EPA-650/2-74-054
OCCURRENCE AND DISTRIBUTION
OF POTENTIALLY VOLATILE
TRACE ELEMENTS
IN COAL
by
R.R. Ruch, H.J. Gluskoter,
and N.F. Shimp
Illinois State Geological Survey
Urbana, Illinois 61801
Contract No. 68-02-0246
Program Element No. 1AB013
ROAP No. 21ADD-72
EPA Project Officer: William J. Rhodes
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park , North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
July 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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EGN 72
ENVIRONMENTAL GEOLOGY NOTES
AUGUST 1974 • NUMBER 72
OCCURRENCE AND DISTRIBUTION
OF POTENTIALLY VOLATILE
TRACE ELEMENTS IN COAL:
A Final Report
R. R. Ruchf H. J. Gluskoter, and N. F. Shimp
With Contributions From
L. R. Camp, G. C. Dreher, J. K. Frost, J. R. Hatch, L. R. Henderson,
J. K. Kuhn, P. C. Lindahl, «. G. Miller, P. M. Santoliquido,
J. A. Schleicher, G. D. Strieker, and Josephus Thomas, Jr.
ILLINOIS STATE GEOLOGICAL SURVEY
John C. Frye, Chief • Urbana, IL 61801
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CONTENTS
Page
Abstract 1
Introduction 3
Acknovledgment 5
Type and Source of Coal Samples 5
Results of Analyses of Whole Coal 6
Statistical Analyses of Analytical Data 16
Enrichment and Depletion of Elements in Coal 31
Results of Analyses of Washed Coals 33
Identification of Mineral Phases Containing Trace Elements 52
Summary and Conclusions 5^
TEXT TABLES
1. Trace Elements in Coals 7
2. Major and Minor Elements in Coals 11
3. Proximate and Ultimate Analyses of Coals 13
IK Sulfur Analyses 15
5. Mean Analytical Values for All 101 Coals 18
6. Mean Analytical Values for 82 Coals from the Illinois Basin 19
7. Linear Regression (Least Squares) Correlation Coefficients
of Analytical Determinations on 101 Coals 20
8. Linear Regression (Least Squares) Correlation Coefficients
of Analytical Determinations on 82 Illinois Basin Coals 22
9- Enrichment Factors of Chemical Elements in Coal 32
10. Trace Elements in Laboratory-Prepared Coals 3^
11. Major and Minor Elements in Laboratory-Prepared Coals 3T
12. Proximate Analyses and Ash Content of Laboratory-Prepared Coals ... 38
13. Sulfur Analysis of Laboratory-Prepared Coals 39
1*K Affinity of Elements for Pure Coal and for Mineral Matter,
as Determined from Float-Sink Data 51
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ILLUSTRATIONS
Figure Page
1. Distribution of low-temperature ash in coals analyzed 2k
2. Distribution of high-temperature ash in coals analyzed . 2k
3. Distribution of arsenic in coals analyzed , 2k
k. Distribution of boron in coals analyzed , 2k
5. Distribution of beryllium in coals analyzed , 25
6. Distribution of bromine in coals analyzed . 25
T. Distribution of cadmium in coals analyzed , 25
8. Distribution of cobalt in coals analyzed , 25
9. Distribution of chromium in coals analyzed . 25
10. Distribution of copper in coals analyzed 25
11. Distribution of fluorine in coals analyzed , 26
12. Distribution of gallium in coals analyzed . 26
13. Distribution of germanium in coals analyzed 26
lk. Distribution of mercury in coals analyzed 26
15. Distribution of manganese in coals analyzed 26
l6. Distribution of molybdenum in coals analyzed 26
17- Distribution of nickel in coals analyzed 27
18. Distribution of phosphorus in coals analyzed 27
19. Distribution of lead in coals analyzed 27
20. Distribution of antimony in coals analyzed 27
21. Distribution of selenium in coals analyzed 27
22. Distribution of tin in coals analyzed 27
23. Distribution of vanadium in coals analyzed 28
2k. Distribution of zinc in coals analyzed 28
25. Distribution of zirconium in coals analyzed 28
26. Distribution of aluminum in coals analyzed 28
27. Distribution of calcium in coals analyzed 28
28. Distribution of chlorine in coals analyzed 28
29. Distribution of iron in coals analyzed 29
30. Distribution of potassium in coals analyzed 29
31. Distribution of magnesium in coals analyzed 29
32. Distribution of sodium in coals analyzed 29
33. Distribution of sulfur in coals analyzed; determined by
X-ray fluorescence 29
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Figure Page
3^. Distribution of sulfur in coals analyzed; determined by
ASTM method ........................... 29
35. Distribution of sulfate sulfur in coals analyzed .......... 30
36. Distribution of organic sulfur in coals analyzed .......... 30
37. Distribution of pyritic sulfur in coals analyzed .......... 30
38, Distribution of silicon in coals analyzed .............. 30
39- Distribution of titanium in coals analyzed ............. 30
hO. Low-temperature ash in specific gravity fractions of a sample
from the Davis Coal Member .................... ^0
Low-temperature ash in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member
Low-temperature ash in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
Aluminum in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
Calcium in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member
Iron in specific gravity fractions of a sample
from the Davis Coal Member
h6. Potassium in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
Magnesium in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
Sodium in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
Phosphorus in specific gravity fractions of a sample
from the Davis Coal Member
50. Sulfur in specific gravity fractions of a sample
from the Davis Coal Member
51. Silicon in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
52. Titanium in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
53. Arsenic in specific gravity fractions of a sample
from the Herrin ( No . 6 ) Coal Member
5^. Boron in specific gravity fractions of a sample
from the Davis Coal Member .................... kk
55. Beryllium in specific gravity fractions of a sample
from the Davis Coal Member .................... ^5
56. Cadmium in specific gravity fractions of a sample
from the Davis Coal Member
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Figure Page
57- Cobalt in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member ... ............. 1^5
58. Chromium in specific gravity fractions of a sample
from the Davis Coal Member ........ ............. h6
59- Copper in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member ............. U6
60. Gallium in specific gravity fractions of a sample
from the Davis Coal Member ........ ............. h6
6l. Germanium in specific gravity fractions of a sample
from the Davis Coal Member ........ ............. Uj
62. Mercury in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member
63. Manganese in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member . ............... U7
6k. Molybdenum in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member ............. U8
65. Nickel in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member ............. k8
66. Lead in specific gravity fractions of a sample
from the Davis Coal Member ...... ............... hQ
67. Antimony in specific gravity fractions of a sample
from the Davis Coal Member ...... ............... U9
68. Selenium in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member . .............. U9
69. Vanadium in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member ............. U9
70. Zinc in specific gravity fractions of a sample
from the Herrin (No. 6) Coal Member ............... 50
71. Zirconium in specific gravity fractions of a sample
from the Colchester (No. 2) Coal Member ............. 50
APPENDIX
Preparation of Coal Samples 59
Low-Temperature Ashing (LTA) and Trace Element Volatility 59
High-Temperature Coal Ash (HTA) and Trace Element Volatility 60
Methods of Analyses 65
X-Ray Fluorescence Analysis of Whole Coal and Coal Ash ,. 65
Low- and High-Temperature Coal Ashes 66
Whole Coal 67
Effect of Whole Coal Particle Size on Precision , 68
Comparative Analyses . 68
Precision 70
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Page
Optical Emission Spectrometric Analysis of High-Temperature Coal Ash. . TO
Construction of Calibration Curves TO
Internal Standardization Tl
Standard Conditions T2
Comparative Analyses T3
Optical Emission Spectrographic Analysis of High-Temperature Coal Ash . T3
Construction of Calibration Curves T3
Standard Conditions T^-
Comparative Analyses T5
Atomic Absorption Analysis of Coal Ash T5
Reagents and Construction of Calibration Curves T5
Sample Decomposition Procedure T5
Atomic Absorption Spectrophotometric Procedure j6
Comparative Analyses T6
Neutron Activation TT
Determination of Se in Low-Temperature Coal Ash TT
Determination of As in Low-Temperature Ash T8
Radiochemical Separation and Determination of As in Coal
with an Inorganic Exchanger (Acid Aluminum Oxide) T9
Determination of Ga in Low-Temperature Coal Ash T9
Determination of Zn and Cd in Low-Temperature Coal Ash 80
Determination of Hg in Whole Coal 80
Alternate Determination of Hg in Coal 8l
Determination of Sb in Whole Coal 82
Determination of Br in Whole Coal 83
Instrumental Neutron Activation Analysis of Mn in Whole Coal .... 83
Instrumental Neutron Activation Analysis of Na in Whole Coal .... 83
Ion-Selective Electrode Method for Determination of F in Whole Coal . . 8^
Trace Element Detection Limits for All Methods 85
U.S. EPA-NBS Trace Element Symposium 85
Preferred Analytical Procedures 85
Summary of Analytical Methods Used for the Determination of
Trace Elements 89
Antimony (Sb) 89
Arsenic (As) 89
Beryllium (Be) 89
Bromine (Br) 89
Cadmium (Cd) 89
Chromium (Cr) 90
Cobalt (Co) 90
Copper (Cu) 90
Fluorine (F) 90
Gallium (Ga) 90
Germanium (Ge) 90
Lead (Pb) 91
Mercury (Hg) 91
Nickel (Hi) 91
Selenium (Se) 91
Vanadium (v) 91
Zinc (Zn) 91
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Page
Phosphorus (P), Boron (B), Zirconium (Zr), Molybdenum (Mo),
and Tin (Sn) 92
Summary of Analytical Methods Used for the Determination of
Major and Minor Constituents 92
References 93
APPENDIX TABLES
A - Concentrations of Trace Elements in Moisture-Free Coal from High-
Temperature Ash Samples Prepared at Various Temperatures in Used
Porcelain Crucibles ......................... 6l
B - Ashing Temperature Study with Platinum Crucibles and Covers ..... 62
C - Ashing Time vs. Trace Element Concentrations ............. 6k
D - Volatility of Trace Elements in Coal ................. 6k
E - X-Ray Fluorescence Settings for the Analysis of Coal and Coal Ash . . 66
F - Differences Between Duplicate Analyses of Whole Coal Size Fractions. . 69
G - Range of Relative Differences Between Duplicate Analyses for Each
Trace Element at Three Coal Mesh Sizes ................ 69
H - Comparison of ISGS X-Ray Fluorescence Analyses of Coal Ash
with BCURA Analyses ......................... TO
I - Concentrations in Standard Materials of G-2 Base in 3:1
Si02-Al203 Matrix + 1000 ppm Synthetic Standard for
Spectrometric Method ......................... 71
J - Analytical Wavelengths and Relative Standard Deviations for the
Determination of Trace Elements in High-Temperature Coal Ash by
Direct Reading Spectrometry ..................... 72
K - Analytical Wavelengths and Relative Standard Deviations for the
Determination of Trace Elements in High-Temperature Coal Ash by
Photographic Optical Emission .................... 7^
L - Comparison of Mean Arsenic Valves Obtained by Inorganic Exchanger
and Distillation Techniques ..................... 79
M - Comparison of Hg Values with Published Data ............. 82
N - Summary of Detection Limits for Methods Used in This Investigation . . 86
0 - Comparative Results for EPA-NBS Interlaboratory
Trace Element Study ......................... 87
P - Analytical Procedures Used to Determine Recommended
Trace Element Values ......................... 88
Q - Analytical Procedures Used for Recommended Values
for Float-Sink Samples ........................ 88
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OCCURRENCE AND DISTRIBUTION OF POTENTIALLY
VOLATILE TRACE ELEMENTS IN COAL:
A Final Report
R. R. Ruch, H. J. Gluskoter, and N. F. Shimp
With Contributions From
L. R. Camp, G. C. Dreher, J. K. Frost, J. R. Hatch, L. R. Henderson,
J. K. Kuhn, P. C. Lindahl, W. G. Miller, P. M. Santoliquido,
J. A. Schleicher, G. D. Strieker, and Josephus Thomas, Jr.
ABSTRACT
Chemical analyses of 101 whole ooal samples and of 32 separate
fractions of four laboratory-prepared (washed) coals have been made in the
laboratories of the Illinois State Geological Survey. The four laboratory-
prepared coals and eighty-two of the 101 whole coals are from the Illinois
Basin. The remaining 19 coal samples were collected from other parts of
the United States.
Trace elements determined were antimony (Sb), arsenic (As),
beryllium (Be), boron (B), bromine (Br), cadmium (Cd), chromium (Cr),
cobalt (Co), copper (Cu), fluorine (P), gallium (Ga), germanium (Ge), lead
(Pb), manganese (Mn), molybdenum (Mo), nickel (Hi), mercury (Hg), phos-
phorus (P), selenium (Se), tin (Sn), vanadium (V), zinc (Zn), and zirco-
nium (Zr). Major and minor elements determined were aluminum (Al), calcium
(Ca), chlorine (Cl), iron (Fe), magnesium (Mg), potassium (K), silicon
(Si), sodium (Na), sulfur (S), and titanium (Ti). Procedures for the ana-
lytical methods used—neutron activation, optical emission, atomic absorp-
tion, X-ray fluorescence, and ion-selective electrode—are given in detail.
Wherever practical, accuracy was evaluated by comparing results
obtained by the various methods from splits of the same coal samples. Fur-
ther comparisons were made by analyzing whole coal and'its low- and high-
temperature ashes, thus permitting a thorough evaluation of trace-element
losses resulting from volatilization during sample preparation.
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In general, results from the various analytical procedures com-
pared favorably, although exceptions are noted, e.g., from V and from F.
Certain techniques have been chosen as preferred methods for determining
specific elements because they are more accurate, their precision is
superior, or they take less time for analysis.
Statistical analyses of the large amounts of data generated on
the 101 whole coal samples have resulted in several preliminary findings:
1. The elements Al, Fe, F, Ga, Br, B, Be, Or, Cu, K, Ni, Si, Ti,
Se, and V display a more or less ncrmal distribution of ana-
lytical values with small standard deviations and ranges. A
second group is composed of Cd, Zn, P, As, Sb, Pb, Sn, Cl,
Ge, and Hg, each of which exhibits highly skewed distribu-
tions with large ranges and standard deviations.
2. The highest positive correlation coefficient (r) for any two
chemical elements in coal is that between Zn and Cd
(r = 0.93). Other significant positive correlations were
found between the elements within the following groups: As,
Co, Cu, Mi, Pb, and Sb; Si, Al, Ti, and K; Mn and Ca; and Na
and Cl.
3. The average concentration of an element in the earth's crust
(the clarke value) was compared to the mean value of that
element in coal. Only three elements were found to be en-
riched in coals by at least one order of magnitude: Cd, B,
and Se. Similarly, only three elements, F, Mn, and P, were
found to be depleted in the coals by at least one order of
magnitude.
The data from the analytical determinations on the washed coals
are plotted as washability curves and as histograms. These data allow the
elements to be classified into four groups. The elements in the first
group (Ge, Be, and B) have the greatest organic affinity and tend to be
concentrated in the clean coal fractions. The elements in the second group
(Hg, Zr, Zn, Cd, As, Pb, Mn, and Mo) are those found concentrated in the
mineral matter in coal and have the least organic affinity. A third group
(P, Ga, Ti, Sb, and V) contains elements which are apparently associated
both organically and inorganically in coals but are more closely allied to
the elements with the highest organic affinities, The last group contains
those elements (Co, Ni, Cr, Se, and Cu) which are also found in both modes
of combination but which tend to be more inorganically associated. The
washability studies (analyses of specific gravity fractions of coals) indi-
cate the potential effective removal of major portions of several trace
elements, e.g., Zn, Cd, and Pb, from raw coals by conventional specific
gravity methods of separation.
Several trace and minor elements have been identified as oc-
curring in discrete mineral phases in the coals. Among these are Zn and Cd
in sphalerite (ZnS), Pb in galena (PbS), and P and F in apatite
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INTRODUCTION
Because huge tonnages of coal are burned each year for electric
power generation, volatile materials, such as sulfur oxides, and the fine
particulate matter emitted into the atmosphere during coal combustion are
considered to be potential environmental hazards. Further, it has been
clear for some time that the major chemical constituents retained in fly
ash, bottom ash, and other coal combustion products may constitute long-
term disposal hazards if they become soluble and enter ground- or surface-
water systems. However, it has only recently become evident that the
growing concern over environmental pollution will ultimately require a
thorough knowledge of the elements present in coal in only trace amounts.
These so-called trace elements have come under scrutiny because they are
known to occur in coal (Goldschmidt, 1935, 1937) and because of the general
knowledge that such elements as As, Be, Cd, Hg, and Pb are toxic to plant
and animal life at relatively low concentrations. Many trace elements are
now being considered not only as potential environmental pollutants, but
also as poisons of costly catalysts in certain of the proposed coal gasification
and liquefaction schemes.
It has therefore become imperative to develop accurate and reliable
data on the amount of these elements present in coal, on their distribution
and mode of occurrence, and on their volatility during combustion of the
coal. Only with the development of a sufficiently large fund of such data
will the general public and the agencies with the responsibility of protecting
the environment be in a position to make intelligent decisions concerning
utilization of coal.
The chemical nature of coal ash has been amply summarized in recent
review articles (Francis, 196l; Ode, 1963; Nicholls, 1968; Watt, 1968; and
Magee, Hall, and Varga, 1973), which deal in part with trace elements. However,
research on trace elements in coal ash has not been extensive because until now
they have been of little more than academic interest and because they occur in
such small amounts that their determination is both costly and difficult.
Trace element investigations in coal prior to 1970 were based on
analyses of high-temperature coal ash (Deul and Annell, 1956; Zubovic,
Stadnichenko, and Sheffey, 196l, 196U, 1966; Zubovic, Sheffey, and Stadnichenko,
1967; Abernethy, Peterson, and Gibson, 1969), which measure the oxides of the
elements in the altered mineral matter. Although such investigations are
valuable for estimating concentrations of refractory constituents, or elements
of low volatility, they do not reliably measure total amounts of volatile
trace elements in whole coal. In this study, we have determined not only the
amounts of the trace elements present in the coals but also their volatility
when the coals were ashed at both high (up to 700° C) and low (< 150° C)
temperatures.
Ruch, Gluskoter, and Kennedy (l97l) published whole coal Hg values
for Illinois coals, and 0'Gorman and Walker (1972) determined a number of trace
elements in low-temperature ashes from United States coals. Ruch, Gluskoter,
and Shimp (1973) reported major, minor, and trace element concentrations in
25 coals, most of them from Illinois, in which results from high- and low-
temperature ashes were compared with those obtained from the whole coal.
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Many of their results were verified by comparing determinations obtained by
analyzing the coals by two or more independent methods.
The need for verification of trace element results has recently
been emphasized (von Lehmden, Jungers, and Lee, 197*0 in an EPA-NBS inter-
laboratory comparison study, which included both a coal sample and a fly
ash sample. A wide range of values was obtained for many of the trace elements,
and an urgent need for better standard samples and analytical methods was
indicated.
Reports of investigations of trace element fallout from power plants
(Oak Ridge, 1973; and Klein and Russell, 1973), fate of trace elements during
coal gasification (Attari, 1973; and Forney et al., 197*0, trace element
beneficiation of coal (Capes et al. , 197**), trace element concentration in fly
ash (Natusch, Wallace, and Evans, 197*0 , and mercury mass balance in a coal-
fired power plant (Kalb and Baldeck, 1973) have all appeared within the past
year and are indicative of the mounting interest in trace element research.
This report contains the results of analyses for major, minor, and
trace elements of 101 coals, most of them from within Illinois; however, a
significant number of eastern and western coals were analyzed for comparative
purposes.
The following trace elements are reported in these coals: antimony
(Sb), arsenic (As), beryllium (Be), boron (B), bromine (Br), cadmium (Cd),
chromium (Cr), cobalt (Co), copper (Cu), fluorine (F), gallium (Ga), germanium
(Ge), lead (Pb), manganese (Mn), molybdenum (Mo), nickel (Ni), mercury (Hg),
phosphorus (P-) , selenium (Se), tin (Sn), vanadium (V), zinc (Zn), and
zirconium (Zr). In addition, the major and minor elements aluminum (Al),
calcium (Ca), chlorine (Cl), iron (Fe), magnesium (Mg), potassium (K),
silicon (Si), sodium (Na), sulfur (S), and titanium (Ti) are reported.
The techniques used to prepare the samples for chemical analyses
and the analytical methods developed for determination of many of the trace
elements in coal are discussed in detail in the appendix. The appendix also
includes a discussion of the results obtained by two or more analytical methods
for the same element and compares the determinations for a single element on
samples prepared at different ashing temperatures. As a result of such cross-
checking, a high degree of confidence can be placed in the "recommended" or
"best" values reported.
A partial statistical analysis of the chemical analytical data has
been done, and the arithmetic mean, standard deviation, and range for each
element are given. The data have also been tested for the relationships of
the elements to each other, and a matrix of correlation coefficients has been
generated. Many of the better correlations between elements are those to be
expected from most types of geologic samples.
A second set of analytical values was determined on a series of
"washed" coal samples. These samples were separated into specific gravity
fractions and each fraction was analyzed for most of the same major, minor,
and trace elements as were the whole coal samples. The results of the analyses
of these samples are of special value for two purposes. First, they demonstrate
which of the elements can be removed from the coals by specific gravity techniques
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and the amount of each element that can be so removed. The second use for
such data is to indicate the mode of occurrence of an element in the
coal—to indicate whether it is in organic or inorganic combination and, if
in inorganic combination, to suggest with which group of minerals it is most
likely to be associated.
The total amount of data reported here is very large, and the
complete geologic interpretation of these data requires more time than is
available before the publication of this report. The areal and stratigraphic
distributions of the trace elements in Illinois coals and the paleoenviron-
mental and diagenetic significances of these distributions will be reported
in the near future.
The Illinois State Geological Survey expects to continue investigations
of trace elements in coal, extending the closely spaced sample grid into that
part of the Illinois Basin which lies in Indiana and Kentucky, and including
more samples from the eastern and western United States.
Acknowledgment
The work on which this publication is based was performed under
Contract No. 68-02-02^6 and Grant No. R-800059 from the U.S. Environmental
Protection Agency, Clean Fuels and Energy Branch, Control Systems Laboratory,
Research Triangle Park, North Carolina. This partial financial support for
this investigation from the Environmental Protection Agency is gratefully
acknowledged.
TYPE AND SOURCE OF COAL SAMPLES
Chemical analyses of 101 whole coal samples were made for this study.
Seventy-six of the samples were composite face-channel samples collected in
coal mines by Illinois State Geological Survey personnel. Each face-channel
sample was cut by hand with a pick and represented the full height of the coal
seam, excluding only mineral bands, partings, or nodules more than three-
eighths of an inch thick. This procedure follows a long-standing practice at
the Illinois State Geological Survey and is based on a technique described by
Holmes (1918) in which mineral bands greater than three-eighths inch in
thickness were excluded. Generally, three face-channel samples were collected
in each mine, but in some mines only two could be collected. The face-channel
samples were crushed to pass a one-eighth-inch screen, combined into a composite
sample, and then riffled to the desired quantity.
