15
2.1 1.5 2.22
Coal- Fired Fly Ashes
NBS
No. 1
No. 2
No. 3
No. 4
No. 5
SUM 1633 Total Sample
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Uater Insoluble Content
Total Sample Content
Uater Soluble Content
Water Insoluble Content
Total Sample Content
Uater Soluble Content
Water Insoluble Content
12.7
11.3
10.9
0.63
10.27
8.79
1.63
7.16
1.2
0.6
0.6
13.0
0.4
12.6
6.5
12.6
14.1
0.56
13.54
7.90
1.94
5.96
7.56
6.55
1.0
3.64
0.02
3.6
0.01
0.06
0.02
0.01
0.01
0.05
0.04
0.02
0.02
0.02
0.05
0.01
0.04
0.02
0.02
0.03
0.01
0.02
0.05
0.04
0.02
0.03
0.02
0.01
0.04
<0.01
0.03
2.0
0.52
0.2
0.01
0.01
0.5
0.2
0.4
0.3
0.3
0
2.0
0.01
2.0
4.2
1.5
0.40
0.18
0.22
3.0
1.8
1.2
2.65
2.6
0.05
21.3
1.0
20.3
0.30
0.60
0.05
0.03
0.02
0.08
0.06
0.02
0.1
0.1
0
1.0
<0.1
1.0
1 .
1.
1.
0.
0.
1.
0.
0.
1.
0.
0.
1.
<0.
1.
75 ^0.1 3.5
54 0.04 5.3
0 0.072 13.0
5
5
1 0.11 34.0
6
5
0 <0.1 79.2
4
6
0 <0.1 9.1
1
0
0.03 <0.1 11.35
1.0 <0.1 4.5
4.0 2.0 3.17
5.0 2.1 2.73
3.9 16.5 2.2
1.0 0.1 11.3
-------
TMM.t 18. OIL ANI> UUL-FlRlil) FLY ASH COMPOSITIONS - TRACE CONSTITUENTS
LI
Be
B
f
St
Ti
Cr
Nn
Co
C-
?n
Ga
Gt
As
Se
Br
Rc.
Ag
cc
Ir.
$'
io
Tt
I
C$
b«
Li
Ce
ic
Ft
Au
hr,
7)
Pt
bi
Oil-fireO fly
No. 1
0.5
C.05
30.
1.
iX
IOC
•2?:.
5c::.
«; .
4j.
5.
10.
3:.
7 .
1C
5
50C
s:.
s '.
10.
'O'j.
- 1 .
1.
• 1 .
] .
<1
;30.
J400.
O.
20.
30.
ho. 5
20.
10.
400
20.
so.
7000.
200.
SOO.
io.
200.
300.
S.
40.
JO-
5.
IP-
200.
3000.
100.
200.
5.
70.
<1 .
<1 .
<1 .
1.
IS.
<1 .
is!
10.
-------
second graduated centrifuge tube, add 2 ml of deionized water and shake
vigorously to extract the H2SOi4 acid from the organic to the aqueous phase.
Break up any resulting emulsion by centrifuging briefly at 850 rcf. Remove
the aqueous layer by use of a water-wettud medicine dropper. Add 4 times
the aqueous volume of isopropanol and a drop of 0.2 percent aqueous Thorin.
Titrate with 0.01 N Ba"1"1" (perchlorate) in the 1:4 HoO: isopropanol mixture—
one drop 0.01 N Ea++ solution = 5 ug H2SOi+ acid.
Chemical-Physical Separations—
The chemical and physical complexities of particulates from fossil
fuel sources make the task of identifying their chemical forms quite diffi-
cult. Generally, compound identification efforts can be simplified if the
samples can be readily fractionated into a few separate phases without
changing their chemical forms. Many of the available techniques for phase
separation such as particle picking and/or use of the electron tnicroprobe,
scanning electron microscope, scanning transmission electron microscope or
secondary ion mass spectrometer are useful but are too time consuming and
tedious to be practical in examining in detail multiple samples for their
quantitative inorganic compound identifies. Separation procedures based on
density differences suffer because many of the fly ash particles are hollow
spheres within spheres. Fractionations based on particle size are difficult
to achieve because of particle agglomeration. Magnetic separation, appli-
cable to coal fly ash samples, results only in enriching, but not completely
separating, the magnetite phase of the samples.
The microscopic techniques do have merit, particularly in identi-
fying trace metal associations with anion components, but many particles
need to be deagglomerated and analyzed for their elemental concentration
ratios and thus indirectly obtaining compound forms. This work is quite
tedious whether performed by electron microprobe, scanning electron micro-
scopy, secondary ion mass spectroscopy or scanning transmission electron
microscope, and in fact only the latter technique has the capability of
resolving very fine particles. However, since other compound identification
techniques such as XRD and FT-IR cannot detect phases much below 0.5 percent,
the STEM or other modes of microscopic examinations are needed for direct
trace component compound identifications. Indirectly, compound types of
trace metals may be deduced by performing spark source mass spectrogrpahic
analyses on the total sample and on the sample after water extraction. The
difference between the two values for a given element represents the soluble
concentration. In fossil fuel fly ashes the principal soluble-phase anions
is SO^ and the principal insoluble phase anions are oxides and silicates.
Water Solubility Separation—
Separation on the basis of water solubility has been found to
offer several advantages. The separation is readily achieved by simply
stirring a 2-gram sample in 150 ml of water at room temperature for 1 hour by
the use of a mechanical ("Mag-Mix") stirrer, filtering, washing, and drying
the insoluble residue, and gently taking to dryness an aliquot of the soluble
phase. After drying the insoluble residue is weighed to give the percent
insoluble fraction and the percent soluble is obtained by difference. Based
on experimental findings on the 12 fossil fuel-derived fly ashes given in
Table 17 and other samples, the only anion of any significant concentration
38
-------
in the soluble phase_is the SO^ and, in fact, the soluble phases contain
nearly all of the S0,4 percent in the total unfractionated samples.
In the oil-fired fly ash work samples used in this program, the
water-soluble phase represents from 66 to nearly 100 percent of the sample
components exclusive of the inert, soot-like carbon. The soluble phase
components of the oil fly ashes are primarily metal and NH^ sulfates plus
any I^SO^ acid, while the insoluble phase components are carbon, oxides,
and a minor amount of insoluble sulfates. The coal-fired fly ash samples
also contain a water-soluble sulfate phase. These are much lower in con-
centrations due to the high percentages of insoluble iron-aluminum-calcium
silicates and lesser amounts of insoluble cyrstalline minerals such as
quartz, hematite, and magnetite in the coal fly ashes.
From the elemental analyses shown in Table 17 and 18, the data
given in Table 19 for oil-fired fly ash samples were calculated basedon
the assumptions that:
(1) The cation concentrations contained in the soluble
fractions are sulfate forms since no other anions
of any significant concentrations are present.
(2) The cation concentrations contained in the insoluble
fractions are oxide forms primarily, plus limited
concentrations of insoluble sulfates.
(3) The carbon of course is present as a water- insoluble
component.
For example, considering the Mg in Sample No. 1, of the 18.1
percent present in the total sample, 4.71 percent is contained in the solu
ble phase and the remaining 13.7 percent in the insoluble phase. From the
gravimetric factor for Mg->Mg SO^l^O of 5.69, the MgSOi+'l^O content would be
5.69 x 4.71% = 26.8 MgSCVH20
Similarly, with the gravimetric factor for Mg MgO of 1.66 x 13.7%, the calcu-
lated insoluble MgO would be 22.8 percent.
These assumptions are not at odds with equilibrium thermodynamic
calculations as discussed in a later section. As can be seen in Table 19,
the possible calculated combinations total close to 100 percent for the
No. 1 and No. 2 samples. The No. 5 combinations total only 95 percent, and
the No. 6 total 91 percent. These are somewhat greater than the expected
analytical accuracies and the discrepancies in these two samples are believed
to be derived from inaccuracies in the sulfuric acid determinations and/or
use of incorrect waters of hydration values. The total SOi* contents of the
compounds given at the bottom of Table 19 check reasonably well with deter-
mined concentrations given in Table 17 except for the No. 5 sample where the
calculated SO^ total 46.8 percent versus the determined value of 57.6 percent.
39
-------
TABLE 19. POSSIBLE COMPOUND COMPOSITIONS OF OIL-FIRED FLY ASH
SAMPLES BASED ON CHEMICAL ANALYSES OF SOLUBLE AND
INSOLUBLE PHASES
Calculated Species
C as C
H20 *
H2SOH*
NHt+ as (NHOHSOI+
Mg as MgO
Mg as MgS04-H20
V as V20s
V as VOSOi+'3H20
Fe as Fe20s
Fe as FeSOi*
Ni as NiO
Ni as NiSOi+
Al as A1203
Al as Al2(SOi+)3
Si as Si02
Na as Na2SOit
K as K2S04
Ca as CaO
Ca as CaSOi,
Other Elements as
oxides/sul fates
Totals of above
Sulfates**
No.l
12.4
7.0
0.1
0.08
22.8
26.8
3.2
2.1
0.45
0.8
0.85
2.65
1.4
3.2
0.55
12.1
0.3
0.55
2.0
1.3
100.7
32.6
No. 2
63.7
5.0
0.2
0.83
3.8
6.6
7.9
9.5
0.2
0.7
0.3
1.6
0.06
0.15
0.4
0.95
0.2
0.2
0.5
0.35
103.2
11.6
No. 4
21.5
4.5
0.05
5.18
1.6
28.5
2.2
38.2
0.3
0.5
0.3
2.8
0.3
1.45
0.45
1.55
0.2
0.04
0.25
0.75
110.6
45.0
No. 5
1.5
5.5
1.0
1.03
0
14.8
0
54.9
0
1.3
0
6.0
0.02
0
0.05
6.25
0.2
0.01
0.65
1.0
95.2
46.8
No. 6
14.5
2.0
1.5
46.6
0
13.6
0.6
3.3
0
1.1
0.06
0.8
2.2
1.7
0.5
0.6
0.25
0.2
0.55
1.0
91.1
54.3
* H20 and ^SOi, values are those determined as given in Table 16 rather
than calculated values based on H.
** SOj^ contents of the calculated species.
40
-------
These postulated chemical forms of inorganic compounds proved
useful for both the XRD and subtractive FT-IR work in the interpretation
work still in progress. MgO, V2C>5, carbon and CaO patterns have been
readily identified in the total sample, anl, semiquantitatively, in the
relative concentrations given in Table 19. MgSO^t^O and VOSO[+.3H20 patterns
have been identified in the total samples and in the soluble fractions
(evaporated to dryness and baked under arg)n at 350 C) again in the approx-
imate ratios given in Table 19. Interpretative searches are being continued
to identify other compound forms with emphases being place on the oxides
since it is known that the IR work may be ;nore successful on the sulfate
forms.
Chemical Valence of Vanadium—
In conjunction with the water sclubility studies, it was noted
that in several of the samples vanadium it present principally in a water-
soluble form in the fly ash emissions. It was noted also that the water
soluble solutions had a greenish to greenish-blue color proportional to the
concentrations of vanadium determined present. Valence state measurements
of vanadium in the oil fly ash samples were made with an adaption of an
extraction-photometric method describes by Shcherbakova, et al.,(°'' for the
determinations of Vv and VIV in vanadium catalyst samples. Vv was deter-
mined in the presence of V^ at an acidity of 0.2 N since it was determined
that at pH > 1 vanadium (IV) is oxidized to vanadium (V) by atmospheric
oxygen.
Following the procedure described by Shcherbakova, et al., 0.1
gram of oil fly ash sample was dissolved an 10 ml of 0.2N HC1, the insoluble
portion was filtered and washed with 0.2 N HC1 and diluted to a volume of
100 ml. Extraction was carried out on a 2 ml aliquot using 5 ml of 10~2
PMBP solution (l-phenyl-3 methyl-4 benzoy]pyrazolone-5), 1 ml pentanol, 4
ml chloroform and 8 ml 0.2 N HC1. V in the presence of any reduced vanadium
was read spectrometrically at 500 NM. Total V in the sample was determined
by oxidizing another aliquot of the above sample solution to Vv and re-
peating the extraction-photometric procedure. Reduced vanadium was found
by the difference between the total vanadium determination result and the
V value was determined in the presence of reduced vanadium. Total vanadium
in the sample and in the water-soluble phase also were determined by atomic
absorption analyses with better precision and accuracy than obtained by use
of the extraction-photometric procedure.
The results obtained on the oil fly ash samples by use of the
above methods are given in Table 20. As can be seen in the table, the
reduced vanadium values (Column 6) coincide closely with total vanadium
contents of the water-soluble fraction (Column 5). Since V^ and V
vanadium states are very unstable, it is highly probable that the water-
soluble vanadium is in the V^V state.
41
-------
The water solubilities of two reference vanadium compounds (ICN
Pharmaceuticals vanadium sulfate and Alfa vanadium oxysulfate were compared
with oil fly ash samples Nos. 2, 4, and 5 before and after heating under
argon at 350 C. The vanadium sulfate was found to be very water insoluble
both before and after heating. The VOSO^'SH^O was found to be highly water
soluble before heating, exhibiting a det>p greenish-blue color, but was only
very slightly water soluble after heating. Anhydrous VOSO/^ is reported as
insoluble in the literature. The oil fly ash samples behaved similarly with
the unheated samples giving deep greenish coloration in the water solutions
and the heated samples imparting no color. Semiquantitative analyses of the
two reference vanadium compounds and fly ash samples showed no vanadium
(<0.1%) was dissolved in water after thf samples had been heated.
Based on the valence state determinations and the water solubility
color tests, it appears that the oil fly ash samples contain water soluble
V^OSOi+'XH20 and water insoluble V205, although there may be a possibility
of a water soluble VCSO^^'XI^O being present.
TABLE 20. VV IN THE PRESENCE OF REDUCED VANADIUM AND TOTAL
VANADIUM DETERMINATIONS (OIL-FIRED FLY AHS)(a)
Extrac tion-Pho tome trie
T,Total(c)
Atomic Absorption
Total
Water-Soluble
Reduced
(d)
1 1.70 2.25 2.27
2 4.50 5.7 6.68
4 0.90 10.7 10.2
5 0.14 11.75 11.85
6 0.35 1.1 ].10
(a) Results in percent.
(b) Vv in presence of reduced vanadium.
(c) V after oxidation of reduced vanadium.
(d) Difference between Column 1 (V^ in presence of
Column 4 (total V determined by AAS) results.
0.50
2.23
8.98
12.90
0.78
reduced
0.57
2.18
9.3
12.71
0.75
vanadium) and
X-Ray Diffraction Analyses
Samples were prepared for XRD analyses by heating under argon at
300 C for two hours to drive off loosely bound and capillary waters. (Thermal
analyses had shown little change of other component structure occurs by this
"stabilization" treatment.) The samples were mechanically ground and mixed
42
-------
and either mounted in a Debye-Sherrer camera or in planchet holders and
analyzed with CuKa excitation and a graphite monochrometer to obtain either
powder film patterns or strip chart recordings over a 29 range of 15 to
70 degrees. The resultant powder film patterns were exceedingly complex
and difficult to assign d-values and intensities with sufficient accuracies
to search X-ray pattern reference files for correct identifications of the
component structures present in the samples. The strip chart recordings were
somewhat easier to interpret but identifications were hampered by erratic
changes attributed to variations in sample orientation, sample thickness and
configuration in the beam. To resolve these factors efforts were turned
toward the use of a thin sample uniformly dispersed on a silver membrane
filter, rotated slowly during the X-ray irradiation. According to Altree-
Williams(^2) a microsample presented as a thin flat layer has the potential
to eliminate or greatly reduce sources of error in quantitative XRD due to
variation from calibrating standard to sample in mass absorption, particle
size and orientation and degree of crystallinity, all of which can introduce
significant systematic errors. The theory developed by Altree-Williams is
stated to provide a practical means for compensating for variations in mass
absorption. In his work he found that mass absorption coefficients of phases
used varied from 35 cm2/g for a-quartz to 230 cm3/g for hematite but still the
method quantitated these phases in mixtures to ±10 percent accuracy relative
to the 1 mg level. He notes that most particulate samples are of small
particle size which reduce orientation variations and also notes that the
thin layer sample gives very high diffraction intensity relative to its mass,
giving detection limits of 20 ug or better depending on the phase considered.
A conventional powder pattern with a planchet holder was compared
with one obtained with the sample on a silver membrane filter. The quality
of the diffraction patterns appeared equivalent—the planchet technique needed
about 200 mg (most of which was recovered) and the silver membrane only 10 mg.
A group of Ag filters were run as a check on uniformity based on the peak
heights of the Ag lines. These were readily reproducible within ±10 percent
as were the Ag line 20 positions. [Note: The overall technique takes varia-
tions among filters into account by running the Ag filters before and after
sample loadings.] Next a sample spinner was obtained and aligned in the X-ray
beam to ensure good representation of samples loaded into the silver filters.
Loading the filters posed a problem. It was impossible to weigh a sample
onto the filter and get good uniform distribution due considerably to an
electrostatic charge on the filter. However, it was found possible to weigh
samples, place them in a small beaker, add Freon TF, ultrasond to obtain a
suspension, and then transfer the suspension to an 18-mm I.D. straight sided
funnel and, under suction, draw the Freon suspended particulate samples onto
the silver filters. This proved successful in giving a uniform thin-layer
distribution of 1 to 10 mg quantities of samples on the silver membrane
filters.
With the above problems apparently solved, the work turned to selec-
tion of reference compounds to further test the procedure. A sea sand was
-------
obtained and, by means of diffractometry, was found to be pure quartz.
Similarly, an Fe203 was run and found to be Fe203. PbSO^ was prepared from
Pb(N03)2 and Na2SO(+ with the precipitate found to be pure PbSO^. A CaSO(+'2H20
was heated for 24 hours at 300 C to CaSO^ anhydrous. These were used to set
up reference curves where the weight of a given phase on the filter relates
to its diffraction intensity and is independent of the filter loading in the
sense that this parameter is determined from silver diffraction line measure-
ments. Quantitation is achieved from measurement of 1^. (intensity of diffrac-
tion line i of phase j), I^g (diffraction intensity of the silver line before
loading), and I°Ag (diffraction of the silver line after loading).
Continuing this mode of sample preparation analyses and by use of
reference components to aid in pattern identification and quantitatlon, the
XRD analyses have proven far more useful in identifying compounds in the oil-
fired fly ash samples. An important aspect of the XRD work is the building of
a set of XRD reference patterns of known compounds and compound mixes. In
this regard it has been found important to check each reference'substance to
ensure that it is in the proper crystalline and hydration state. Many pure
compounds, at least structurally are not as indicated on the bottle label.
Lesser efforts have been expended thus far on the coal fly ash
samples. Microscopically these appear to be largely glassy, noncrystalline
particles and this is pretty well confirmed by their XRD pattern structures
as compared to synthetic standards. The synthetic standards were made from
Pyrex glass as a diluent or amorphous phase and quartz, mullite, magnetite,
hematite, calcite, orthoclose (feldspar), and gypsum as crystalline phases.
The minerals were made up at 5, 10, and 25 percent concentrations in the
diluent. The results were far from satisfactory due primarily to the impurity
of the minerals used to make the synthetic standards. The experiment was
repeated in part using an assayed Alabama sea sand for quartz and chemical pure
Fe203. Patterns derived from these were more typical of those which appeared
in the coal fly ash sample pattern structures. Overall the XRD experimental
work confirmed that the crystalline components in the coal-fired fly ashes
are low in concentrations. Subsequent work is being continued to quantify
these ashes by using chemically pure metal oxides and sulfates as reference
standards. The crystalline phases definitely identified so far are a-quartz
Fe203, CaSOij, and MgO plus large patterns indicating the presence of large
amorphous structures.
Infrared Spectroscopy
The frequency accuracy of Fourier Transform Infrared (FT-IR) and
the capability of the FT-IR computer to subtract spectra combined with the
use of known reference compounds provide good possibilities of identifica-
tion of specific inorganic compounds in the fly ash samples. Most efforts
have been on the sulfate components of oil-fired fly ash samples. The pro-
cedure utilizes the storage capacity of the FTS-14 unit which can handle
^20 low resolution files. This storage capacity is not adequate for the
-------
many compound possibilities encompassed in the fly ash samples but is
sufficiently good to develop the methodology. The acquisition of a new
FTS-10 has been made and this new unit with its greater resolution, unlimited
storage capability, and capacity to work in the far IR region will make it
possible to catalog a large library of reference spectra in various hydra-
tion states.
Spectra were obtained on several of the reference sulfates poten-
tially present in the samples and these were compared with spectra obtained
on the oil fly ash samples. For example, it appeared possible that MgSO^
would be present in oil fly ash No. 1 (per Table 19, MgS04-H20, ^26.8 percent),
so the spectra of No. 1 and MgS(\ were subtracted. This provided added
evidence that MgSO^ was present in No. 1 because MgSO^ could be subtracted
out without seeing many negative absortpion bands. (Negative absorption
bands would appear if the sample did not have bands of the same shape and
frequency as the MgSO^ reference spectrum.) The subtraction simplified the
remaining sample spectrum permitting the determination that CaSO^ also was
present (see Table 19, CaS04 ^2%). Subtraction of CaSOij showed that other
sulfates were also present.
One problem immediately recognized was the the hydration state of
the sample and the reference compound need to be the same in order to suc-
cessfully identify specific inorganic compounds. As a check on this, several
reference compounds were heated nearly to their decomposition states, stored
in a vacuum desiccator, and then were run with as little exposure to air as
possible. Spectra from these were compared with spectra obtained after
allowing the dried references compound stand in air for a short period. In
every case splitting seen in the "dry" samples were not observed in the "wet"
(atmosphere-exposed) samples. For instance, the 1150 cm'1 band in NiSCV
6H20 was lost after 30 minutes exposure in air which shows that the hydra-
tion state can be critically important in identification of specific com-
pounds. Since broad bands (little splitting) are observed in the spectra of
the fly ash samples, it is highly useful that they be dried. Attempts were
made to recrystallize reference compound in an endeavor to ensure that the
entire compound was in a single hydration state. However, the results from
this (recrystallization from H20) were similar to the effect from samples
exposed to moisture—i.e., splitting of the IR bands were lost.
Unfractionated Sample Examinations—
Initially four oil-fired fly ash samples and a synthetic fly
ash (containing a number of mixed sulfates with various hydration states)
were examined. With the capacity of the FT-IR computer to subtract spectra
and with reference compounds and the synthetic ash, listed in Table 21,
several sulfates were identified. These were:
45
-------
TABLE 21. REFERENCE COMPCUND AND MIXTURE USED
FOR FTIR ANALYSES
Reference Percent of Total
Material Synthetic Ash
MgSOi+'7H20
MgO
MgSO,
VIVOS(V3H20
VV205
Ni^I03.6H20
NiS04'6H20
FeIIIS01+-7H20
20
10
5
20
10
1
1
1
1
Reference Percent of Total
Material Synthetic Ash
CaSCV2H20
CaO
Al2(SOi+)3-18H20
A1203
Graphite
Total Synthetic
Mixture
1
1
2
1
26
100
46
-------
Synthetic Mixture - FeIIIS01+- 7H20; CaSO(+'2H20; MgSOi+j
Fly Ash No. 1 - FeIIIS04- 7H20; CaSO^ 2H20;
Fly Ash No. 2 - FeIIISOtt- 7H20 possibly; MgSO^ possibly;
VOSOi+<3H20 possibly; an unidentified band
Fly Ash No. 4 - FeIIISOi4- 7H20 possibly, CaSOi+'2H20; and
unidentified band - possibly 7(30^)2 or
VOSOtf
Fly Ash No. 5 - FeIIISOi+- 7H20 possibly; MgSOit possibly;
VOSO[+-3H20 possibly; a large unidentified
band.
As listed above there is an unknown sulfate present in the Nos. 2,
4, and 5 samples which has (among others) absorption bands near 990 and 1050
cm"1. The unknown closely resembles the reference spectrum of the VOSOi^'
3H20 except for the 990 and 1050 cm"1 bands. The intensities of the unknown
roughly follows the known vanadium concentrations in Samples 2, 4, and 5
and was not seen in the No.l sample in which the vanadium concentration is
low. The spectra of the unknown and the spectrum of the VOSO^'SI^O are the
only sulfates showing a band at 490 cm"1.
A sample of vanadium sulfate (ICN Pharmaceuticals) was obtained
and its spectrum run and stored in the computer memory. This spectrum
shows bands at 990 and 1050 cm"1 which were seen in the Nos. 2, 4, and 5
samples. However, its spectrum shows a complex splitting in the 600 to
700 cm"1 region and shows an abnormally high ratio of the intensities of
the 990 and 1050 cm"1 bands to the intensities of the S-0 vibrations near
1100 cm"1. This may be due to a mixture of hydrated forms. This complex
splitting and the intensity ratio change is not seen in the fly ash samples
and makes computer subtraction difficult.
Computer subtractions were made of the synthetic mixture (see
Table 21. Infrared bands were seen which indicated the presence of MgSO^
(or hydrates). A spectrum of MgSO^ was subtracted from the spectrum of the
synthetic mixture. This simplified the resultant spectrum in the 1100 cm"1
region so that Fe2 (8(^)3 was detected. Succeedingly by subtraction, CaSO^ and
VOSO^ also were detected and subtracted from the spectrum of the mixture
and at this point the resultant spectrum was nearly a straight line. The
Al2SOtf*18H20 and NiSOi+'St^O, possibly present in the mixture in low concen-
tractions, were not detected. This work on the synthetic mixture showed that
computer subtractions could successfully identify inorganic sulfate when
appropriate reference compounds are available.
Because of the problems in obtaining the appropriate vanadium
sulfate or oxysulfate reference compound, computer subtractions of the fly
ash samples Nos. 2, 4, and 5 have not worked well. As discussed above for
fly ash No.1 (which contains low vanadium as indicated by the water soluble
47
-------
determination), MgSOi^ was subtracted successfully permitting the identifi-
cation of Fe2(SOt+)3 in th£ resultant spectrum. The presence of CaSO^ is indi-
cated by a band in the 670 cm"1 region but after subtracting the spectra
of MgSOt,. and Fe2(S04)3, the 1100 cnT1 causing broadening of the bands. Since
the computer subtraction worked well for the synthetic mixture and not as
well for the fly ash samples, the probl?m may be due to the presence of
mixed cation sulfates.
Water Soluble Fractions IR Examination--
Spectra were obtained on the vater soluble fractions of the oil-
fired fly ash samples Nos. 1, 2, 4, and 5 in the hope of gaining increased
detection and some simplification of spactra. These fractions were dried
and baked under argon at 350 C. In eaci case the spectrum of the water
soluble portion was better defined (mor2 splitting) in the 1100 cm"1 region
and in the 650 cm"1 region. It appeared as if broad underlying absorptions
were removed. This better definition wis most pronounced for the No. 1
sample.
The spectra obtained on these water soluble extracts, dried,
heated under argon and presumably in the same hydration state after mathe-
matical subtraction against stored reference spectra showed:
(a) Oil-fired fly ash No.l showed a predominance of
MgSOi^ anhydrous and lesser amounts of CaSO^. Much
improved subtraction matches were obtained indi-
cating that the MgSO^ had been in a hydration state other
than the stored MgSO^^l^O or anhydrous MgSOi^. Sub-
traction of the MgSC\ component left a 670 cm"1 and
a 1170 cm"1 band of CaSOf. Na2SO,+ and FeS04 previously
seen were not confirmed nor was the positive presence
of VOSO^ although there were indications of its
presence. (MgSOi^, Fe2(S04)3, and CaSO had been detected
in the unfractionated samples in previous IR runs.)
(b) Oil-fired fly ash No.2 did not show a predominance
of any one component, nor was a good matched obtained
to the stored reference spectra which suggest the
presence of mixed cation sulfates, discussed later.
VOS04, V^O^, MgS04, CaSO^, and NiSOtf all are
possibly present in this treated water soluble fraction.
(MgSOij, FeSOi,, VOSOI+, and an unidentified sulfate band
had been detected in the total sample.)
(c) The treated water soluble fraction of oil-fired fly ash
No.4 showed some changes over the untreated.sample
fraction as evidenced by the loss of a few bands. The
major change was a sharpening of the 1200 to 1100 cm"1
region into one intense L160 cm"1 band. Subtractions
yielded a band at 870 cm"1 of moderate intensity and
a weak 1400 cm"1 both of which are present in the un-
fractionated No. 6 sample but not as yet identified.
48
-------
Based on chemical analyses similarities, an ammonium
sulfate is suggested for the No. 4 and No. 6 samples.
The No. 4 treated water soluble fraction has a large
amount of V(S04)2 plus MgS04 and NiS<\. The V(SO[+)2
spectra in the treated No. 4 are similar to VOSO^ so
it could be present at least in minor quantities.
(d) The treated water soluble No. 5 fraction showed changes
from the nonheated fraction notably showing sharper
absorption bands and fewer bands indicating the proba-
bility of having a greater percentage of the sample in
a single hydration state. The sample had a large amount
of VOSOtf. Subtracting this from the spectrum, although
the subtraction was not perfect, it was possible to
identify the presence of MgSCV 7H20 and NiSOLf-6H20.
(Prior work on the unfractionated sample had shown the
presence of VOSO^-Sl^O, Fe2 (SO^) 3'7H20, MgSOi+j and an
unidentified sulfate band.)
Total Sample IR Examination of
No. 6 Oil Fly Ash-
Oil fly ash No. 6 was examined by IR. From comparison with
reference spectra and literature spectra, it was possible to identify:
• A predominant component indicated by a very sharp
band at 1400 cur1 of NHlfHS02 — this is in agreement
with analyzed chemical data, although the possi-
bility of (NH[t)2SOi+ or a mixture of the two salts
exists. Minor components of MgSO^, NiSOi^, and
were identified.
No work has been done on the water soluble fraction of No. 6.
Mixed Sulfates IR Experiments —
The soluble fraction of sample No. 2 did not show a predominance
of any one component suggesting a possibility that mixed sulfates may form
when several sulfates are dissolved together, taken to dryness and baked.
This was noticeable in the No. 2 sample spectrum where there seem to be some
sort of interaction occurring among the various components making it diffi-
cult to sort out and assign absorption bands". It is thought that a mixed
sulfate could form if for example a magnesium cation were to displace a
vanadium cation in the vanadium salt lattice on dissolution, evaporation
to dryness and heating. Such a mixed sulfate, if formed, would be expected
to display a spectrum different from either of the parent sulfates due to
lattice changes. To investigate this a mixture of 46 percent VOSO^'SI^O,
41 percent MgSOi4*7H20, and 13 percent NiS04-6H20 was prepared and divided
into five portions.
Four of the portions were taken up in solution after which they
were recovered simply by evaporating the water off. The fifth portion was
49
-------
examined spectroscopically as just the physical mix of the sulfates to
serve as a comparison with the dissolved samples. The four recovered
samples were treated as follows:
• The first was simply air dried
• The second was baked overnight at 80 C in air
• The third was baked overnight at 120 C under argon
• The fourth was baked overnight at 350 C under argon.
The samples were then run in the usual KBr pellet fashion, and
then all five were compared to each other and to a computer generated
synthetic spectra derived from previously stored reference spectra.
Figures 2 and 3 show the spectra of the five fractions and also
the computer generated spectrum. Figure 4 illustrates the stored reference
spectrum of NiSOi+'6H20, VOS04'5H20, and MgSO[+-7H20. From these spectra,
the following may be deduced:
(1) Allowing for the fact that the stored reference
spectra of MgS01+-7H20, NiSOtf'6H20, and VOSO^ do not
exactly match the actual MgSOi+«7H20, NiSOi+'6H20,
and VOSOi+'SI^O used in this study, it seems that
the physical mixture of the sulfates, before they
were dissolved, matches fairly well with the com-
puter generated spectra. This is of course not at
all surprising.
(2) In Figure 2, the spectra of the mixture of sulfates
recovered from solution is quite different from that
of the sulfates before they were dissolved.
(3) There are some minor differences in band intensity
between the unbaked sample and that baked at 80 C
overnight, but there is virtually no difference at
all between the samples baked at 80, 120, and 350 C.
(The difference in ratio of the 1100 to 1200 cnr1
band in the 120 C sample spectra is a computer
artifact.
(4) The difference between the baked and unbaked samples
seems to be primarily a sharpening of the bands in
the baked samples. Thus, it is useful to bake the
samples to sharpen the bands and also to help achieve
a reproducible hydration state.
(5) The amazing similarity between the three baked spectra
illustrates two important points:
(a) Once the water has been driven off, no further
changes occur in the sulfate lattice
50
-------
A- Computer generated spectrum
B- Mixture before solution
C- Mixture after solution but
no baking
2000 1600
Frequency, cm1
1200
800
FIGURE 2. SPECTRA OF COMPUTER GENERATED SPECTRUM (A), MIXTURE
BEFORE SOLUTION (B), AND MIXTURE AFTER SOLUTION
AND AIR DRIED (C).
51
-------
A- Mixture baked at 80 C
B - Mixture baked at 120 C
C - Mixture baked at 350 C
2000
yw v
s \ 1 1
D 1600 1200
1
800
Frequency, cm
-i
FIGURE 3. SPECTRA OF MIXTURES DISSOLVED, DRIED AND BAKED
AT 80 C (A), AT 120 C (B), AND 350 C (C)
52
-------
A-VOS04 baked at 350 C
B-MgS04-7H20
C-NiSCU .6H20
2000 1600 1200 600
Frequency, cm"'
FIGURE 4. STORED REFERENCE SPECTRA
53
-------
(b) The sample handling technique, including the
manufacture of our KBr pellets, seems to be
quite reproducible.
In spite of the major changes which occur upon dissolution of a
mixture of sulfates, it is still felt that the major components can be
accurately identified assuming the appropriate precautions are taken. One
factor which helps identification of components is that, while the sulfate
bands in the spectra of a dissolved mixture of sulfates broaden, they do
not completely disappear, nor do new bands appear. This factor, coupled
with having the proper reference spectra in the proper hydration state on
file, should allow, through spectra subtraction, the identification of the
unknown sulfate(s). Also running the ash sample before the soluble frac-
tion is extracted (as was done on oil ash No. 6) gives a before and after
solution spectra for comparison purposes. Computer generated spectra are
still of great value in spectral matching; however, it will probably be
advisable to start running synthetic mixtures in the future for those
samples demonstrating more than one sulfate in major proportions. Running
synthetic mxitures which had been dissolved would be advisable for the
following reason: Even if reference spectra are available before and after
solution and baking, it is not expected that the large degree of broadening
of the sulfate band between 1000 and 1200 cm""1 in these reference spectra
will be seen. It is believed that the sulfate broadening is due to the
mixed sulfates discussed previously.
The effect of having various cations in the sulfate's lattice is
to "smear" energy levels and thus broaden existing bands. The only way to
accurately duplicate the spectrum of a mixed sulfate is to prepare a syn-
thetic mixture and dissolve it so that smearing of the sulfate bands occurs
Preparation of these synthetic mixed sulfates should not be required for
the identification of the two or perhaps three major components in an
unknown, but the detection of minor components will only be possible if
reference spectra of this nature are available to perform subtractions
with. It is appropriate to emphasize at this point that this mixed sulfate
phenomena will only be a problem when more than one sulfate is present in
large amounts in the unknown sample. To date only fly ash No. 2 has presented
this difficulty. To summarize, one needs to be aware that spectral changes
of fair magnitude do occur upon the dissolution of a mix of sulfates con-
taining more than one predominant component, presumably due to band broaden-
ing caused by the formation of a mixed sulfate. Baking the recovered
sample is advisable, and the identification of minor components by FT-IR
will require the actual preparation of synthetic mixed sulfates which could
then be mathematically manipulated by the computer. In general, the FT-IR
has indicated that examination of a fly ash should include a spectrum before
water extraction, after water extraction, and after water extraction and
baking under argon at 350 C.
54
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Preliminary Evaluation of Calculated
Equilibrium Fly Ash Compositions
A preliminary evaluation was made of the usefulness of equili-
brium thermodynamic calculations for predicting the composition of fly ash
from a particular fuel. For this evaluation a comparison was made of
previous calculations for a "typical" No. 6 fuel oil (Kircher, et al.,
EPA-600/7-77-041) with analyses of oil-fired fly ashes Nos. 1, 2, and 4
(Table 19).
To make the desired comparisons, some assumptions were required.
Since the thermodynamic calculations were based on equilibrium, there
would be no unburned carbon in the presence of excess air or oxygen. How-
ever, in real fly ash there is always carbon present and it can be large
fraction of the fly ash. Since the carbon is essentially inert, it was
subtracted from the fly ash analysis and the distribution of metal oxides
and sulfates recalculated on a mole percent basis.
The analyzed fly ashes have large amounts of MgO and MgSO because
additives were used for corrosion control in the combustion systems from
which samples were obtained. The calculated fly ash compositions did not
assume any additive. In order to compare the calculated and measured values
it was assumed that 95 percent of the Mg in the actual fly ash samples re-
sulted from the additive and this was subtracted from the sample analyses
so they could be compared more directly with the thermodynamic calculations.
The measured data for No. 6 fuel oil fired fly ash are based on
oil fired fly ash samples Nos. 1, 2, and 4 (Table 19). A range is indicated
in the accompanying Table 22 for the minimum and maximum reported concentra-
tion for the three samples. The reported values for VzOs and VOSOt* have
been summed since VOSCH was not included in the thermodynamic calculations
so results can only be compared on the basis of total vanadium. Also, several
oxides, e.g., NiO, were calculated to be below analytical detection limits
but in fact were observed. Such differences are to be expected, however,
since the actual fuel ash compositions are not well known and are undoubtedly
different from the composition assumed in the calculations.
Recognizing the fuel compositions are different, the agreement
between calculated and measured values is about as good as one could expect.
The larger relative amounts of iron and silicon in the calculated fly ash,
for instance, could simply reflect the difference between assumed "typical"
fuel and that actually used in the tests. It must also be remembered that
the amount of Mg additive assumed and corrected for was completely arbitrary.
If the calculations had been based on the actual fuel composition, the
results would very likely have shown much better agreement.
Further comparisons of this type are not warranted at this time
because of the differences in fuel compositions. However, since the pre-
liminary results are promising, the calculations should be redone using
known fuel compositions Nos. 2, 4, 5, and 6. The predicted calculations
using the known fuel compositions could aid the analytical efforts by
55
-------
identifying low concentration species which could be observed and also by
confirming the possible existence of unexpected but observed species.
(Note: It is anticipated that the high concentration components can be
obtained directly using the developed methodologies.) An end result might
be predictions of trace metal compositions from the fuel compositions.
TABLE 22. COMPARISON OF CALCULATED AND MEASURED
FLY ASH COMPOSITIONS
Calculated
Si02
A1203
A12(S04) 3
Fe,0,
2 3
FeSOtt
V2°5
VOSO^
MgO
MgSO^
NiO
NiSO^
Na2SO[|
CaO
CaS04
CoSO^
Cr.O,
Ti02
31.
12.
11.
6.
11.
11.
—
8
8
2
4
2
4
—
0*
4.
2
0*
3.
2.
0*
1.
0.
0.
0.
4
7
5
8
5
5
Measured
1.2 - 1.9
0.8 - 4.5
0.7 - 10.4
0.8 - 1.5
1.3 - 3.3
- 15 - 73
0.2 - 3.7
1.4 - 3.8
0.8 - 2.8
7.3 - 8.6
4.1 - 39.3
0.1 - 1.8
0.7 - 6.5
- 1.6 - 4.2**
* Less than 0.03
** Other sulfates and oxides
56
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(61) Ramsden, A. R., "Application of Electron Microscopy to the Study of
Pulverized-Coal Combustion and Fly-Ash Formation", J. Inst. Fuel, 451,
(December 1968).
(62) DeNee, P. B., "Mine Dust Characterization Using the Scanning Electron
Microscope", Am. Indust. Hyg. Assoc. J., (October 1972).
60
-------
(63) Fisher, G. L., Chang, D.P.Y., Brummer, M., "Fly Ash Collected from
Electrostatic Precipitators: Microcrystalline Structures and the
Mystery of the Spheres", Science, 192, (May 7, 1976), 553-555.
(64) Ferguson, J. S., Sheridan, E. G., "Some Applications of Microscopy
to Air Pollution", J. Air Pollution Control Assoc., 11, 12, (December
1966), 669-672.