The coal sample was comminuted further to 20 mesh (7^-0 ym) , 60 mesh
(250 Vim), 100 mesh (lU9 ym), or finer, depending on the analytical technique
to be applied. In all cases, the sample was subdivided into aliquots by
riffle-type sample splitters or by quartering the sample. The parts are thus
considered representative of the original coal sample.
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Of the 25 coal samples that were not face-channel samples, four
(C-13321+, C-13^33, C-159^3, and C-1591^) were drill cores. The first two
drill cores are from the Herrin (No. 6) Coal Member, and the last two are from
the Davis and DeKoven Coal Members, respectively. The drill cores were
treated much like a face-channel sample (omitting mineral bands more than
three-eighths of an inch thick). The following ik samples represent production
from individual mines and were provided by coal companies or state
or federal agencies: C-17095 and C-172H3 (Beliaont County, Ohio), C-lJOh6
and C-170V7 (Montana), C-170l*5 (Arizona), C-1T098 (Cambria, Pennsylvania),.
C-17092 (Coshocton County, Ohio), C-17096 (Utah), C-lJ2hh (Harrison County,
Ohio), C-17099 (Marion, Pennsylvania), C-17305 (Muhleriberg, Kentucky),
C-17309 (Arizona), C-17051^ (Colorado), and C-17097 (Colorado). Samples
C-17970 and C-18009, National Bureau of Standards (NBS) samples SRM-1632 and
SRM-1630, respectively, are combinations of several West Virginia coals. Four
samples, C-1730H (Clay County, Indiana), C-17307 (Henry County, Missouri),
C-172^5 (Jefferson County, Ohio), C-172^6 (Kanawha County, West Virginia)., and
C-17303 (Washington County, Pennsylvania), are not raw coal samples but repre-
sent commercially washed coal from the mines. The samples were obtained by
other agencies and sent to the Survey.
RESULTS OF ANALYSES OF WHOLE COAL
The results of the chemical analyses of the 101 coal samples
investigated are given in tables 1 through h. All analyses in this report are
given on the "whole coal" basis and not as a percentage of ash. Table 1 lists
the results of the analyses for 23 trace elements, all reported in parts per
million (ppm). Table 2 consists of the major and minor element determinations
on the same coals. The standard coal analyses, proximate, ultimate, and
heating value, are given in table 3. In addition, table 3 contains the low-
temperature ash values as well as the high-temperature ash values for each
coal. Table k contains the results of the analyses for varieties of sulfur
and two total sulfur determinations, one by the standard ASTM method and the
other by X-ray fluorescence.
In all four of the tables the first 82 samples are from the Illinois
Basin (Illinois, Indiana, and western Kentucky), and the last 19 are from
other states. The 82 samples from the Illinois Basin are listed in stratigraphic
order beginning with the oldest coal seam. Coals from Illinois are identified
with the following symbols: Reynoldsburg Member (Rb), coal in Abbott Formation
(AT), Delwood Member (DW), Murphysboro Member (MU), Davis Member (DV) , DeKoven
Member (DK), coal in Mattoon Formation (MF), and the numbers 1, 2, k, 5, 6, and
7 for the following coal members: Rock Island (No. l), Colchester (No. 2),
Summum (No. h), Springfield or Harrisburg (No. 5), Herrin (No. 6), and Danville
(No. 7). Coals from states other than Illinois are identified by a two-letter
state abbreviation. The last two samples listed are National Bureau of Standards
(NBS) samples 1630 (our sample Number C-l8009) and 1632 (our sample Number
C-17970).
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TABLE 1—TRACE ELEMENTS IN COALS
(parts per million, moisture-free whole coal)
SAMPLE NB, CgA
till
CU
C0
CR
GA
Hi
C. 13854
C-17089
C-16787
C. 15678
C-16919
O16408
C. 19943
C- 17*01
C. 15944
C-13039
C-17J04
C. 14646
C»14650
C-15263
C-15566
C- 15331
C-IS496
C-16564
C»12495
C-13046
C-13963
C- 14194
C. 14609
C-14T35
C. 14774
C. 14796
C-15012
C.15208
CM5384
C.15448
O16264
C. 16729
C. 17001
C. 17305
C.17721
C. 17984
C. 17968
C. 18040
C. 18059
C-1JB31
C.12942
C. 13324
C. 13433
C- 13464
C-13895
C- 13975
C. 14574
C. 14613
C-1463D
C. 1*684
C. 14721
RB
RB
»F
1
OH
MU
0V
uv
OK
IN
IN
2
2
2
2
4
4
a
5
IN
5
5
5
5
5
5
5
S
5
5
5
*
5
KY
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
4.0
22,0
20,0
7.5
17,0
57,0
3,»
5,0
37.0
3,0
4,«
5.'
66,0
73,0
93,0
19,0
15,0
5,5
5.5
8.0
'•3
9.1
56,0
7.S
4,5
28,0
32,0
17,0
7.4
4.1
9,6
32,0
9.4
14, a
66.0
61,0
47,0
3,6
8.6
1.2
4,2
8.1
6,5
4.3
2.1
6,7
31,0
4.0
9.2
3,7
4,6
37
IS
137
31
49
33
33
38
110
125
131
115
43
126
137
164
159
119
15
58
70
141
48
79
129
no
170
139
75
37
60
105
60
63
126
106
100
65
93
no
132
122
138
86
82
122
0.7
0.5
1.8
I.'
2,2
0,9
3,4
1.4
4,0
2,4
3.4
2.7
2.1
3,0
2.5
lit
3.2
2.6
1.1
1,8
1.2
1.1
0,9
1.2
1.8
1.2
1.3
1.4
1.2
1.6
3.0
1.0
1.6
2,6
2.4
1."
0.9
(J.8
2.3
1.4
0,8
0,9
0,8
1.8
1.5
1|2
2,2
0.8
1.2
0.8
1.4
19
12
22
11
19
11
18
14
17
11
13
12
9
13
10
11
16
23
12
14
16
15
17
3J
14
22
16
11
It
12
14
14
16
11
18
18
17
12
17
17
14
14
20
15
15
IS
14
16
21
19
17
<0.l
<0.2
<0.3
0,4
-------
- 8 -
TABLE 1 —Continued
S4MPLI NB,
»S
Bfc
CD
cu
st
MS
C-14636
C»14970
O14962
C-t503«
C-15079
c-15117
C. 15125
O1523I
C-I5432
C-I5436
O15456
C-15717
C. 15791
C-15666
C-15B72
C-15999
O16030
C-I6139
C-16265
C. 16317
C- 16501
C.I6543
C-16741
O16993
C. 17016
C-17278
C. 16044
C.15276
C- 15416
C. 17053
C-17215
C.1704S
C. 17046
C. 17047
C. 17054
C. 17096
C. 17097
C»)7307
C-17309
O17092
C. 17095
C. 17098
C-17099
C. 17241
C-17244
C. 17245
C. 17246
C. 17303
C.17970
C- 18009
6
6
6
6
6
b
6
6
6
6
6
6
b
6
6
6
b
b
6
b
b
b
b
b
b
b
b
7
IN
7
MF
AZ
MT
MT
CB
UT
CB
MZ
AZ
BH
0H
ft
PA
BH
0M
BM
HV
PA
NBS
NBS
4,0
2.1
2.3
5.9
11. U
30,0
9,4
a."
5.7
3.8
1.7
1.9
30,0
1.8
10,0
3.1
".5
5,1
10,0
24,0
8.7
8.1
1.2
9.0
J.3
2.3
4.6
3.6
2.3
5.8
20.0
1.2
1.2
2.5
0.7
0.5
0.5
•».3
1.3
14,0
b,7
27,0
19,0
13.0
25.0
35.0
S.I
b.7
5.7
19.0
195
1*6
159
117
171
155
21b
179
156
163
91
102
171
HI
34
154
104
107
132
81
196
145
177
149
130
30
92
64
39
138
6b
17
63
45
9
38
78
59
68
9
5
13
5
8.4
1.6
t.o
1.0
1.8
3.9
1.6
0.8
2.5
1.8
1.4
1.2
1.4
l.u
1.7
1.5
<;.'
1.0
2.7
2.8
0,7
2.4
1.4
1.3
1,2
1.1
1.0
1.3
2.3
1.5
4.0
O.b
1.0
1.1
1.4
0.4
0,8
1.2
0.2
1.5
0,9
1.1
O.b
1.4
1.6
1.4
2.6
1.3
1.7
1.0
13
16
11
12
10
6
15
13
17
19
15
13
20
13
11
14
15
12
52
14
15
8
13
16
11
13
13.
13
19
13
13
7
20
25
10
23
19
7
4
8
12
13
17
11
17
14
26
23
20
29
< 0.4
< U.4
< 0.4
0.8
<0.5
1.2
7.«
1.4
< 0,4
3.3
-CO. 4
-------
- 9 -
TABLE 1—Continued
SM
O13854
C-17089
C. 16787
015678
016919
O16408
O15943
OI7601
C- 15944
C- 13039
O173D4
O14646
C- 14650
O15263
C. 15566
C-15331
C- 15496
O16564
O12495
O13046
C. 13983
014194
O14609
C. 14735
C- 14774
C. 14796
C.13012
O1520!
C. 15364
C. 15446
C- 16264
C. 16729
O17001
C. 17305
017721
C. 17984
O1T968
C-18040
C. 12059
O128S1
012942
C. 13324
C-13433
C. 13464
O1SB95
C-1397S
014574
C. 14613
C-14630
C- 14684
O14721
US
us
»F
1
DM
MU
0V
UV
UK
IN
IN
2
2
2
2
4
4
4
5
IN
5
5
5
5
5
5
s
5
5
5
5
5
5
K Y
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
16
7
44
9
13
15
17
10
32
74
42
IB
12
90
28
66
170
86
46
26
161
52
22
100
43
63
181
62
32
21
76
22
56
10
21
62
93
87
28
53
19
23
69
54
44
17
26
27
30
65
<1
<2
10
<1
6
3
7
3
4
5
5
2
6
14
<1
9
6
6
16
18
5
19
7
3
9
4
9
24
5
4
14
11
2
3
3
6
11
11
a
29
3
11
8
4
<1
i
2
3
4
22
20
39
14
32
26
18
33
27
15
24
16
36
40
65
15
27
13
10
11
14
25
24
17
9
21
27
16
16
26
22
19
17
11
21
24
22
8
32
14
14
16
21
16
12
26
18
25
23
12
17
53
163
65
48
56
195
34
118
144
49
US
14
40
24
29
24
12
30
21
25
80
11
162
80
29
120
10
30
<10
159
110
69
48
71
339
149
112
42
< 10
29
7
5
118
48
< 10
26
264
55
135
IB
23
11
59
22
38
46
40
64
52
192
10
7
25
176
96
218
103
36
52
6
a
16
45
114
52
28
24
59
12
40
10
51
50
56
11
40
116
87
4
40
7
eo
34
14
10
6
18
50
12
21
11
11
1.1
1.5
1.2
0.4
1.2
2.0
0.6
0.8
1."
0.4
0.6
2.8
3.7
5.7
8.9
2.7
5,2
1,2
0.6
1.2
0,5
0.4
2.4
1.6
0.9
0.8
1.2
l.B
2.6
0.3
0,8
0,9
2.5
1.6
1.5
2.3
1.2
0.4
1.4
0.3
0.5
0.5
1.0
1.1
0.3
0,6
1.6
0.8
0.7
0.2
0.7
0.4
2.2
2.7
3.2
3.2
2.3
1.9
1.8
3.0
1,7
2.7
1.7
1.1
2.0
1.2
2.5
1.6
1.6
1.3
2.2
1.9
1.5
1.1
3.0
1.9
1.7
2.1
2.5
1.6
J.2
1.5
1.8
3,3
2.6
1.5
1.4
1.7
1.7
3.2
1.3
1.6
2.1
l.o
2.3
1.9
2.1
1.6
1.7
1.6
1.2
1.4
1
3
<1
1
<2
2
<2
2
30
5
3
<3
<1
«-'2
7
<3
-------
- 10 -
TABLE 1—Concluded
s»MpLfc NB,
MB
Nl
SN
IN
ZR
C. 14838
C-14970
C-14982
01503H
C-15079
C. 15117
C- 15155
015231
C-15432
C-1S436
O 15456
015717
015791
C-1S868
015872
C-15999
C-16030
O16139
016265
016317
016501
C-16543
C-16741
C-16993
C. 17016
C. 17278
C-18044
C. 15278
C. 15418
C. 17053
017215
C-1704S
C-17046
C-17047
017054
O17096
O17097
C-17307
C- 17309
O17092
O 17095
O17098
017099
C- 17243
q»17244
017245
O17246
O17303
C-17970
C. 18009
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
IN
7
Hf
»z
MT
MT
CB
UT
CB
MB
AZ
0H
BH
P»
P»
BH
BH
8H
HV
PA
NBS
NBS
80
72
41
42
69
72
ISO
39
160
21
25
48
23
37
181
12
15
61
67
67
22
92
70
43
36
25
34
78
11
77
63
22
101
88
16
< 8
12
108
6
55
27
14
18
48
29
12
9
12
39
6
9
6
15
5
11
6
7
9
-Cl
10
13
14
2
3
12
15
19
14
10
9
6
15
12
4
9
20
7
5
--1
5
10
< I
30
8
2
1
2
14
2
11
< 4
2
8
6
4
5
1
1
5
2
16
13
14
36
34
25
10
16
36
20
14
16
22
22
36
18
42
36
28
30
14
25
33
26
20
16
25
8
68
14
12
7
4
6
8
4
3
80
5
11
16
16
16
16
22
12
19
20
20
10
66
22
42
53
41
28
9
28
21
28
12
76
8
72
77
10
40
57
35
21
18
24
39
84
22
31
31
68
100
17
99
109
48
39
10
80
400
248
125
»6
94
94
131
179
70
64
16
104
118
17
5
5
6
12
116
206
24
6
18
5
7
5
44
11
75
24
52
4
65
72
18
37
16
34
6
5
10
9
18
9
10
6
7
7
6
4
5
102
4
11
4
18
8
8
10
6
7
7
23
4
0.3
0.3
0.4
0.4
2.7
2.6
0.8
0.4
2.4
0,4
0.3
0.4
1.1
0.4
2.2
0.4
1.0
1.4
2.0
4.3
0.4
1.7
0.7
0.3
0.3
0.6
0.4
0.2
4.4
0.4
0.9
0.4
0.9
0.9
0.6
0.2
0.2
1.2
0.3
0.6
0.6
0.9
0.3
1.2
1.5
1.0
1.3
0.9
3.0
0.6
1.0
1.7
1.9
1.3
2.3
2.0
1.1
1.6
1.5
1.6
1.9
2.1
2.6
l.T
2.0
1.3
2.0
7.7
1.7
2.4
2.1
8.1
4.7
2.0
2.2
1.4
2.2
0.9
0.7
1.2
8.5
1.6
0.8
0.8
2.3
1.2
1.0
8.9
1.2
3.2
3.8
6.6
8.2
2,0
6.3
1.8
3.1
1.3
8.8
2.0
< 4
< 2
< 2
<• 4
< 7
2
< 5
< 4
< a
< 4
4
-------
- 11 -
TABLE 2—MAJOR AND MINOR ELEMENTS IN COALS
(percent, moisture-free whole coal)
SAMPLt NB. C|AL AL C» CL ft K HG N* SI TZ
C-13854
O17089
C1-U787
C-15676
C>16919
C- 16406
C. 15943
C. 17601
C. 15944
C. 15039
C- 17304
C- 14646
C. 14650
O15J63
C. 15566
CM5331
C-15496
C. 16564
012495
C. 13046
C- 13983
C. 14194
C. 14609
C-14735
C. 14774
C.U796
C. 15015
C. 15808
CP15384
C. 15448
C-16264
C. 16729
C. 17001
C. 17305
C.17721
C. 17984
C. 17988
C- 18040
C-12059
C-12831
O12942
C. 13324
C. 13433
C. 13464
C. 13895
C- 13975
C. 14574
C. 14613
C. 14630
C.I 4*80
C.14721
RB
RB
AF
1
DM
MU
DV
DV
OK
IN
IN
2
i
2
2
«
a
4
!
IN
5
5
5
5
5
5
5
5
5
5
S
5
5
KY
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
0,60
0,67
1,07
0,66
1,34
1.02
l.l«
1,16
1.28
1,1>
1,72
1,20
0.63
1.01
0.43
0.84
1,04
1,05
0,73
0,71
1.11
0.97
1.05
1,08
1,00
1,58
1.15
0,94
1,04
2.77
0,92
1.02
0,86
1.25
1.21
1,11
1,16
1,14
1.29
1.20
1,16
1.11
1,01
1,18
1.29
1.39
1.20
1.41
1.31
1.11
1,04
0.38
0,39
0,24
1.02
0,18
0.23
0,14
0,17
0.14
0.87
0,52
0,49
0,53
0.10
0.93
0.67
0.42
U.37
0.89
0.65
U.63
2,18
0,94
0,76
1.31
0,46
1.07
1.60
0,61
0,48
0,56
1,23
0,82
1.18
0.21
0.37
1.22
1,86
0,62
0,93
1.68
U.27
0.30
O.SO
0,50
0,70
0,30
0,45
o.sa
0,54
0.66
0,30
0.24
U.19
0.02
0.15
0,10
0,28
0,18
0,31
0.37
0,02
0,04
0,02
0,02
0,01
U.16
0,02
0,03
0.13
0,23
0,02
0,15
0,16
0.33
0,02
0,03
0,09
0.21
0,23
0,03
0,01
0,39
0,27
0.03
0.31
0,20
0,30
0,03
0,03
0,28
0,20
0.31
0,48
0,33
0,04
0,03
0,10
0.54
0,47
0,42
0,02
1.90
0,68
1.73
3.00
1,44
3.51
2.1'
2.38
2.19
2.07
2.05
2.84
4.06
2.65
2,81
2.42
1.92
3.87
2.63
2.40
2.89
2.42
1.91
1.96
i.n
0.89
1.92
1.87
2.69
2.6S
2.05
2,12
2.76
2.54
1.69
1,66
1.56
1.59
1.74
1.50
2,45
2.02
1.4*
2.34
2,94
1.79
1.41
1.09
0,95
1,72
1.75
0.04
0,08
0.15
0,04
0,24
0,13
0,18
0,18
0.18
0.12
0,21
0.17
0,08
0.14
0.06
0.19
0.15
0.16
0.10
0.11
0.17
0.16
0,16
0.15
0.14
0.2T
0,17
0,11
0,17
0,13
0.15
0.15
0,14
0.22
0,21
0,17
0.17
0.15
0.14
0,16
0.17
0.17
0.16
0,17
0.15
0.18
0.16
0,17
0,18
0,15
0.15
0.03
0,02
0.02
0.03
0.04
0,03
0,04
0,04
0,04
0.02
0.06
0.05
0.02
0,04
0,01
0,01
0,04
0,04
0.04
0,04
0.04
0,17
0.06
0,03
0,05
0,06
0,04
0.01
0.11
0.05
0.04
0,04
0,02
0,05
0,05
0.03
0.04
0,05
0,04
0,04
0,05
0.05
0.05
0,06
0,04
0.05
0,04
0.04
0,04
0,02
0,03
0,009
0,004
0,016
0.030
0,018
0,007
0,017
0,011
0,010
0.149
0,021
0.018
0.005
0,014
0,022
0,018
0,018
0,037
0,089
0,078
0.033
0,011
0,016
0,098
0,025
0.026
0.017
0.119
0,036
0,020
0.051
0,033
0,048
0.024
0.071
0.016
0,027
0,020
0,065
0,060
0,022
0,045
0,041
0,190
0,029
0,012
0.043
0.145
0.099
0,108
0.021
0.58
0.74
l.»4
0,94
2,38
1.41
2,09
2.24
2,04
1,80
3.24
2,09
1,07
1,65
0,88
2,04
2.21
2,88
2.24
l.»7
2,67
2,55
1.99
2,68
2,68
2.08
2.52
2.50
2,56
2,77
l.«2
2,27
2.08
2,63
2,07
2,07
2,30
2,77
2,18
2,45
2.48
2,20
1,«
2.65
2,77
2,81
»•'!
2.S9
2.31
2,10
2,00
0.02
0,03
0,08
0,02
0,08
0,05
0,07
O.Ob
0,07
0,06
0,07
O.U6
0,04
0,05
0.02
0,05
0,0k
0,08
0,04
0,04
0.07
0,06
0,07
0,0k
0,05
0.08
0,07
O.OS
0,06
0,07
0,05
0.06
0,06
0,06
0,07
0,07
0.07
0.05
0,06
0,06
0,07
0,06
0,06
0,05
0,0k
0,07
0,0k
0,08
0,07
0,0k
0,0k
Note: The first 82 samples are from the Illinois Basin (Illinois, Indiana, and
western Kentucky) and are listed in stratigraphic order beginning with those
from the oldest coal seam. The last 19 are from other states and are
identified by two-letter state abbreviations, with the exception of the
last two, which were obtained from the National Bureau of Standards (UBS).