(65) Yakowitz, H., Jacobs, M. H., Hunneyball, P. D., "Analysis of Urban
Particulates by Means of Combined Electron Microscopy and X-Ray
Microanalysis", Micron, J3, (1972), 498-505.
(66) Bolton, N. E., Fulkerson, W., et al., "Trace Element Measurements at
the Coal-Fired Allen Steam Plant", Progress Report, (June 1974),
Contract W-7405-eng-26, Report No. ORNL-NSF-EP-62.
(67) Fisher, G. L., et al., "Physical and Morphological Studies of Size-
Classified Coal Fly Ash", Environ. Sci. and Tech., JL2, 4, (April 1978)
447-451.
(68) Linton, R. W., Loh, A., Natusch, D.F.S., "Surface Predominance of Trace
Elements in Airborne Particles", Science, 191, (February 27, 1976),
852-854.
(69) Craig, N. L., Harker, A. B., and Novakov, T., "Determination of the
Chemical States of Sulfur in Ambient Pollution Aerosols by X-Ray Photo-
electron Spectroscopy", Atmos. Environ., _8_, (1974), 15-21.
(70) Dod, R. L., Chang, S. G., and Novakov, T., "Ammonium and Sulfate Species
in Atmospheric Aerosols", Lawrence Berkeley Laboratory, Annual Report
LBL-5214, (1975-76).
(71) Novakov, T., Chang, S. G., Harker, A. B., "Sulfates as Pollution Parti-
culates: Catalytic Formation on Carbon (Soot) Particles", Science, 186,
(1974), 259-261.
(72) Appel, B. R., Wesolowski, J. J., Hoffer, E., Twiss, S., Wall, S. , Chang,
S. G., and Novakov, T., "An Intermethod Comparison of X-Ray Photoelectron,
Spectroscopic (ESCA) Analysis of Atmospheric Particulate Matter", Intern.
J. Anal. Chem., _4, (1976), 169-181.
(73) Grieger, G. R., "Electron Spectroscopy for Chemical Analysis of Airborne
Particulates", American Laboratory, (April 1976), 77-81.
(74) Chang, S. G. Novakov, T., "Formation of Pollution Particulate Nitrogen
Compounds by NO-Soot and NH3~Soot Gas-Particle Surface Reactions", Atmos.
Environ., j>, (1975), 495-504.
(75) Novakov, T., "Chemical Characterization of Atmospheric Pollution Parti-
culates by Photoelectron Spectroscopy", (1973), ISA JSP 6693.
(76) Karasek, F. W., "Surface Analysis by ISS and ESCA", Research/Development,
(January 1973), 25-30.
61
-------
(77) Novakov, T., Dod, R. L., and Chang, S. G., "Study of Air Pollution
Particulates by X-Ray Photoelectron Spectroscopy", Lawrence Berkeley
Laboratory Report No. LBL-5217, (June 1976); submitted to Zeitschrift
fur analytische Chemie.
(78) Novakov, T., Chang, S. G., Dod, R. L., and Rosen, H., "Chemical Charac-
terization of Aerosol Species Produced in Heterogeneous Gas-Particle
Reactions", Lawrence Berkeley Laboratory Report No. LBL-5215, (June 1976),
Presented at the Air Pollution Control Assoc. Annual Meeting, Portland,
Oregon, June 27-July 1, 1976.
(79) Lockmuller, C. H., "Report on Techniques for Characterization of Inorganic
Compounds", private communication, (August 1976).
(80) McAlister, A. J., "Evaluation of the ESCA Technique for Characterization
of St. Louis Particulate Matter", private communication, (1976).
(81) Steger, H. F., "Chemical Phase Analysis of Ores and Rocks", Talanta, 23,
(1976), 81-87.
(82) Leahy, D., Siegel, R., Klotz, P., Newman, L., "The Separation and Charac-
terization of Sulfate Aerosol", Atmos., Environ., £, (1975), 219-229.
(83) Barton, S. C., McCadie, H. G., "A Specific Method for the Automatic
Determination of Ambient I^SOi^ Aerosol", Proc. 2nd Clean Air Congress,
Washington, D.C., pp 379-382 (1970).
(84) Shafer, H.N.S., "An Improved Spectrophotometric Method for the Deter-
mination of Sulfate with Barium Chloranilate as Applied to Coal Ash and
Related Materials", Anal. Chem., _39, 14, (1967), 1719-1726.
(85) Scaringelli, P., Rehme, K., "Determination of Atmospheric Concentrations
of Sulfuric Aerosol by Spectrophotometry, Coulometry, and Flame Photometry",
Anal. Chem., 41, 6, (1969), 707-713.
(86) Maddalone, R. F., Thomas, R. L., West, P. W., "Measurement of Sulfuric
Acid Aerosol and Total Sulfate Content of Ambient Air", Environ. Sci. and
Tech., 10, 2, (1976), 162-168).
(87) Shcherbakova, S. A., Mel'chakova, N. V., Peshkova, V. M., "Determination
of Vanadium (V) and Vanadium (IV) in Each Other's Presence", J. Anal.
Chem. of USSR, _31, 2, Part 2, (1976) 271-273.
(88) Rao, G. G., Rao, P. K., "Potentiometric Titration of V Alone and in
Mixture with VIV", Talanta, 13, (1966), 1335-1340.
(89) Grosjean, D., "Solvent Extraction and Organic Carbon Determination in
Atmospheric Particulate Matter — Thu OE-OCA Technique", Anal. Chem.,
47, 6, (1975), 797-805.
(90) Appel, B. R., Colodny, P., Wesolowski, J. J., "Analysis of Carbonaceous
Materials in Southern California Atmospheric Aerosols", Environ. Sci.'&
Tech., 10, 4, (1976), 359-363.
62
-------
(91) Mueller, P. K., Mosley, R. W., Pierce, L. B., "Chemical Composition of
Pasedena Aerosol by Particle Size and Time of Day - Carbonate and Non-
carbonate Carbon Content", J. Colloid & Interface Sci. , 39, 1, (1972).
(92) Sant, B. R., Prasant, T. B., "Determination of Metallic Iron, Iron II,
and Iron III Oxides in a Mixture", Talanta, _15_, (1968), 1483-1486.
(93) Brimblecombe, P. , Spedding, D. J., "The Dissolution of Iron from Ferric
Oxide and Pulverized Fuel Ash", Atmos, Environ., 9^, (1975), 835-838.
(94) Abell, M. T., Carlberg, J. R., "A Simple Reliable Method for the Deter-
mination of Airborne Hexavalent Chromium", Am. Ind. Hyg. Assoc. J., 35,
4, (1974), 229-233.
(95) Young, R. S., "Determination of Calcium Oxide in Calcined Phosphate
Ores", Talanta, 2Q, (1973), 891-892.
(96) Konopicky, K., Kohler, E., "Determination of the Mineral and Glass
Content of Ceramic Materials, Ber. Deut. Keram. Ges., 35, 6, (1968),
187-193.
(97) Anderson, P. L., "Free Silica Analysis of Environmental Samples - A
Critical Literature Review", Am. Ind. Hyg. J., (1975), 767-778.
(98) Wagman, J., Bennett, R., Knapp, K. T., "X-Ray Fluorescence Multi-
spectrometer Analysis for Rapid Elemental Analysis of Particulate
Pollutants", EPA-600/2-76-033 (March 1976).
(99) Wagman, J., Bennett, R., Knapp, K. T., "Simultaneous Multiwavelength
Spectrometer for Rapid Elemental Analysis of Particulate Pollutants
in X-Ray Fluorescence Analysis of Environmental Samples", Ann Arbor
Science Publishers, Inc., Ann Arbor, Michigan (1977).
(100) Gilfrich, J., Pickerar, M. , Birks, L., "Valence States of Sulfur In
Pollution Samples by X-Ray Analysis' EPA 600/2-2-76-265 (October 1976).
(101) Uruch, D. S., Wood, P. R., "The Determination of the Valency of
Manganese in Minerals by XRF Spectroscopy", 7_, No. 1, (1978), pp 9-11.
(102) Yasuda, S., Kakiyama, "X-Ray K Emission Spectra of Vanadium in Various
Oxidation States", Ibid, pp 24-25.
(103) Paris, B., "Direct Determination of Organic Sulfur in Raw Coals"
Reprint from ACS Symposium Series 64, Coal Desulfurization, T. D.
Wheelcock, Editor, (1977).
(104) Knapp, K. T., Conner, W. D., and Bennett, R. L., "Physical Characteriza-
tion of Particulate Emissions From Oil-fired Power Plants", In Proceed-
ings of the 4th National Conference on Energy and the Environment,
A.I.Ch.E., Dayton, Ohio, 1976, pp 495-500.
(105) Bennett, R. L., and Knapp, K. T., "Chemical Characterization of Particu-
late Emissions From Oil-Fired Powor Plants", In Proceedings of 4th National
Conference on Energy and the Environment, A.I.Ch.E., Dayton, Ohio, 1976,
pp 501-506.
63
-------
(106) Bennett, R. L., and Knapp, K. T., "Particulate Sulfur and Trace Metal
Emissions From Oil-Fired Power Plants", Presented at the 70th Annual
A.I.Ch.E. Meeting (To be published in A.E.Ch.E. Air Symposium Series).
(107) Flegal, C. A., et al., Technical Manual for Process Measurement of
Trace Inorganic Materials, TRW Document No. 244446-6017-RU-OO prepared
for EPA, Contract No. 68-02-1392 (July 1975).
(108) Compendium of Analytical Methods", Vol. II - Method Summaries, Mitre
Corporation, PB 288-425 (April 1973).
(109) Ray, S. S., and Parker, F. G., "Characterization of Ash from Coal-
Fired Power Plants, prepared for EPA, PB-265-374 (January 1977).
(110) Magee, E. M., et al., "Potential Pollutants in Fossil Fuels", prepared
for EPA, PB-225-039 (June 1973).
(Ill) Leahy, D., Siegel, R., Klotz, P., Newman, L., "The Separation and Charac-
terization of Sulfate Aerosol", Atmos. Environ., _9, 219-229, (1975).
(112) Tanner, R. L., et al., "Separation and Analysis of Aerosol Sulfate
Species at Ambient Concentrations", BNL Report 21879R, in press, Atmos.
Environ. (1977).
(113) Barrett, W. J., et al., "Development of a Portable Device to Collect
Sulfuric Acid Aerosol", Interim Report, EPA-600/2-77-027 (February 1976).
64
-------
APPENDIX A
COMPOSITIONS OF CRUDES FROM VARIOUS ORIGINS
Tables A-l through A-5 are taken from Tables 13, 14, 17,
18, and 19, respectively, of Report PB-225-039 prepared by Magee,
Hall, and Varga of Esso Research and Engineering Company for the U.S.
Environmental Protection Agency.
-------
TABLE A-l
SULFUR AND NITROGEN CONTENT
OF THE GIANT U.S. OIL FIELDS
__ State/Region and Field
ALABAMA
Citronelle
ALASKA
Granite Point
McArthur River
Middle Ground Shoal
Prudhoe Bay (North Slope)
Swanson River
APPALACHIAN
Allegany
Bradford
ARKANSAS
Magnolia
Schuler and East
Smackovcr
CALIFORNIA
SAN JOAQU7N VALLETf
Belridge South
Buena Vista
Coalinga
Coalinga Nose
Coles Levee North
Cuyama South
Cymric
Ediscm
Elk Hills
Fruitvale
Greeley
Kern Front
Kern River
Kettleman North Dome
Lost Hills
McKittrick - Main Area
Midway Sunset
Mount Poso
Rio bravo
COASTAL AREA
Carpenterin Offshore
Cat Canyon West
Dos Cuadras
Elwood
Sulfur,
Weight
Percent
0.38
0.02
0.16
0.05
1.07
0.16
0.12
0.11
0.90
1.55
2.10
5.07
Nitrogen,
Weight
Percent
0.02
0.039
0.160
0.119
0.23
0.203
0.028
0.010
0.02
0.112
0.08
0.23
0.59
0.43
0.25
0.39
0.42
1.16
0.20
0.68
0.93
0.31
0.85
1.19
0.40
0.33
0.96
0.94
0.68
0.35
0..773
' —
0.303
0.194
0.309
0.337
0.63
& ."446
0.472
0.527
0.266
0.676
0.604
0.212
0.094
0.67
0.42
0.475
0.158
0.54
* Oil and Gas Journal, January 31, 1972 pp. 95-100.
1971
Production
(Thousands
of Barrels)*
6,390
5,552
40,683
11,277
1,076
11,709
388
2,470
850
800
2,800
9,211
5,429
7,866
4,752
1,006
2,034
3,345
1,417
951
1,109
761
3,440
25,542
840
2,328
5,348
33,583
1,378
425
5,295
2,705
27,739
108
65
-------
TABLE A-l (Cont'd)
State/Region and___Field_
Orcutt
Rincon
San Ardo
Santa Ynez**
Santa Maria Valley
South Mountain
Ventura
LOS ANGELES BASIN
Beverly Hills
Brea Olinda
Coyote East
Coyote West
Domlnguez
HunLington Beach
Inglewood
Long Beach
Montebello
Richfield •
Santa Fe Springs
Seal Beach
Torrance
Wilmington
COLORADO
Rangely
FLORIDA
Jay
ILLINOIS
Clay City-
Dale
Loudon
New Harmony
Salem
KANSAS
Bemis-Shutts
Chase-Silica
Eldorado
Hall-Gurney
Kraft-Prusa
Trapp
LOUISIANA
NORTH
Black Lake
Caddo-Pine Island
Delhi
Haynesvillc (Ark.-La.)
Homer
Lake St. John
Rodcssn (La.-Tex.)
Sulfur,
Weight
Percent
2.48
0.40
2.25
4.99
2.79
0.94
2.45
0.75
0.95
0.82
0.40
1.57
2.50
1.29
0.68
1.86
0.33
0.55
1.84
1.44
0.56
0.32
0.19
0.15
'0.27
0.23
0.17
0.57
0.44
0.18
0.34
0.27
0.41
0.37
0.82
0.66
0.83
0.17
Q.46
Nitrogen,
Weight
Percent
0.525
0.48
0.913
0.56
—
0.413
0.612
0.525
0.336
0.347
0.360
0.648
0.640
0.55
0.316
0.575
0.271
0.394
0.555
0.65
0.073
0.002
0.082
0.080
0.097
0.158
0 . 102
0.162
0.13
0.085
0.108
0.171
0.076
0.026
0.053
0.022
0.081
--
0.032
1971
Production
(Thousands
of Barrels)*
2,173
4,580
9,939
1,966
1,962
10,188
8,400
4,228
864
2,436
1,717
16,249
3,992
3,183
740
1,910
953
1,468
1,338
72,859
10,040
.370
4,650
690
4,420
2,740
3,360
2,590
1,600
1,500
2,480
3,200
1,930
3,500
5,870
2,730
330
1,170
900
* Oil and Gas Journal, January 31, 1972, pp. 95-100.
**
Undeveloped field, Santa Barbara Channel. Uncorroborated
estimate of reserves of 1 to 3 billion bbl.
66
-------
State/Rcp.iog and Field
OFFSHORE
Bay Marchancl Block 2
(Incl. onshore)
Euftcne Island Block 126
Grand Isle Block 16
Grand Isle Block 43
Grand Isle Block 47
Main Pass Block 35
Main Pass Block 43.
Main Pass Block 69
Ship Shoal Block 208
South Pass Block 24
(Incl. onshore)
South Pass Block 27
Timhalier S. Block 135
Titnbalier Bay
(Incl. onshore)
West Delta Block 30
West Delta Block 73
SOUTH, ONSHORE
Avery Island
Bay DC Chene
• Bay St. Elaine
Bayou Sale
. Black Bay West
Caillou Island
(Incl. offshore)
Cote Blanche Bay West
Cote Blanche Island
Delta Farms
Garden Island Bay
Golden Meadow
Grand Bay
Hackberry East
Hackberry West
Iowa
Jennings
Lafitte
Lake Barre
Lake Pel to
Lake Salvador
Lake Washington
(Incl. offshore)
Lcevillc
Paradis
Quarantine Bay
Romere Pass
Venice
Vinton
Weeks Island
West Bay
TABLE A-l (Cont'd.)
Sulfur, Nitrogen,
Weight Weight
Percent Percent
0.46
0.15
0.18
0.23
0.19
0.16
0.25
0.38
0.26
0.18
0.66
0.33
0.33
0.12
0.27
0.39
0.16
0.19
0.23
0.16
0.10
0.26
0.22
0.18
0.31
0.30
0.29
0.20
0.26
0.30
0.14
0.21
0.14
0.37
0.20
0.23
0.27
0.30
0.24
0.34
0.19
0.27
0.11
0.030
0.04
0.04
0.071
0.025
0.098
0.02
0.068
0.049
0.088
0.081
0.09
0.060
0.04
0.04
0.04
0.033
6.01
0.055
0.06
0.054
0.039
0.02
0.035
0.02
0.146
0.019
0.061
0 .044
0 .071
1971
Production
(Thousands
of Barrels)*
30,806
5,621
21,681
22,776
4,271
3,504
18,469
12,775
10,038
20,330
21,425
13,578
30,988
26,390
15,987
3,400
6,643
7,775
5,293
9,892
31,828
15,658
8,797
1,278
16,096
2,738
6,680
2,226
3,760
876
292
10,877
7,592
4,891
4,380
10,913
4,343
1,898
7,117
3,759
5,475
2,299
10,183
9,563
* Oil and (.'as Journal, January 31, 1972, pp. 95-100.
67
-------
TABLE A-l (Cont'd.)
Stn^e/Reglon and Field
MISSISSIPPI
Baxterville
Heidelberg
Tinsley
MONTANA
Bell Creek .
Cut Bank
NEW MEXICO
Caprock and East
Denton
Empire Abo
Eunice
Hobbs
Maljamar
Monument
Vacuum
NORTH DAKOTA
Beaver Lodge
Tioga
OKLAHOMA
Allen
Avant
Bowlegs
Burbank
Cement
Gushing
Earlsboro
Edmond West
Eola-Robberson
Fitts
Glenn Pool
Golden Trend
Healdton
Hewitt
Little River
Oklahoma City
Seminole, Greater
Sho-Vel-Tum
Sooner Trend
St. Louis
Tonkawa
Sulfur, Nitrogen,
Weight Weight
Percent Percent
2.71
3.75
1.02
0.24
0.80
0.17
0.17
0.27
1.
1.
14
41
0.55
1.14
0.95
0.24
0.31
0.111
0.112
0.08
0.13
0.055
0.034
0.014
0.014
0.071
0.08
0.062
0.071
0.075
0.019
0.016
0.70
0.18
0.24
0.24
0.47
0.22
0.47
0.21
0.35
0.27
0.31
0.15
0.92
0.65
0.28
0.16
0.30
1.18
0.11
0.16
0.21
—
0.140
0.051
0.152
0.08
—
0.045
0.115
~
0.096
0.15
0.15
0.148
0.065
0.079
0.016
0.27
0,04
0.033
1971
Product
(Thousands
of Barrels)*
9,300
3,450
2,450
5,950
5,180
905
2,350
9,520
1,330
5,700
6,040
3,720
17,030
3,140
1,790
2,920
365
2,260
5,240
2,370
4,300
765
730
4,850
1,420
2,480
12,330
4,600
5,660
440
1,750
1,640
36,500
15,240
1,350
290
* Oil and Gas Journal, January 31, 1972, pp. 95-100.
68
-------
TABLE A-l (Cont'd,)
State/Region and Field
TEXAS
DISTRICT 1
Big Wells
Darst Creek
Luling-Branyon
DISTRICT 2
Greta
Refugio
Tom O'Connor
West: Ranch
DISTRICT 3
Anahuac
Barbers Hill
Conroe
Dickison-Gillock
Goose Creek avid East
Hastings E&W
High Island
Hull-Merchant
Humble
Liberty South
Magnet Withers
Old Ocean
Raccoon Bend
Sour Lake
Spindletop
Thompson
Webster
West Columbia
DISTRICT 4
Agva Duke-Stratton
Alazan North
Borregas
Government Wells N.