-------
- 12 -
TABLE 2—Concluded
SAMPLE NB. CBAL AL CA CL Ft K HG NA SI TI
C-14B38
C. 18970
O14982
C. 15058
015079
c-15117
C-15185
O15231
CM5432
OI5436
C. 15456
C-1S717
C-15791
C-15868
C-15872
C-1S999
C-16030
C-16139
C. 16865
C. 16317
C. 16501
CM6543
Cpl*74l
C. 16993
C. 17016
C-17278
C- 18044
C. 15178
C.15418
C. 17053
C-17215
C. 17045
O17046
C- 17047
C. 17054
C. 17096
C. 17097
C. 17307
O17309
C- 17092
C. 17095
C. 17098
C. 17099
O17243
C. 17244
C. 17245
C- 17246
C. 17303
C. 17970
C. 18009
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
*
7
IN
7
MF
AZ
MT
MT
CB
UT
ce
Me
AZ
BH
BM
PA
PA
BH
BH
BM
MV
PA
NBS
NBS
1.31
1.00
1.40
1.20
3.04
1.31
1.01
1.36
1,55
1.27
1,38
1.30
1.50
1,30
1.65
1.57
1,23
1.33
1.42
1.12
1,3«
1,51
1,40
1.05
1,40
1,41
1.65
1,13
1.53
1.15
1.91
1.76
1,71
1.63
2,23
0,72
1.82
2.37
0.73
1.18
2.46
2,66
1,53
1,75
1,81
1.24
1,1«
1.1«
2.21
0.53
0.73
0.80
0.97
0.68
0.52
0.76
1.76
0,90
1,14
0,24
0,67
1,91
0,41
0.91
1.32
0,21
0,21
0.71
1.28
0,73
0.72
2.67
1,09
0,63
0.43
0,34
0.49
0.82
0,05
1.01
0.69
1.44
1.65
1.49
0,60
0,93
0,62
1,16
2,47
0,87
0.30
0.35
0.25
0,76
0.30
0.11
0.11
2.57
0,70
0,07
0,16
0.14
0,09
0.11
0.01
0,01
0,03
0.14
0.20
0,10
0.01
0,03
0.52
0.5«
0,01
0,07
0.18
0.22
0.02
0,02
0,43
0,03
0,02
0,12
0.13
0,07
0.02
0.11
0.03
0.1T
0,02
0,01
0.02
0,0|
0,03
0,03
0,02
0,06
0,02
0.37
0,04
0,07
0,01
0,05
0,22
0,10
0,19
0,12
0,10
0,22
1.78
1.72
i.se
1.22
3.26
2.72
1.89
1.83
1.35
1.50
1,«3
1.77
1.36
0.48
2.14
1.95
1.91
1.78
1,86
1.57
1.99
1.59
1.80
2.96
4.32
2.24
1.64
1.63
1.00
2,34
3.17
0,49
0,60
1.23
0.51
0.48
0.34
3,07
0.55
2,32
2,45
1.06
2,01
2.53
1,79
2.60
0,54
0,93
1.11
1,04
0.18
0.13
0.17
0.21
,0.1*
0.16
0,14
0,17
0,15
0,17
0,20
0,14
0,20
0.17
0,16
0.22
0,20
0.16
0,12
0.17
0.16
0.14
0,16
0,20
O.lt
0,18
0.20
0,17
0,30
o.ie
0,20
0,06
0.11
0.12
0.08
0,02
0,12
0.43
0,02
0.12
0.27
0.32
0.15
0,27
0.29
0,15
0,15
0.13
0,33
0,08
0.06
0.03
0,06
0,04
0,11
0.05
0,04
0,07
0,03
0,06
D.05
0,05
0.06
0.03
0,09
0,05
0,05
J.06
0.06
0,05
0.04
0.04
0,04
0,07
0,05
0.01
0.06
0.01
0.06
0.05
0.07
0.09
0.23
0.25
0,03
0,03
0,09
0,10
0,07
0.02
0.07
0.06
0,04
0,09
0,05
0,04
0,02
0.04
0.11
0,02
0,138
0.096
0,072
0,034
0,037
0,013
0,046
0,091
0,097
0,112
0,032
0.031
0.140
0,101
0.018
0.015
0.015
0.127
0,019
0.017
0.119
*), 033
0,013
0.032
0.121
0,116
0.015
0.048
0.028
0,082
0.038
0.027
0.020
0,019
0,013
0,200
0.028
0,072
0,069
0,061
0.023
0,030
0,02*
0,035
0,036
0.023
0,082
0,022
0.03*
0,032
3,03
1,69
2.89
2,65
4,63
2,17
2,78
2,87
3.12
2,79
2.70
2,79
2,56
2,38
2,72
3.01
2,47
2,95
2,25
2,48
2.64
2.46
2,44
3.47
2.66
3.11
3.43
2.17
J.27
2.30
3.11
3.11
3,09
3,10
3.40
K99
3,32
6,09
1.25
1.80
4,90
3,94
2.12
l.«3
3.20
2. SI
1.S1
2.01
S.»2
O.T2
0,06
0.05
0,06
o.or
0.15
0,07
0,06
0,06
0,09
0,06
0,07
0,06
0,07
0,06
0,07
0,08
0,07
0,06
0,06
0.07
0.06
O.OS
0.07
0,12
0,06
0.07
0.08
0,06
0.09
0,05
0.10
0.06
0,06
0.06
0.13
0,06
0.06
0.08
0.01
0.06
0,11
0.15
0.08
0.08
0.10
0.06
0.08
0,07
0.11
0.05
-------
- 13 -
TABLE 3 —PROXIMATE AND ULTIMATE ANALYSES OF COALS
(percent of whole coal, except for Btu values)
SAMPLE NO. CBAL
»DL
FIKC
8TU
LT*
C-13654
C-17089
O16787
C-15676
C-16919
c-16408
C-15943
O17601
C-159ao
O 13039
C-17304
C«14646
C»|465D
C-15263
OI5566
C-153J1
C«15496
C-16564
c-12495
C. 13046
C-13983
C-14194
C-14609
C-14735
C.M774
C. 10796
C. 15012
C-15208
C- 15384
C-I5448
C-16264
C-16729
C-17001
C. 17305
C. 17721
C. 174811
017966
C. 18040
C-12059
C. 15831
O12942
O13324
C-13433
C- 13464
O13695
C-13975
C.I4S74
C. 14613
C. 14630
C. 14684
C. 14721
Note:
RB
»B
»F
1
0»
MU
DU
UV
OH
IN
IN
2
2
t
2
4
4
4
5
IN
5
5
5
5
5
5
5
5
5
5
5
5
5
KY
5
5
5
3
6
6
6
6
6
6
6
6
6
6
6
6
6
The
2.1
U(4
13.2
6,3
3,'
1,8
1,6
6,3
10.8
12.1
10.5
9,0
2.2
10,7
7,3
8.7
7.5
7.4
3,1
5,5
5,3
1.1
5.9
3,6
12,0
2.8
5,6
13,6
1.5
«.l
10,3
4,6
4,4
7,6
11,5
5,6
7.9
6,0
1.3
5.4
6.8
10,2
7.1
7,1
6,0
7.9
first
4.2
6,7
14. «
9.1
5.3
3.1
1.6
2.9
10,2
2.6
12,9
14.5
13.9
11.2
4.1
14,7
12.5
13.4
11.4
9,9
4,2
7,8
7,0
4,6
7,9
5,2
14,7
«.l
8,7
15.8
7.6
5,9
3.1
12.2
6.7
6.1
9', 4
ia.o
7,9
10,7
4.0
8.7
9.5
10.5
9,7
13.5
10,7
10,4
8,5
10,8
82 samp
40.4
32,0
44,1
35,0
37,0
37,7
36,3
37.1
43,7
11.3
44,5
42,9
41,0
43,5
38,4
45,5
45.8
42.5
43.1
40.5
31,9
36,3
39,4
42.1
34.3
37.2
41.7
36,9
40,2
43.3
37, U
39,5
37,9
38,9
36.3
37,4
40.9
40,7
38.0
37.1
37,6
36,6
36.1
42.6
36.6
43.6
38.2
36.4
38.2
38.6
iles are
55,0
61, B
45.6
56.7
51.8
51.8
52.7
53.0
45.4
45.7
44,5
47.6
51.0
46,4
47.3
45.3
44,2
46,8
46,0
48,9
54,6
53.2
46,5
45.1
55.4
51.3
43,5
5U,9
47,1
44,3
50,8
46,7
48.8
53,1
54.5
52.2
46.7
49,1
51.5
50,3
51.0
54,0
49.2
44,5
51.8
49.0
52,7
55,0
51. 6
51,6
from
4.6
'.1
1U.J
6,2
11,2
10,5
11,1
9,9
10.9
13.0
11,0
9.5
6.0
10.1
14,3
9.2
10,0
10,7
10.9
10,6
13,5
10,5
12.1
12.8
10.3
11.5
14,8
12,2
12.7
12,4
12.2
11.8
13,3
6.0
9.2
10,5
12.4
10,2
10,5
12.6
11.4
9.4
12.7
12.9
11.6
'.4
9,1
a. 6
10.0
9.6
the
14362
13794
12952
13260
12990
13392
13112
13517
12927
12629
11951
13102
13042
12367
12996
12920
12466
13096
12736
12973
13137
12724
12465
13000
12673
11973
12997
12390
12«80
12726
12947
13324
13276
13087
12«S6
12616
12895
12621
12779
13060
12303
12729
13460
13027
13162
12934
12547
Illinois
79,94
77,72
71.49
75,43
71.21
74,53
70,91
74,92
71.28
67.07
71,70
72,73
73.24
72,33
66,23
72,06
70,61
69,98
70.43
70,76
72,28
73,20
71,16
70,31
74,60
71,66
67,16
71,94
66,66
68,99
71.23
71,57
66,66
73,49
74,20
73,46
70,27
72,16
69,91
70,76
73,33
64.06
67,64
71.16
74,72
73,42
73,72
74,49
68,25
Basin
5,76
4,81
4.98
4,93
4.91
5.05
5,01
5,09
5.64
5,10
5,43
5,47
5,3«
4,66
5,04
5.13
5,22
4,9«
5.13
5.30
5,07
5,22
5.15
4,91
S.I*
s.u
5,01
5,06
5,10
4.68
4,66
5,03
4,94
4,81
4,99
5,00
4.93
4,99
5,00
4,85
5,09
4.5S
4.79
5.19
5.68
S.31
4,61
5.13
4,67
(HI
1,83
1.43
1.15
1,50
1.35
1.27
1,86
1.44
1.16
1.20
1.18
1.29
1.37
1.43
l.«2
1,36
1,18
1.20
1.39
1.26
1.33
1.20
1.02
1.19
1.52
1.34
1.43
1.70
1.35
1.14
1.42
1.48
1.15
1,46
1.84
1.61
1.36
1.55
1.49
1.30
1,39
1.09
1.16
1.47
1.34
1.62
1.60
1.48
1.19
inois,
5,98 4.56 3.82
3,26 6,17
7.32 7.06 9.84
6,73 10.29 14,78
6.67 6,24 11,80
6,43 11.20 16.61
4.27 10.55 13,41
7,95 11,06 14,35
5.44 9,91 14,59
7,05 10.61 14,29
9,52 12.96 16,25
5.96 10.91 19,00
6.24 9.46 14,44
6,97 7.92 12,85
6,41 10.12 14,61
5,46 14.26 16.66
6,56 9,22 12,31
9,16 10.01 17,13
6,67 10.66 23,53
7.46 10,68 16,16
7,61 10.61 16,92
4,15 13.54 17.25
7.06 10.40 12.65
6,56 12.06 16,51
7,09 12.82 ia,*a
7,05 10,33 12.62
7.10 11.42 15.98
7.55 l«.77 zo.O.
5,19 12.21 16,40
7.08 12,64 |T, 77
7,94 12. S3 15,67
7.36 12,16 14,01
6,00 11,79 16,01
9.26 13,29 17,26
9.96 6,00 10,99
7,72 «,I6 10,66
7.10 10,47 14,24
7,17 11.40 |S,40
16,05
8.22 10.46 t«.oe
7.11 11.55 1T,55
7.45 11,34 14,78
7.71 4,45 llt,U
13.52 11. Tl IT.60
6,64 11.90 18,71
6,10 11.54 n.j.
8.74 7.34 10,36
9.16 4.06 ,0,69
10.04 1.60 10.42
6.18 4,44 J2.31
12.94 4,62 U.TB
Indiana, and
western Kentucky) and are listed in stratigraphic order beginning with those
from the oldest coal seam. The last 19 are from other states and are
identified by two-letter state abbreviations, with the exception of the
last two, which were obtained from the National Bureau of Standards (NBS).
All values are on a moisture-free, whole coal basis except for air-dry loss
(ADL) and moisture (MOIS).
Other abbreviations: volatile matter (VOL), fixed carbon (FIXC), high-
temperature ash (HTA), low-temperature ash (LTA).
-------
- 14 -
TABLE 3 —Concluded
SANPUt N8,
ADI
«B IS
FIXC
BTU
LT*
c-14838
C-14970
oi«<>e2
C-15038
C-15079
015117
C-15125
C-1S231
CM5432
C. 15436
C-15456
C- 15717
O15791
C. 15868
C. 15875
C-I5999
C. 16030
016139
C-16265
C-16317
C-16501
C-16543
O16741
C. 16993
C-17016
C. 17278
C-18044
C. 15278
C. 15418
017053
C. 17215
C-17005
C. 17046
C-17047
C-17054
C. 17096
C. 17097
C. 17307
C-17309
C»17092
C. 17095
C. 17098
C»17099
C. 17203
C-17244
C. 17245
C. 17246
C. 17303
C-17970
C. 18009
6
6
b
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
IN
7
MF
AZ
MT
MT
CO
UT
CB
MB
• Z
BM
BH
PA
PA
BH
BH
BH
HV
PA
MBS
NBS
11.8
12,2
8, 4
6,3
12,6
13,3
12,8
7,9
11,5
9,5
5,9
8,6
7,1
5,6
10,1
«,1
1.9
10,5
15,6
7.2
5,7
9,"
12.0
o.u
16.7
9.6
8,8
9,5
9.3
8.9
6,2
11.0
14.7
Id. 9
7.7
14.7
17.3
15.6
10.8
16.5
14, 0
9.3
1U.8
9.2
10.2
15.8
7.3
3.2
13.7
18,2
13,0
8.3
17,0
16.0
5.5
23.7
13. 9
10,7
11.9
15.1
12.8
10.6
7.1
20.1
20.7
2.2
2.2
8.9
2.2
6.2
3.4
2.0
0.0
1.0
2.4
1.5
1.7
0.9
1,6
U.4
43.3
40.3
40,5
35.4
38,1
40,7
43,0
«S. I
40,0
44,4
40,5
42,3
35,8
36,8
42.0
38.0
37.7
41.2
41.4
39,4
38,3
43,0
43,3
39,4
43,6
39.4
43,5
35.1
46.4
43.4
44.9
49.6
52.7
32.8
45.2
45.6
36.3
44.7
38.2
36,7
18,9
39,9
37,8
35.5
37,7
34.1
36,1
44.6
48.1
46,9
54,1
46. »
45.7
44.0
45,5
47,8
45.5
47.1
45.5
53.9
54.3
43.5
49,6
50,3
44.7
49.1
48.6
51.4
45.1
43.8
97.5
46.1
48.2
45.5
54.7
42.5
41.3
41.5
34.6
35.4
54,9
47.1
43.5
37.9
48.8
47.0
45.0
65.4
49,0
46.2
51.7
51.7
59.7
57.3
12.1
11.6
12.6
10,5
15.3
13,6
13. U
12,4
12,2
10,1
12,4
12.2
10.3
8.9
14,5
12,4
12.0
14.1
9.5
12,0
1U.3
11,9
12.9
16.0
U.l
10.3
12.4
11,0
10.2
11.1
15.3
13.6
15.8
11.9
12.3
7.7
10. 6
25.8
6.6
14.8
18.3
15,7
U.l
16.0
12.7
10.5
6.1
6.7
2,2
12465
12419
12255
13005
11900
12074
12220
12222
12438
12442
12274
12449
13008
13290
12109
12470
13140
1205U
12810
12400
12980
12380
1245S
11562
12510
12348
12630
12850
11908
69,49
69,25
68.57
73.76
66,24
67,44
68,68
68,09
70,58
68,97
69.23
69,11
72,92
75.13
67,70
69,49
71,96
66,25
71.79
69,97
72,06
68,71
69,53
64,57
62.49
63,18
69,87
71.01
71.06
65,30
65.83
63.32
66.26
72,57
73.84
67.75
55.23
70,99
64.65
62.86
64.16
65,27
70,47
70,62
80,14
78,01
4,98
4,85
4,88
5,14
4,88
5,00
4.99
5.01
4,63
5,12
4,72
4.76
4,96
4,90
4,63
4,54
4,83
4,59
4.97
4,58
5,08
5.07
4.91
4,19
4.55
4,99
4,92
4,82
5,06
5,02
4.73
4,08
4,26
4,58
5.79
4,76
4,03
5,05
4,55
4,45
4,79
4,70
«,8l
4,91
5,29
5,26
1.27
1,10
1.15
1,33
1,04
0.93
1.07
1,43
1,70
1.39
1,54
1,11
1,75
1,52
1,04
1,27
1.35
1.23
1.11
1.25
1.56
1.11
1.10
1,39
1.07
1.39
1.54
1.48
1.33
1,60
0,96
0,90
0,91
1,06
1.23
1.46
0,78
1,01
1,05
0.94
1.05
0,95
1,00
1.16
1,07
1.29
1.29
7.91
8.90
9,03
7,67
8,54
8,82
8.72
8.71
9.16
11.08
7.64
8,68
8,15
8,77
8.51
8,96
6.44
9.01
9.43
8.95
8,61
10,02
8,02
9,67
12,96
14.36
8.76
11,33
7,70
8.64
14.36
14.79
15. 3T
8,77
10,79
14,64
7,*4
15.98
10.34
9.44
16.03
8.75
8,12
9.22
6,22
7.49
12,10
11.65
12.67
10,56
15.31
13.60
13.07
12,45
12.19
10.11
12.42
12.15
10,34
8.83
14,44
12,43
11,92
14,08
9,50
12,00
10,32
11,94
12,69
16,04
13,09
12,37
10,93
10.21
11,08
15.27
13.65
15,83
11.92
12,27
7,72
10.63
25.85
6.56
14.76
18.27
15.67
11.10
16,02
12.72
10.53
6.15
6,66
14,22
3.83
15.47
15.68
14,94
13.33
20.66
15.88
19.07
15.41
13.97
14,49
15.37
17.71
12.94
10,56
19.69
15,09
14.26
18.89
14,56
17.89
15.55
16,19
15.73
20.65
19,49
14.01
17.4IS
12.41
10, rs
13.95
21.94
22.65
14.80
16.54
14.01
7.79
15,19
31.70
7.90
21.10
22.21)
18.81
14,61
21,3,!
15,9ii
14,51)
7.57
8,53
15,4
-------
- 15 -
TABLE 4—SULFUR ANALYSES (percent, moisture-free coal)
SAMPLE MB,
Sift
BUS
SUS
TBS
SAMPLt Ml,
BRS
fit
sus
TBS
SXRF
C-13854
O17089
C-16787
C-1567B
C-16919
C. 16406
C-IS943
C-176D1
C-15944
C. 13039
C-17304
Ol4k«6
C-14k50
C-15263
C-lSSkfc
C-15331
O1549k
C-U564
O12495
C-13046
O13983
C. 14194
C. 14609
C- 14735
O14774
C. 14796
C-IS012
O15208
C-15384
O15448
C'16264
C-16729
C. 17001
CM7J05
C.I772I
C. 17984
0.179(8
C. 18040
O12059
C-12831
C-1Z94J
C. 13324
C. 13433
C. 13464
O13695
C-13975
C.14S74
C. 14613
C. 14630
C. 14664
C-14721
KB
KB
AF
1
Dw
«U
UV
DV
UK
IN
IN
I
i
I
i
4
4
4
5
IN
5
5
5
5
5
5
5
5
:
5
5
S
5
KY
9
5
5
S
6
6
6
6
k
6
6
6
6
6
6
k
6
0,6k
0,0
0,S4
2,10
0,37
1,07
1.26
1,28
0.91
1,60
2,0»
2.07
1.32
0.6?
l.»2
1.75
2.34
2.10
1.62
1.66
1.78
1,29
1.07
1.6S
2.2«
0.58
1,11
2.03
1,63
2.2k
2.U
0.83
1.51
1,44
0,8*
0,57
0,80
2.11
1,28
1,38
1.59
0.85
1.75
2.12
0.71
1.20
0,77
O.k3
1.33
1,94
1.27
0,0
1,10
3.21
0,76
3.78
3.02
2.35
2.27
2.41
1.52
2.72
3.38
2.27
3.38
3.78
1.28
1.67
2.67
3,02
2.47
2.26
1.81
2.34
1,42
0.74
2,04
1,96
2,13
2,56
2.33
2,30
2.62
2,00
1,37
1.50
1,35
1.74
1.29
2,42
2.69
2.17
1.63
2.43
1.82
0.94
0.65
0.57
1.44
1.7k
0.0
0.0
0,03
U,OS
0,10
0,05
0,05
0,18
0.02
0,01
0,51
0.04
0,11
0,04
0,05
0,0k
0,05
0,03
0,0k
0.01
D.02
0,08
0.04
0,02
0,02
0,02
0,02
0,07
0.14
0.12
0,05
0,0«
0.02
1.0*
0,01
0,01
0,01
0,01
0,03
0.12
0,02
0,01
0.67
0.02
0.01
0,04
0.01
0,02
0,02
0,03
t.93
0.56
1,66
5.3k
1.23
4.90
4.33
3.81
3.20
4,02
4.13
4. S3
4.81
3.16
4.85
5.59
3,k7
3.80
4.35
4,k9
4.27
3.k3
2.92
4.01
3,k8
1.34
3.17
4.0fc
3,90
4,94
4.52
3.17
4.14
4.50
2,2k
2.09
2.17
3.86
3.14
a, 60
3.92
4.30
3.03
4,05
4.57
2,54
2.18
1.43
1.22
2,79
3.73
2.18
0.88
l.kO
4.83
1.05
3.24
2,99
3.18
3,48
3.9fc
3.83
4.34
4.27
2.58
4,70
«.23
3.94
4.48
4.47
4.23
4.27
3.18
2.35
3.43
3.74
1.44
2.59
S.fck
3.63
4.43
4,47
2,48
3.49
3,61
2,01
1.92
1,95
2.8S
3.55
2,70
3.87
3.37
1.87
4.08
4.55
2.34
2.18
1.35
1.23
2.4fc
3.24
C.1483!
C-14970
CM4982
C.1503B
C. 15079
C. 15117
C. 15125
C. 15231
C. 15432
C. 15436
C. 15456
C. 11717
C.I579I
C- 15868
C. 15872
C. 15999
C- 16030
C-16139
C. 16265
C. 16317
C. 16501
C. 16543
C. 16741
CM699J
C. 17016
C. 17278
C. 16044
C-15278
C. 15418
C. 17053
C. 17215
C. 17045
C. 17046
C. 17047
CP17054
C. 17096
C. 17097
C. 17307
C.17J09
C. 17092
C. 17095
C. 17096
C. 17099
C.I7J43
C. 17244
C. 17245
C. 17246
C. 17303
C. 17970
C. 18009
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
6
k
k
k
6
6
6
k
k
7
IN
7
MF
AZ
MT
MT
Ce
UT
CB
Me
AZ
BM
en
PA
PA
8H
BH
en
NV
PA
NB8
NBJ
2,5k
2,19
2,12
0.53
1,78
1,8k
2.02
2.59
0.71
1,89
2.03
2,5k
0,72
0,5k
1,82
1.44
1.60
2.4k
1.94
!•»»
1.15
1.91
1.9k
1.50
2.59
3.20
1,85
1,65
0,42
1,78
1,41
0,31
O.Sk
0.70
0,49
0,40
0,4k
1,84
0.34
1,41
1.42
0.4k
1.01
1,32
0,fc9
1,05
0.74
0,75
0.0
0.72
1.66
2.02
1.57
0.99
2.13
2.2k
1,42
I.k9
0.98
1,17
2.3k
1,59
1.14
0.29
1,81
1.79
1,87
2,27
1.22
0,97
1.21
1.20
1,54
1,75
2,87
1.47
1.85
1,60
0.54
1.97
2.67
0,10
0.53
1.16
0,31
0.24
0,07
3.65
0.06
2,37
2.59
1.01
1.82
2,41
1,85
2.39
0.19
0,48
0,0
0.27
0,03
0,04
0,01
0.01
0,07
0.08
0,01
0.03
0,05
0,07
0,06
0,04
0,02
0,0
0,05
0,08
0,04
0,11
0,04
0,33
0.01
0,04
0,05
0,90
0,10
0,18
0,01
o.io
0,02
0,02
0.10
0.02
0,01
0.02
0,02
0,04
0,02
0,9*
0,01
0.16
0,19
0,05
0,21
0,42
0.12
0,24
0.02
0,06
0,0
0.08
4,25
4.25
3.70
1,51
3,98
4,20
3.45
4.31
1,74
1.11
4.45
4,19
I,**
0.85
3.68
3.31
3,51
4.84
3.20
3.25
2,37
3.15
3.55
4.15
5.56
4.85
3.71
3,35
0.98
3.77
4,18
0,44
1.11
1.88
0.83
0.69
0.55
6,47
0,42
3,94
4.20
1,53
3.04
4.15
2,66
1.68
0,96
l.I»
0,0
1,07
3,96
4.13
3.37
1.12
3.15
1,74
3.40
4.12
1.14
4,63
1,26
4.11
1,49
0,68
3,29
1,04
3.20
4.01
3,51
3.22
2.79
3.32
3,63
3.07
5.40
5.0J
3,29
1.27
0,79
4,00
2,81
0,54
0.80
0,98
0,87
0,68
0.57
4.02
0,54
1,»6
2.94
0,92
2.11
1.21
1,82
2,85
1.21
1.46
1.25
1.17
Note: The first 82 samples are from the Illinois Basin (Illinois, Indiana, and
western Kentucky) and are listed in stratigraphic order beginning with those
from the oldest coal seam. The last 19 are from other states and are
identified by two-letter state abbreviations, with the exception of the
last two, which were obtained from the National Bureau of Standards (NBS).
Abbreviations: organic sulfur (ORS), pyritic sulfur (PYS), sulfate sulfur
(SUS), total sulfur (TOS), sulfur by X-ray fluorescence (SXRF).
-------
- 16 -
STATISTICAL ANALYSES OF ANALYTICAL DATA
As a first step in the statistical analyses of the large amount of
data generated, arithmetic means, standard deviations, ranges (minimum and
maximum values), and linear correlation coefficients were calculated on the
trace elements, major elements, high- and low-temperature ashes, and the
proximate and ultimate coal analyses for the 101 coal samples. These are
summarized in tables 5 and 7- Because determinations for all variables were
not reported for all samples (see appendix), a missing-data statistical
analysis, called MISR (IBM-SSP) (IBM Corp., 1970, p. 3k) t was used in this
study. This computer program identified the missing data and omitted them
when calculating the statistical values. Other statistical analyses were
used on parts of this study in which the data were complete as a check on
the validity of the missing-data analysis and the same statistical results
were obtained. This particular program was used because the output (computer
print-out of means, etc.) could be modified so that it could be photographed
directly; and it appears in the original form in tables 59 6, 7, and 8.
The 101 coal samples were grouped into three geographic regions:
Illinois Basin (82 samples), eastern United States (ll samples), and western
United States (8 samples). Arithmetic mean values, standard deviations,
ranges, and linear correlation coefficients were determined using the missing-
data correlation analysis (MISR) on the trace elements, major elements, high-
and low-temperature ashes, and the proximate and ultimate coal analyses for
each group. Because of the small sample population in the eastern U.S. and
western U.S. groups, only the statistics for the Illinois Basin are presented
separately in this paper (tables 6 and 8) in addition to the data for all coals
analyzed.
The trace element concentrations of Cd, Ge, Mo, and Sn were reported
in some samples as "less than" values. To estimate the effects of these less
than values on the statistics, the means for these four elements were calculated
three different ways. First, the "less than" values were used as the accepted
values (< Q.k would be equal to O.U) with the following means as the result:
Cd = 2.53, Ge = 6.59, Mo = 7.5*1, and Sn = U.79- Second, half the less than
values were used as the accepted values (< Q.k would become 0.2) with the
following results: Cd = 2.kk, Ge = 6.1*9, Mo = 7-50, and Sn = 3-70. Third,
zero was used in place of the less than values (< O.k then equals 0.0) with the
following means: Cd = 2.3^, Ge = 6.39, Mo = 7.U8, and Sn = 2.67. For all
samples in which these four elements were not reported as less than values, the
accepted value was used in the three trials. For Ge, Cd, and Mo, the difference
between the various means in the three trials was less than 10 percent. Similarly.
the correlation coefficients for these three trace elements did not vary signi-
ficantly. Therefore, the statistics reported for these three elements on
tables 5, 6, 7, and 8 were calculated using the less than value as the true value
(< 0.1* equal to 0.10. The different means for tin in the three trials vary by
more than 30 percent and although statistical values are shown in the various
tables, the results are not thought to be highly significant.
-------
- 17 -
Histograms of the distribution of trace, minor, and major elements
and of the high-temperature and low-temperature ashes are given in figures 1
through 39. The data for 98 of the 101 coal samples are plotted on the
histograms (omitting a weathered coal sample, C-17089, and the two NBS samples)
so that the three geographic groups may be differentiated. The data from the
Illinois Basin coals are plotted as unpatterned bars , those from the western
United States as horizontally striped bars, and those from the eastern United
States as vertically striped bars. The horizontal axis is divided into class
intervals and the vertical axis represents the number of samples in each class.
Those samples whose values are well beyond the last regular class interval are
plotted following a break in the abscissa and are identified with a plus sign (+).
On the basis of analyses of the histograms, ranges, and standard
deviations, elements can be grouped with those of similar type. Within one
group, elements display a more or less normal distribution of analytical
values, with small standard deviations and ranges. Included within this group
are Al, Fe, F, Ga, Be, Br, B, Or, Cu, K, Ni, Si, Ti, Se, and V. Within this
group are several elements with high organic affinities (discussed later in
this report and in Gluskoter, 197^0, and also elements which are thought to be
syngenetic and therefore were contributed to the coal early in the coal swamp
history. The data obtained from the second group of samples are highly skewed,
with large ranges and large standard deviations. This group includes Cd, Zn,
P, As, Sb, Pb, Sn, Cl, Ge, and Hg. A number of the analyses of the elements
in this group were reported as "less than" values, which contributed to the
skewed distribution shown for these elements. Other elements in this group
are commonly found in nature as sulfides and carbonates, which when present in
coal are often the result of epigenetic mineralization and may be locally
concentrated. As is the case with most geologic samples, there is also an
intermediate group of elements whose analytical data present a moderate range
and standard deviation, including Mg, Cu, Mn, Na, Mo, and Zr.
Coefficients resulting from the correlation of one parameter with
every other parameter in the four groups (all 101 coals, coals from the Illinois
Basin, eastern coals, and western coals) were tested at the 1 percent level
(highly significant) using the standard F test. Correlation coefficients
calculated for the coals of the eastern and western United States were found to
be nearly insignificant at the 99 percent confidence level because of their
small sample population and thus are not shown in this report. Correlation
coefficients for the Illinois Basin coals and for all 101 samples were calculated
on a sufficiently large population to be significant and demonstrate the fol-
lowing geochemical associations:
l) An excellent positive correlation (0.93 for coals of the Illinois
Basin and also for all 101 samples) is present between Zn and Cd. Zinc is
present in coals, at least in part, as ZnS (sphalerite) as was previously re-
ported by Gluskoter, Hatch, and Lindahl (1973); cadmium has been identified as
occurring in solid solution with Zn in this mineral in Illinois coals (Gluskoter
and Lindahl, 1973).
2) The elements of the following group have positive correlations
with each other: As, Co, Cu, Ni, Pb, and Sb. These elements are commonly
found in nature as sulfides (and are included among the chalcophile elements—
elements which have a strong affinity for sulfur). Germanium is postively
correlated with many chalcophile elements in the Illinois Basin coals and in
the 101 coal samples.
(Continued on page 31)
-------
- 18 -
TABLE 5—MEAN ANALYTICAL VALUES FOR ALL 101 COALS
CBNS7I7UEN7
AS
B
BE
BR
CD
CB
CR
CU
F
GA
CE
HS
MN
MB
NI
P
pa
SB
SE
SN
V
ZN
ZR
AL
CA
CL
FE
K
MS
NA
SI
Tl
BRS
PYS
SUS
TBS
SXRF
ADL
MBIS
vet
FIXC
ASH
BTU/LB
C
H
N
a
HTA
LTA
MEAN
14.02
\0i.il
1.61
15.42
2.52
'.57
13.75
15.16
60, 44
3.12
6,59
0,20
49.40
7.54
21,07
71.10
34.78
1.26
2,08
4,79
32,71
272.29
72.46
1.29
0.77
0.14
1.92
0.16
0,05
0.05
2.49
0,07
1.41
1,76
0,10
3,27
2.91
7.70
9,05
39,70
48.82
11.44
12748.91
70. as
4,95
1,30
8,68
11.41
15,28
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
STO
17,70
54,65
0,82
5,92
7,60
7,26
7,26
8.12
20.99
1,06
6.71
0.20
40,15
5,96
12.35
72.81
43.69
1.32
1.10
6.15
12.03
694.23
57.78
0,45
O.S5
0.14
0.79
0.06
O.U4
0.04
0.80
0.02
0.65
0.86
0.19
1.35
1.24
3.47
5.05
4.27
4,95
2.89
464,50
3.87
0.31
0,22
2.44
z.«
4,04
WIN
0.50
5.00
0.20
4,00
0,10
1.00
4,00
5,00
25,00
1.10
1.00
0.02
6,00
1.00
3.00
5.00
4.00
0.20
0.45
1.00
11.00
6,00
8.00
0.43
0.05
0.01
0.34
O.Oi
0.01
0.00
0.58
0.02
0.31
0.06
0.01
0.42
0.54
1.40
0.01
18.90
34.60
2.20
11562.00
55.23
4.03
0,78
«.15
3.28
3.82
MAX
93.00
224.00
4.00
52.00
65.00
43.00
54.00
61.00
143,00
7,50
43.00
1.60
181,00
30,00
80,00
400.00
218,00
8,90
7,70
51,00
78,00
5350.00
133.00
3.04
2.67
0,54
4,32
0.43
0.25
0.20
6,09
0.1!
3.09
3,78
1,06
6,47
5.40
16,70
20,70
52.70
65,40
25,80
14362,00
80,14
5.79
1,84
16,03
25.85
31,70
Note: Abbreviations other than standard chemical symbols: organic sulfur (ORS),
pyritic sulfur (PYS), sulfate sulfur (SUS), total sulfur (TOS), sulfur by
X-ray fluorescence (SXRF), air-dry loss (ADL), moisture (MOIS), volatile
matter (VOL), fixed carbon (FIXC), high-temperature ash (HTA), low-
temperature ash (LTA).
-------
- 19 -
TABLE 6—MEAN ANALYTICAL VALUES FOR 82 COALS FROM THE ILLINOIS BASIN
CBNSTITUENT
AS
6
BE
BR
CD
CO
CR
CU
f
GA
G£
HG
MN
MB
NI
P
pa
SB
SE
8N
V
ZN
ZR
Al
CA
CL
FE
K
MS
NA
SI
TI
0RS
PYS
sus
res
SXRF
AOL
MBIS
VBL
FIXC
ASH
BTU/LB
C
H
N
e
HTA
LTA
MEAN
10, VI
113.79
1,72
15,27
2,69
9.15
14.10
14.09
19,30
3.04
7.51
0,21
53,16
7,96
22.35
62,77
39,83
1.35
1,99
4.56
33,13
313,04
72,10
1.22
0,74
0,15
2,06
0.16
0.05
0.0!
2,39
0,06
1.54
1.68
0,09
3.51
3.19
7,70
10,02
39,60
46,96
11.28
12746,91
70.69
4,96
I."
6.19
it. 16
15.22
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
PPM
I
I
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
STD
16,94
51,72
0,83
5.60
6,32
5.76
7.48
6,78
19,79
1.03
7,06
0,22
40,96
5,66
10,61
65,66
45.94
1.42
0.9J
6,64
11.63
749,92
58,01
0,37
0,49
0,15
0.71
0,04
0,02
0.04
0.62
0,02
0,62
0,74
0.18
1.12
1.06
3.47
4.2)
3.17
3,92
1.98
464,50
3.11
0.16
0,20
1,64
2. IT
3.22
MIN
1,70
12.00
0.50
6,00
0,10
2,00
4,00
5,00
30,00
1,60
1,00
0,03
6,00
1.00
6,00
5.00
4,00
0.20
0,45
1.00
16,00
10.00
12,00
0.43
0,05
0,01
0,46
0,04
0,01
0,00
0,56
0,02
O.J7
0,29
0,01
0.85
0,79
1.40
1.60
31,90
41,30
4,60
11562,00
62.49
4,19
0,93
4.19
3,28
1.62
MAX
93.00
224,00
4.00
52,00
65,00
34,00
54,00
44,00
143,00
7,50
43.00
1.60
161.00
29,00
66,00
339,00
216,00
6.90
7,70
51,00
78,00
5350.00
133.00
3.04
2.67
0.54
4.3Z
0.30
O.IT
0,19
4,63
0,15
J.09
3,76
1,06
5.59
5.40
16,70
18,20
46.40
61,00
16,00
14162,00
79,94
5,76
1,64
14,36
16.04
23. S3
Note:
Abbreviations other than standard chemical symbols: organic sulfur (ORS),
pyritic sulfur (PYS), sulfate sulfur (SUS), total sulfur (TOS), sulfur by
X-ray fluorescence (SXRF), air-dry loss (ADL), moisture (MOIS), volatile
matter (VOL), fixed carbon (FIXC), high-temperature ash (HTA), low-
temperature ash (LTA).
-------
- 20 -
TABLE 7—LINEAR REGRESSION (LEAST SQUARES) CORRELATION COEFFICIENTS
BE BR CO CB CR CU
IN ZP,
AS l.u
8 -0,2
BE O.I
BR .0.1
CD 0,0
CB 0,11
CR .0.1
cu o.i
r 'O.o
Gt 0.2
SE 0,4
M5 0.1
UN .0.1
MB '0,2
NI 0,3
P O.J
PB 0,7
IB 0.6
ie o.o
IN .0.1
V '0,1
ZN 0,0
Zll 0,3
AL .0,2
CA .0,2
Cl 0,0
FE Q,2
K .0,0
MG .0 2
NA .0,1
«n i
— • *
Tt .0.1
IRB .0,3
PVI 0.3
IUI *0.0
Ttl 0.0
IXRP .0.0
ADL .0,0
MBit .0.0
VIL .0.2
PIXC 0.2
AIM .0.2
BTU 0,3
C 0.2
H 0.1
N O.I
1 .0,2
HTA .0.2
LTA .0,1
.a, 2
1,0
0.2
• 0,2
0.3
.0,2
-0.0
•0.1
.0,0
.0,0
0.3
0.1
0,4
0,2
0,0
-0,2
.0,1
0.0
• 0.1
0.1
-0,1
0,3
• 0,D
0.1
0,1
-0,2
0,2
• 0,1
.0.0
0,1
0.2
•0.1
O.t
0.1
.0.1
0,4
0.5
0.7
0.7
O.I
.0.5
0.2
.O.t
.0.3
.0.0
.0.1
0.2
0.2
0.1
0,1
0,2
1,0
0,0
0,2
0,2
0.2
0.3
-0.1
0,4
0.5
0.1
0.2
•0,1
0,3
.0,1
0,4
0.4
0,0
0,1
0,0
0,2
0,0
0.0
.0.2
.0,2
0,3
0,1
•0,1
•0 i
•O.I
0,1
0,2
0.2
0.1
0.2
0.3
0.2
0.3
0.1
•0,1
-0.0
0.0
0.1
0.1
.0.0
•0.2
.0.0
o.l
•0,1
•0.2
0.0
1,0
-0.1
.0.1
0.1
•0.1
-0,2
• 0,0
0,0
0,0
-0,1
•0.1
.0,1
o.o
•0,1
-0,0
-0,1
0.1
0.1
.0,1
•0.1
•0.1
• 0.1
0.2
•0.3
•0.0
0.1
On
,u
•0,1
•0,0
•0,2
• 0,3
• 0,2
• 0,3
.0,3
.0.0
0,0
.0,0
0.2
-0,4
0,3
0,4
0.1
0.2
.0,0
.0,3
.0,4
0,0
0.3
0.2
•0.1
1.0
0.1
0,1
0,1
-0.1
0,0
0,3
0.1
0.2
0.1
0.2
-0.1
0.1
0,2
0,0
0,0
-0.0
0.4
• 0,0
0,0
0.3
•0.2
0.0
• 0.0
*0 1
•0, 1
0.0
0.0
0.2
•0.1
0.1
O.I
0.1
0.1
0,3
0.1
-0.1
0.1
-0.1
•0.1
0.0
-O.I
0.0
0.1
0.1
0.4
•0.2
0,2
•0.1
0.1
1.0
0,1
0,5
-0,0
0,3
0,2
0.3
-0.1
.0.0
0.7
0,1
0,4
0,4
0.2
-0,1
0.1
0,1
0,2
0,1
.0,2
0,0
0,2
0,3
• 0 1
•W, 1
•0,2
0.1
0,0
-0.2
0.2
0.4
0,1
• 0,0
-0.1
-0.2
-0,3
0.2
0,1
0.4
0.0
-0,1
.0.0
• 0.2
0.1
0.1
-0.1
-0.0
0.2
0,1
0.1
0.1
1.0
0.2
0.1
0.2
-0.1
0.1
0,0
0.2
0.2
-0.0
-0.0
0.0
0,4
0,0
O.t
0.1
• 0,0
0.2
-0.1
0.1
0,0
0,4
0,0
0*
,c
O.J
0.8
0.2
0,0
0.4
0.1
0.2
•0.1
-0.0
• 0.2
0.1
0.2
• 0.2
•0.2
-0.2
-0.1
0.0
0.2
O.i
0,3 -0.0 0.2 0.4 0.1 .0.1 .0,2 0,3 0.3 0.7 0,6 0,0
.0.2 -0,0 -0,0 0.3 0,1 0.4 0,2 0,0 .0,2 .0.1 0,0 .0,1
0,3 .0,1 0,4 0.5 0.1 0,2 -0,1 0,3 >0,1 0.4 0,4 0,0
•0,1 «0,2 -0,0 0,0 0,0 -0.1 -0,1 >0,1 0,0 -0,1 -0,0 -0,1
0.1 -0.1 0,0 0,3 0.1 0,2 0,1 0,2 -0,1 0,1 0,2 0,0
0.5 -0,0 0.3 0.2 0,3 -O.I -0,0 0.7 O.I 0,4 0,4 0.2
0.2 0.1 0,2 •O.I 0,1 0,0 0,2 0,2 -0,0 -0.0 0,0 0,4
1.0 0,1 0,5 0.2 0,0 .0.0 -0,0 0.5 0.2 0,3 0.4 0,)
0,1 1,0 0,2 -0,3 .0,1 .0.2 0,0 .0,0 0.5 -0.2 >0,2 O.I
0,5 0,2 1.0 0,2 0,2 -0.0 "0.1 0.4 0.1 0,2 0,3 0,2
0,2 .0,3 0,2 1,0 0,2 0,3 0,0 0.4 .0,2 O.t 0,7 .0,2
0,0 .0,1 0,2 0,2 1,0 .0,1 -0,1 0,4 0,1 0.2 0.4 .0,0
.0,0 .0,2 -0.0 0,3 -0,1 1.0 0,2 0.1 -0,2 O.t 0,1 >0.1
• 0,0 0,0 -0,1 0,0 -0,1 0,2 1,0 0,0 -0,2 0,0 '0,1 0,1
0,5 .0.0 0,4 0,4 0,4 0.1 0,0 1,0 0,1 0.5 O.t 0,1
0,2 0,5 0.1 -0,2 0,| .0,2 .0,2 0,1 1,0 0.1 -0,1 .0,0
0,3 -0,2 0,2 O.t 0,2 0,1 0,0 0,5 0.1 1.0 O.t -0.0
0.4 -0,2 0,3 0,7 0,4 0,1 -0,1 O.t -0,1 O.t 1,0 -0,0
0,3 O.I 0,2 .0.2 .0.0 .0,1 0,1 0,1 .0.0 .0,0 -0,0 1,0
0,1 0.1 0.1 0.0 .0,1 0,1 .0,0 .0,1 >0.1 .0,1 .0,1 0.0
0,1 0,1 0.1 .0,1 0,1 0,2 0.3 0,2 .0.1 0.0 0.0 0,4
0,2 -0,1 0,1 0,3 O.I 0.2 0,2 0,3 .0.1 0,2 0.2 0,0
0.2 .0.0 0,2 0,2 .0,0 .0,0 0,2 0,1 0.0 O.I 0.3 0,2
0.3 0.4 0.3 .0,2 .0.1 0,0 0,1 0,1 0,2 .0,1 .0.1 0,3
•0,1 .0,1 .0.1 0.0 .0.2 0,5 0,2 -0,2 .0.1 .0,1 .0.1 .0,2
.0.2 0.0 .0,2 .0,3 .0,0 .0,2 -0,2 .0,1 .0,0 .0,1 >0.i 0,0
0.1 .0,0 .0.0 0.4 .0,0 0.2 0,3 0,2 .0.2 0.3 O.i 0,1
0.4 0,3 0.3 .0.1 0,1 0,0 0,0 0,4 0,2 0.0 0.0 0,1
0.1 0.0 0.1 .0,1 .0.1 0.3 Oi3 *0.1 0.1 .0,1 *0,l .0,1
•0 1 .0 0 .0.1 *0 2 .0 1 00 .0 0 .0 i .0.1 .0 I .0 2 00
O.i 0.3 O.I *0.i *0»l O.i O.i O.i 0.1 *0.i .O.i O.i
0,2 0.2 0,3 .0,2 .0.) .0,1 .0,1 0,1 0.1 .0,1 -0,1 0,3
•0.1 0.0 -0,0 0.2 -0.1 0,4 0,,5 -0,0 -0.3 .0.0 -0,0 0,1
0.1 0,1 -0,0 0,3 0,0 0,1 Oi,4 0,2 -0,1 0,4 O.i 0,1
0,3 0,2 0,1 -0,1 -0.0 0,1 0,,1 0,2 0,2 0.0 .0.0 O.I
O.I 0,1 -0,0 0,3 -0,0 0,3 0,,5 0.1 >0.i O.i 0,1 O.i
•0.0 -0.0 -0.0 0.4 .0.1 0,3 0,,5 0.1 .0.3 O.i 0.1 0.1
0,1 .0,2 0.1 0.4 0,0 0,3 .0,0 0,1 .0,1 .0.0 0.1 0.1
.0,1 .0.3 0.0 0.4 0.1 0.5 0,1 0.1 -0.2 0.1 0.2 .0.1
-0.2 -0,2 -0,1 0,3 .0,1 0,3 0.2 .0,3 .0,1 .0.1 0,0 .0,4
.0.0 0,0 0,0 .0.2 0.2 -0.5 -0,4 0,1 0.1 0.0 0,0 0,1
0.2 0,3 0,2 -0.0 .0,1 0.4 0.4 0,2 0,0 0.1 '0,1 0,1
0,1 .0.0 .0.1 0.0 0.2 .0.4 .0,3 0,2 0,3 0.1 0,1 .0.1
•0,2 -0.2 -0,1 O.I 0,1 -0,3 -0,4 .0,0 .0.0 0,1 0,1 .0,2
.0.1 .0.1 .0.2 0,1 0,1 .0.2 .0,2 .0,1 .0,0 0,1 0.1 -0,2
• 0.2 -0,0 >0.l -0,0 0,1 .0,2 .0,3 0,1 0,0 0.0 0,1 .0,1
•0,0 0,0 0,0 .0,2 .0,1 .0,0 .0,1 .0,2 0,2 .0.3 >0.2 .0,1
0.1 0.2 0.1 .0,0 .0,2 0,4 0,4 0,1 .0,0 0,0 .0,1 0,1
0.1 0,2 O.i 0,1 -O.J O.I 0,1 0.1 -0,0 0.0 .0,0 0.1
•0,1
0.1
0.1
0.1
0,0
•0,1
0.0
0.1
0.1
o.l
o.o
.0.1
0.1
.0.0
-0.1
•0,1
-0.1
•O.I
0.0
1.0
0.0
0.1
• O.I
O.I
0.1
•0.1
0.0
•Ot 0
0(|
o, i
01
• 1
0,0
o.o
o.o
0.0
0.0
0.1
o.t
0.2
0.1
•0.2
O.I
•0.1
•0,1
0,0
• 0.2
0.1
o.t
0,1
•0.1
•O.l
0.0
o.l
•0,0
o.l
o.t
0.1
0.1
O.I
•O.I
o.l
O.i
0.1
O.i
•0.1
0.0
0.0
0.4
0.0
1.0
0.0
0.1
O.I
O.I
0,1
O.i
Q»4
Otl
•ovo
0(4
0.4
0.1
O.i
O.i
O.I
0.1
•O.i
-O.i
.o.t
0,1
0.4
•0.1
•O.i
•O.I
-0,0
•O.i
O.I
0.1
0.0
0.3
O.i
• 0,1
o.i
O.I
0.1
0.2
•0,1
0,1
0.3
0.1
0.2
0.2
0.1
•0,1
0,2
0,2
0,0
0.1
0.0
1.0
•0,0
0,0
0.3
•0,2
0,0
On
«U
•0,0
•0,1
On
,u
• 0,0
0.2
•0,0
0.1
0,1
0,1
0,1
o.a
0,1
•0,1
0.1
•O.l
•0.1
•0.0
•O.I
•0,0
0.1
o.t
0.1
•0,0
o.o
-0,1
•0,0
O.i
.0,0
0.2
.0,0
0.2
O.i
.0,0
.0,0
O.i
0.1
o.o
0.1
0.3
O.i
•0.1
O.I
•0,0
1.0
•O.I
0,1
•0,1
O.i
n *
•HI i
Oil
•0|Q
• Q 1
• U, |
•o.t
•0,0
O.I
O.i
0.1
0.1
0,0
0.0
O.I
-0.1
0,0
•0.0
•0.1
•O.I
-O.I
0.1!