Kclsey
La Gloria and South
Plymouth
Seeligson
Tijo.rina-Canales-Blucher
White Point East
DISTRICT 5
Mexia
Powell
Van and Van Shallow
Sulfur, Nitrogen,
Weight Weight
Percent Percent
1971
Production
(Thousands
of Barrel.'))*
—
0.78
0.86
0.17
0.11
0.17
0.14
0.23
0.27
0.15
0.82
0.13
0.20
0.26
0.35
0.46
0.14
0.19
0.14
0.19
0.14
0.15
0.25
0.21
0.21
<.l
0.04
<.l
0.22
0.13
<.l
0.15
<.l
<.l
0.13
0.20
0.31
0.8
—
0.075
0.110
0.038
0.027
0.038
0.029
0.041
0.06
0.022
0.014
0.028
0.03
0.048
0.081
0.097
0.044
0.033
0.029
0.048
0.016
'0.03 ,
0.029
0.046
0.055
0-015
0.014
0.029
0.043
0.008
0.008
0.049
0.015
0.010
0.02
0.048
0.054
0.039
5,840
1,971
1,679
3,577
657
23,360
17,009
9,052
766
12,994
2,920
1,095
17,191
2,081
1,643
1,241
949
3,869
1,132
2,409
1,058
328
12,885
16,206
1,351
2,518
3,723
4,818
511
6,059
936
986
6,424
5,986
1,606
109
109
12,337
* Oil and Gas Journal, January 31, 1972, pp. 95-100.
69
-------
TABLE A-l (Cont'd.)
State/Region and Field
DISTRICT 6
East Texas
Fairway
Hawkins
Neches
New Hope
Qui traan
Talco
DISTRICT 7-C
Big Lake
Jameson
McCamey
Pegasus
DISTRICT 8
Andector
Block 31
Cowden North
Cowden South, Foster,
Johnson
Doilarhide
Dora Roberts
Dune
Emma and Triple N
Fuhrman-Mascho
Fullerton
Goldsmith
Headlee and North
Hendrick
Howard Glasscock
latan East
Jordan
Kermit
Keystone
McElroy
Means
Midland Farms
Penwell
Sand Hills
Shatter Lake
TXL
Waddell
Ward South
Ward Estes North
Yates
Sulfur,
Weight
Percent
0.32
0.24
2.19
0.13
0.46
0.92
2.98
0.26
<.l
2.26
0.73
0.22
,0,11
1.89
1.77
0.39
<.l
3.11
<.l
2.06
0.37
1.12
* <.l
1.73
1.92
1.47
1.48
0.94
0.57
2.37
1.75
0.13
1.75
2.06
0.25
0.36
1.69
1.12
1.17
1.54
Nitrogen,
Weight
Percent
0.066
—
0.076
0.083
0.007
0.036
— —
0.071
0.034
0.139
0.200
0.033
0.032
0.095
0.127
0.074
0.023
0.111
0.025
0.085
0.041
0.079
0.083
0.094
0.096
0.120
0.10
0.092
0.042
0.080
0.205
0.080
0.205
0.085
0.041
0.067
0.098
0.08
0.107
0.150
1971
Production
(Thousands
of Barrels)*
71,139
14,271
29,054
3,942
292
3,103
4,380
474
1,387
985
4,052
5,694
6,242
9,782
14,198
7,592
3,066
11,425
3,030
1,935
6,607
20,951
1,460
766
6,606
3,687
3,212
2,007
8,322
9,015
7,921
6,059
2,044
6,606
2,956
4,854
4,453
803
10,184
13,359
* Oil and Gas Journal, January 31, 1972, pp. 95-100.
70
-------
TABLE A-l(Cont'd.)
State/Region and Field
DISTRICT 8-A
Cogdell Area
Diamond M
Kelly-Snyder
Levelland
Prentice
Robertson
Russell
Salt Creek
Seminole
Slaughter
Spraberry Trend
Wasson
DISTRICT 9
KMA
Walnut Bend
DISTRICT 10
Panhandle
UTAH
Greater Aneth
Greater Redwash
WYOMING
Elk Basin (Mont .--Wyo. )
Garland
Grass Creek
Hamilton Dome
Hilicht
Lance Creek
Lost Soldier
Oregon Bauin
Salt Creek
Sulfur,
Weight
Percent
0.38
0.20
0.29
2.12
2.64
1.37
0.77
0.57
1.98
2.09
0.18
1.14
0.31
0.17
Nitrogen,
Weight
Percent
0 .063
0 .131
0 .066
0 .136
0 .117
0 .100
0 .078
0 .094
0 .106
—
0 .173
0 .065
0.068
0.05
0.55
0.20
0.11
0.067
0.059
0.255
1.78
2.99
2.63
3.04
0.10
1.21
3.44
0.23
0.185
0.290
0.311
0.343
0.055
0.076
0.356
0.109
1971
Production
(Thousands
of Barrels)*
14,235
7,373
52,487
9,746
5,913
2,774
4,234
9,271
9,125
35,515
18,688
51,210
2,920
3,942
14,235
7,660
5,800
14,380
3,500
3,760
4,500
11,300
325
4,820
12,260
11,750
* Oil and Gas Journal, January 31, 1972, pp. 95-100.
71
-------
TABLE A-2
TRACK ELEMENT CONTENT OK U.S. CRUDE Qll.S
Trace
St^te and Field
ALABAMA
Toxey
Toxey
ALASKA
Kuparuk, Prudhoe* Buy
Kuparuk, Prud'ioe Bay
KcArthur River, Cook Inlet
Prudhoc Bay
Put River, Prudhoe Bay
Redoubt SI. on I, Cook Inlet
Trading Buy, Cook Inlet
ARKANSAS
BrisUr, Columbia
El Dorado, East
Schuler
Stnackover
Stephens-Smart
Tubal, Union
Weat Atlanta
CALIFORNIA
Ant Hill
Arwln
Bradley Sanda
Cat Canyon
Cat Canyon
Coal Inge r
Coal Oil Canyon
Coles Levee
Coles Levee
Cuyaaa
Cymric
Cymric
Cymric
Cymric
Cymric
Cymric
Edtson
Elk Hills
Elvood South
Gibson
Cots Ridge
He In
Helm
Huntlngton Beach
Inglewood
Kettleiun
Kettlcaan Hills
La» floret
Lompoc
Lonpoc
tost milt
Midway
Nlcolat
Hoctli telrldgc
Horth Bclrldge
North tel ridge
North Belridge
Orcuct
Oxnard
furtama.
Mliln city
V HI re Bj Cr Mil Mu Sn Ha
9 14
10 16
32 1J
28 12
nd nd
31 11
16 6
nd 4
nd nd
nd nd
12 11
IS. 2 10.3 1.2 <1 <1 <1 nd nd
nd 4
18.5 22.7 6.3 <1 <1 <1 nd <1
ad nd
<1 <1 <1 <1 <1 <1 nd nd
I •
14.3 66. 5 28. S <1 <1 nd nd nd
9.0 28.0
134.5 --
128 75
209 102
5.1 21.9 5.1 <1 <1 <1 <1 nd
6.0 20.0
11.0 31.0
2.2 21.6 2.2 <1 <1 nd <1 nd
10.0 32.0
30.0 43.0
0.8 2.3 2.0
t.fh
J.4}
1.9J
0.6 1.1 2.0
21. (T\
14.0)
2.9J
1.0 2.0 2.0
6.0 11.0
S.3 38.5 38.5 <1 <1 <1 <1 nd
nd 11
37 125
188 80
14.0 27.0
2.5 10.5 2.5 <1 <1 nd nd <1
29 104
125.7 125.7 125.7 <1 1.3 nd <1 ad
34.0 35.0 24.0
11.0 24.0
106.5 --
37.6 —
199 90
39.0 8.0
82.6 82.6 82.6 1.8 1.8 <1 <1 nd
246.5 —
-- 107
~ 80
.. 0)
23 83
162.5 —
403.5 —
218.5 —
8.0 21.0
Analytical Method
Emission upectroacopy
EnJaslon spectres copy
EniHflion npcctroacopy
EnluBlon apectroacopy
Emiufiion opcctroacopy
Emission apectroscopy
Emission spccti-oacopy
Ealsslon apectroscopy
Emission spectroacopy
Enlsslon spectroscopy
Emlaalon speetroscopy
Emission spcctrnscopy
Emission spectroscopy
Ealsslon spectroscopy
Emission apectroscopy
Emission apectroscopy
Emission apectroscopy
Ealsslon apectroscopy
(I)
Emission spectroscopy
Emission spectroscopy
Enission spectroscopy
Ealsulon apectroscopy
Emission spectroscopy
Emission ipectroscopy
Emission apectroacopy
Emission ipectrotcopy
Emission spectroscopy
Emission spectroscopy
Emission apectroscopy
Emission spectroacopy
Emission apectroscopy
Emission spectroscopy
Emission spectroscopy
Emission apectroacopy
X-ray fluorescence
Emission spectroseopy
Emission spectroscopy
Emission spectroacopy
Emission cpectroscopy
Emission spectroscopy
Colorioetrlc
(1)
(I)
»*/
(1)
Emission spectroscopy
Emission apectroscopy
Emission apactroscopy
(1)
X-ray fluorescence (Inter, std)
Colorlswtrli:
Emlaalon upectroscopy
X-ray fluoreae. (ext. atd.)
(1)
(1)
Emission apactroacopy
(I) Hot upoclftorf.
nd SoughI but not dattctsd.
72
-------
TABLE A-2
Suite and Field
Rio Uravo
Rio Eravo
Rio Hravo
Russell Ranch
San Joaquin
Santa llarla
Santa Maria
Santa K.irfa
Santa Maria
Santa Marl* Valley
Santa H.-.ria Valley
Santa Maria Valley
Santa Maria Valley
Signal Kill
Signal Hill
Tcjoti Hills
Ventura
Ventura
Ventura Avenue
Wheeler Ridge
Wilmington
Wilroinp.ton
WllialnRton
Wilmington
Wilmington
Wilmington
Wilmington
COLORADO
Badger Creek
Badecr Creek
Cramps
Cramp
Hiawatha
Hoffat Dome
RanRcly
Range ly
Rangely
Seep
While kivcr Area
FLORIDA
Joy
V
—
—
—
12.0
44.8
223
202
180
280
207
240
280
174
28
25
64
42
49
25.2
7
43
41
53
—
—
46
36.0
Ba Cr Mn Mo Sn A
2.2
2.6
2.5
26.0
—
97 17
—
106
130
97
—
—
174 1.7 <1 1.7 <1 4.0 »d
—
57
44
51
33 31
—
1.9
61
46 28
51
53
60
60
84 36 3.6 <1 nd 1 nd
<1 <1 <1 <1 <1 <1 <1
*1 *1 *1 nd *1 *1 *1
*1 *1 <1 <1 <1 8
Rhodes
Rhodes
Rhodes
Solomon
1.22
0.56
2.1
<1
I
3.8
44.2
24.0
15.6
4.5
— .
<1
21.3
39.0
12.3
145
165
133
—
—
«
30
0.62
"
1.3
3.9
2.4
1.2
9.9
24.0
9.0
4.5
>5
>J1
6.3
6.0
9.1
3.4
—
--
--
36
38
32
7
0.57
41
<1
10.2
7.2
<1
<1
3.9
<1
<1
<1
9.1
<1
<1
Erniesion Bpcctroscopy
(i)
nd nd nd Emission spectroscopy
<1 nd nd Emission spectroscopy
<1 <1 nd Emission spectroscopy
<1 <1 <1 toiHslon spectroscopy
<1 nd nd Emission r.pcctroscopy
<1 nd nd Emission spectroscopy
<1 nd n
-------
TABLE A-2
gia.ta_ and Tltlt.
I.UUIS1ANA
Bay Kan-hard
Col'|iiltt, Cltlrborne
Culqtidt, i:i«lrbornc
Coli|u(l(. Cvillrborne
(!,mukovrr B)
Delta (Wr-,ii) OHahore
Block 117
Orlts (W^sl) Mock 27
Pelta (Went) Blork 41
tuR«ir Island, Offshore,
Block 276
lakrtir Islnnd, Of/shore,
Block 238
take Wastilngton
Main Pass, Block 6
Main r»a. Block 4
Oils
Ship Shoal, Offshore,
Block 176
Ship Shonl, Offshore.
Block 176
Ship Shoal, Block 208
Shnngftloo, N. Red Xock
South Pana, Offshore
Block 62
Tlai>alivr, S.. Offshore,
Block 54
V
nd
nd
nd
nd
'' nd
r nd
nd
•re.
4
ire,
nd
nd
nd
Dd
nd
nd
1 nd
:k nd
nd
>re.
nd
Trace) Xlanant. cm .
Nl Fe B« Cr Hn Mo Sn J«
2
nd
nd
nd
2
2
2
nd
nd
4
3
1
s *tft 0 07
J . JO *»« ft
nd
nd
2
nd
4
nd
Analytical M»tf
Ealnalon sprct roacopy
EnlHuiou spcctroacopy
Cnlsaton npcctroacopy
Ealasion apcctroacopy
Eatlsulou apoctroscopy
Emlsuton upcctroacopy
Ealaalon apcctroacopy
Ettlaulon api.-ct roacopy
Entitle Ion opcctcoecopy
Eaiaelon apectroacopy
Eaiioion apcctroacopy
Intselon api-ccroacopy
Ealaalon spcctroacopy
Enlailon apectroacopy
Enlvalon apectroacopy
HICHZCAN
Trent
0.2)
Ealasion apeccroacopy
MISSISSIPPI
Daxtervllle,
Marton
Heidelberg
aar and
TallhalU Creek, Ss.lt h
Tallhall'a CreeV, Snlth
Tallh/illa Creek, Smith
(Snjckovcr)
Tlngley, tatoo
MONTANA
Bell Creek
Bl| Wall
Soap Creek
NEW MEXICO
Rattlesnake
Rattleanak*
Table Meaa
40
15.35
nd
nd
nd
7
nd
24
132
«
15
6.02 1.78
nd
nd
nd
i
2
13.2 <1 <1 <1
13.2 <1 <1 <1
<1 <1 n ^ 5
<1 nd
<1 nd
<1 nd
<1 od
Znlaaion spectrotcopy
Ealaaion spectroacopy
«;,003 F-nlsaion «|>cctroacopy
Zalaalon spectroacopy
Eolation apcctroacopy
EnlaDion apectroscopy
Ealaalon spcctroacopy
Eslnalon spcctroicopy
Eulaaion spcctroicopy
Eaila»loa apcctroacopy
Ealailon epectrotcopy
Ealoalou epcctroacony
Eaiiaalon apectroacopy
OKLAHOMA
Allurve (Howata)
Allurve (Kowata)
Allurve (Novata)
Bethel
Burbank
Cary
Chtlaea (Howata)
Chelaea (Novata)
Clieleea (Novata)
Chcynrha
Clityarh*
Chiyarha
Cheyarha
Croavell
CroKwall
Cloawall
Creawel 1
Croavell
Cro~.ll
Dill
Dover, Southeast
Dimtln
E. Llndaay
F. Senlnolt
E. Yeagar
Flah
Clen Pool
(1) Mot
<1
1.1
<1
i..
nd
0
1.
<1
1.2
6.0
O.tl
ad
15 0.65
4 1.4
0.10
0.
nd
23
0.11
1.4
51.0
1.4
2/.0
6.0
6.0 <1
11.9 <1
6.0 <1
<1
-------
TABLE A-2
Traco EJoannt,. Pirn
State and Field
Crief Creek
Hawkins
Hawkins
Horns Corner
Katie
Katie
Katie
Katie
Kcndrlck.
Kon
-------
TABLE A-2
-------
TABLE A-3
SULFUR AND NITROGEN CONTENT OF CRUDE OILS
FROM NATIONS WHICH EXPORT TO THE U.S.
NORTH AMERICA
Province and Field
Canada
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bbl/day
Acheson, Alta.
Bantry, Alta.
Bonnie Glen, Alta.
Boundary Lake, B.C.
Coleville, Sask.
Daly, Manitoba
Dollard, Sask.
Excelsior, Alta.
Fenn - Big Valley, Alta.
Fosterton-Dollard, Sask.
Gilby, Alta.
Golden Spike, Alta.
Harmattan, East, Alta.
Harmattan-Eklton, Alta.
Innisfail, Alta.
Joarcam, Alta.
Joffre, Alta.
Kaybob, Alta.
Leduc, Alta.
Lloydminster, Alta.
Midale, Sask.
North Premier, Sask.
Pembina, Alta.
Redwater, Alta.
Steelman, Sask.
Stettler, Alta.
Sturgeon Lake, S., Alta.
Swan Hills, Alta.
Taber, East, Alta.
Taber, West, Alta.
Turner Valley, Alta.
Virden-ttosclca, Man.
Virden-North Scallion, Man,
Wainwright, Alta.
Westerose, Alta.
West Drumheller, Alta.
Weybum, Sask.
Wizard Lake, Alta.
0.46
2.41
0.32
0.72
2.62
0.18
2.18
0.71
1.89
2.91
0.12
0.37
0.37
0.44
0.58
0.13
0.56
0.04
0.53
3.67
2.24
2.92
0.22
0.22
0.73
1.59
0.85
0.46
3.08
2.55
0.34
1.43
, 1.47
2.60
0.25
0.51
1.89
0.24
--
—
—
0.126
—
—
0.027
—
0.120
—
—
—
—
—
—
—
—
0.016
—
—
— •
— —
0.041
— -
0.055
— —
0.034
—
__
— —
— —
— • •
*•••
•*•
—
— —
0.023
9,400
6,900
36,800
27,700
4,700
1,400
8,800
1,600
19,600
7,600
5,300
37,400
6,000
4,500
5,500
5,900
6,600
10,900
16,700
2,200
11,700
6,300
140,000
58,000
28,200
3,200
11,700
76,900
4,500
2,900
3,700
7,500
10,800
9,400
1,900
33,300
27,600
77
-------
TABLE A-3 (cont'd)
SOUTH AMERICA
Field and State
Venezuela
Aguasay, Monagas
Bachaquero, Zulia
Boca, Anzoategui
Boscan, Zulia
Cabimas, Zulia
Caico Seco, Anzoategui
Centre del Lago, Zulia
Ceuta, Zulia
Chimire, Anzoategui
Dacion, Anzoategui
El Roble, Anzoategui
Guara, Anzoategui
Guario, Anzoategui
Inca, Anzoategui
La Ceibita, Anzoategui
Lago Medio, Zulia
Lagunillas, Zulia
Lama, Zulia
La Paz, Zulia
Leona, Anzoategui
Mapiri, Anzoategui
Mara, Zulia •
Mata, Anzoategui
Mene Grande, Zulia
Mercy, Anzoategui
Nipa, Anzoategui
Oficina, Anzoategui
Oritupano, Monagas
Oscurote, Anzoategui
Pilon, Monagas
Pradera, Anzoategui
Quiriquire, Monagas
Ruiz, Guarico
San Joaquin, Anzoategui
Santa Ana, Anzoategui
Santa Rosa, Anxoategui
Sibucara, Zulia
Silvestre, Barinas
Sinco, Barinas
Soto, Anzontegui
Santa Barbara, Monagas
Tacat, Monagas
Taman, Guarico
Tcmblndor, Monagas
Tia Juana, Zulia
Tucupita, Amacuro
Vopalcs, An/oategui
Zapaton, Anzoategui
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bbl/day
0.82
2.65
0.89
5.54
1.71
0.13
1.42
1.36
1.07
1.29
0.10
2.95
0.13
—
0.41
1.16
2.15
1.47
1.29
1.38
0.54
1.16
1.09
2.00
2.52
0.38
0.59
1.89
1.19
2.11
0.75
1.33
1.05
0.14
0.42
0.09
0.82
1.17
1.38
0.52
0.88
1.55
0.14
0.83
1.70
1.05
1.15
0.48
_
0.377
0.178
0.593
0.249
—
—
—
0.119
0.274
0.001
0.314
0.003
0.223
0.055
~
0.319
0.203
—
— -
0.058
0.116
0.238
_- .