0.0
O.I
• 1
e
IE
BR
CO
CB
CR
CU
p
GA
61
MB
MN
M<
NI
P
PI
II
IE
IN
V
IN
If
AL
CA
CL
PE
*
HI
NA
II
Tt
Iftl
PTI
aui
Til
IXP.P
AOL
Hilt
VIL
PIXC
AIM
ITU
N
I
HT»
LTA
CD Cl CR CU f UA EC HE MN He NI P PB IB IE IN V IN ZP.
Note: All values are rounded to one significant figure. Abbreviations are the
same as those used in preceding tables.
-------
- 21 -
OF ANALYTICAL DETERMINATIONS ON 101 COALS
AL
AS -0,2
B 0,1
BE 0.0
BR .0,1
CO 0,0
ce 0,1
CR 0,2
CU 0,3
r 0,4
GA 0,]
GE '0,2
MG .0,1
HN 0,0
MB 0,1
MI 0,1
P 0,2
PB .0,1
9B .0,1
se o.i
SN 0,1
V 0,3
IN 0,0
ZR '0,1
«L 1,0
CA .0,1
CU .0,2
FE .0,1
K O.i
1C 0,«
N» .0,1
31 0,1
TI O.t
IRS .0,0
PYS .0,1
SUI 0,2
res .0,1
SXRP .0,2
AOL 0,1
Hill .0,1
V1L .0,2
FIXC .0,1
ASH 0,6
BTU .0,4
C .0,1
H .0,*
N .0,3
t 0,3
HTA 0,«
LTA 0.4
CA CL ft
-O.i 0,0 0,2
0.1 .0,2 0,2
• 0.2 .0.2 0.3
.0,1 0.2 -0.3
0,3 -0.2 0,0
-0,2 0.0 0,2
.0.1 0.1 0,0
-0.1 -0.2 0,1
.0.1 0.0 -0.0
-0,1 -0.2 -0,0
0,0 .0.3 0,4
-0.2 -0.0 -0,0
o,: -0,2 0,2
0,2 »0.2 0.3
-0.2 .0.1 0,2
-0,1 .0.0 -0,2
-0,1 .0,1 0,3
.0.1 -0,2 U.2
-0,2 0,0 0,1
0.1 .0,1 0,0
0,1 0,1 0,2
0.3 .0,2 0,0
0,1 .0.1 0,2
.0.1 .0.2 .0.1
1,0 .0.2 -0.2
•0.2 1.0 .0,2
-0,2 .0.2 1.0
-0,3 -0.0 0,1
0,3 *0,2 .0,1
0.0 O.S .0.1
0.1 .0.2 0,0
.0,1 .0.1 -0,1
0,1 -0.3 0,5
.0.1 -0,1 0,8
-0,0 -0,1 0,3
-0,0 -0,2 O.i
-0.0 .0.2 O.t
0.1 .0,4 0,2
0,2 .0,2 0,0
0,3 .0.3 0.1
.0,3 0,4 -0.2
0,2 .0,2 0,3
.0,4 0.4 .0,1
•0,1 0,4 .0,3
.0,1 0,1 -0,0
-0,2 0,5 .0,2
0,1 .0,2 .0,3
0,2 .0,2 0,3
0,2 .0,3 0,5
K MG
-0,0 -0,2
-0.1 -0.0
0.1 -0.1
-0,0 0,1
-0,0 -0.1
0,3 -0,1
0,4 0,0
0,4 0,1
0,3 0,0
0,3 0,1
-0,1 -0,1
0,1 .0,1
0,0 0.3
0.0 0.3
0.4 -0,1
0,2 0,1
0,0 -0.1
0.0 .0.1
0,3 .0,1
-0.0 0,1
0,4 0,1
0,0 -0,0
-0,1 0,1
0,6 0,4
.0,3 0,3
.0,0 .0.2
o.i -o.i
1.0 0.2
0.2 1.0
-0,1 .0,1
0,7 o,;
0,6 0,2
0,0 -0,1
0,1 -0,1
0.4 0.1
0,1 -0,1
.0,0 .0.2
-0,2 .0,0
-0,2 0,2
-0.5 0.2
0,2 .0,4
0,5 0,4
•0,2 .0.2
.0,3 .0,4
-0,3 .0,4
0,0 .0,3
-0,1 0,4
0,4 0,3
0,4 0,3
NA SI TI
-0,3 -0,3 .0.1
0.3 0,2 -0,1
.0.2 .0,1 0,1
0.0 .0,1 -0,0
-0.1 0,0 0.0
-0,2 0,1 0.0
0.2 0.3 0,2
.0.1 0,2 0,2
-0,0 0,3 0,2
-0,2 0,2 0.3
-0.2 -0,2 -0.2
-0,1 -0,1 .0,1
0,0 0,2 -0.1
•o.o 0,2 .0,1
.0,2 0,2 0,1
.0,1 0,1 0.1
-0,3 -0,2 -0.1
.0,2 .0,2 .0.1
0,0 0,2 0.3
0,1 0,1 0.0
•0,0 0,4 0,4
•0,1 0,0 .0.0
•0.0 .0,1 -0.1
-0.1 0,9 0,«
0,0 0,1 .0,1
0.5 "0,2 .0,1
.0,1 0,0 .0,1
.0.1 0.7 0,6
.0,1 0.5 0.2
1.0 0.1 -0.1
0,1 1,0 0.7
-0.1 0.7 1,0
0.1 0,1 .0,2
.0,1 -0,0 .0.2
0,0 0,4 0,1
-0.0 0,1 .0,2
0.1 -0.0 .0.3
0.2 0.1 0.1
0,1 >0,| .0.2
0.2 .0,2 -0,5
•0,1 .0,3 0,2
•0,0 O.t 0.4
.0,1 .0,6 .0,4
.0,1 .0,7 -0,2
0,1 .0,5 .0,3
0,1 .0,3 .0.1
0,2 0,2 0.1
0,0 0,7 0,3
.0,0 0,6 0.3
0RS
.0,3
0.6
0.2
-0.2
0,2
.0,2
0.2
-0,1
0,0
.0,0
0,2
-0,1
0.4
0.5
'0,0
.0,3
• 0,0
• 0,0
0,1
0,0
0,1
0.2
.0,0
.0.0
0,1
.0.3
0.5
0.0
•0.1
0.1
0,1
-0,2
1,0
0,5
0.1
0,8
0.9
0,4
0,3
0.4
•0,5
0,3
• 0,6
• 0,4
• 0.1
• 0.3
-0.2
0.3
0.4
PYS SUS
0,3 .0,0
0,1 -0,1
0.2 0,1
-0.3 .0.2
-0.1 0,1
0,2 0,4
0,0 0,4
0.1 0,3
0,1 0,2
•0,0 0,1
0,3 -0,1
0,0 .0,0
0.1 0.1
0,4 0,1
0,2 0,2
.0.1 0.2
0,4 0,0
0,2 .0.0
0.2 0.1
0.0 0,0
0.2 0,2
•0,0 0,1
0.2 0.2
•0,1 0,2
.0,1 -0,0
•0.1 -0.1
0,8 0,3
0,1 0,4
.0,1 0,1
.0.1 o.o
-0,0 0,4
-0,2 0,1
0,5 0,1
1.0 0,2
0,2 1,0
0,9 0.3
0.7 0,2
.0,0 .0,0
.0,0 .0,3
0.0 -0,1
-0,3 .0,8
0.4 0.5
•0,2 .0,4
•0,3 .0,5
.0.0 -0,4
-0.1 .0.3
-0.4 0,1
0,4 0.5
0.5 0,4
res SXRF
0,0 -0,0
0,4 0,5
0,2 0,3
.0,3 .0,3
U.I 0,1
0,1 -0,0
0.1 0,2
0,1 .0,0
0,1 -0,0
-0,0 .0,0
0,3 0,4
-0,0 -0,1
0.3 0.3
0.5 0.5
0.1 O.I
-0.2 .0,3
0.2 0,2
0.1 0,1
0,2 0,1
0.0 0,1
0.2 0,1
0.1 0,1
0,1 0,1
•0,1 .0,2
.0,0 .0,0
.0.2 .0.2
O.t O.t
0.1 .0.0
•0.1 .0,1
•0,0 0,1
0,1 -0,0
.0,2 .0,3
0,8 0,9
0,9 0,7
0.3 0,2
1.0 0,9
0.9 1,0
0.2 0.3
0,1 0,2
0.2 0,3
•0.4 .0.4
0,5 0,3
•0,5 .0.4
•0,5 -0,4
-0,1 0,0
•0,3 -0.2
•0.3 .0.3
0.5 0,3
0,6 0,5
AOL MDIS
.0,0 -0,0
0,7 0,7
0,2 0,3
.0,0 0,0
0,1 0,3
-0,1 .0.2
.0,1 .0,0
0,1 .0,1
-0,2 .0,3
0.1 0,0
0,4 0,4
0.0 0.1
0.3 0,5
•0,0 0,1
0.1 0,1
.0,1 .0,2
.0,0 0,1
0,1 0,2
0,1 .0,2
0,1 0,2
.0,2 .0,2
0.1 0.2
0.0 0,0
0.1 -0,1
0.1 0,2
•0,4 «0,2
0,2 0,0
•0,2 >0,2
.0,0 0,2
0,2 0,1
0,1 .0,1
0,1 .0,2
0,4 0.3
•0.0 -0,0
.0,0 .0,3
0,2 0,1
0,3 0,2
1,0 0,9
0.9 1,0
0,5 0,6
-0,5 .0,5
0,1 0,0
•0.4 >0,4
•0,4 .0,1
•0,1 .0,1
.0,4 .0,1
0,4 0,2
0,1 .0,1
0,2 0,1
VBL FIXC
-0,2 0,2
0,5 .0,5
0,1 .0,1
.0,0 0,2
0,1 -0,1
.0,3 0,2
.0,2 0,1
.0,2 .0,0
.0,2 0.0
.0.1 0.0
0,3 -0.2
-0.1 0,2
O.I -0.5
-0.3 0,1
.0.1 0,1
-0,1 0,0
.0,0 0,0
-0,4 0.1
0.1 .0.2
-0.4 0,1
0.1 .0.1
0,1 .0,1
•0,2 .0,1
0,3 .0,3
•0,} 0,4
0,1 -0,2
•0,5 0,2
0,2 .0,4
0.1 -0,1
.0,1 .0.3
.0,5 0,2
0,4 .0,5
0,0 "0,3
•0.1 .0,2
0,2 .0,4
0,1 >0,4
0,5 .0,5
0,6 -0,5
1,0 .0,1
•O.t 1,0
.0,1 .0,5
•0,4 0,7
•0,3 0,7
0,0 0,3
.0,3 0,5
0,4 .0,3
-0,0 -0,5
0,0 .0,5
ASH BTU
-0.2 0,3
0,2 .0.6
-0,0 0,0
•0,4 0,3
0,1 -0,1
0,1 0,4
0,2 -0,2
0.2 0,1
0.3 -0.0
O.i .0,1
.0.0 0.0
.0.1 0,2
0,4 .0,4
0,2 0,2
0,0 0,3
0,1 0,1
.0,1 0,1
0,3 .0,2
0,1 .0,1
0,4 .0,3
0.1 .0,1
0.0 .0.0
0.6 >0,4
•0.2 .0,4
-0,2 0,4
0,3 .0,2
0,5 -0,2
0,4 .0,2
-0,0 -0,1
0,1 .0,6
0,4 '0.4
0.3 -0.6
0.4 -0.2
0,5 .0,4
0,5 .0,5
0,3 -0.4
0,1 -0,4
0.0 >0,4
.0,1 .0,4
-0,5 0.7
1.0 .0,9
•0,9 1.0
•0,1 0,9
•0,6 0,5
•0,4 0,4
0,0 .0,4
0,9 .0,9
0.9 .0,7
C
0.2
•0.3
0.1
0.4
.0,1
0.0
•0.2
.0.2
.0.1
•0.1
0.1
0.1
.0.3
.0.0
.0.0
0.1
0.1
.0,2
.0,1
•0.2
•0,1
•0.1
• 0.5
•0.1
0,4
.0,3
.0.3
.0,4
•0,1
.0,7
.0,2
.0,4
• 0.3
•0.5
• 0,5
•0,4
.0.4
•0.1
• 0,3
0.7
• 0,8
0.9
1.0
0,6
0,6
.0.5
.0.9
.0,8
H N
0.1 0.2
•0.0 .0.1
0.1 -0.0
0.1 0.2
o.o .0,1
•O.t .0.0
•0.2 -0.1
.0,1 .0.2
-0.1 -0.0
•D.2 -0.1
0,1 .0,0
0.1 0,1
•0,2 -0,1
•0.1 0,1
•0,0 0,0
0,1 0,0
0,1 0,1
•0,2 .0,2
0,0 .0,2
•0,1 -0,0
•0,0 .0,1
•0,1 .0,1
•0,4 -0.3
•0,1 .0.2
O.I 0.5
•0.0 -O.Z
.0,3 0,0
.0,4 .0.3
0.1 0.1
•0,5 .0,3
•0.3 .0,1
•0,1 -O.J
•0,0 .0,1
.0,4 .0,3
.0,1 .0,3
0,0 .0.2
•0,1 .0,4
•0,1 -0,1
0,0 -0.3
0.1 0.5
•0,6 .0.4
0.5 0.4
0,6 0,6
1,0 0,4
0,4 1,0
•0,4 .0,4
•0,6 .0.5
•0.5 .0.5
B
• 0,2
0,2
•0,2
• 0,0
0,0
•0.2
0,0
-0,0
o.o
0.0
-0,2
-0.1
-0,0
.0 1
••1 *
•o.i
0.2
.0,1
•0,2
•0.1
0,1
•0,2
•0,0
0.2
0.3
0,1
•O.I
•0.3
•0.1
0,4
0.2
0.2
0.1
•0.2
.0,4
0,1
.0.1
"0.1
0,4
0.2
0.4
•0,3
o.o
•0.4
•0,5
•O.t
• 0,4
1,0
0,0
0,0
MTA LTA
.0,2 .0,1
0,2 0,3
•0,0 0,1
•0,1 .0,4
0,1 0,1
O.I 0,1
0,1 0.2
0,1 0,1
0.1 0.1
0.1 0.1
•0,0 0,1
•0,2 >0,1
0,1 0.4
04 01
• • "1*
0.1 O.I
.0,0 "0,0
0,0 0,0
•0,1 .0,0
O.I 0,1
0,1 0,1
0,1 0,1
0,1 0,1
0,0 0,1
0,4 0,4
0,1 0.1
•0,1 -0.1
0.) 0,5
O.t 0,1
0,1 0,1
0,0 .0,0
0,7 0,6
0,1 0,3
0.1 0,4
0,4 0,5
0,5 0,4
0.5 0,6
0.1 0,5
0,1 0,1
•0,1 0,1
•0,0 0,0
•0,5 -0,5
0.9 0,9
•0,9 .0.7
.0,9 .0,8
•O.t .0,5
•O.S .0,5
0,0 0,0
1,0 0,8
0,8 1,0
At
8
1C
IK
CD
Cl
CR
CU
F
>A
Cl
H8
MN
MB
NI
P
PI
II
1C
IN
V
IN
IR
*L
CA
CL
FC
K
HI
NA
II
TJ
8R8
PTI
IUI
Til
IXRP
AOL
Mill
VII
FIXC
AIN
ITU
C
H
N
1
HT»
LTA
CL FC
BUS Pyt SUS TBS SXRF
AOL HBIS VBL PIXC ASH BTU
-------
- 22 -
TABLE 8—LINEAR REGRESSION (LEAST SQUARES) CORRELATION COEFFICIENTS
P5 SB IE SN
AS 1.0
8 .0.1
BE 0.2
8R .0.1
CO 0.0
C« 0,1
CD -0.2
CU 0.4
F -0.0
6* 0.2
GE o.a
HG 0,0
HN -0.1
«e -o.l
Nl 0,11
P 0.4
PB O.T
9B 0.6
1C -0,1
IN -0.1
V -0.2
IN 0.0
ID O.a
•L .0,3
C* -0,1
CL .0.0
n 0.2
K .0,2
MS -O.t
UK .0.3
it .0.:
n .0,2
BUS -0.4
P»l 0.2
SUS .0.1
TBi .0,1
SXDP .0,2
ADL '0,0
NBII .0.0
VBL -0,1
rinc 0,2
AIM .0.3
BTU 0.3
C 0.3
H 0.1
N 0.2
( -O.I
HI* .0.)
LTA -0,8
.0.3 0.2 -0,1
1,0 0.1 -0,2
0.1 1,0 0,0
-0.2 0.0 1,0
0.3 0,2 -0,1
.0,2 0,2 0,0
-0,1 0.1 0,2
-0,0 0,5 -0,1
-0,1 -0.1 >0,1
0.1 O.A 0,0
0.2 0.5 0,1
0,0 0,0 0,0
o.a 0,1 -0,1
0.1 -0,1 -0,1
-0,1 0,2 0,0
-0,3 0,0 0,1
.0,3 0,4 -0,1
.0,1 o.a .0,1
.0,0 o.o -0,1
0,2 0,1 0,0
.0.1 -0,1 0,2
0,2 0,2 -0,1
.0,0 0,1 -o.i
0.3 0.1 -0,0
0,3 -0,2 -0.1
-0,4 -0.3 0,2
0,0 0,2 -0,1
•0,1 0.1 0,1
0,1 .0.0 .0,0
0.3 .0,2 0,0
0,4 .0.0 .0,0
0,1 0.1 0,1
0,6 0,1 '0.2
.0.1 0,1 .0.3
.0,1 0.2 .0.1
0,2 0,1 .0,3
0,4 0,2 -0,2
0,7 0.2 .0.0
O.T 0,2 0.0
O.t 0.3 .0,2
-0,7 .0,3 0,3
0,3 0.0 -0,4
• 0,6 0,0 0,3
.0,5 .0,1 0,3
.0,1 0,1 0,1
.0,4 .0,2 0,1
0,9 0,0 0,0
0.3 0.1 .0,3
0.3 0,1 .0,2
0,0 o.a
0.3 -0,2
0.2 0.2
-0.1 0.0
1.0 0.1
0,1 1,0
0,0 -0.0
0.1 0.4
-0,2 -0,2
0,1 0.3
0,3 0.3
0.1 0,3
0.2 -0,2
0,1 -0.1
0,1 0,7
-0,1 0,0
0,1 0,5
0.2 0.5
0,0 -0,0
0,0 -0,2
-0,0 -0.1
0.4 0.1
0,0 0,3
o.o -0,1
O.a .0,2
-0,2 0.0
.0.1 0,1
-0,1 -0.1
-0,1 -0.2
.0.1 .0.2
•0,0 -0.3
0.1 -0,1
0,2 -o.a
-0.2 0.0
0.0 0.1
.0,0 -0.2
0,1 -0,2
0.1 .0.1
0.3 -0.1
0,2 -0.3
-0.2 o,a
.0,0 >0,3
.0.1 o.a
.0,1 0,3
0.0 0,0
-0,2 0,1
0.1 .0.1
0,0 .0.2
0.1 .0,2
•0,2 o.a
•0,1 -0,0
0,1 O.S
0,2 -0,1
0,0 U.I
-0,0 u,a
1.0 0,1
0.1 1.0
o.o o.o
0.1 0,5
-0,2 0.3
0.0 0.1
-0.0 .0,1
0,2 -0,1
0,1 0,5
-0.0 0.1
•o.l O.a
•0.1 0.5
O.A 0.2
-o.o o.i
0,5 -0.0
0.1 0.2
-0,0 0.3
0.2 0,1
-0,1 -0,3
0.1 .0,3
.0,1 0,2
0,3 O.i
0,2 .0,0
0.3 -0.2
0.3 -0,1
0,2 0,1
0.1 .0.2
-0,2 0,1
o.a o.i
.0,0 .0,0
0.1 0.0
•o.i o.i
0,0 0,1
•0.1 .0.0
-0.0 0,1
0,2 -0.1
.0.2 0,1
-0.3 0.1
.0,2 0,1
•0,2 .0.1
0,3 .0.1
0.2 -0.1
0,1 0,1
.0,0 0.2
-0,1 U.I
.0,1 0.4
-0.1 0.0
'0.2 0.1
-0.2 0,3
0,0 O.I
0,0 0,5
1,0 0,1
0,1 1.0
>o,a 0,3
-0,1 0,3
.0.2 -0,0
0.1 -0,1
-0,1 0,4
0,4 0,1
-0.2 0,2
.0,3 o.a
-0.1 0,0
0,1 0,0
0,0 '0,1
-0,1 0,1
-0,0 0,2
o.a 0.2
•0,1 -0.2
0,0 >0,3
-0,1 -0.0
0,2 0,2
0.0 0,0
0,0 -0,1
0,1 -0,0
0.1 0,2
0.0 0,0
-0.0 -0.1
0.1 0.1
0,0 -0,0
.0,0 0.0
-0.2 0.1
•0.3 0.1
.0,2 0,1
0,1 .0,1
0.1 0,1
.0,0 .0,1
.0.1 .0,1
.0,0 .0,1
0,0 .0,0
.0,0 0,1
0.1 0,0
.0,1 0.1
o.a 0,0
0,2 0,0
0,5 0,0
0,1 0.0
0.3 0,1
0.3 0.3
.0,2 0.0
0.3 0.1
-0.4 -0.1
0,3 0.3
1.0 0.1
0,1 l.U
0.3 *0,1
-0,0 .0.1
0,4 0,4
-0,2 0,1
0,5 0,1
0,< 0.3
.0,1 .0,1
0.1 '0.1
-0,1 0,0
0.2 0,1
0.3 .0,0
.0,2 .0,1
0,1 .0.2
.0.4 .0.1
0.3 -0,2
.0.3 0.1
-0.1 -0.1
-0,2 .0,2
.0,2 -O.S
.0.2 .0.1
0,1 .0,2
0.2 .0,1
-0.1 -0.0
0,2 -0,2
0.3 .0.]
o.a 0,0
o.a o.l
0.5 .0.1
.0,3 0,1
.0.1 .0.2
o.a 0.2
0.1 0.1
0,1 0.0
-0,2 0,1
•0,1 0.1
.0,1 -0,3
0,1 -0.3
-0,1 .0.3 0,4
o,a o.i .0.1
0,1 .0.1 0.2
.0,1 .0,1 0,0
0,2 0,1 0,1
-0,2 -0,1 o,r
-0,0 0,2 0,1
-0.1 -0,1 0,5
•0.2 O.I -0,1
•o.o -0,1 o.a
0.3 -0.0 O.a
.0,1 .0,1 0.4
1,0 0,0 .0,1
0.0 1,0 -0,1
.0,1 -0,1 1.0
-0,3 .0.3 0.1
-o.o .0.1 o.a
0.1 .0,2 0.6
-0.0 0,3 0,1
0.1 -0,0 .0.1
0.2 o.a 0,0
0,2 0,2 0,2
.0,0 0.1 0.2
0,0 0,.! 0.1
0.6 0.2 -0,2
.0,3 -O.i -0,2
0,1 0,3 -0,1
.0.2 -0,0 0,1
0.3 0,2 0,0
0,0 *0,0 -0.3
0.2 0,2 -0,1
0.0 0.0 0,2
0,3 0,3 -O.a
.0,1 0,4 .0.1
0.0 0,1 -0,0
0,1 0,5 -0,3
0.2 0.5 -0,3
0.3 .0.0 0,1
0,4 .0,1 0,1
0,3 0(1 -0,3
.0.5 .0,3 0,3
0.5 O.a .0,2
-0,4 -0,3 0.2
-0.3 -0.3 0.2
.0,2 .0,1 .0,1
.0.3 .0,4 0.1
0,0 -0,1 0,1
o,; o,a -0,1
0,4 0,4 .0,2
0.4 0.7
-0.3 .0.3
0.0 0.4
0.1 -0.1
-0.1 O.t
0.0 0.5
.0,0 .0,1
o.l o.a
0,4 .0.2
O.I 0.2
•O.i 0.5
O.I O.I
•0.3 -0,0
-0,3 .0.1
O.I 0.4
1.0 O.I
0.1 1.0
•0.0 0.6
•0.0 -0.0
-0,1 >0.1
-O.I -0.1
•O.i O.I
0.0 0.1
0.1 -0.1
-0,3 .0.1
0.1 .0.1
-0.2 0.3
0.2 -0.1
-0.0 .0.1
-O.I .0.4
-0.2 .0.3
O.t -0.0
-0.3 .0.2
.0,2 0.3
0.0 -0.1
•0,3 O.I
-O.a 0.0
.0.1 -0.0
.0,1 0.0
-0.2 .0.1
0.3 0.1
-O.i -0.1
0.3 0.1
0.3 0,2
0,1 0.1
0.1 '0,1
.0,0 -0.3
•0.1 .0,1
•0.3 .0.1
0,6 -0,1
-0,1 -0.0
0,4 0,0
•0,1 .0.1
0,2 0.0
0,5 -0.0
-O.l 0.4
0.5 0.2
-0,3 .0,1
0.4 0,0
0,6 .0,1
0,3 .0,1
0,1 -0.0
-O.i 0.3
0,6 0,1
-0.0 .0,0
0,6 -0,0
1,0 .0,0
-0,0 1,0
-0.1 -0.0
-0.1 0.3
0,2 0.1
o.a 0,3
.0.2 O.i
.0.1 .0,0
.0,2 -0.0
0,2 0.1
•0.1 0,0
•0.1 .0,0
.0.3 0.1
.0.3 0,1
-0,1 0.1
-0.1 0,2
O.i O.i
-0.0 0,1
0,0 0,2
0,0 0,1
0.1 O.I
O.i 0.0
0,1 -0,0
-0.0 -O.i
-O.I 0,3
0,1 .0.2
0,1 -0.3
0,1 .0.2
0.0 -O.i
-0.1 0,0
•0,1 0,3
-O.I 0.3
-O.I -O.S
0,2 -O.I
0.1 -0,1
0.0 O.i
0,0 -0.0
-0.2 -0.1
-0,0 0.5
0.1 -0.0
O.I 0,0
0,0 -0.1
0.1 -0.1
•o.i o.o
O.I O.i
•0,0 0.4
-0.1 0,0
-0,1 -0,1
-0.1 .0.1
-O.I -0,1
•0,0 0,3
1.0 0,0
0.0 1,0
0.1 0.0
-O.I 0.1
.0.0 0.3
O.I O.i
-0.0 0.0
0.1 0.1
-O.i 0.3
.0.0 0.5
O.i O.I
0.0 0,5
.0.0 0.4
0,1 0.0
0.1 0.0
-0,0 0,3
o.l a.t
0.2 0.0
0,1 -0,2
0,1 -0,1
o.i .o.a
.0,2 -0.0
0.0 0.4
•0,1 .0.1
-O.t -0.3
0.1 -O.i
•0.1 .0.1
O.I .0.1
0.0 0.]
0.3 0.4
0.0 0,4
0.2 -0,0
O.i 0,1
-0.1 -0.1
0.1 0,0
0.1 0,3
O.I -0,0
0.2 0.3
-0,1 -0.0
O.I O.S
O.i 0.3
O.I -0,0
0.2 -0.0
O.i 0,1
O.i O.i
-O.i 0,0
O.I 0.1
O.i 0.4
0.1 0.3
D.I .0.1
0.0 0,1
1,0 .0,0
-0.0 1,0
0.0 -0,1
0.3 0,0
-O.i -0,1
.0.1 0,3
.0.1 .0.1
.0.0 .0.0
.0.1 .0,0
.0,0 .0,1
0,0 .0,1
0.1 0.0
•O.i 0.3
.0.0 0.3
.0.0 O.i
O.I O.i
O.I 0,0
0.3 .0.0
0.1 0.1
.0.1 -0.1
0.0 O.I
.0,1 .0,0
-0.0 .0,1
.0.0 .0,1
.O.i 0.0
O.I .0,0
0.0 O.I
0,1 0.2
At
B
BE
BO
CO
C«
CA
CU
r
BA
61
MO
HN
He
NI
P
PB
SB
IE
BN
V
IN
in
AL
CA
CL
PC
K
M
NA
II
TI
Ml
fit
SUI
rai
IXftP
AOL
HBII
VBL
FUC
AIH
»IU
C
N
N
•
HTA
LTA
tl e IE BII co eg c« cu r SA st no UN ne NI p PB IB IE IN v IN z*
Note: All values are rounded to one significant figure. Abbreviations are the
same as those used in preceding tables.
-------
- 23 -
OF ANALYTICAL DETERMINATIONS ON 82 ILLINOIS BASIN COALS
AS
8
BE
8R
CD
CB
CD
cu
F
SA
GE
HG
MN
He
NI
p
PS
86
st
an
y
ZN
z«
AL
CA
CL
FE
K
M6
NA
SI
TI
0RS
PYS
SUS
TBS
$»RF
AOL
nei>
V0L
FIXC
AfH
ITU
C
H
N
^
HTA
LTA
•L CA CL fl « "« NA SI II
-0,5-0,1 -0,0 0,2 -0,2 -0,2 -0,3 -U,5 -0,2
0,3 0,3 -0,11 0,0 -0,1 0,1 0,3 0,4 U..1
0,1-0,2 -0,3 0,2 0,1 -0,0 -0,2 -0,0 0,1
-0, 0-0,1 0,2 -0,2 0,1 -0,0 0,0 -U,0 0,1
0,0 0,4 -0,2 -0,1 -0,1 -0,1 -0,1 -0,0 0,1
-0,1-0,2 0,0 0,1 -0,1 -0.2 -0,2 -0,3 -0,1
0,2-0,1 0,1 -0,1 0,3 0,2 0,3 0,3 0,2
0,1-0,3 -0,3 0,2 0,2 -0,0 -0,2 -0,1 0,1
0,4-0.1 0,0 -0,1 0,2 0,0 0,0 0,1 0,1
0,2*0,2 -0.3 -0.0 0,2 0,0 -0,1 -0,0 0,2
-0,2 0.1 -0,« 0,3 -0,3 -0,1 -0,2 -0,2 -0,2
-0,1-0,2 -0,1 -0,2 0.1 -0,1 -0,2 -0,2 -0,1
0,0 0,6 -0,3 0,1 -0,2 0,3 0,0 0,2 0,0
0,2 0.1 -0,2 0,3 -0,0 U,2 -0,0 0,2 0,0
0,1-0,2 -0,2 -0.1 0.1 0,0 -0.3 -0,1 0,2
0,1-0,3 0,1 -0,2 0,2 -0,0 -0,1 -0,2 0,1
-0,1-0,1 -0,1 0,3 -0,1 -0,1 -0.4 -0,3 -0,0
0,2-0,1 -0,2 0,2 -0,1 -0,1 -0,3 -0,3 -0,1
0,2*0.0 -0,0 0,1 0,0 -0,0 0.1 0,1 0,1
-0,0 0,1 -0,0 0,1 -0,2 -0,0 0,2 0,0 -0,0
0,3 0,2 0,0 0,1 0,3 0,5 0,1 0,5 0,4
0,0 0,3 *0,2 -0,1 -0,1 -0,0 -0,1 *0,0 0,0
•0,1 0,0 *0,l 0,3 -0,1 -0,0 -0,0 -0,1 -0,1
1,0*0,1 .0,2 -0,0 o,; 0,4 0,1 o.r 0,7
•0,1 1,0 *0,2 -0,1 -0,2 0,2 -0,0 0,1 -0,1
• 0,2*0,2 1,0 -0,3 -0,0 .0.2 0,5 -0,2 -0.1
-0,0*0,1 *0,3 1,0 -0,3 0,1 -0,2 -0,0 0,0
0,5*0,2 .0,0 -0,3 1,0 0,4 -0,0 0,6 0,7
0.4 0,2 .0.2 0,1 0,4 1,0 -0.1 0,5 0,4
0,1*0,0 o.: -0.2 -0,0 -0,1 1,0 0,2 -0,0
0,7 0,1 -0,2 -0.0 0.6 0.5 0,2 1,0 0,8
0,7*0,1 .0.1 0,0 0,7 0,4 -0,0 0.8 1,0
1,1 0,3 .0.5 0,3 -0.3 0,1 0,2 0,3 -0,1
•0*2.0,0 *0,2 0,7 -0,4 .0,1 -0,2 -0,3 -0,3
0,0.0,0 -0,1 0,2 0,2 0,2 0,0 0,2 0.2
.0,1 0,1 .0,4 0,7 -0,4 0,0 -0,0 -0,0 -0,2
•0,1 0,2 .0,4 0,7 -0.4 0.0 0,1 0,1 .0,2
0,1 0,1 .0,4 0,2 -0,2 .0,0 0,2 0,1 0,1
0,1 0,2 .0.3 >0,1 -0,2 -0,1 0.2 0,0 0.0
.0,1 0,2 .0,4 0,3 -0,4 .0,2 0,2 .0,0 -0,3
-0,1 .0,3 0,5 .0,4 0,3 -0.0 -0.1 -0.3 0.1
0,3 0.4 .0,3 0,3 0,2 0,4 0,0 0,6 0,3
.0,4 '0,4 0,4 -0.2 -0,2 -0.2 -0.1 -0.6 .0,4
.0,3.0,2 0,4 -0,4 -0,1 .0.3 .0.2 .0,6 .0,3
• 0,2.0.1 0.1 0.0 -0.2 -0.2 -0.1 .0,4 .0,3
*0,1 >0,i 0,5 -0,3 0,1 .0,1 0,0 .0,1 0,0
0.3.0,1 -0,1 .0.1 0.2 0.0 0.3 0.4 0.3
0.4 0,4 -0,3 0,4 0,3 0,4 0,1 0,7 0,4
0,2 0,3 -0.4 0.5 0.0 0.3 0.0 0,5 0,3
DBS P»S
-0,« 0,2
0.6 -0.1
0,1 0.1
-0,2 -0,3
0,2 -0,2
-0,4 0,0
0,1 -0,2
-0,2 0,1
0,0 -0,0
0.0 -0,1
0.1 U,2
-0,2 -0,1
0.3 -0.1
0,5 0,4
-0,4 -0,1
-0,3 -0,2
-0,2 0,3
-0,1 0,2
0,2 0,2
0.1 0.1
0.0 0,0
0.1 -0.2
0.0 0.3
0.1 -0,2
0.3 .0,0
.0,5 -0,2
0,3 0,7
.0,3 .0,4
0.1 -0,1
0.2 .0,2
0,3 .0,3
-0,1 .0,3
1.0 0.3
0,3 1,0
0,1 *0,0
0,9 0.»
O.I 0,6
0,4 -0,0
0,2 .0,2
0,7 0,2
• 0.8 -0.3
0.5 0.3
.0.6 .0.2
.0.7 .0.3
.0,2 0,0
.0,6 .0,3
0.2 .0,4
0,5 0.3
0,5 0,4
SUS TUS
-0.1 -D.I
-0.1 0.2
0.2 0.1
-0.1 .0.3
0.0 -0.0
0,1 -0,2
0,4 -0,0
0,1 .0,0
U.I 0.0
0.1 -0,0
•0,1 0,2
-0,0 -0,2
0,0 0.1
0.1 0.5
-0,0 -0,3
0,0 -0.3
-0.1 0.1
-0.0 0,0
0.1 0.2
-0,0 0,1
0,3 0,1
-0,0 -0,0
0,3 0,2
o.o .0.1
-0.0 0,1
-0.1 -0,4
0.2 0.7
0.2 .0.4
0,2 0,0
0,0 .0,0
0,2 -0,0
0,2 .0.2
0.1 0.9
-0.0 0,9
1.0 0,2
0.2 1,0
0,1 0,9
-0,0 0,2
-0,3 -0.0
.0.1 0.5
.0.1 .0.7
0,4 0,5
-0,4 .0,5
.0,4 .0,6
•0,3 .0.1
•0,2 .0,5
0,2 -0,1
0,4 0,6
0,3 0,6
SXRF
•0.2
0,4
0,2
'0,2
0,1
-0,2
0,1
0.0
-0.0
0.0
0.3
•0.3
0,2
0,5
-0.3
-0.4
0.0
0,0
O.I
0.2
0.0
0,1
0.2
-O.I
0.2
-0,4
0,7
-0,4
0,0
0,1
0,1
-0,2
0,9
0,6
0,1
0,9
1,0
0.3
0,1
0.6
.0,7
0.4
.0,4
.0,6
.0,0
•0,6
.0,0
0,5
0.6
AOL M0IS
-0,0 -0.0
0,7 0,7
0,2 0,2
.0,0 0,0
0,1 0,3
•0,1 -0,1
.0,1 0.0
0,1 0,1
•0,2 -0,3
0,1 0.1
0,4 0,4
0,0 0,1
0,3 0,4
.0,0 -0,1
0,1 0,1
-0,1 -0,1
-0,0 0,0
0,1 0,2
0,1 0,0
0,1 0,2
.0,2 .0,1
0,1 0,3
0,0 -0,0
0,1 0,1
0,1 0,2
•0,4 .0,3
0,2 '0,1
.0,2 «0,2
•0,0 '0,1
0,2 0,2
0,1 0,0
0,1 0,0
0,4 0,2
-0,0 .0,2
-0,0 *0,3
0,2 .0,0
0,3 0.1
1,0 0,9
0,9 1.0
0.! 0,5
.0.5 .0,5
0,1 0,0
.0,4 .0,4
.0,4 .0,2
.0,1 .0,0
.0,4 "0,3
0,4 0,4
0,1 0,0
0,2 0,1
vaL FIXC
-0,1 0.2
0.6 -0,7
0,3 -0,3
-0.2 0,3
0,2 -0,2
-0,3 0.4
-0,1 .0.0
•0,0 0,1
-0,2 0,1
0,1 -0,1
0,5 -0,3
-0,1 0.2
0.3 -0.5
0.1 -0.3
-0.3 0.3
-0.2 0,3
-0.1 0.1
0.1 -0.0
-0.0 -0.2
0.2 '0.2
•0,2 .0,0
0,1 .0.1
0,1 -0,1
•0,1 .0,1
0.2 .0,3
.0,4 0,5
0,3 .0,4
-0,4 0,3
.0,2 -0,0
0.2 .0.1
-0.0 .0,3
.0,3 0,1
0,7 .0,9
0,2 .0,3
-0,1 .0.1
0,5 .0,7
0,6 .0,7
0,5 .0,9
0,5 .0.5
1,0 -0.9
.0.4 1,0
0,1 .0,6
.0.4 0.7
.0,3 0,7
0,2 0,1
-0,3 0,5
0,1 .0,1
0,1 .0,6
0,2 .0,5
ASM 8TU
-0,3 0,3
0,3 -0,6
0.0 0,0
-0.4 0,3
-0.0 .0,1
-0,3 0,4
0.2 .0,2
.0,1 0.1
0,1 .0,0
0,1 -0,1
-0,1 0,0
-0.2 0,2
0,5 .0,4
0,4 -0.3
-0.2 0,2
-0,2 0,3
-0,1 0,1
-0,1 0,1
0,3 -0,2
0,0 -0,1
0,4 .0,3
0,0 .0,1
0.1 .0,0
0,3 .0,4
0,4 .0,4
.0,3 0,4
0,3 .0,2
0.2 .0.2
0,4 "0,2
0,0 .0,1
0,6 .0,6
0,3 .0,4
0,5 .0,6
0,3 .0,2
0.4 .0,4
0,5 .0,5
0,4 .0,4
U.I .0,4
0.0 .0,4
0.1 .0,4
.0,6 0,7
1,0 .0,9
*0,9 1,0
.0,9 0,9
.0.5 0.5
.0,4 0,4
0,1 *0,4
1,0 .0,9
0.9 .0.7
C
0.3
-0,5
.0,1
0.3
-O.I
0,3
-0,3
0.1
•0,1
-0.1
0.1
0.1
.0.3
-0,3
0,2
0,3
0.2
0.1
.0.3
"0.1
.0.3
• 0,0
.0.1
• 0,3
.0.2
0.4
.0.4
.0,1
• 0,3
.0,2
.0,6
.0,3
-0,7
•0.3
• 0,4
.0,6
•0.6
•0.4
• 0,2
.0,3
0,7
.0.9
0.9
1.0
0,5
0,9
•0,5
.0,9
.0.7
H N
0.1 0,2
.0,1 .0,4
0,1 .0.2
0.1 0,1
0,0 .0,2
0,0 0,1
.0,2 .0,2
0.1 -0.1
.0.0 0,0
.0,1 .0,0
0,1 .0,2
0.0 0,1
•0.2 .0,3
•0,1 -0,4
•0,1 0.1
0.1 0.1
0.1 -0.1
0,1 0,0
.0,2 .0,2
0,1 *0,1
.0.2 .0.1
.0,0 .0.2
•0,1 0,0
•O.I -0,1
•0,1 .0,2
0.1 0,5
0,0 .0,3
.0,1 0,1
.0,2 .0,1
•0,1 0,0
•0,4 .0,1
•0,3 0,0
•0,2 .0,6
0,0 .0.]
•0,3 .0,2
.0,1 .0,5
•0,0 .0,6
•0.1 .0.4
-0.0 .0.3
0.2 .0,3
0.1 0,5
.U.I .0,4
O.I 0,4
0,1 0.5
1.0 0,1
0.1 1,0
•0.4 .0.2
.0,5 .0,4
•0,4 -0,5
0
•0.2
0.5
0,0
0,0
0,1
•0,1
0,3
•0.1
.0,0
0,1
•0.1
0.1
0,0
•0,1
0,1
•0,0
-0,3
.0,1
o.o
0.1
.0.1
0,1
.0,0
0,1
•0.1
•0,1
•0,1
0,1
0.0
0,3
0.4
0.3
O.I
.0.4
O.i
•0,1
•0.0
0,4
0.9
o.l
•0,1
0,1
• 0,4
•O.i
.0,4
•0,1
1.0
O.I
0,1
MTA
.0,3
0.3
0.1
.0,1
0,0
.0,2
O.I
•0.1
0.1
0.0
•0,1
-0,3
0,5
0,4
•0,1
.0,3
-0,1
•0.1
0.3
0,0
O.I
0,0
0,1
o.«
0,4
•0.3
0,4
O.J
0.*
0,1
0.7
0,4
0.3
0.1
0,4
0,6
0,9
o.t
0.0
0.1
• 0,6
1,0
• 0,9
•0,9
.0,5
.0,4
0,1
1.0
0.9
LTA
.0,2
0,3
0,1
•0,!
0.1
• 0.2
0,1
0,1
•0,1
0,1
0.1
• 0,3
0,4
0,4
• 0,2
•0,3
-0,1
•0,1
0,3
0,3
0,4
0,1
0,1
O.i
0,3
• 0.4
0.9
0.0
0.!
0.0
0,9
0,3
0,9
0,4
0.3
0.6
0,*
O.i
0.1
O.i
.0.1
o<>
•0.7
•0,7
• 0,4
.0,5
0,1
0,9
1.0
BBS PYS SUS TitI SXRF
ADI "BIS V0L FIXC OH BTU
MT» LTA
-------
- 24 -
Figures 1-39
In figures 1 through 39, the data from Illinois Basin coals
are plotted as unpatterned bars, those from the western United States as
horizontally striped bars, and those from the eastern United States as
vertically striped "bars.
s:
=3
1
I
l.D 7.0 114.0 2! .0 28.0
LOW TEMPERRTURE RSH (X)
Fig. 1 - Distribution of low-
temperature ash in coals
analyzed.