•0.429
—
0.202
—
—
0.360
0.033
0.252
0.161
0.036
—
0.006
0.074
0.261
0.284
0.159
0.125
—
0.025
0.338
0.269
0.312
0.275
0.075
14,800
738,900
6,100
68,400
82,000
4,200
132,200
63,800
17,100
10,900
1,000
26,900
1,100
9,500
14 , 300
58,100
940,100
320,000
23,500
11.900
2,800
10,100
55,800
12,200
. 27,500
29,200
48,100
14,500
11,400
23,900
700
22,000
600
2,300
7,000
34,700
2,000
12,200
28,400
10,000
6,100
3,500
400
5,300
373,000
3,700
15,700
19,300
78
-------
SOUTH AMERICA (Cont'd)
Covmtry and Field _
Colombia
Casabe
Colorado
Galan
Infantas
La Cira
Payoa
Rio Zulia :
Tibu
TABLE A-3 (cont'd)
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bhl/day
1.07
0.25
1.11
0.88
0.96
0.83
0.32
0.71
0.147
7,500
900
1,300
4,500
17,200
8,200
23,700
12,900
Bolivia
Camirl
0.02
2,800
Chile
Cerro Manatiales
0,05
79
-------
TABLE A-3 (cont'd)
MIDDLE EAST
Country and Field
Saudi Arabia
and Neutral Zone
Abqaiq
Abu Hadriya
Abu Sa'Fah
Berri
Dammam
Fadhili
Ghawar
Khafji
Khursaniya
Khurais
Manifa
Qatif
Safaniya
Wafra
Abu Dhabi
Bu Hasa I
Bu Hasa II
Habshan
Murban-Bab-Bu Hasa
Iran
Agha Jari
Cyrus
Darius
Gach Saran
Haft Kel
Naft-i-Shah
Sassan
Kuwait
Burgan
Magwa-Ahmadi
Minagish
Raudhatain
Sabriyah
Iraq
Bai Hassan
Kirkuk
Rumaila
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bbl/day
2.03
1.69
2.61
2.24
1.47
1.25
1.89
2.99
2.53
1.73
2.75
2.55
2.88
3.91
0.74
0.77
0.71
0.62
1.41
3.68
2.44
1.57
1.20
0.76
2.06
2.58
2.21
2.12
2.13
1.62
1.36
1.93
2.1
0.105
—
0.232
0.206
. —
0.029
0.107
0.159
0.093
0.307
0.338
0.109
0.126
0.145
0.032
0.031
0.026
0.028
0.015
0.300
0.089
0.226
—
—
0.082
0.122"!
0.125 I
0.103 )
0.102 (
0.096J
0.28
—
MM
892,500
103,700
82,900
155,900
21,600
47,900
2,057,900
~.
74,300
22,300
5,100
95,100
791,400
141,000
_
_
— •
564,100
• -
848,000
24,000
100,000
882,000
45,000
10,000
137,000
2,950,000
57,000
1,097,000
480,000
80
-------
TABLE A-3 (cont'd)
AFRICA
Country and Field
Nigeria
Afam
Apara
Bomu
Delta
Ebubu
Tmo Riyer
Meji
Meren
Obagi
Oloibiri
Umuechem
Amal
Beda
Bel lied an
Brega*
Dahra
Defa
El Dib
Es Sider*
Farrud
Gialo
Hofra
Kotla
Nafoora
Ora
Rakb
Samah
Sarir
Umra Farud
Waha
Zaggut
Zelten
SulfurjNitrogen,
Weight Weighc Production,
Percent Percent bbl/day
0.09
0.11
0.20
0.18
0.20
0.20
0.15
0.09
0.21
0.26 •
0.14
0.14
0.45
0.24
0.22
0.41
0.28
1.04
0.42
0.39
0.56
0.32
0.84
0.55
0.23
0.23
0.25
0.16
0.13
0.24
0.30
0.23
0.027
0.050
0.084
0.096
0.113
0.121
0.041
0.048
0.060
0.179
0.076
0.093
0.203
0.120
—
0.106
0.140
0.127
0.160
0.070
0.121
0.082
0.274
0.091
0.119
0.118
0.127
0.079
0.033
0.134
0.188
0.090
8,400
1,000
46,000
69,800
2,600
104,100
19,400
82,700
43,100
4,200
32,800
162,400
7,900
6,600
33,300
165,800
2,200
4,500
359,400
5,200
11,900
238,800
11,300
11,500
57,000
440,000
4,200
129,300
2,700
357,900
Export crude mixture delivered to
pipeline terminals.
81
-------
AFRICA (Cont'd)
Country and Field_
TABLE A-3 (cont'd)
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bbl/day
Egypt
Asl
El Alaraein
El Morgan
Sudr
2.05
0.84
1.67
2.06
0.075
0.183
24,600
260,900
*
Angola (Cabinda)
Tobias
1.51
Algeria
Edjeleh
Gassi Touil
Hassi Messaoud
Ohanet
Rhourde el Baguel
Tin Fouye
Zarzaitine
0.095,
0.020
0.15
0.06
0.31
0.13
0.06
0.058
0.008
0.018
—
0.087
0.061
0.018
18,900
59,000
387,200
8,600
65,900
46,200
44,200
These fields on the Sinai Peninsula are being produced by Israel.
Data are not available.
82
-------
TABLE A-3 (cont'd)
ASIA
Country nnd Field
Indonesia
Bekasap
Duri
Kalimantan
Lirik
Minas
Pematang
Seria
Tarakan
Sulfur, Nitrogen,
Weight Weight Production,
Percent Percent bbI/day
0.17
0.18
0.07
0.08
0.115
0.10
<.10
0.13
0.124
0.337
0.132
0.159
111,100
37,900
4,500
408,700
67,300
1,600*
* Production data from International Petroleum Encyclopedia,
1972 edition, Petroleum Publishing Co., Tulsa, Oklahoma.
83
-------
TABLE A-4
NORTH AMERICA
trace Elements ppm
Country and FlelJ
Canada
Acheson
Achcaon
Aclieaon
Armcna-Camroso
Bantry
Bavlf
Big Valley
Big Valley
Bonnie Glen
Bonny vl lie
Campbell
Cantaur
Centaur
Chamberlain
Colevllle
Colevllle
Colevllle
Colevllle
Conrad
Daly
Bollard
Drunheller
Drunheller
V. Druraheller
Duhanel
Duhauel
East end
Elk Island
Excelsior
Flat Lake
Forget
Fosterton
Glen Park
Golden Spike
Grassy Lake
Gull Lake
Hamilton lake
Jqffre
Joseph Lake
Kathyrn
Lac. Ste. Anne
Leduc
Leduc
Leduc
Lloydnlnster
Halmo
Malmo
Malao
Midway
Morlnville
Morlnville
McMurray
Peiuolna
N. Prenler
Rapdan
Ratcllffe
Redwater
Redwater
Redwater
Roaclea
Skaro
Sprlngburn
Sal ley
Stettler
Stettler
Succaaa
B. Taber
W. Taber
Wabt.kav
Wagner
Vapella
Vapell*
V
' 0.53
3.5
0.81
0.59
56.9
1.94
6.83
6.14
0.04
135
11.2
86.8
135.5
17.9
111
13.3
105
95
73.3
7.04
99.7
19.4
4.32
0.55
0.67
2.8D>
83.5
0.7
2.82
145
20.8
76.5
0.16
0.37
17.9
97.5
1.01
0.15
0.48
4.0
83.7
0.56
0.50
<0.56
105
0.9
0.58
0.83
90.8
105
2.21
220
0.58
77.3
103.1
5.60
4.03
4.J
<0.56
4.26
0.89
1.24
1.14
11.4
16.2
88.0
103
88.8
20S
19.4
29.8
23.1
Nl
1.30
1.88
4.50
0.74
19.1
4.75
12.3
11.08
0.09
57.0
4.91
33.5
52.3
8.64
33
5.03
36
32
25.4
5.26
48.5
9.59
13.4
1.26
7.46
3.91
33.0
1.66
5. JO
60.2
12.74
30.8
1.38
3.63
5.9
34.2
1.98
0.29
0.55
2.43
26.6
1.27
1.23
—
51.5
1.19
0.72
4.41
40.1
31.1
2.75
75.7
1.24
30.5
47. S
7.61
9.43
10.6
—
2.90
2.51
6.24
2.84
15.2
13.8
31.6
38.3
36.3
76. «
9.S9
17.0
13.46
Kc
0,7
2.0
0.7
0.8
1.0
4.9
1.1
0.7
0.2
9.0
0.7
1.3
8.4
0.8
—
4.1
0.9
—
0.7
0.8
1.7
2.0
0.3
1.0
0.5
0.4
0.8
—
0.3
629
0.3
4.6
0.6
0.7
0.2
0.9
0.9
0.9
0.3
16.5
2.4
0.7
0.6
—
3.3
0.5
0.2
0.3
1.8
4.2
0.8
75.5
0.5
1.1
2.1
1.0
0.5
3.4
--
0.4'
_.
_.
1.7
0.7
0.5
4.1
3.5
1.0
58.7
2.0
0.7
1.5
Cr Analytical Method
Colorlmutrlc
Colorlmctrlc
Colorloctric
Colorlmucrtc
Color Iructric
Colorlmctrlc
Colorimctrlc
Colorlmctrlc
Color Ircctrlc
Color (mo trie
Colorltaetrlc
Colorlmctrlc
Colorluctrlc
Colorlmctrlc
Emission apcctroacopy
Color li.e trie
X-ray fluorescence (int. »td)
X-ray fluorescence (ext. *td)
Color Icctrlc
Colorlmctrlc
Colorlmetrlc
Colorlnetrlc
Colorlmetrlc
Colorlrcetrlc
Colorlnetrlc
Colorlaetrlc
Colorinetrlc
Colorlmetrlc
Colorlnetrlc
Col ortme trie
Colorlmetrle
Colorlnetrlc
Colorliuutrlc
Colorlmetrlc
Colorlaetrlc
Colorlnetrlc
Colorlmetrlc
Colorlmetrlc
Colorlnetrlc
Colorluetrlc
Colorlmetrlc '
Colorlmetric
Colorlmetrlc
(1)
Colorlmotrlc
Colorlmetrlc
Colorlmetric
Colorlnetrlc
Colorlaetrlc
Colorlmctrlc
Colorlaetrlc
Colorlnetrlc
Colorlnetrlc
Colorlmetrlc
Colorlrcetrlc
Co lor Ine trie
Colorlmatrlc
(1)
U)
Colorlnetrlc
Colorlnetrlc
Colorlnetrlc
Colorlnetrlc
Colorlmetrlc
Colorlnetrlc
Colorlnetrlc
ColorWtrlc
Colorloetrlc
ColorJiatrlc
Colorloctrle
Colarlaetrlc
ColorlMtrlc
(1) Not specified
84
-------
TABLE A-4 (cont'd)
TRACK EI.EHO1T CONTKHT OT CRUDE OILS FROH NATIONS WHICH EXPORT TO THE U.S.
SOUTH AMERICA
Country and FlolJ ( ) *
Venezuela
Amana (1952 Blend)
Bachaquoro
Bachoquero
Bachaquero
Bachaquero
Bacliaquero
Bachiqucro
Bachaqvicra
Barhaquero
Bacliaquero
Rachaqucro (2)
Bachaqucro Light
Barliaquero Heavy
Barlnas (3)
Boca
Jtoscan
Boscan
Boscan
Boscan
Boa can
Boscan
Boscan
Cnchipo
Cantaura
Centre- dnl Lago
Chlolrc
Cunarcbo
Daclon
Esqulna
Esqulna
Cuanlpa
Guarlo
Culco (3)
Jusepln
Jvificpln
Juscpln
La Celbita
Lagonar
Latolreco
l.ngotrcco/l.agocinco
Lacunlllas
Laf.unlllas
Lagunlllas
tagunillas
LsjuulUas
Lacunlllas
Lagunlllaa
laguntllaD
Uir.unl))os Heavy
l.aroa
L«nw (7)
Lama
tatua/Lamar
Laoar (2)
La Kosa
La Sosa
L« Koaa Medium
Lcona (3)
Huplrl (3)
Kara
Kar«
Kara
V
29
370
430
430
413
348
320
390
370
49
413
49
390
117-165
48. 5
1400
1580
937
819
1200
1100
1150
14
0.6
179
56
0.7
133
2.5
1.3
110
1.9
17-63
26
16.8
14.8
0.66
179
163
101
290,315
303
303
265
236
116
151
22)
300
55
8-26
104
240-300
4-55
185
156
230
86-140
11-14
220
206
173
m
8
46
—
M.38.
53
49
45
42
45
46
5.5
39
5.5
45
43-57
—
100
123
119
112
160
105
--
3.3
—
30
13
0.8
29
--
— -
27
—
~
5.5
--.
2.0
—
22.0
15
—
—
34,29
41
39
35.0
~
8.2
—
30
38
12
--
—
22-28
--
.-
10.0
24
24-36
—
18
15
16.3
Fc Cr Analytical Method
Eels* ton spectroscopy
Colorlnctric
5.4 X-ray fluorescence
X-ray fluorescence
EnlBston epcctroacopy
Ealsalon (pectroacopy
3.9 0.08 (1)
(1)
U>
(1)
(1)
Colorlnetric
Colorlnetrlc
-------
TABLE A-4 (cont'd)
TRACE KI.KHKNT CONTEKT OP CRUDE OILS TROH NATIONS WIUCH EXTORT TO THE
SOUTH AMERICA (CONT'D)
Country im^ Klcld ( }•
Mata, Aiizontcqul
Mata, Anzoatequl
Mercy
Mercy (2)
Keaa (2)
Monagaa
Motacan H
Oflclna
Oflclna
Oflclna
Oflclna Light
Oflclna Heavy
Oscurotc (2)
Oscurote, Nurte
Paeons Ib
Pedcrnalcs
rilon
Pilon
Qulrlquire
Qulrlqulro
Qulrlquire
Quirlqulre
Ruiz (East)
San Joaquln
San Joaquln
San Joaquln
San Joaquln
San Joaquln
San Roque
Sllveatre
Tapaalto
Tarra
Teiblador
Tla Juana
Tia Juana
Tla Juana
Tia Juana
Tla Juana Light
Tla Jiwna Mcdlun
Tla Juana Mediun
Tla Juana Mcdlua
Tla Juana Heavy
Tla Juana Heavy
Tla Juana Heavy
Tlgre
Tlgre
Tucuplta
Urdancta
Zapatoa
Colombia
Colombian
Ccsabe
Payoa
Tlbu-Pacrolea
Trace Elem-nts, pj
V
130
21
290
242-247
45-56
212
390
129
54
37
57
62
20-68
187
164
230
510
181
95
102
39
31.3
111
0.6
2.3
2.4
11.2
0.331
<4.5
205
450
42.0
56
180,185
182
170
216
100
200
185
134
300
303
269
160
153
84
430
4
101
135
59
60
Nl
25
5
64
31-59
12.7-15
--
43
—
»
6
6
14
--
—
—
67
98
72
16
18
— •
S.9
0.2
0.9
32.0
2.0
0.14
—
63
40
6.6
35
—
16.20
24
16
24
11
22
— •
7.6
25
27
— •
28
31
45
— .
<1
_
14.4
13
9
Fe
2.0
13.1
0.45
0.49
2.44
18
1.6
Cr
Analytical Method
EalBslon apectroscopy
Enlsulon spectroacopy
Ealsalon apectroacopy
(I)
(1)
(1)
Colorlnetrlc
(1)
EiUaeton apactroacopy
(1)
Colorlnetric
Colorlnetric
(1)
(1)
(1)
Colorlnetric
Colorlmetrlc
Enlaelon apectroacopy
Colorinetrle
Eniaalon apectroacopy
(1)
Chenlcal
(1)
Colorlmetrlc
Kalaalon apactroacopy
0.024 (1)
Cheolcal
(1)
Enlaalon apactroecopy
Colorlnetrlc
0.009 (1)
Colorlnetric
X-ray fluoraacance
X-ray fluorescence
X-ray fluorescence
Ealaalon apactroacopy
Colorinetrle
Colorlmatric
(1)
Chemical
ColorInetrlc
Ealsalon apectroacopy
(1)
Colorlaiatrle
Balaaion apectroacopy
Colorlnetric
Color Uetrlc
Enlaalon apactroacopy
(1)
(1)
blaalon apactroacopy
(1)
* Hunger In rnrcnthcsli Indlcatca nunber of aumplaa Involved.
(1) Not apectllcd
86
-------
TABLE A-4 (cont'd)
TRACE ELEMENT.CPintllT .OP.CRIfPR (,.
Abu Sa'rall . ..-.,. ;,
Aln Dar •:-•,,-, , • • •... ,...•>•.,•
Aln Dar,, Zone Arab D
Arabian It. , .. .. ...
Khursanlyph , . ... ,. , ... „•-. ;
Khursaniyah , .......
Hanlta v,.',~.;. '•-;.,:' .. -. . .• :
Safanla Q).,?, ••-, ,.( . .- • i
Safanla, .BaUrafn . .
Shedgum , . ,-,-, , .,,, .,.,
Southern fields
Southern Arabian Fields
Uthmanlyah
Keutral t6ttV' ' ' ;
Khofjl
JDiaijl .,.,,. ,,,,.. ,: , ..:
Wafra (2). ..... ,,.... :
Vafra ^-.:.-,., , :,.. • .-.,.•,
Abu Dhabi , ....... ; ,....;, .„!
Abu Dhabi1" (2) < ; • -
t-T.i - '-i-::-.1 i-.-t
Abu Dhabtiuind^;;^;; ;;;;'
v-.|.- ,tf.:». '•.-...:,• i-..
^^.:.' ••..:^'.. 5 .. '..^ V. 6'OJ1
Agha Jar-1^-,0 j;;o ;. } .- ^.-... .;*-".
Ahwaz :; •>•• -.:!' •••... uj'i
Cyrus v ;.):M: ;.'. ; :.'>qt. f-... '
Cyrus
Cach Saran
Cech Saran
Haft Kcl
Iranian Heavy
Sassan
Saesan
M. : • :i' .f7 ?- -x ^ 'Vl'-
Kuwait Vs"J •" ' ' ' l'v<1 '"'
Kuwait
Kuwait
Kuwait
Kuwait
Magwa-AlltiiNH."''-. •> •';« -'''I
Iraq
Aln '/alah
Boi llabgan
Ral Hassan
Jambur
vAtobur RjSj. _U«a|.pm s
Kirkuk ,0-i,,, ,-,.,•'.„ „...
KirVuk O),.'-,,-. -.;< (,'-
Zubalr '[„,'.' j.<... 1 ^.'. ,,..
Zubalr
V
49
6
^ 50»56
• J2
,27
51
16'
Hr-iZ.
,«*!
.. 47-
it A;
'. !•-•••
.'..i«i
J.8
- ,.. J^?i
. AB-80
. .,.{t7<;
. J,8;
16
21
51
V . - "\»
"M!
.'.... .-,4,.'
46r>2
,.. jjji
, V
., . I
Livii*
'- .'- -•'*•' 5
•;$3
,«»,..
(••- .,-i
Vi.jil*
Vr.tfa
.'.iSrll
118
Itj
145
25
107
16,
10. 8
b*.i«.J
aa'':
29*
27
22.5
22.5
.';!?£
a.-
95
19
10
6
jyj..
,>W'
20-^
' 'if
Trace £li*mer
Nl
7
<1
—
12
10
10
3
4 J-3.7
3
2
7
5
3
<1
1
14
20
4
4
4
9
12
_
7
—
0.43
—
—
, 8
39
--
33
31
—
37
3
,
8
9
6.6
6.0
7
15
~
--
--
—
11
I 10-11
4
—
te Ci Analytical Method - . '• in
: ; " "' -•• ' '• ;... -.1 .i\-.- -; • •( '• '.•
E»l86lon 6|>cctroscopy ' -
Emission opcrcroscopy
(W ,, ••-• • • •
Emission upcctroocopy
Enlasion spectroacopy .
Colorlmotrlc
Enisaion spectroscopy :. >.
O) ... !..... : . / • .-.-.T
i Evlssion •peetroscopy. : .
: Enlasion epcctroscopy i i
Ettiaslon syectroscopy. - •
Ealsslon epcctrovcppy • , ,
Enlflftion opectroscopy
Emission Bpcctroecopy , •
Eailsslon spectroccopy - .
(1) .,:-•• J .:•••.. -.-.
Ealgslon spectroscopjr ,. : '
Eeleslon sfiectroscppy- .
Emission spcctroscopy
Emission epcctroscopy
'('"•-' .••)...•"» . r- : '. '. : -
< (4) " ^ "'"'"' ''-!''' '
'(U -.>..,- ..,.. ',•'.'.;
(1) ....•,...•• .,.:, ••.:•.
(1) ...... .•• ,. •- .-; -.t
<} • '.. - ' ^ ..'-.''•• '''•': -»»'/ '• '•" - .
; - ;, ' V' r. '' ""' ,;'.'., ,
;, ii . -,{ • ; '';..' ••' '. -ik*\
... • \»f
- - •• •'' 1 '" •'•"•.-' - ;' •' :< ' ' •
•;: o> '• '",.'.,, V',V \n.»
'1 ' • :•:•<. -•.'.* ',,-..J
,' ' ' •':-. ••.••• .!'' ".I'.; ;
;, C«lorlmctric i ... , ,-t' •:••;
* * • * (1) • •'. ; ••• i
. • Eajlsalon Bpcctrosoopy . ; .... :
;, (1) --.-•,•
-. B»l»sion spectroscopy. .v..;.-
Eaiscion spectroscopy
(1)
X-ray fluorescence >• '
E»isaion spectroucopy (. ,i, ,,
^ ., .... ^ii, • _ "'..'.'.!,.
'; :-•. ."> --.si' t.
; ' ,',
i( Cplortaietric ,,,,,, ..!','„.'»'
(1)
* Numlicr in I'Ctcntlirui'i indlcaicu number of snuplei involvrd.
(1) Not npcctficd
87
-------
AFRICA
Country and Field ( )*
Hlgerls
TABLE A-4 (cont'd)
TRACE ELEMENT COMTEK Of CRUDE OILS FROM HATIONS WH1CII EXPORT TO THE U.8,
truce Elementg. ppn
Nl
Fe
An.ilytlcnl Method
Afan, E. Region <1 <1
Apara, E. Region <1 1
Bomu, R. Region <1 2
Delta, Offshore «1 4
Kbuba, E. Region <1 5
Ino River, E. Region 4 9
Ino River, E. Region 2 3
Kanusklrl, E. Region <1 5
Kanusklrl, E. Region <1 ft
Ke, E. Region *1 <1
Keren, Offshore <1 <1
"Hlgertan Medlun" 7 <0.8
Ollbtrl. E. Region 2 13
Robert Klrl, E. Region 1 2
Tubu, Offohore <1 <1
Uouechea, E. Region <1 3
Emission apectroacopy
Emission npectroscopy
Cnlsslan upectrovcopy
Emission tpectroscopy
Eailsslon spectroscopy
Emission spectroacopy
Eaisalon spectroscopy
Evlsslon spcctroacopy
Eailsalon spectroscopy
Eataaion apectroncopy
Emission ipcctroscopy
X-ray fluorescence
Esiiaslon apectroacopy
Galsslon epectroscopy
Ealsalon apectroacopy
Ealaaion apaetroscopy
Libya
Aaal, Cyrenalca <1 <1
Dallrn, Concession 32 <1 3
Dallra, Trlpolltanla <1 2
Dahrt 0.6 —
Defa, Cyrenalca <1 6
Ed Dlb, TripoHtania 7 11
Ed Dlb. Trlpolltanla 7 15
El Slder (2) ' 0.92-1.8 5-5.6
F-90, Concession 90 <1 <1
Facha, Tripolttania 4 7
Farud, Tripolttania «1 *
Khuff, Cyrenalca 6 12
Kotla, Concession 47 28 35
Ora, Cyrenalca <1 <1
Cra, Cyrenalea <1 6
Rakb, Cyrenalca <1 6
Sarlr, Concession 65 <1 5
Sarlr, Concession 65 <1 2
Sarlr <-5 5
Umn Farud, Concea. 92 <1 <1
Zalten 1.1 —
Zueltlna 0.7 —
Eailsslon apectroacopy
Emission apectroaeopy
Ealsslon apaetroscopy
(1)
Bailcaion apactroscopy
Ealsslon apectroacopy
Ealaslon spsctroscopy
(1)
Ealsslon spectroscopy
Ealsslon spectroscopy
talssion spectroscopy
Evlsslon apectroscopy
Eailaalon apectroscopy
Catiaaloa spectroscopy
EaUaaion spectroscopy
lalsslon apeccroscopy
EaUsslon spcctroocopy
Ealsslon spectroscopy
X-ray fluoreacenca
EsJaalon spactroscopy
(1)
(1)
Egypt
Balaytm
Belayla
El Alaneln
El Morgan
El Morgan
23
120
IS
52
37
71.9
7
18
24
58
(1)
(1)
Emission spactroscopy
Eaiaalon spactroscopy
(1)
Cassl Toull
Rourda «1 Baquel
Zarxaltlna
Zaracaltlna (?)
0,2-1.J —
Ealsslon spactroscopy
Eailsslon spactroscopy
X-ray fluorescence
0)
ASIA
Indonesia
Bekasap
Durt
Mines
31
7
11
Calsslon apactroaroay
laUaslon spactroscopy
iMlssloo spectroscopy
Caitasloa spactroscopy
* Nunber In parenthesis indicates nmbar of samplea tnrolvad,
(1) Not specified
88
-------
TABLE A-5
TRACE ELEMENT CONTENT OF CRUDE OILS
AS DETERMINED BY ACTIVATION ANALYSIS
oo
vO
Region
NORTH
AMERICA
SOUTH
AMERICA
MIDDLE
EAST
AFRICA
ASIA
State/Country and Field
California, Wilmington
Louisiana, Timbalier
Texas, East Texas
Texas, Goldsmith
Texas, Headlee
Texas, Kelly-Snyder
Texas, Sprayberry
Texas, Ward Estes N.
Venezuela, Ceuta
Venezuela, Mesa
Colombia, Orito
Iran, Agha Jari
Arabian Light (blend)
Kuwait Blend
Kuwait Blend
Middle East Blend
Egypt, El Morgan
Libya, Sarir
Indonesia, Duri
Indonesia, Minas
Sulfur,
Weight
Percent
1.10
0.36
0.29
1.60
0.07
0.28
0.12
.1.30
0.22
1.10
0.40
1.10
1.50
2.90
1.80
2.20
1.30
0.17
0.280
0.06
1
V
48.0
1.0
0.79
5.0
<.02
0.6 .
0.2
5.0
140.0
53.0
24.0
39.0
14.0
29.0
26.0
60.0
48.0
0.28
1.3
0.1
Ni
77.0
<4.4
<3.7
<4.1
<2.8
<2.4
<3.9
<2.6
21.0
14.0
21.0
21.0
<9.6
9.0
11.0
32.0
36.0
<4.0
47.0
16.0
As
<.007
0.05
<.007
<.01
<.004
<.006
<.01
0.7
0.018
<.006
<.006
<.005
<.008
<.005
<.006
<.007
<.008
<.008
0.09
<.01
bpm
Sb
<.01
<.009
<.01
<.01
0.017
<.007
<.01
<.008
<.006
<.006
<.006
<.006
<.01
0.8
<,005
0.8
0.002
<.008
0.7
<.007
Ba
<.06
0.09
<.06
<.06
<.06
<.05
0.6
<.04
<.5
<.06
.08
<.06
<.09
<.5
0.9
<.07
0.12
<.06
<.06
<.07
Mn Mo Sn
0.018 <-15 <.6
0.027 <.16 0.5
0.15 <.I6 <.4
0.033 <.19 <.6
<.001 <.l <1.0
0.008 <.12 <.6
0.026 <.18 <1.2
0.06 <.13 2.4
0.044 <.13 <.6
0.044 <.12 <.7
0.006 <.12 1.5
0.024 <.12 <.9
0.012 <.16 <.4
0.005 <.14 <1.0
0.014 <.13 <1.4
0.01 1.5 <1.2
0.029 <.16 <.5
0.05 <.13 <.5
0.044 <.ll <.8
0.006 <.ll <.8
-------
TABLE A-5 (cont'd)
Region
State/Country and Field
NORTH AMERICA Alaska, Nikiski
Alaska, Nikiski
Alaska
California, Wilmington
California
California
Louisiana, South Fields
Texas, Clam Lake
Texas, High Island
Texas, Smithbluff
SOUTH AMERICA
MIDDLE EAST
AFRICA
ASIA
Bolivia
Abu Dhabi, Murban
Iran
Nigeria
Indonesia, Katapa
Indonesia,.Katapa
Sulfur,
Weight
Percent
nd
0.13
2.00
3.34
3.04
3.00
0.38
0.227
0.09
0.147
0.031
1.01
2.40
0.21
0.0522
0.061
V
62.3
.0.358
0.447
52
93.6
89.5
0.778
0.22
0.076
0.058
0.0058
0.118
40.9
0.435
0.032
0.0218
Ni
79.5
nd
nd
58.0
58.0
55.7
nd
3.04
nd
nd
nd
nd
13.6
nd
nd
nd
ppm
As
0.037
0.013
0.0006
0.26
0.147
0.147
0.058
0.106
0.031
0.091
nd
nd
nd
0.15
0.042
0.074
Ba
0.3
nd
0.047
nd
nd
nd
nd
0.078
0.104
0.059
nd
nd
nd
nd
nd
nd
Mn
6.39
0.026
0.023
0.045
2.11
2.47
0.249
0.019
0.043
0.033
nd
0.046
0.021
1.29
0.0053
0.011
nd » not detected
-------
TABLE A-5 (cont'd)
Sulfur,
vo
Region
NORTH AMERICA
AFRICA
NORTH AMERICA
SOUTH AMERICA
MIDDLE EAST
State/Country and Field
California
California
California
California
California
Louisiana
Wyoming
Libya
Libya
Libya
California, Casmalla
Kaasas-1
Kansas-2
Mississippi
Texas
Venezuela
Mid East-1
Hid East-2
Weight
Percent
1.590
1.395
0.920
0.977
2.387
0.082
2.467
6.469
1.203
1.628
*
V
100.6
167.6
4.0
17.5
121.5
105.0
298.5
8.2
7.6
46.8
Ni
199.0
217.0
137.5
264.1
152.9
344.5
112.9
49.1
76.5
104.8
81
28
48
<2
<2
<2
109
22
ppm
Fe
79.65
26.53
16.84
85.53
59.51
3.736
5.78
4.938
120.84
3.365
Mn
1.31
1.13
1.01
2.54
0.73
0.63
0.91
0.79
1.15
1.45
Se
0.765
0.690
0.151
0.395
1.396
0.026
0.321
1.096
0.236
0.219
Cr
12.34
8.06
7.87
17.473
9.144
1.565
8.715
2.. 302
15.280
1.942
Sb
44.035
38.20
51.13
49.715
68.8
29.51
71.75
55.2
106.8
38.40
ppb
As
516.9
91.8
62.9
1112.4
111.7
46.4
111.1
77.3
151.7
343.4
0.142
0.031
0.056
0.010
0.005
0.092
0.03
0.021
Kg
114.0
81.4
88.2
29683.0
77.83
22.54
76.75
2077.8
62.39
75.83
-------
TABLE A-5 (cont'd)
Region
MIDDLE EAST
vo
to
State/Country and Field
Iraq, Ain Zalah
Iraq, Ain Zalah
Iraq, Ain Zalah
Iraq, Ain Zalah
Iraq, Bai Hassan
Iraq, Bai Hassan
Iraq, Bai Hassan
Iraq, Jambur
Iraq, Kirkuk
Iraq, Kirkuk/
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Kirkuk
Iraq, Rumaila
Iraq, Rumaila
Iraq, Rumaila
V
75
70
102
109
26.5
29.0
48
9.0
26.9
34.0
26.3
—
25.5
25.0
25.7
26.0
26.5
47
43
44
35.4
13.6
10.6
Ni
20
—
24.5
26
17.2
—
14.5
—
19.0
16.6
15.3
13.8
15.9
16.7
17.0
18.0
15.8
22.9
20.0
20.3
13.6
—
__
-------
TABLE A-5 (ccmt'd)
Region State/Country and Field V Ki
Iraq, Zubair 57.0 19.5
Iraq, Zubair 15.0 8.9
Iraq, Zubair 11.7
Iraq, Zubair 19.6
Iraq, Zubair 1.6 <0.7
Iraq, Zubair 2.1 —
-------
APPENDIX B
TABULAR DATA ON COAL ASH COMPOSITIONS
-------
TABLE B-l. CONCENTRATIONS OF TRACE ELEMENTS IN COAL
(1)
Element
••••••••••••^•••w
Antimony
Arsenic
Barium
Beryllium
Boron
Coocn in
whole coal
(ppm)
0.6-1.5
0.1-2.0
-------
TABLE B-l. (CONTINUED)
Element
Cadmium
Chlorine
(*t*)
Chromium
Cobalt
uoncn in
whole coal
(ppm)
<0.6
O.OU-0.7
30-<300
O.U1+-0.50
0.1-65
11.0
-------
TABLE B-l. CONTINUED)
Element
Copper
Fluorine
Lead
Manganese
Concn in
whole coal
(com)
lU-17
3-180
11-28
5-20
11
50-100
5-33
61
15-18
15
1-15
10-22
60-180
9.6
50-120
1-19
no
50-125
50-100
30-143
65-120
91
60-70
1*2-52
8
39-105
<50. 0-220.0
k-Ik
U-18
2-36
8-lU
7.«*
U-218
102
It
7
7
1-2
U-7
5-U8
9-55
25-95
51-54
6-181
108
88-101
Source
A
A
A
IE
IE
IE
IE
IW
N
N
SW
sw
SW
sw
A
A
A
IE
IE
IW
IW
N
N
SW
. sw
sw
A
A
A
IE
IE
IE
IW
IW
N
N
SW
SW
A
A
IE
IE
IE
IW
N
Analytical
method
—
SSMS
AAS/OES
•
-
SSMS-ID
AAS/OES
AAS/OES
AAS/OES
-
-
AAS/OES
SSMS
XRF
_
SSMS
ISE
.
ISE
_
ISE
.
ISE
SSMS
ISE
ISE
«
AAS/OES
SSMS
_
SSMS-ID
AAS/OEjS
AAS/OES
.
AAS/OES
.
SSMS
AAS/OES
SSMS
NAA
.
INAA
NAA
NAA
NAA
< Ash
m
-
6.15-18.27
6.8-10.9
.
10.9-11.2
3.28-16.0!*
25.85
n. 29-15. 83
-
-
6.56-13.65
_
6
.
.
6.15-18.27
•
3.28-16.04
•
25.85
11.29-15.83
.
6.56-13.68
3.85-29.60
•
6.15-1B.27
.
•
10.9-11.2
3.28-16.0U
25.85
.
11.29-15.83
•
.
6.56-13.65
.
6.15-18.27
6.8-17.26
10.9-11.2
3.28-16.0U
25.85
11.29-15.83
(continued)
96
-------
TABLE B-l. (CONTINUED)
Element
Manganese
(Cont.)
Mercury
Molybdenum
Nickel
Concn in
whole coal
(ppa)
6-22
10-2UO
5-200
0.12-0.21
•^o.s-o.s
0.08-0.46
0.16-1.91
0.13
0.170-0.063
0.04-1.60
0.19
0.18
0.07
0.07-0.09
0.11-0.74
0.02-0.06
<0.3
0.02-1.20
0.07
0.05-0.38
1.5-5.8
1-5
10
1-11
4.3
10-20
-------
TABLE B-l. (CONTINUED)
Element
Selenium
Tellurium
Thallium
•
Tin
Titanium
(vt %)
Uranium
Concn ID
vhole coal
(ppn)
0.04-0.3
1.3-6.6
2.6-3.4
0.4-7.7
2.9
0.8
0.5-3.9
1.2-2.3
0.40-3.90
1.9
<0. 1-0.4
1-3
0.2
<0. 02-0.10
2-36
2.4-3
<0.20-1.UO
0.1-0.9
1-47
<3-8
1-5
20
<1-51
<10
0.6-1.6
<5-15
4-35
<2-8
0.02-0.18
0.06-0.15
0.05-0.17
0.07
0.02-0.15
0.08
0.06
0.05-0.09
0.03-0.13
0.3-1.0
0.09-3.70
Source
A
A
IE
IE
IW
N
SW
SW
SW
SW
A
IE.-
SW
SW
A
IE
SW
A
A
A
IE
IE
IE
IW
IW
N
SW
SW
A
A
IE
IE
IE
IW
N
SW
SW
A
SW
Analytical
method
SSMS
NAA
INAA
NAA
NAA
NAA y
•
NAA
XRF •
XRF -
SSMS
SSMS
SSMS
we
SSMS
INAA
AAS
_
SSMS
OES
.
SSMS
OES
OES
.
OES
SSMS
OES
SSMS
XRF
_
NAA
XRF
XRF
XRF
SSMS
XRF
SSMS
INAA
•
4 Aah
.
6.15-18.27
10.9-11.2
3.28-16.04
25.85
11.29-15.83
.
6.58-13.68
3.85-29.60
6
«•
10.9-11.2
.
3.85-29.60
m
10.9-11.2
3.85-29.60
—
—
6.15-18.27
_
10.9-11.2
3.28-16.04
25.85
11.29-15.83
_
6.56-13.68
6.15-18.27
6.8-17.26
10.9
3.28-16.04
25.85
11.29-15.83
_
6.56-13.68
—
3.85-29.60
(continued)
98
-------
TABLE B-l. (CONTINUED)
Element
Vanadium
Zinc
•
i
Concn in
whole coal
(PFBU
19-25
3-77
2l*-52
35
21-69
16-78
to
1U-18
n-26
2-8
10-22.5
17-22
U.U-12
3-80
21-UO
U8-<3000
M»
85-250
10-5350
22-53
1UW*
- 59
10-12
1-17
U-26
7-15
7.3
Source
A
A
A
IE
IE
IE
IW
N
SW
SW
.
IW
A
A
A
IE
IE
IE
IE
IW
IW
H
N
SW
SW
SW
SW
Analytical
method
.
SSMS
XRF/OES
_
IKAA
XRF/OES
XEF/OES
XRF/OES
XRF/OES
SSMS
OES
-
^
SSMS
AAS
_
m
SSMS
AAS
-
AAS
.
AAS
_
SSMS
AAS
XRF
* Ash
^
_
6.15-18.27
_
10.9-11.2
3. 28-16.01*
25.85
11.29-15.83
6.56-13.68
.
-
-
^
m
6.15-18.27
6.8-17.26
_
10.9-U.2
3.28-16.CA
_
25.85
.
U.29-15.83
.
_
6.56-13.68
6
a. Abbreviations for coal sources
A - Appalachian (Pennsylvania, Maryland, Virginia, West Virginia,
Ohio, Eastern Kentucky, Tennessee, Alabama).
Av U.S. B A representative average for U.S. coals.
IE * Interior Eastern (Illinois, Indiana, Western Kentucky).
IW * Interior Western (Iowa, Missouri, Kansas, Oklahoma, Arkansas),
N * Northern Plains (Montana, North and South Dakota).
SW « Southwestern (Arizona, Mew Mexico, Colorado, Utah).
(continued)
99
-------
TABLE B-l. (CONTINUED)
b. Abbreviations for analytical methods
AAS = Atomic Absorption Spectroscopy
AS = Absorption Spectroscopy
FAAS = Flameless Atomic Absorption Spectroscopy
GC-MES = Gas Chromatography with Microwave Emission
Spectroscopic Detection
INAA = Instrumental Neutron Activation Analysis
ISE = Ion-Selective Electrodes
NAA = Neutron Activation with Radiochemical Separation
OES = Optical Emission Spectroscopy-Detection
Method Unspecified
OES-DR = Optical Emission Spectroscopy with Direct
Reading Detection
OES-P = Optical Emission Spectroscopy with
Photographic Detection
PAA = Photon Activation Analysis
FES = Plasma Emission Spectroscopy
SSMS = Spark Source Mass Spectroscopy
SSMS-ID = Spark Source Mass Spectroscopy with
Isotope Dilution
WC = Wet Chemistry
XRF * X-Ray Fluorescence Spectroscopy
100
-------
TABLE B-2. QUANTITATIVE ANALYSES (in ppm) FOR 13 TRACE ELEMENTS IN
DRILL-CORE COAL SAMPLES, POWDER RIVER BASIN(2)
Sample
interval
(ft)
100-109
109-112
2UO-2U7
231-232
116-127
127-137
137-lUO
100-lOU
60-68
166-176
108-118
216-226
71-72
80-88
88-98
11+3-150
92-101
101-106
lUO-ll+7
1CD-110
110-120
Drill-core
sample
no.