1[
0.0 12.0
21.0 36.0
RRSENIC
H8.0
(PPM)
35.0
28-
2>4-
20-
16-
12-
8
>4 -
0
0.
0 6.
1
—
I
m
^1
0 12.0 18.0 214. 0 30. 0
HIGH TEMPERRTURE RSH (7.1
Fig. 2 - Distribution of high-
temperature ash in coals
analyzed.
I
I
80 120
BORON
160
(PPM)
200
Fig. 3 - Distribution of arsenic
in coals analyzed.
Fig. 4- - Distribution of boron
in coals analyzed.
-------
- 25 -
21-
18-
15-
12-
9 -
6 -
3
0.
00 0
nn
=
H
M
HI
III
80 1
nn in
HT-TI n,n
60 2.40 3.20 M.OO »
BERYLLIUM (PPM)
21
18
15-
12
6 •
3
n
m
• —
=
Illl
m
1
m
I
=nn
aim n ,( rn
8.0 16.0 24.0
BROMINE
32.0 40.0
(PPM)
Fig. 5 - Distribution of beryllium
in coals analyzed.
Pig. 6 - Distribution of bromine
in coals analyzed.
in
LU
ID
•z.
56-t
L
m
40-p1
2U-
16-
g
Q
0.
nn
~H-r^ _ _„ - ..n
21
en
CL 18~
2:
cr
^ 15-
LJ_
o
LU
CD
-^ 9
z
6
3 .
n
—
P—
~
~
=
=
m
m
m
nm
i
Ml
im m
11 ri fimrn . , e
0 2.4 4.8 7.2 9.6 12.0 * 0.0 8.0 16.0 24.0 32.0 40.0 *
CflDMIUM (PPM) COBflLT (PPM)
Pig. 7 - Distribution of cadmium
in coals analyzed.
Pig. 8 - Distribution of cobalt
in coals analyzed.
21,
,8,
IS-
u
9
6 -
^
0 -
0.0
—
=
m
=
• —
1
1111
M
1
1
8.0 1S.O
1
24
.0
CHROMIUM
In n ,,n
21
to
LU
^ 15-
u_
D
(n 12
CD
6 -
3 .
pT
E3
1111
1
on
V,H
Elll — •
mi uni H
32.0 40.'o + 0.0 8.0 16.0 2M.O 32.0 UO.'o *
IPPMl COPPER (PPM)
Fig. 9 - Distribution of chromium
in coals analyzed.
Pig. 10 - Distribution of copper
in coals analyzed.
-------
- 26 -
28-
in
UJ
E! s<4-
s;
a
en 20.
u_
o
cr 16'
UJ
CD
1 12'
8 -
0
21-
UJ
CL 18~
SI
a:
01 15-
u_
D
NUMBER
-) CO
3 -
0.
21-
en
UJ
cr
<" 15-
u_
o
cr
UJ
GQ
6 -
3
0
0
[PI |
I
fp
F-R . n-,
30 60 90 120 150
FLUORINE (PPM)
Fig. 11 - Distribution of fluorine
in coals analyzed.
1
mi
1111
rr-n m . ., n
0 8.0 16.0 24.0 32.0 40.0 t
GERMRNIUM (PPM)
Pig. 13 - Distribution of germanium
in coals analyzed.
I
I
1
ran
in
=
t r-f^
2!
in
UJ
CL. 18'
s:
cr
^ 15-
u_
0
cc 12'
UJ
CD
I 9 -
-z.
6
3
0
0
42-
en
UJ
CL 36'
^.
CC
en 30.
o
cr
UJ
OQ
~Z_
12-
6 •
UMBER OF SPMPLES
to — — — ro c
ro en co " O
6 •
3 .
= 1
f M
m
1
"PI n rn
0 1.6 3.2 4.8 6.4 8.0
GRLL1UM (PPM)
Pig. 12 - Distribution of gallium
in coals analyzed.
iS
Ml
nh— , . . i— i
00 0.40 0.80 1.20 1.60 2.00
MERCURY (PPM)
Pig. I1*- - Distribution of mercury
in coals analyzed.
I1
HD
Hi m
m ru
In n n . a
40 80 120 160 200 0.0 6.0 12.0 18.0 24.0 30.0 *
MRNGRNESE (PPM) MOLTBDENUM (PPM)
Pig, 15 - Distribution of manganese
in coals analyzed.
Pig. 16 - Distribution of molybdenum
in coals analyzed.
-------
- 27 -
21-
18-
15-
12-
9 -
6 -
3 -
0 -f — '
0.0
TTTT
•
==
N
HE
Ull
rim
1
I
1
—
—
16. Q 32.0
, prn ,j e
28-
01
|j 2«'
en
(n 20.
u_
D
CC 16'
CD
1 12
z
8 -
4 -
n
;
mr
=
=
m||
IW =
Up
\ mij-, s-, n . E=J
48.0 64.0 80.0 <• 0 80 160 2HO 320 400 t
NICKEL (PPM) PHOSPHORUS (PPM)
Pig. 17 - Distribution of nickel
in coals analyzed.
Pig. 18 - Distribution of phosphorus
in coals analyzed.
28-
24-
20-
16-
8 -
4 -
0 -
0
si
n
=
1
1
1
1
nn
32
^nn n
64 96 128 160 »
35-
f/1
CL 3°"
cr
1/1 25-
D
IT 2°-
UJ
CO
^
10-
5 -
0 -
0.
1
M
7TTT1
Illl
I
1
=
1
T^
0 1.6 3.2 4.8 6.4 8.0 *
LEflD (PPM) flNTIMONY (PPM)
Pig. 19 - Distribution of lead
in coals analyzed.
Fig. 20 - Distribution of antimony
in coals analyzed.
28-
24-
20-
1 R
12-
8 -
4 -
0 -
E
[
0.0
—
—
nn
=
52
—
fin
iiii
—
1.6
—
fin
3.
nn
2
Tfm i | inii|iMi! i |
35-
LO
LU
^ 30-
51
cr
^ 25-
u_
D
?n
cc
UJ
CD
§ 15-
10-
5 •
n
'
—
nn
jm
nn
fill
Uil
nrn
Ull
ffl fl i — i ^ . i — i . i 1 1
4.8 6.14 8.0 0,0 1.S 9.6 14.4 19.2 24. "o *
SELENIUM (PPM) TIN (PPM)
Fig. 21 - Distribution of selenium
in coals analyzed.
Fig. 22 - Distribution of tin
in coals analyzed.
-------
- 28 -
21
18
15-
12
9 -
6 -
3 •
o
=
=
m
1
r-
IUTI
ll
nnnn _
rn T
00 16.0 32 0 H8.0 614.0 80.0
VfiNRDIUM (PPM)
1480 720
ZINC
960
(PPM)
1200
Fig. 23 - Distribution of vanadium
in coals analyzed.
Pig. 24- - Distribution of zinc
in coals analyzed.
15-
nn
M
I"
60
120 180
ZIRCONIUM
-T^Tl
210 300
(PPM)
28
20-
8 -
4 -
0 -
0.
n
00 0.
60
—
1
1111
nn =
mr
1 1 IIIIIIIMII 1 . i 1 !
1.20 1.80 2.40 3.00 +
flLUMINUM (X)
Fig. 25 - Distribution of zirconium
in coals analyzed.
Fig. 26 - Distribution of aluminum
in coals analyzed.
21-
18-
15-
12-
6 -
3
n
1
Uil
m
1
II
~~
__
—
1
^
m
III B 1
28-
-------
- 29 -
j:
r>
18-
15-
12
9
6
0
0
0
Illl
mi
1.
1U1
0
m
[ffllj
1
^
1 1 1 1 1 1
2.0 3.0 4.0 5.0
IRON (X)
214--
12--
I
0.000 0.080 0.160 0.2HO 0.320 O.UOO+
POTRSSIUM f/>
Pig. 29 - Distribution of iron
in coals analyzed.
Fig. 30 - Distribution of potassium
in coals analyzed.
s:
=>
28-
21-
20i
16-
12-
8 -
0 -
0.
r
000
M
Uli
1
I
mr
mr
1™ ti M
0.032 0.06^1 0.096 0.128 0.160 +
MB
ro
o
•—
ro
MRGNESIUM
(X)
0.000 O.QliO 0.080 0.120 0.160 0.200 +
SODIUM (7.}
Pig. 31 - Distribution of magnesium
in coals analyzed.
Fig. 32 - Distribution of sodium
in coals analyzed.
X
=D
6 -•
0.0
1.2 2.U 3.6
SULFUR (XRF)
1.8
(X)
Fig. 33 - Distribution of sulfur
in coals analyzed; determined
by X-ray fluorescence.
12
10-
8 -
6
2 -
0 -
0.0
=
I
1
«
-
1
,
—
— |
«
1.2 2.14 3.6 1.8 6.0 +
TOTflL SULFUR (X)
Fig. 34- - Distribution of sulfur
in coals analyzed; determined
by ASTM method.
-------
- 30 -
56
CL 48
s:
ci
en no
0.00
0.20
0.40 0.60 0.80
SULFflTE -SULFUR (X)
1.00
6 --
0.00
n
0.80 1.60 2.40 3.20 4.00
ORGRNIC SULFUR (XI
Pig- 35 - Distribution of sulfate
sulfur in coals analyzed.
Pig. 36 - Distribution of organic
sulfur in coals analyzed.
1.60 2.40
PYRITIC SULFUR
3.20 li.OO
IX)
24-
20-
0.0
nn
1.2
2.4 3.6
SILICON
Fig. 37 - Distribution of pyritic
sulfur in coals analyzed.
Fig. 38 - Distribution of silicon
in coals analyzed.
30
10--
n r
0.000 O.Q140 0.080 0.120 0.160 0.200
TITflNIUM I'/.l
Fig. 39 - Distribution of titanium
in coals analyzed.
-------
- 31 -
3) There are mutually positive correlations between K, Ti, Al,
and Si in the data reported here. These four elements are commonly found in
nature as silicates, and are generally classified as lithophile elements.
They occur in coals in the clay minerals and in quartz (plate 1, B, p. 53).
k) There is a positive correlation of 0.63 between Mn and Ca in
coals of the Illinois Basin; Mn does not correlate as well with any other
element. Manganese commonly substitutes for Ca in calcite (CaCOs) and is
probably in that combination in the coals (pi. 1, A).
5) Sodium and Cl have a positive correlation of 0.53 in both the
Illinois Basin samples and all 101 samples. A similar correlation between
chlorine and total alkalies was reported by Gluskoter and Rees (196M and,
in part, it can be attributed to Na and Cl having been deposited in coals
from saline ground water (Gluskoter, 1965a; Gluskoter and Ruch, 1971)-
The 82 coal samples of the Illinois Basin were further subdivided
into four stratigraphic groups: coals below the Harrisburg-Springfield
(No. 5) Coal Member, the Harrisburg-Springfield (No. 5) Coal Member, the
Herrin (No. 6) Coal Member, and the coals above the Herrin (No. 6) Coal
Member. Means, standard deviations, and correlation coefficients were deter-
mined for these four groups. Although the statistical data are not presented
in this paper, the following relationships have been suggested from the
statistics:
l) The concentrations of As, Cu, Pb, Si, and Al are lower in the
younger coals than in the older coals of the Basin.
2) Boron may act as an indicator of paleosalinity (Bohor and
Gluskoter, 1973). The concentration of boron in coal increases upward in the
stratigraphic section, which suggests that the Illinois Basin became generally
more saline during the period of time between deposition of the older and the
younger coals.
3) The correlation between Na and Cl increased from the older coals
to the younger coals, which is possibly a result of the basin becoming more
saline.
Additional relationships have been suggested by the statistical
analyses, and much more detailed statistical analyses and geochemical inter-
pretations are underway, as is the mapping of the areal distribution of the
elements within the Illinois Basin.
ENRICHMENT AND DEPLETION OF ELEMENTS IN COAL
Several geochemists have attempted to determine the abundance of
chemical elements in the earth's crust; Clarke and Washington (192^) were
among the first to do so. The term "clarke" is defined as the average per-
centage of an element in the earth's crust. The clarke values used in this
report are taken from Taylor (196^).
A comparison of the concentration of an element in coal with the
clarke value for that element provides an approximation as to the amount by
which the element is enriched or depleted by the total coal-forming processes,
-------
- 32 -
The 101 coal samples analyzed were divided into three groups: Illinois
Basin coals, eastern United States coals, and western United States coals,. (The
Mississippi River was arbitrarily taken to be the line dividing eastern and
western coals.)
Mean values were computed for the various trace elements in each group
and the resulting means were divided by their clarke value. The resulting number
is called an enrichment factor. Those elements whose enrichment factors are an
order of magnitude greater or less than their clarke values (present in an amount
greater than 10 times the clarke or less than one-tenth the clarke) are found in
table 9. All other trace elements are present in amounts that approximate their
abundance in the earth's crust (i.e., have the same order of magnitude).
The most significant aspect of table 9 is its brevity; only six of
the elements analyzed were concentrated or depleted in coal by one order of
magnitude or more. Only three elements were found to be enriched to that degree.
Cadmium is enriched in coals from the Illinois Basin but not in the other coals
studied. Cadmium occurs in Illinois coals in solid solution with Zn in the
mineral sphalerite (Gluskoter and Lindahl, 1973). Sphalerite is not distrib-
uted uniformly within the Basin, but rather is concentrated in northwestern
and southeastern Illinois. It occurs as epigenetic cleat (vertical fracture)
filling.
TABLE 9—ENRICHMENT FACTORS OF CHEMICAL ELEMENTS IN COAL
(only those enriched or depleted by one order of
magnitude or more are listed)
Illinois Basin
(8l samples)
Eastern United States
(9 samples)
Western United States
(8 samples)
Element
B
Cd
F
Mn
P
Se
P
Mn
P
Se
Cr
Mn
Se
Enrichment
factor
11.38
0.09
0.06
0.06
39-80
0.10
0.03
0.09
67-33
0.09
0.04
31-31
Mean value
in coal
113-79 PPm
2.89 ppm
59-30 ppm
53.16 ppm
62.77 PPm
1.99 ppm
62.5 ppm
28.5 ppm
9^.5 ppm
3-37 ppm
9.0 ppm
38.0 ppm
1-57 PPm
Clarke
10.0 ppm
0.2 ppm
625 . 0 ppm
950.0 ppm
1050.0 ppm
0.05 ppm
625 • 0 ppm
950.0 ppm
1050.0 ppm
0.05 ppm
100.0 ppm
950.0 ppm
0.05 ppm
-------
- 33 -
Boron is also concentrated in the coals of the Illinois Basin and
not in the coals of eastern and western United States. A number of workers
have used the B concentration in sediments and sedimentary rocks as an
indicator of paleosalinity of the environment in which the sediment was
originally deposited. An investigation of the B in the clay mineral illite
in the low-temperature ash of Illinois coals has recently "been reported
(Bohor and Gluskoter, 1973). Greatly oversimplified, the use of the technique
assumes that the relative concentrations of B in sediments and sedimentary
rocks are directly dependent on the salinity of the water in which the sedi-
ments were deposited and that therefore marine sediments contain more B than
non-marine sediments. However, the interpretation of B paleosalinity from
even a carefully controlled set of samples is difficult. The set of samples
reported upon here was not specifically collected for boron analyses or
specially treated. The most obvious interpretation to be made from the
observation that B is concentrated in the coals of the Illinois Basin and not
in the coals from eastern and western United States is that the Illinois Basin
coals were deposited in waters that had a higher salinity (more brackish or
more marine) than did the waters in which the other coals were deposited.
This interpretation, in general, does agree with the geologic interpretation
of environments of deposition of the various coals based on other criteria.
The coals of the Illinois Basin are generally more closely associated with
marine strata than are the coals in the Appalachians or in the Rocky Mountain
areas.
The third element that is found to be enriched in the coals is
selenium, and it is concentrated to a significant degree in all three groups
of coals. Selenium in the four laboratory-prepared coals (washed coals),
discussed later, is interpreted to be in both organic and inorganic combination.
We would suggest that organically combined Se may be inherited directly from
Se concentrated by the plants in the original coal swamp. Further investigation
of the distribution and mode of occurrence of Se in coals would be necessary
to substantiate or refute this hypothesis.
RESULTS OF ANALYSES OF WASHED COALS
Many of the coals mined in the United States are "washed" or "cleaned"
prior to delivery to the consumer. Cleaning involves reducing the ash and
sulfur contents of the coal by removing a portion of the mineral matter
associated with the coal. Because the specific gravities of the minerals in
coal are from two to four times greater than that of the coal, most coal-
cleaning techniques involve a specific gravity separation. Data on the wash-
ability of Illinois coals, as well as a description of the techniques used,
have been published by Helfinstine et al. (1971, 197^) and Helfinstine et al.
(1970).
Four samples of Illinois coals were separated into specific gravity
fractions and analyzed for most of the same major, minor, and trace elements
as were the 101 whole coals. The gravity separations were, in each case, made
on a 3/8 inch by 28 mesh size fraction obtained by crushing the coal to less
than 3/8 of an inch and then screening it. All separations of 1.60 specific
gravity and below were made in an appropriate mixture of perchloroethylene and
naphtha. The separations at a specific gravity of approximately 2.8 were made
-------
TABLE 10—TRACE ELEMENTS
(parts per million,
SAMPLE N0,
C. 16090
C. 16094
C. 16095
c-iecm
C. 18097
C-18098
C-18099
C-18106
C-18107
C-IB092
C-16100
C- 16105
C. 1S1!«
018133
C. 18135
C. 18116
C. 18137
C. 18138
C- 18139
C. 18140
c«i«i4i
C-18142
C. 18122
c. 18121
C-18123
c.iei24
018125
C. 18126
O18127
OI8128
O18129
C-18130
SPECIFIC
SUAVITY..
FRACTlBN*
3/8X28M
1.28F
1.30FS
1.32F3
1.4UFS
1.60F9
>1.60
2.89FS
>2.90
3/SX28M
1.29F
1.60S
28MXO
3/8X28M
1.25F
1.J6FS
1.30FS
1.40FS
1.60FS
M.60
2.S9F5
>2.90
28MXO
3/8X2BM
1.2SF
1.29FS
1.33FS
1.40FS
1.60FS
M.60
2.B9FS
>2.90
PERCENT
ef
RAN CBAL
100,00
25.87
19.50
1»,70
19.30
7.20
0.50
3.75
1.75
100.00
19.40
9,00
100,00
100,00
28,20
23.60
27,60
10,60
3.20
6.80
J.60
3.?0
100.00
100,00
36,10
17, «0
14.70
9.30
6,90
15,60
12.73
2,87
CgAL
SEAM
DV
DV
DV
0V
UV
0V
DV
DV
0V
DK
OK
UK
2
2
2
2
2
2
2
2
2
2
6
6
6
6
6
6
6
6
6
6
AS
8.7
0.'
1.1
1.5
0.1
12.0
61,0
31,0
80.0
15.0
2.9
1H1.0
83.0
113.0
14.0
22,0
47.0
99,0
175.0
630,0
350,0
1109,0
11.0
15.0
0.9
1."
2,3
«.3
5.8
58,0
23,0
244,0
8
22
29
35
32
31
27
4
36
3
24
35
90
70
100
170
102
96
42
58
137
94
90
120
190
«8
73
80
88
BE
3.0
2.8
3.0
3,1
2,8
2,6
1.8
3,7
4.7
4.8
7,0
',1
3.2
«,5
2,6
3.2
3.2
3,«
3.1
7,g
3.3
5.2
2,5
2.2
a. s
3,0
3.0
3,2
3.1
3,2
1.6
1.7
CD
1.7
(J.I
0.2
0.2
0.4
0.5
20.0
2.«
36.0
0.6
0.1
2.4
20.0
47.0
0.1
0,2
0.4
1.2
11.0
338.0
89,0
710.0
3.2
6,1
0.2
0.2
0.2
0,4
0.7
27.0
4.8
152.0
CD
3
2
3
4
5
3
8
10
22
6
12
19
8
10
5
6
8
16
15
18
1«
12
5
5
2
3
5
6
5
19
20
29
CR
10
7
9
10
13
23
21
27
70
15
15
44
10
18
4
4
5
12
18
140
81
42
25
32
8
12
16
25
33
71
5*
31
CU
11
4
6
7
12
17
18
23
IS
11
7
17
34
35
13
17
20
38
69
140
111
177
25
23
5
7
10
16
25
65
61
69
GA
l.«
1,1
3.3
3.3
4.5
3.8
1.7
4.9
2.2
3.0
3.7
3.1
2.2
2,1
2,3
2.«
0.8
1,4
«,1
13,0
2.8
1,3
4,8
4.7
2,1
0.7
2.6
3.2
s.»
12.0
15,0
2,5
se
8
9
10
7
4
3
4
5
1
6
10
6
30
35
30
31
23
21
14
10
8
8
13
9
15
17
13
10
6
1
1
1
HK
0.24
0,06
0,05
0,08
0,15
0,24
£.10
0,70
2.90
0.62
0,07
4.00
0.24
0.24
0.08
0.12
0.21
0.35
0.38
1,10
1,60
9.40
0.17
0.14
0.07
O.Ofc
0.09
0.13
0.17
0.68
0,77
s.eo
* Specific gravity fractions given followed by the letters PS indicate that
the entire sample would float at that gravity and would sink at the gravity
listed immediately above.
-------
- 35 -
IN LABORATORY-PREPARED COALS
moisture-free coal)
SAMPLE MB,
C. 16090
C.18094
C. 18095
C. 18096
C-1B097
C. 18096
C- 18099
C-lBlOfc
O18107
C-18092
C. 18100
C. 18105
018134
C. 16133
C-1813!