1*58
U59
U62
1+63
U6U
U65
U66
U67
1+68
U69
1+70
1+71
1+72
1+73
1+7!+
1+75
1+76
1+77
U78
U79
1+80
Cd
1.
<1.
<1.
<1.
<1.
1.
a.
i.
-------
TABLE B-2. (CONTINUED)
o
to
SaBple
Interval
(ft)
100-109
109-112
2UO-2U7
231-232
116-127
127-137
137-11*0
100-101*
60-68
166-376
108-118
216-226
71-72
80-88
88-98
11*3-150
92-101
101-106
1UO-1U7
ioo-no
UO-120
J)rill-core
sample
no.
1*58
U59
U62
1*63
1*6U
1*65
1*66
1*67
1*68
1*69
1*70
1*71
1*72
U73
1*7U
1*75
1*76
1*77
1*78
1*79
• x
1*80
ppn. coal
As
2.
2.
2.
3-
1.
1.
3.
2.
2.
2.
3.
1*.
5.
3.
2.
3.
5-
3.
U.
U.
3.
F
1*0
30
10
10
30
20
30
30
60
1C
Hg
0.035
0.082
0.037
0.051
O.OUI*
0.030
0.106
0.035
0.01*9
0.099
0.01*3
0.065
0.039
0.035
0.021
0.058
0.181
0.01*8
0.028
0.01*1
0.035
Sb
0.92
0.62
0.08
0.12
O.OU
o.oi*
0.06
0.08
o.o»*
-------
TABLE B-3. TABULATION OF ELEMENTAL CONCENTRATIONS AND MASS BALANCE RESULTS FROM ALLEN STEAM PLANT
(3)
r«rvcnfr:ition 'ppi
Element Run
Aj:* 5
7
9
A**" 7
Al* 5
7
9
AK 5
7
9
As* 5
7
I-4 9
o
W A** 5
7
9
r s
7
9
Bt* S
9
Bit' 5
7
9
Be* 5
7
9
if 7
fc* 5
9
Coal
<2
<2-5
)%
1%
4.7
18
3.8
5
5
200
100
200
91
79
100
150
100
<5
0.3
IO%
15%
27
349
46
5
1000
40
3000
250
2000
400
3000
300
1700
15
3
17
2
<2-5
<5
rwiM- indica
PO
~1
3
20%
3.5%
20%
>IO%
10%
138
50
100
30
20
300
150
300
300
150
100
5
1
IO% >1.3 x 10*
1.3 X 10*
5.9
93 23
4.7
6.2
100
6.2
250
170 130
250
114
99
130
100 190
130
<6.3
0.3 0.4
<6.3
5 <13
3.3
2.5
S.T
<020
O 0
7..S v |(('
9.9 X 103
7.2 x 10'
5.0 x |0J
1.0 x 10*
5.5 x 103
<0.99
0.05
0.10
0.22
30
20
33
66
30
51
33
0.50
0.05
<1.I
<1.0
<0.1
<0.05
\ia«nou
PI
<0 20 0.33
<0.07
6.8x 10J
7.3 x I03
1.8
24
2.2
0.33
68
2.0
200
17
91
27
200
20
83
1.0
0.21
0.83
0.14
<0.1 3-0.33
<0.24
(g/min)
ImhjIjiK'
<%)"
-14
69
-18
-25
-1.5
-52
-93
-64
-8
-71
-48
77
-63
-11
-35
P.O. Suik
-0.002 0.001
0.0056 0024
3.7 X I02 4.5 x I03
68
3.8 x 10J
>1.9xlOl M.2X102
1.9 x JO2
0.26 0.11
0.097
0.19
0.056 0.12
0.039
0.57
0.28 0.20
0.59
0.57
0.28 0.12
0.19
0.01
0.0019 0.00036
<0.019
0.0037 0.0059
0.019
(continued)
-------
TABLE B-3. (CONTINUED)
Dement
Ca"
ta<
Co'
Cd<
a*
Co6
Coc
Cr«»
Cf
0*
CV
Dyr
Ku^
Him
<
7
^
5
7
9
'»
5
t
9
5
9
5
7
9
5
7
9
5
7
9
5
7
9
5
9
5
7
9
9
5
9
C omen irj lion (ppin tinier otherwise indicated)
Owl S.T P.I. P.O. Stack
ii W
•LSI'
d.38'.
1'
r;
0.5';
-.;o
(l.44'y
0.50rf
407
355
3.5
5
3.3
10
<. 10
7
23
21
65
150
30
1.5
1.5
SO
100
50
00
0.31
0.17
•> IK,"
4.4';
2.7',;
5'.
5';
3''.'
2
2
15
28
19
<50
40
895
111
18(1
300
500
OOO
8.8
8
300
200
200
0.7
1.4
I.57-;
2.2'.'
i .4'.;
3.5'V
>\"-
y:
<2
<2
<\n 20
50
<5 50
35
51
25
50
70
200
356
250
170
70
IS
21
300
400
400
1.6
1.8
1.2'.' | . ;
r;
<(\1 • (1.7
7
1001)
26 11
5K
30 10
40
300
200
200 !50
40
4
200
400 1000
400
Coal
045 * I04
11.64 y II)4
0.47 A III4
1.3 < Id4
1.3 x |04
O.f, • K)4
-37
(1.55
063
510
460
4.4
6.3
41
13
- 13
9
29
26
81
190
37
1.9
l.o
63
130
63
6.K x |0J
1.5 x 10 •'
-.(1.13
;O.I4
<0.49 0.97
3.3
<0.24-2.4
2.3
3.5
1.2
3.4
3.4
14
17
17
12
3.4
1.0
1.02
20
27
19
0.11
0.09
('j/minf
linbjlanee
-32
6.3
22
- 44
20
-14
1.6
19
-13
42
-42
67
-1.6
0
-21
-64
-35
-55
14
P.O. Slack
22 -T2
9.5
5.7
>I9 -12
19
<0.0013 -'.C..00083
0.014
1.9
0.048 0.013
on
0.56 0.012
0.078
059
0.38
0.37 0.18
0.078
0.0078
0.38
0.74 12
0.78
-------
TABLE B-3. (CONTINUED)
Concentration (ppm unless otherwise indicitrd)
Fkmrni
EII*"
Fe»
IV
C.»
Cac
Of
Hf»
««*'
*f
•
K"
Kc
U"
\jf
\f
Run
9
5
7
9
S
7
9
7
5
9
5
9
5
9
5
9
S
7
9
5
7
9
S
7
9
S
7
9
9
5
7
9
Coal
-1
1.46%
2.0%
1.3%
2%
-2%
2%
13
15
5
4.4
3.0
0044
0.170
0.063
0.20%
0.25%
0.22%
0.17%
0.1%
0.06%
4. 8
6
5.0
-10
30
100
25
S.T
10.3%
13.2%
10.1%
10%
-8%
10%
40
<10
2
2%
10%
71
too
70
200
70
0.1 IJ
0.13d
0.04
0.10
0.043
1.17%
1.97%
1.65%
1.7%
1%
0.7%
30
36
32
350
200
300
P.O.
9.6%
23.5%
10%
>2%
10%
93
100
40
200
40
2%
130
0.29%
0.05%
12
SO
Mass (low (g/min)
Coal .
-1.3
1.83* I04
2.5 x 10*
1.6 x 10*
2.5 x 10*
-2.5 x 10*
2.5 x 10*
16
19
6.3
5.5
3.7
0.080
0.212
0.079
0.25 x 104
0.31 x I04
0.27 x 104
0.21 x I04
0.13 x 104
0.07 x I04
6.0
7.5
6.3
-13
37
130
31
S.T
I.OX I04
l.4x 104
i.i x in4
9.9 x 10J
-82 x I03
I.Ox 104
4.0
!.« x lo3
4.9 X 10J
4.8
6.6
3.4
13
3.4
0.007*
0.006*
0.0027
0.007
0.0021
7.8 x 10J
1.3 x 103
8.0 x I02
1.1 x I03
6.8 x 102
3.4 X I02
2.0
2.46
1.5
23
14
15
Imbalance
r*)°
-ii
-6.0
-3.1
-34
-40
-31
-88
-85
-25
-9.7
-33
24
190
27
-8.3
-4.5
-3.2
43
-50
19
P.O Stack
1.8 X 10* 4.8 x JO1
4.6 x 101
1.9 x 102
>3 7 x 10* >2.4 x 101
l.9x I02
0.17 0.15
0.19
0.078
0.38
0.078
<0.0019
-0.019
16 3.5
25
5.7
9.3 0.6
3.9
0.035 0.014
0.13
0.19 0.059
0.39
-------
TABLE B-3. (CONTINUED)
Concentration (pntn
r tenieni
Mp»
Mis'
MB*
Mnr
Mo*
Mof
Na*
Ma*1
Ntf
Ndc
1^
p*
Run
5
7
9
5
7
9
5
7
9
5
7
9
5
9
S
7
9
5
7
9
S
7
9
S
7
9
9
S
7
9
5
7
9
foal
0.15V
o.i7';
0.17V
0.157
O.IV
0.15%
53
St
54
100
200
100
47
20
20
10
20
0.063 -0.63%
0.072%
0.069%
0.05%
015%
0.031
<15
|rj
0.7",
325
316
323
1000
1000
700
150
700
200
0.59%
0.58%
0.7%
0.3%
>l%
0.3%
6
10
IS
500
1000
500
200
300
500
P.O. Stack
2.5'.'
O.XK'.
0.8',:
o.7v r..
0.4';;
335 218
550
1000
500 900
500
200
ISO 70
20
0.40% 0.33%
0.28%
0.15%
0.3% 0.09%
0.2%
20
10 20
10
1000
500 300
1000
200
300 200
200
Coal
0.18 x 10*
0.21 x 104
o.2l x in*
0.18 x |0*
0.12 x |04
0.18 x H>"
66
64
67
130
250
130
59
25
25
12
25
790-7900
900
860
630
0.19 x 10*
370
2
5.9 x Id2
5.1 X Id2
7.7 X 102
41
39
46
99
72
110
9.9
7.2
8.8
3.3 x 10'
3.0 v |0J
3.5 x I02
3.0 X I02
3.1 x I02
2.2 x I02
0.20
6.8 x I02
3.4 x 102
22
21
16
66
68
34
10
48
9.7
3.9 x I02
4.0 x I02
3.4 X I02
3.3 X 102
>6.8 x I02
I.SX I02
0.40
0.68
0.73
33
68
24
13
20
24
Imbalance
<*)"
-13
04
66
31
-38
-4.5
6.3
7.5
27
-44
11
-JO
360
-26
-22
-20
0
-48
0.0
-56
-58
P.O.
17
15
13
7.8
062
11
1.9
0.93
0.97
0.38
0.28
0.039
7.4
S.S
2.8S
5.6
3.9
0.038
0.019
0.019
1.9
0.93
1.9
0.38
0.56
0.39
Stack
30
12
0.26
t.l
0.083
3.9
1.1
0.024
0.36
0.24
-------
TABLE B-3. (CONTINUED)
o
Concentration (ppm unli'sv otherwise indicated) . .
Fir men)
Pbr
P,<
Kb"
Rbf
S*
Sb>
Sbf
Sc»
Sr»
Se*
Sf
Sm*
Snf
Srf
Slr
Run
5
7
9
o
5
7
*
5
7
9
5
9
5
5
;
5
7
9
5
7
9
9
5
7
9
5
9
9
7
7
9
Coal
10%
30%
0.12
200
500
60
P.I.
80
300
2M>
162
5%
30%
20
300
200
P.O. Stack
goo
100 70
100
100
50 30
10
10.5%
10
S% >5%
10%
20 20
100 100
60
Cojl
t,63
~17
<25
- 13
21
21
24J
50
250
21
<.4 x I04
6.4 X 104
<0.75
4.3
4.5
4.0
4.0
3.3
4.0
7.5
6.3 x I04
6.3 x 104
6.3 x I04
1.3
1.3
-13
25
250
S.T.
0.30
1 0
1133
28
1 I
40
4.4
<0.02
079
2.0
2.3
2.4
1.0
1.5
2.2
3.0 x I04
>1.0x I04
3.3 x 104
001
20
51
6.6
MJSS 1'i» ()!/min)
p Imbjljnce
$.3
20
12
11 34
^5.8
43 66
20
9.7 -33
0.2
047
<0.68
1.7 -14
2.0 -4.4
1.2 -10
1.6«4.0)
1.6
3.4 x 101
1.5 x I04 -24
1.4 -M
20 -72
9.7
P.O
1.5
0 19
(1 19
0.19
0.093
0.019
2.0 x 102
n OIQ
93
1.9X I01
0.037
0.19
0.12
Stack
0.083
0.036
<0.012
0.0059
0.052
>59
0.024
0.12
-------
TABLE B-3. (CONTINUED)
('onccntrjiiiin (ppm unices othtTwiM- mil K.I
Element Run
TJ* 5
9
Ta' 7
Thr 9
1o* 5
9
Th6 5
9
Th' 7
Ti* 5
7
9
Tf 5
K 7
§ 9
Tf 9
7
U* 5
7
V
f 7
V^ 5
7
9
V 5
7
9
W^ 9
W* 7
9
foal
O.I.--I
-1
•:lo
-1
3
1
2.4
3
580
MM)
710
650
700
700
<2
3
3.3
167
21
69
21
12
50
30
^s
•-10
1
S.T.
t
200
3
3
20
3300
24IM)
300O
3000
3000
2000
2
1
17
14
135
560
125
30
100
100
|
P.I.
1.2
1.3. <5
50
<|
-10
23
18
10
42(K)
3500
3700
-3000
1500
5000
40
100
15
21
17
100
211
780
200
ICO
200
350
5»»
5
P.O.
20
<|
-10
7
3400
2500
2000
700
1 000
30
30
12.4
7
20
406
63
too
100
too
20
1
It-ill
Stack Coal
0.13. < 1.3
o/n
2.2
330
250
330
30O
310
220
0 22
0.10
1.7
1.5
11
57
14
3.0
10
II
0.11
P.I.
OOK
0.06. <0.24
34
<007
-0.49
1.5
0.87
(I.6K
2HO
240
180
-200
100
240
1.9
6.8
10
1.4
083
6.8
14
53
9.7
66
14
17
3.4
0.24
ImhjbiKc
("1"
17
16
-22
-43
-53
48
70
24
11
38
28
-8.8
36
62
24
73
P.O
0.037
-------
TABLE B-3. (CONTINUED)
Omcrntration (PPm tmlc« olhcrxv™ indicated)
ICIcnicnl Run Coal
In' 5 250
7 <200
9 S5
2\r 5
7 40
9 <30
" ST. * P.I. - coal
coal
**N- • • 1 •
rSpjrk source m
-------
TABLE B-4. AVERAGE TRACE ELEMENT CONTENT IN ASH OF COAL
FROM THREE AREAS,1 PERCENT
Clement
Beryllium
Boron
Cobalt
Gallium
Lead
Lithium
Nickel
Tin
Yttrium
Zinc
Average ash.. pet of dry coal
Number of samples
Cruital
abun-
dance3
0.0425
.00028
.0010
.0100
.0025
.0055
.0015
.00015
.0030
.0013
.0020
.0950
.00015
.0075
.0022
.0375
.0002
.0135
.00034
.0033
.0070
.0165
.00018
. 00002
.0060
.0026
.0020
.0090
.00005
Approx-
imate
lower
limit of
detec-
tion3
0.002
.0001
.0002
.0001
.0020
.0001
.0002
.0003
.01
.0001
.0001
.0001
.0001
.0001
.002
.001
.0001
.0001
.0001
.001
.005
.005
.005
.0001
.02
.01
.001
.001
.0005
Eastern Province
Fre-
quency
of
detec-
tion
100
100
100
100
100
100
100
99
92
100
100
100
99
100
100
100
100
100
100
100
98
100
67
82
31
29
73
97
43
Average
trace
element
content
of ash
0.0876
.0012
.0265
.0230
.0164
.0128
.0071
.0048
.0145
.0055
.0584
.0260
.0082
.0209
.0089
.1052
.0019
.0336
.0007
.0142
.0230
.0704
.0159
(.0107)
.0002
(.0002)
.0238
(.0074)
.0213
(.0062)
.0053
(.0039)
.0239
(.0232)
.0019
9.3
60C
Interior Province
Fre-
quency
of
detec-
tion
100
100
100
100
98
too
100
100
86
100
100
100
99
100
100
100
99
100
100
100
100
100
41
77
11
10
88
100
49
Average
trace
element
content
of ash
0.0399
.0014
.0731
.0224
.0193
.0089
.0039
.0104
.0131
.0131
.0235
.0325
.0073
.0262
.0069
.0658
.0019
.0325
.0005
.0118
.0743
.0825
.0119
(.0049)
.0001
(.0001)
.0214
(.0024)
.0183
(.0018)
.0055
(.0048)
.0276
(.0276)
.0008
10.3
123
Western Stat«t
Fre-
quency
of
detec-
tion
100
100
100
100
98
100
100
95
81
100
100
100
100
100
97
100
100
100
100
100
93
100
16
83
13
15
85
58
9
Averagt
trace
element
content
of ash
0.1467
.0006
.0529
.0066
.0097
. .0067
.0033
.0017
.0128
.0029
.0168
.0212
.0020
.0054
.0052
.1456
.0017
.0152
.0003
.0076
.0258
.0850
.0073
(.0012)
.0001
(.0001)
.0238
(.0031)
.0295
(.0044)
.0053
(.0045)
.0064
(.0037)
.000}
9.6
104
1 Averages calculated for number of samples in which element was detected, except that averages
in parentheses were calculated for all of the samples tested using zero for element contents
below limit of detection.
"Mason, Brian. Principles of Geochemistry. John Wiley & Sons, Inc., New York, 3d *d., 1966,
_ pp. 45-46.
'Peterson, M. J., and J. B. Zink. A Semiquantitative Spectrochemica! Method for Analysis of
Coal Ash. BuMlnes Kept, of Inv. 6496, 1964, pp. 6-10.
110
-------
TABLE B-5. AVERAGE TRACE ELEMENT CONTENT IN ASH OF COALS FROM STATES
IN EASTERN PROVINCE, PERCENT OF ASH*4'
Element
Bo ron .
Nickel
Tin
Yttrium
Zinc
Average ash.. pet of dry coal
Number of samples
Alabama
0. 1195
.0008
.0322
.0207
.0198
.0150
.0055
.0046
.0138
.0040
.0812
.0208
.0117
.0186
.0078
.13%
.0024
.0338
.0005
.0126
.0243
.0607
9.2 .
47
Eastern
Kentucky
0. 1077
.0020
.0255
.0260
.0212
.0156
.0099
.0064
.0175
.0059
.1064
.0361
.0071
.0217
.0131
.1538
.0063
.0400
.0009
.0217
.0203
.0823
7.3
26
Maryland
0 . 0450
.0007
.0140
.0140
.0150
.0075
.0020
.0007
.0100
'.0010
.0140
.0030
.0017
.01.25
.0065
.0900
.0005
.0225
.0003
.0050
0200
1100
9.5
2
Ohio
0.0436
.0009
.OS61
.0235
.0144
.0080
.0050
00 S 9
.0126
.0043
.0394
.0207
.0057
.0203
.0058
.051 1
.0013
.0236
.0007
.01 SO
0?ftA
OROS
11.8
85
Pennsylvania
0 0703
0008
01 SI
0244
017S
012S
0071
0049
01 1O
00 S 2
0642
020 S
009ft
019S
0086
0941
.0011
0330
0006
0127
0222
0680
10.0
117
Tennessee
01?4fl
0006
0947
0700
01 Ifi
01 16
00 S7
no is
Ol ^9
00 SO
OQQA
091&
OOflO
01 Aft
01&1
1 1AR
nni Q
01 S4
OOOfi
'Old?
0249
046O
9.7
25
Virginia
01 771
on 14
ni A4
07S1
. *J£JJ
ni 01
. l_)l
nn 7ft
n44i
• UH«+1
ncAr»
ni HA
fl9R1
. vZOl
OOQ9
1 94n
. l^fvl
on in
O41 7
nni i
ni si
n?oi
ncco
7.8
51
West
Virginia
Onoi n
. U:7lU
nni A
nttt
. U^J/
nooo
• \J /.£.{.
nono
. uzuz
ni TJ
.Ul J^
nn77
. uu / /
nn/.c
.UUHO
ni CT
.VJl;)/
nnca
. UUjO
neon
. Uj^U
no/, Q
.U/H9
nmt
.uu / J
no 1 1
,\Ji\.i
nnot
,UU5*J
i i n/<
. 1 1UH
nni 7
• vUl /
ni4R
.UJHO
nnn7
ni 4s
noni
n7ifl
8.5
247
-------
TABLE B-6. AVERAGE TRACE ELEMENT CONTENT IN
INTERIOR PROVINCE, PERCENT OF
H
OF COALS FROM STATES IN
Element
Arkansas
Illinois
Indiana
Iowa
Kansas
Missouri
Western
Kentucky
Barium. 0.1000
Beryllium 0003
Boron .0175
Chromium .0300
Cobalt 0550
Copper .0055
Gallium 0025
Germanium , .0010
Lanthanum . 0300
Lead 0035
Lithium .0100
Manganese .0150
Molybdenum 0125'
Nickel 0325
Scandium 0040
Strontium 2500
Tin 0012
Vanadium 0350
Ytterbium .0003
Yttrium 0060
Sine 0190
Zirconium .0600
Average ash.........pet of dry coal.. 8.3
Number of samples. 2_
0.0423
.0011
.0690
.0252
.0131
.0071
.0035
.0116
.0105
.0279
.0386
.0621
.0075
.0211
.0077
.0697
.0022
.0297
.0004
.0089
.1193
.0755
11.7
29
0.0290
.0016
.0803
.0182
.0226
.0091
.0035
.0139
.0169
.0068
.0231
.0245
.0.049
.0308
.0074
.0660
.0007
.0327
.0004
.0098
.0690
.0945
10.6
31
0.0300
.0010
.0833
.0400
.0343
.0067
.0070
.0133
.0133
.0200
.0300
.0433
.0100
.0567
.0050
.0667
.0009
.0300
.0008
.0100
.1333
.0667
15.5
0.0150
.0005
.0250
.0150
.0450
.0150
.0020
.0060
.0150
.0100
.0050
.0300
.0050
.0550
.0040
.0900
.0010
.0150
.0003
.0275
.0750
.0750
10.5
0.0183
.0010
.0667
.0433
.0233
.0108
.0065
.0088
.0100
.0267
.0137
.0350
.0108
.0767
.0047
.0417
.0016
.0375
.0009
.0142
.0620
. .0733
12.4
0.0468
.0015
.0752
.0197
.0167
.0095
.0040
.0082
.0115
.0069
.0171
.0201
.0079
.0170
.0067
.0578
.0027
.0341
.0005
.0142
.0514
.0824
9.3
50
-------
TABLE B-7. AVERAGE TRACE ELEMENT CONTENT IN ASH OF COALS FROM WESTERN
STATES, PERCENT OF ASH(4)
Element
Coba 1 i
N1 rkel
Tin
Yttrium.
Zinc
Average ash. .pet of dry coal.
Arizona
0.0400
.0010
.0500
.0100
0
.0050
.0050
.0050
0
.0040
.0200
.0100
.0010
.0050
.0010
.1000
.0010
.0100
.0001
.0100
.0100
.0400
9.7
1
Colorado
0.0795
.0006
.0494
.0049
.0104
.0049
.0032
.0019
.0129
.0031
.0095
.0216
.0018
.0053
.0056
.0974
.0023
.0125
.0003
.0083
.0362
.0872
9.2
40
Montana
0.3000
.0012
.0475
.0024
.0061
.0025
.0039
.0025
.0097
.0038
.0215
.0456
.0038
.0026
.0034
.2612
.0009
.0097
.0004
.0060
.0337
.0612
12.6
8
New
Mexico
0.2250
OOOR
0361
0091
0126
0050
0034
OO32
01 SO
0040
.0138
.0165
0017
.0069
0068
0800
0016
.0213
.0005
.0085
.0164
0914
11.8
14
North
Dakota
026 SO
OOO7
0117
om4
00 S7
0013
002O
OOQA
OO96
0099
009S
03OO
no1??
OO14
OO4S
2612
0013
0094
.0004
.0060
0250
.0662
12.0
8
Utah
01 1 92
noni
Oftftl
ODRR
OO66
nniR
orno
OOOR
O1 11
on?A
O7R1
O1 S7
OO1 1
on si
0017
14S7
O01 1
Ol 17
O002
O067
0109
0861
7.0
' 23
Washington
01 71 A
nnn/.
n^i L
ni 01
noi 7
ni 91
no^o
. \J\J JJ
nftfiQ
niii
• UUJ
nnoc
no 77
• U£ / /
ni 01
• ui^l
nn*>&
. uuzo
ni i L.
• Ui It
nnoQ
.UUO7
1O71
. JU / 1
nrtno
AAOQ
Oflfl4
0094
O941
i on A
12.7
7
Wyoming
01 Q£~l
. 1 TO /
flAOO
.OU28
n/. i T
.U»»l /
t\r\t n
.UUo /
nntn
. uuou
nncn
. UUjU
f\f\ 1 "7
. UU1 /
nni Q
.UUlo
nncA
.UU5U
flrtrt"7
.UUO /
no i T
• Uil /
n i £n
. UlbU
nnoc
. UUZ3
nn/.T
.UUH/
nn/.n
. UUHU
1 Ift7
• llo /
nni t
. UU1Z
ni A7
.uio /
nnni
nos^
n^oi
n4so
8.7
3
u>
-------
TABLE B-8. RANGE IN AMOUNT OF TRACE ELEMENTS PRESENT
IN COAL ASHES (ppm)<5)
Anthracites
Element
Ag
B
Ba
Be.
Co
Cr
Cu
Ga
Ge
La
Mn
Hi
Pb
Sc
So
Sr
V
y
Yb
Zn
Zr
Max
1
130
13UO
11
165
395
$40
71
20
220
365
320
120
82
l*250r
3^40
310
120
12
350
1200
» • Insufficient
Min.
1
63
5^0
6
10
210
96
30
20
115
58
125
Ul
50
19
80
210
70
5
155
370
figures to
Average (5)
*
90
866
9
810
30U
1*05
U2
*
ll*2
270
220
81
61
962
177
2U8
106
8
*
688
compute an average
High rolatlle
Max.
3
2800
U660
60
305
315
770
98
285
270
700
610
1500
78
825
9600
81*0
285
15
1200
1U50
value.
Min.
1
90
210
U
12
7U
30
17
20
29
31
*5
32
7
10
170
60
29
3
50
U5
bituminous
Average (21^
*
770
1253
17
6U
193
293
uo
*
111
170
154
183
32
171(22)
1987
21*9
102
10
310 @
1*11
0 » Figures encircled indicate the number of samples used to compute average values.
114
-------
TABLE B-8. (CONTINUED)
Low
Element
Ag
B
Ba
Be
Co
Cr
Cu
Ga
Ge
La
Mn
Ni
Pb
Sc
Sn
Sr
V
Y
Tb
Zn
Zr
Volatile
Mu.
l.U
180
2700
UO
W*0
1*90
850
135
20
180
780
350
170
155
230
2500
Wo
l*6o
23
550
620
Bituminous
Min.
1
76
96
6
26
120
76
10
20
56
1*0
61
23
15
10
66
115
37
U
62
220
Average (8)
*
123
71*0
16
172
221
379
in©
*
110
280
1U1
89
50
92©
818
278
152
10
231
U58
Medium
Max.
1
780
I8oo
31
290
230
560
52
20
11*0
Woo
Wo
210
UO
160
1600
860
340
13
U60
51*0
Volatile
Min.
1
7U
230
U
10
36
130
10
20
19
125
20
52
7
29
UO
170
37
U
50
180
Bituminous
Average 0
*
216
896
13
105©
169
313
*
*
83
ll*32
263®
96
56
75
668
390
151
9
195(6)
326
* » Insufficient figures to compute an average value.
0 - Figures encircled indicate the number of samples used to compute an
average value.
115
-------
TABLE B-8. (CONTINUED)
Lignites and Subbituminous
Element
Ag
B
Ba
Be
Co
Cr
Cu
Ca
Ge
La
Mn
Ni
Pb
Sc
Sn
Sr
V
y
Yb
Zn
Zr
Max.
50
1900
13900
28
310
140
3020
30
100
90
1030
k20
165
58
660
8000
250
120
10
320
1*90
Min.
1
320
550
1
11
11
58
10
20
3U
310
20
20
2
10
230
20
21
2
50
100
Average Q3)
«
1020
5027
6
U5
&
655
23©
*
62
688
129 8
60
18©
156
1*660
125
51
U
*
2«»5
••Insufficient figures to compute an average value.
0 "Figures encircled indicate the number of samples used to
compute average values.
116
-------
TABLE B-9. CONCENTRATIONS OF TRACE ELEMENTS IN COAL FLY
ASH AND FLUE GAS (ppm)
Coacn in Concn suspended
fly ash in flue gas
Element
Antimony
Arsenic
Barium
Beryllium
Boron
Bromine
Cadmium
Chlorine
Concn in
coal
^
<700
-
-
0.72-l.U
.
-
0.5
5.U
-
-
-
20-32
-
-
Ik
<300
130-210
59
<2
<5
100-200
32J»5
-
6
-
-
0.146
355-1*07
A
Source
A
IE
IE
IE
.
SW
sw
IE
Av U.S.
A
A
IE
-
SW
SW
IE
A
IE
IE
A
IE
IE
IE
A
IE
-
.
A
IE
IE
IE
IE
IE
Control
nethod0
ESP
Mecfa
ESP
cy
ESP
ESP
WS
ESP
„
ESP
ESP
Cy
ESP
ESP
WS
ESP
ESP
Necb
ESP
ESP
ESP
Mech
Cy
ESP
ESP
ESP
ESP
ESP
ESP
Mech
ESP
Cy
ESP
ESP
Before
control
<600
.
.
.
.
1U
12
-
130
120
<1*00
1*50
10
3-17
•
250-3000
-
•
i6o~
•
•
8.0
<5-50
After Before
control control
265
<600
689
17-53
16
22
55
0*7
1*11*
1513
680-1700
.
150
280
UUO
1644
-------
TABLE B-9. (CONTINUED)
Concn in COOCD suspended
fly ash In flue gas
Element
Chromium
Cobalt
Copper
.
Fluorine
Iodine
Lead
Manganese
Mercury
Concn in
coal
20
-
_
25-35
20
m
0
_
fc.9-6.2
3.0
_
20
-
9.6
9.6
50-100
<2-60
25-61*
_
<30
6. 5-12. 1*
-
.
U.9
.
-
90
31^*5
3k
o.u 0.63
o.n-o.63
0.33
-
«2
0.122
Source*
A
IE
IE
IE
.
IE
A
IE
IE
.
IE
A
IE
IE
SW
SW
IE
-
-
A
IE
IE
.
SW
SW
IE
«
A
IE
IE
.
IE
SE
SE
-
A
IE
IE
Control
nethod
ESP
Mech
ESP
Cy
ESP
ESP
ESP
Mech
Cy
ESP
ESP
ESP
Mech
Cy
ESP
WS
ESP
-
ESP
ESP
Mech
Cy
ESP
ESP
WS
ESP
ESP
ESP
Mech
Cy
ESP
ESP
Mechd
ESP
ESP
ESP
Mech
ESP
Before
control
.
500
-
.
-
310
^
60
-
.
1*1
—
100
-
_
280
300-1*00
< 10-100
-
_
200
_
_
-
no
80
«
-
500
.
_
290
-
.
-
<0.2
0.05
After Before
control control
1671*
7UOO
300
290-3300
-
900
227
70
60-130
-
65
620
200
270-390
320
290
200-1*00
-
-
649
200
1100-1600
_ .
130
31*0
650
1.65
1362
600
150-U70
.
1*30
• •
O.I*
89
20
<• •
After
control
20
.
0.7
.
i3.e±5.i
-
20
_
_
3.fc*2.1
-
1*8
_
_
_
_
-
-
28.3*3.1
9*
.
13.8*2.8
_
_
-
_
23
.
.
85*13
62
k3
31
15
.
.
Analytical
method
OES-P
„
JAAS
AAS
IRAA
IHAA
OZS-P
.
OES
ISM.
IRAA
OES-P
_
SSMS
XRF
XRF
SSMS
SSMS
IHAA
OES-P
•
AAS
PAA
XRT
XRF
8SMS-ID
0X8
OES-P
_
OES
IHAA
IHAA
mss
mss
INAA/ASV/PES
OES-P
—
nss
118
-------
TABLE B-9. (CONTINUED)
Concn in Concn suspended
fly ash in flue gas
Element
Molybdenum
Hlcltel
Selenium
Tellurium
Thallium
Tin
Titanium
Concn in
coal
—
<20
0.99
0.99
3.6
10-30
-
90
-
21-1*2
< 100-1 50
<600
*
2.8-7.8
1-9
1.9
2.2
1-3
<100
2
<700
•
20
<960
900-11*50
510
Source*
A
IE
SW
SW
IE
_
A
IE
IE
IS
IE
IE
IE
IE
SW
SW
IE
IE
IE
IE
IE
A
IE
IE
IE
A
IE
IE
IE
IE
Control
method
ESP
Mech
ESP
WS
ESP
ESP
-
Mech
ESP
Cy
ESP
ESP
Mech
ESP
Cy
ESP
ESP
WS
ESP
ESP
Mech
Cy
ESP
Mech
Cy
ESP
ESP
Mech
Cy
ESP
ESP
Before
control
.
<30
-
5l*
118
—
-
500
-
After Before
control control
181
< 30,
60
no
-
50-290
792
2000
395
U6o-I6oo
500-1000 500-1000
<500
-
"
73
73
25
<1-10
100
1*0-100
<600
-
20
5800
;
6080
<500
uu
U-59
62~ I
M*0
88
< 1-10
50
29-76
30
f - 570
<600
7-19
20
16320
6600
9200-15900
10000
After Analytical
control method c
13 OES-P
_ _
XRF/WC
XRF/WC
IHAA
OES
18 OES-P
1.3 FAAS
AAS
IS liWi 1 MA
*^»~*w.J» fTWl
SSMS
6.5 INAA
FAAS
12*5 IHAA
XRF
XRF
GC-MES
SSMS
ESMS
SSMS
61 OES-P
SSMS
SSMS
26U OES-P
XRF
1*801260 IHAA
INAA
119
-------
TABLE B-9. (CONTINUED)
Concn in Cencn suspended
Element
Vanadium
Zinc.
Cone In
coal
22.5
.
<200
»
.
37-1*6
28.5
noo
.
55-110
-
7.3
7.3
1*6
Source
—
A
IE
IE
IE
.
IE
IE
IE
_
IE
8V
SV
IE
Control
•ethod
tSP/VS
ESP
Hech
ESP
Cy
ESP
ESP
Mech
ESP
ESP
cy
ESP
WS
ESP
fly ash In flue gas
Before After Before
control control control
116
88U2
200 300
970
150-480
• _
W»o 1180
5900 900
l£2
After
control
—
lit
.
1.5
27132
—
0.7
Analytical
method0
OES
OES-P
.
MAS
88MS
IHAA
DMA
m
AAS
U3±23 IHAA
8100-13000
370
360 600
740 5900
1134O-182OO 8SMS
_
.
MAS
MAS
88M6-ID
Control equipment:
4
Hech • Mechanical collector
Cy • Cyclone collector
ESP • Electrostatic precipltator
WS • Wet scrubber
b. Sample was collected upstream fron the mechanical collector.
c. Abbreviations for analytical methods.
OES • Optical Emission Spectroscopy-Detection Method
Unspecified
OES-P • Optical Emission Spectroscopy with Photographic
Detection
MAS nameless Atonic Absorption Spectroscopy
S8MS Spark Source Mass Spectroscopy
DMA Instrumental Neutron Activation Analysis
AAS Atonic Absorption Spectroscopy
SSMS-ID Spark Source Mass Spectroscopy with Isotope Dilution
120
-------
REFERENCES
(1) Oglesby, S., Jr., "A Survey of Technical Information Related to Fine
Particle Control". Southern Research Institute. Publication No. EPRI
259, April, 1975.
(2) U.S. Geological Survey and Montana Bureau of Mines and Geology, "Pre-
liminary Report of Coal Drill-Hole Data and Chemical Analyses of Coal
Beds in Sheridan and Campbell Counties, Wyoming and Big Horn Montana.
U.S. Geological Survey Open-File Report (1973).
(3) Bolton, N. E., Van Hook, R. I., Fulkerson, W., Lyon, W. S., Andren, A. W.,
Carter, J. A., and Emery, J. F., "Trace Element Measurement at the Coal-
Fired Allen Steam Plant", ORNL, Progress Report June 1971-June 1973,
National Science Foundation, Publication No. EP-43, March 1973.
(4) McGee, E. M., et al., "Potential Pollutants in Fossil Fuel", Esso
Research and Engineering Company. Report prepared for EPA, PB-225 039,
June 1973.
(5) O'Gorman, J. W., and Walker, P. L., "Mineral Matter and Trace Elements
in U.S. Coals", Pennsylvania State University Research and Development
Report No.61, Department of Interior, July 1972.
121
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing]
1. REPORT NO.
EPA-60Q/7-79-2Q6
4. TITLE AND SUBTITLE
METHODS FOR ANALYZING INORGANIC COMPOUNDS IN PARTICLES
EMITTED FROM STATIONARY SOURCES
Interim Report
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
William M. Henry
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle, Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
September 1979
6. PERFORMING ORGANIZATION CODE
10. PROGRAM ELEMENT NO.
1NE833D EB005 (FY-79)
11. CONTRACT/GRANT NO.
68-02-2296
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Interim 1/77 - 7/78
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This research program was initiated with the objective of developing methods
to identify and measure inorganic compounds in particulate emissions which
emanate from sources using or processing fossil fuels.
An extensive literature review was carried out to ascertain prior knowledge on
the possible compound forms present in these emissions and to review analytical
methodologies. Based on the findings of the literature review, appropriate
methodologies were selected for laboratory trial. Concurrent with the method
trial work, large masses, 20 to 100 grams, of field samples were collected
representative of a range of both coal and oil-fired fly ashes, and the selected
methodology development efforts were evaluated on these field samples as well
as on synthesized samples.
Fourier transform infrared spectroscopy, x-ray diffraction, and chemical phase
separations and analyses are the methods which have provided the most definitive
identification of inorganic compounds. The structural findings by these methods
are complemented by complete cation-anion chemical determinations. Extensive
data on the composition of crude oils, coal and ashes are also presented.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
*Air Pollution
*Particles
*Inorganic compounds
*Chemical analysis
*Infpared analysis
*X-ray diffraction
Evaluation
Reviews
13B
07B
07D
14B
20F
05B
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
"T3?
20. SECURITY CLASS (Thispage)
ECURITY CLASS (T,
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
122
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing]
1. REPORT NO.
EPA-600/7-79-206
r
4. TITLE AND SUBTITLE
METHODS FOR ANALYZING INORGANIC COMPOUNDS IN PARTICLES
EMITTED FROM STATIONARY SOURCES
Interim Report
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
September 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
William M. Henry
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle, Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
1NE833D EB005 (FY-79)
11. CONTRACT/GRANT NO.
68-02-2296
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Interim 1/77 - 7/78
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This research program was initiated with the objective of developing methods
to identify and measure inorganic compounds in particulate emissions which
emanate from sources using or processing fossil fuels.
An extensive literature review was carried out to ascertain prior knowledge on
the possible compound forms present in these emissions and to review analytical
methodologies. Based on the findings of the literature review, appropriate
methodologies were selected for laboratory trial. Concurrent with the method
trial work, large masses, 20 to 100 grams, of field samples were collected
representative of a range of both coal and oil-fired fly ashes, and the selected
methodology development efforts were evaluated on these field samples as well
as on synthesized samples.
Fourier transform infrared spectroscopy, x-ray diffraction, and chemical phase
separations and analyses are the methods which have provided the most definitive
identification of inorganic compounds. The structural findings by these methods
are complemented by complete cation-anion chemical determinations. Extensive
data on the composition of crude oils, coal and ashes are also presented.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
*Air Pollution
*Particles
*Inorganic compounds
*Chemical analysis
*Inf»>ared analysis
*X-ray diffraction
Evaluation
Reviews
13B
07B
07D
14B
20F
05B
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
slO. OF
130
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
122
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