C. 18136
C. 16137
C-16138
C-16139
C-16UO
C.18U1
C. 16142
C-18U2
c-18121
C-18123
C-16128
C.181Z5
:. I6ia6
C.181ZT
C.181J6
C.1S1J9
C. 18130
SPECIFIC
GRAVITY.,,
FRACTlBN*
3/8X28"
i,28F
1.30F8
1.32FS
1.40F8
1.60FS
M.60
2.89F*
>?.90
3/8X28M
1.29F
1.60S
28MXO
3/8X28M
1.25F
1.26FS
1.30F*
1.40F8
1.60F8
>1,60
2,8«FS
»2,90
28MXO
3/8X2SM
1.2SF
1.29FS
1.J3F8
1.40FS
1.60FS
>1,60
2.69F3
>2,90
PERCENT
RAW COAL
100.00
23.87
19, SO
19.70
19.30
7.20
8.50
3.75
1.75
100.00
19.40
9.00
100,00
too.oo
28.20
23,60
27,60
10,60
3.20
6,80
3.60
3.20
100,00
100.00
36.10
17.40
14.70
9.30
6,90
15.60
12.73
2.87
CBAL
8EAM
ov
0V
ov
ov
DV
DV
DV
OV
OV
OK
OK
OK
2
2
2
2
2
2
2
2
2
2
6
6
6
6
6
6
6
6
6
6
MM
20
8
8
10
15
34
81
55
13
8
26
65
26
5
6
8
12
24
209
65
130
89
7
8
10
18
34
365
«57
74
MB
9
i
1
1
]
10
61
24
821
12
3
135
12
14
2
4
8
15
20
111
34
145
13
11
5
r
8
9
12
28
14
215
NI
19
9
14
16
20
19
46
33
44
17
18
38
30
40
16
20
26
47
60
116
98
114
29
38
9
10
15
21
25
77
76
102
p
7
13
17
24
30
22
25
85
81
167
23
28
21
25
21
24
21
14
64
39
12
15
1«
24
100
P»
131
12
17
19
40
1U1
986
392
1465
125
15
8BU
183
237
81
119
205
321
448
753
633
905
100
135
13
14
25
42
58
530
210
2162
58
0.5
0.3
0.3
0.4
0.5
U.9
1.0
3,6
1.2
0.5
0.6
0.8
3.4
4.5
3.9
6.0
3,5
14,0
16.0
11.0
18,0
13.0
1.9
1.9
1.2
1.1
1.3
1.6
1.6
4.2
2.8
12.0
SE
2,4
1.6
1.7
1.6
2.1
3.2
6,4
5.4
7.2
1.5
2.1
5.8
1.1
1.4
0.6
0.9
1.2
2.1
3.1
3.5
3.7
3.1
3.7
3.4
1.1
1.2
1,8
2.8
3.5
8.8
6.8
21.0
V
20
13
13
18
35
90
26
29
rs
26
3
58
iO
17
8
9
11
32
36
46
52
44
39
32
16
20
26
34
38
72
60
as
ZN
266
31
37
41
56
121
2525
<447
4992
120
54
429
1905
4772
13
11
23
115
665
32140
7759
70160
313
603
7
9
12
IS
41
3128
570
1S170
ZR
4
1
2
a
4
12
18
18
17
6
2
19
4
2
1
2
3
6
9
14
14
20
10
12
1
2
4
7
8
32
21
-------
- 36 -
in bromoform or in bromoform which contained a small amount of ethyl alcohol.
Three of the coals were each separated into six specific gravity fractions in
the perchloroethylene and naphtha and the heaviest of each of these fractions
(l.60 sink) was separated into two parts in bromoform. The fourth coal was
also separated in the perchloroethylene and naphtha but only two fractions were
analyzed, one with specific gravity of less than 1.25 and one with specific
gravity greater than 1.60. The results of the analyses for Cl and Br in the
washed coals are not given,since relatively large amounts of these elements
were added to the coals from the washing media,
Results of the trace element determinations of the laboratory-
prepared coals are given in table 10; the major and minor elements in table 11;
the standard coal analyses in table 12; and varieties of sulfur in table 13.
Samples are listed in order of increasing specific gravity. Those samples
identified as to their size distribution (e.g., 3/8 in. by 28 mesh) are "whole
coal," or the sample prior to washing.
The float-sink (washability) data may be displayed as. washability
curves and as histograms. Figures ho through 71 are sets of such diagrams
which are intended to show the "typical" distribution of each element in the
four washed coal samples. There is a single set for each element determined,
and the set may come from any one of the coals analyzed. A washability curve
for the amount of low-temperature ash (LTA) in each of the three coals for
which complete sets of washed samples were analyzed is also given for reference
purposes. The washability curve is a type of cumulative curve on which can be
read the concentration of an element that would be expected at any given rate
of recovery of a coal, assuming a separation based on differences in specific
gravity. Therefore, the abscissa is "recovery of float coal—percent" arid
should be applicable to any specific gravity separation, without regard to the
medium in which it is done or the method used. The raw coal concentration of
an element is read at the 100 percent recovery point, and concentration in the
cleanest coals (most mineral-matter-free) is read at the low recovery end of
the curve (20 to 30 percent recovery). All of the washability curves shown
are drawn with the ordinates the same length and the origin at zero concentra-
tion. The slopes of the curves can therefore be compared and interpreted.
A positive slope of the washability curve shows that the element is
concentrated in the inorganic (mineral matter) portion of the coal. Conversely,
a negative slope demonstrates organic affinity for an element. Table lk lists
the trace elements in order of decreasing "organic" affinity. The sequence was
determined by comparing ratios of the amount of an element in the lightest float
fraction (always less than 1.30 specific gravity) to the amount of that element
in the 1.60 sink fraction. The numerical values thus determined are not given
since they will vary with the particle-size distribution of the coal, the
specific gravity of the liquid used to make the first (lightest) separation, and
the size distribution of the mineral fragments in a single coal. However, the
sequence given in table lk does indicate which elements are primarily in organic
combination, which are in inorganic combination, and which are, apparently,
both inorganically and organically combined in coals of the Illinois Basin.
The sequences shown in table lU can be divided into several general
groups. First, there are those elements which, when determined, are alwsiys in
the group most closely associated with the clean coal and which, therefore,
(Continued on page 51)
-------
- 37 -
TABLE 11 —MAJOR AND MINOR ELEMENTS IN LABORATORY-PREPARED COALS
(percent, moisture-free coal)
SAMPLE N0.
C. 18090
C-18094
C-18095
C- 18096
C-18097
C-18098
C.18099
C-18106
C-18107
C-18092
C-18100
C-18105
C-18134
C. 18133
C-18135
C-18136
C-16137
C- 18138
C-18139
C-18140
C-16141
C-18142
C. 16122
C-18121
C-18123
C-18124
C-18125
C- 18126
C-18127
C. 18128
C-18129
C-18130
SPECIFIC
GRAVITY „
FRACTI0N*
3/8X28M
1.28F
1.30FS
1.32FS
1.40FS
1.60FS
>1.60
2.B9FS
>2.90
3/8X28M
1.29F
1.60S
28MXO
3/8X28M
1.25F
1.26FS
i.JOFS
1.40FS
1.60FS
>l,feO
2.89FS
>2.90
2BMXO
3/8X28M
1.25F
1.29FS
1.33F9
1.40FS
1.60FS
>1,60
2.89FS
>2,90
PERCENT
0F
HAW C0AL
100,00
25,87
19,50
19,70
19,30
7,20
8,50
3,75
4.75
100,00
19.40
9.00
100.00
100,00
28,20
23.60
27.60
10.60
3.80
6.80
3.60
3.20
100.00
100,00
36,10
l',40
14.70
9.30
6,90
15.60
12,73
2,87
Stih
DV
OV
ov
ov
uv
ov
ov
ov
nv
UK
OK
OK
2
z
z
z
z
z
Z
s
z
z
6
6
6
b
6
6
6
6
6
6
AL
0,91
0,43
0,5 '4
n.77
1.28
2,23
1.39
",21
0.23
1.21
0,53
1.50
1.15
0.61
0,26
0,28
0.38
0,87
2,00
3,05
6.19
0,33
3,21
2,67
0,41
0.52
0,84
l.«3
2,92
9,50
11,89
1.93
C*
0.21
0.21
0,17
0,41
0,73
U.S3
U.41
0,49
0.24
0,11
0.18
0.03
1.16
0.40
0.07
0,07
0,07
0,08
0,16
«,53
7.85
0.70
0.79
0.56
0,06
0,05
0,06
0,08
0.12
3.20
4.?7
0.11
Ft
2.70
0,51
0.83
1.04
1.39
2.00
26,10
8.92
34.84
2.98
0,86
6.64
2.84
3.03
1.19
1.54
2.40
3.10
3,72
21,21
16.00
29.67
1.46
1.72
0.54
0,72
1.07
1.61
1.69
9.88
5.19
35.13
K
0,14
0.06
0,09
0.12
0.23
0.37
0.07
u.as
0.18
0.08
0.31
0.09
0.08
0.05
0,05
O.Ob
0,11
0,26
0.36
0.76
0.26
0.25
0,06
0.09
0.12
0.20
0.36
1.20
1.44
0,07
MB
0,040
0,020
0.020
0.030
0.040
0,080
0.170
0.006
0.003
0.010
0.004
0.001
0.001
0,001
0.001
0.003
0.008
0.010
0,009
0,008
0.003
0.003
0.004
0.006
0.010
0.030
NA
0.010
0.010
0.010
0.010
0.020
0,020
0.020
0.020
0.020
0,010
0,010
0,020
0,010
0,008
0.008
o.oeo
0,010
0.020
0,020
0,060
0,040
0,020
0.020
0.020
0,040
0.050
0.140
0,040
SI
2,11
0.77
1,16
1.58
2,80
5.51
5,62
8,27
2,02
0.78
2.63
1,69
1.05
0.49
0,58
0,77
1.53
3,44
5.31
11.41
4,49
4,16
0,59
0.87
l.«S
2.52
4,98
19,35
23,19
2,69
TJ
0,06
0,04
0,05
0,06
0,09
0.12
0,04
0.11
0,07
0,04
0,04
0,03
0,03
0.03
0,03
0.03
0,05
0,07
0,10
0,19
0,11
0,11
0,03
0,05
0,06
0,09
0,13
0.56
0,65
0.09
Specific gravity fractions given followed by the letters PS indicate that
the entire sample would float at that gravity and would sink at the gravity
listed immediately above.
-------
- 38 -
TABLE 12—PROXIMATE ANALYSES AND ASH CONTENT OF LABORATORY-PREPARED
COALS (percent, moisture-free, except for air-dry loss and moisture)
SAMPLE MB,
C-18090
C»18094
£•18095
C-18096
C-1BQ97
C-18098
C-18099
C-18106
C. 18107
C.16092
C-18100
C-18105
C- 18134
C-18133
C»18135
C. 18136
CM6137
C-18138
C-16139
C-18140
C-18141
C-16HJ
C-18122
C. 18121
C-18123
C. 18134
C- 18125
C. 18126
C. 16127
C-18128
C»18129
C-18130
SPECIFIC
GRAVITY
FRACTI0N*
3/8X28M
1.2BF
1.3DFS
1.32FS
1.40FS
1.60FS
>1.60
«!.89FS
>2.90
3/8X28M
1.29F
1,608
28MXO
3/8X28M
i,25F
1.26FS
J.30F3
1.40FS
1.60FS
>1,60
a,89F8
>2.90
28MXCI
3/8X28M
I.Z5F
1.29FS
J.33F8
1,«OFS
1.60FS
>1,60
2.89FS
>2.90
PERCENT
0F
RAN C0AL
100.00
25,87
19,50
19,70
19,30
7,20
8. SO
3.75
«,75
100,00
19.40
9.00
100,00
100, 00
28.20
23,60
27.60
10.60
3,20
6.80
3,60
3.20
100,00
100,00
36,10
17, 40
14,70
9.30
6,90
15,60
12,73
2,87
C0AL
3EAR
UV
DV
0V
DV
UV
DV
UV
UV
0V
DK
DK
UK
2
2
2
2
2
2
2
2
2
2
6
6
6
6
6
6
6
6
6
6
AUL
1.9
0.5
0.6
1.4
0.3
0,1
2.40
0.20
10.30
10,90
10,00
8,00
7,40
7,00
3.10
0,70
9,50
11.30
7.90
8,60
5,20
3,70
1,90
1.20
M0IS V0L FIXC
8.7 38,1 51,0
1,3
1.3
2.1
1,3
1.0
0,8
3,1
0.6
3.20 38.00 48,60
1.10
0,40
12,00
13,10 41,50 47.40
11,90
9,90
9.50
9.10
5.00
1.50
4.40
0.30
10.80
12.90 37.80 41.50
9,90
10.50
7,30
5.40
3,70
2.10
1,00
0,20
ASH BTU HTA
10,9 13311 10.90
3.00
3.90
5,40
9,40
19, 80
51.40
39,20
61.00
13.40 12745 13,40
5,40
49.80
16.60
11,00 12740 11,00
2.60
3,50
5,00
1U.50
21,70
56.50
46.90
65.00
23,80
20,70 11256 20,70
3.10
3,70
6.10
11.20
21.90
72,60
75,20
65,60
LTA
15,80
3,61
5.68
6,67
12,74
23,06
73,53
47,76
92,66
15,73
4.79
74.07
20,15
15,57
3,56
6,30
9,48
16,21
26,75
741,20
60,14
99,61
28,23
26.28
3.8J
5,01
3,18
14,86
25,92
88,40
86.02
98,71
* Specific gravity fractions given followed by the letters FS indicate that
the entire sample would float at that gravity and would sink at the gravity
listed immediately above.
Air-dry loss (ADL), moisture (MOIS), high-temperature ash (HTA), low-
temperature ash (LTA).
-------
- 39 -
TABLE 13 —SULFUR ANALYSIS OF LABORATORY PREPARED COALS
(percent, moisture-free)
SAMPLE N0,
C-16090
C- 18094
C-1809S
C. 18096
C-18097
C. 16098
C. 18099
C-18106
C- 18107
C«18092
C-18100
C»18105
C. 16134
C- 18133
C-18135
C-16136
C- 18137
C-16138
C-18139
C.18140
C- 18141
C. 18142
C- 16122
C- 18121
C- 16123
C-18124
C« 18115
C- 18126
C- 18127
C-18128
C-18129
C. 18130
SPECIFIC
GRAVITY
FRACTI0N*
3/6X26M
1.28F
1.30FS
1.32FS
1.40FS
1.60FS
>1,60
2.B9FS
>2,90
3/8X28M
1.29F
l.bOS
28MXO
3/6X2BM
1.25F
1.26FS
1.30F8
1.40F3
1.60FS
>1,60
2.89FS
»2,90
26MXO
3/8X28M
,esF
,29FS
,33FS
.40FS
,60F8
M.60
2.69FS
»2.90
PERCENT
0F
RAW C0AL
100.00
25,87
19,50
19,70
19,30
7,20
8,50
3,75
«.75
100,00
19,40
9.00
100,00
100,00
28,20
23.60
27,60
10,60
3,20
6.60
3,60
3.20
100,00
100,00
36.10
17,40
14.70
9,30
6.90
15.60
12,73
2.87
COAL
SEAM
ov
ov
ov
DV
OV
DV
DV
DV
DV
DK
DK
UK
2
2
2
2
2
2
2
2
2
2
6
6
6
6
6
6
6
6
6
6
0RS
1,17
1,20
1.19
1.^1
1.26
1.11
0,02
2.03
1.24
0,76
0,96
0.24
1.26
1,27
1,1'
1,00
1.03
1,16
0,96
0,01
0,01
0.01
1,56
1,70
1,60
1,61
l.«7
1,26
l.«3
0,61
0,30
0,01
PYS
3.25
0.40
0.45
0,62
1,04
2,«7
29,26
9,09
44,23
4,73
1.52
31.20
4.79
4.38
0,78
1,09
2,08
3.98
6,84
27.46
12.94
45.81
2.17
2.23
0.46
0,57
0,97
1,75
2.13
9.90
1.44
42,96
sus
0,01
0,0
0,0
0,0
0,0
0,0
0.10
0.10
0,15
0,01
0,01
0.15
0,04
0,03
0,20
0,02
0,03
0,06
0,06
0,15
0,13
0.04
0,04
0,03
0,02
0.02
0,03
0,03
0.03
0,06
0,31
0.12
TBS
4,43
1.60
1.64
1.83
2,30
3.59
29,39
11.23
45.42
5.50
2,49
31.60
6,11
5.68
1.98
2,11
3.14
5.19
7,88
27.62
13.08
45.66
3.76
3.96
2,07
2.20
2.46
3.04
3.60
10.59
2,05
43.09
SXRF
3.21
2.37
2,29
2.32
2.20
2,17
29.39
3.25
1.69
11.48
3.28
3.68
2.17
2.40
3.21
3.76
3,89
27,00
2.32
2.81
3.04
3.07
3,10
3.11
2.52
2.16
* Specific gravity fractions given followed by the letters FS indicate that
the entire sample would float at that gravity and would sink at the gravity
listed immediately above.
Organic sulfur (ORS), pyritic sulfur (PYS), sulfate sulfur (SUS), total
sulfur (TOS), sulfur by X-ray fluorescence (SXRF).
-------
13.5-
1 1 6-
9.7 -
7. 7 •
5.8 -
3.9 •
1.9 -
0.0 -
/"
/
m
/
m/
*^^
_— — — ffl
92.7
79 H
66.2-
~ 52.9^
cc
^39.7,
25.5
13. 2-
0.0 -
r~
m n .n ,
10 20 30 10 50 60
PERCENT RECOVERY
DRVIS CORL
1.28 1.29 1.31 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRHCTION
DRVIS CGRL
Fig. UO - Low-temperature ash in specific gravity fractions of a sample from the
Davis Coal Member. Left: washability curve. Right: distribution of LTA in
individual fractions.
85.M--
71 1
56.9
%2.7
30 HO 50 60 70 8
PERCENT RECOVERY
COLCHESTER (NO.2) CORL
1 . 21 1 .26 1 . 30 1 . MO 1 . SO 2 89
SPECIFIC GRRVITT FRACTION
COLCHESTER (NO.2) CORL
Fig. 41 - Low-temperature ash in specific gravity fractions of a sample from the
Colchester (No. 2) Coal Member. Left: washability curve. Right: distribution
of LTA in individual fractions.
20.2-
17.3-
114.14-
11.5-
8.6 -
5.8 -
2.9 -
n.n -
/
ffi
/
/
/
a
B^
_ffl '"
98. 1-
814.6-
70.5-
" 56.14-
CH
t—
42.3-
28.2-
114. 1-
0.0 -
r-|
[ — i n~i 1 1
— .
20 30 14'0 50 60 70
PERCENT RECOVERY
HERRIN (NO.6) CORL
90
1.25 1.28 1.33 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRHCTION
HERRIN (NO.6) COHL
Fig. 4-2 - Low-temperature ash in specific gravity fractions of a sample from the
Herrin (No. 6) Coal Member. Left: washability curve. Right: distribution
of LTA in individual fractions.
-------
- Ill -
3 --
9 --
6 --
3 --
0 --
6 --
3 --
to-
30 140 50 60 70
PERCENT RECOVERY
HERRIN (NO.6) CORL
80 90 !00
1.28 1.33 1.140 1.60 2.89
SPECIFIC GRRVITY FRRCTION
HERRIN (NO.6) CORL
Fig. M-3 - Aluminum in specific gravity fractions of a sample from the Herrin
(No. 6) Coal Member. Left: washability curve. Right: distribution of
aluminum in individual fractions.
L_
3C 140 50 60 70 83
PERCENT RECOVERY
COLCHESTER (NO.2\ CQRu
1 .26 1.30 1 .HO 1 .60
SPECIFIC GRRVITY FRRCTION
COLCHESTER [NO. 2) COflL
Fig. 4-4 - Calcium in specific gravity fractions of a sample from the Colchester
(No. 2) Coal Member. Left: washability curve. Right: distribution of
calcium in individual fractions.
140 50 60 70 80 90 100
PERCENT RECOVERY
DRVIS CGRL
2.9 -
2.S •
2. 1
1.6-
1.2-
0.8 •
0.14 -
n n .
a 314.8-
j
i 29.9
/
ffl
/
^BJ
-^ffl
^^___^ffl
ffl
1 1 1 4 1 1 1 1 L__-__ ~l .
24. 9-
;x
19.9-
l_LJ
^1U.9-
10 DJ
5.0 •
o n
.-^ r-r-, r— i rri rn
—
j— ,
1.29 1.31 l.MO 1.60 2.89 >2.9
SPECIFIC GRRVITY FRRCTION
DRVIS CORL
Pig. 45 - Iron in specific gravity fractions of a sample from the Davis Coal Member.
Left: washability curve. Right: distribution of iron in individual fractions.
-------
0.29 •
0.25
0.21 -
0. 17 .
0. 12 -
0.08
0 04 -
0.00
]
I
/
^m
_-B "
10 20 30 140 50 60 70 80 90
G-ffl
100
1.1414 -
1.23 •
1 .03 •
~ 0.82 -
^ 0.62
0.141
0 21 •
0.00 -
r^ n n
1.25 1.28 1.33
1
m
1.140 1.60 2.89 >2.9
PERCENT RECOVERY
HERRIN (NO.6) COflL
SPECIFIC GRRVITT FRflCTION
HERRIN (NO.6) COflL
Fig. U6 - Potassium in specific gravity fractions of a sample from the Herrin
(No. 6) Coal Member. Left: washability curve. Right: distribution of
potassium in individual fractions.
o
X
5
£
8.121 -
6.961 -
5.801 -
14.6141 -
3.1480 •
2.320 -
1 . 160 -
0.000 -
0
m
I
v
/O 20 30 140 50 60 70 80 90 100
PERCENT RECOVERY
HERRIN (NO. 6) COflL
0.030
0.026
0.021
0.017
>
"0.013
0.009 --
0.0014 .•
0.000
n n
1.25 1.28 1.33 1.1(0 1.60 >1.6
SPECIFIC GRflVITT FRflCTION
HERRIN (NO.6) COflL
Fig. iJ-7 - Magnesium in specific gravity fractions of a sample from the Herrin
(No. 6} Coal Member. Left: washability curve. Right: distribution of
magnesium in individual fractions.
0.03 -•
0.01 -
0.00 -I—
/
ffl
«, /
0. 12 -
0. 10 •
""O.OB
cc
Z 0.05 •
0.00 -
140 50 60 70
PERCENT RECOVERY
HERRIN (NO.6) COflL
1 .28 1.33 1.140 1 .60
SPECIFIC GRRVITY FRflCTION
HERRIN (NO.6) COflL
Fig. 4-8 - Sodium in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of sodium in
individual fractions.
-------
Fig. ^9 - Phosphorus in specific gravity fractions of a sample from the Davis
Coal Member. Left: washability curve. Right: distribution of phosphorus
in individual fractions.
1 .23 I .23 1.31 1.110 1 .60 2 B9
SPECIFIC GRflVITT FRHCTIQN
DPVI5 CQPL
Pig. 50 - Sulfur in specific gravity fractions of a sample from the Davis Coal
Member. Left: washability curve. Right: distribution of sulfur in
individual fractions.
1.25 1.28 1 33 I.HO ! 60 2.89
SPECIFIC GPHVITT FRRCTION
HERRIN (NO.6) CdflL
Fig. 51 - Silicon in specific gravity fractions of a sample from the Herrin (No.
Coal Member. Left: washability curve. Right: distribution of silicon in
individual fractions.
6}
-------
0.13 -
0.11-
0.09 -
0.08 -
0.06 -
0.04 •
0.02 -
0.00 -
.,
/
/
/ffi/
m — — • "
H 1 +- 1- +-_ +- 4- 4- 4- +—
0.65 -
0.56 -
0.146 •
0.37 -
*~ 0.38 -
0. 19 •
0.09 -
0.00 -
._. n
nn H H n .
| 1
n
10 20 30 140 50 60 70 80 90 100
PERCENT RECOVERY
HERRIN (NO.6) COflL
1.25 1.28 1.33 1.140 1.60 2.89 >2.9
SPECIFIC GRflVITY FRflCTION
HERRIN (NO.6) COflL
Fig. 52 - Titanium in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of titanium in
individual fractions.
1 1 5-
9.8 -
8.2 -
6.6 -
,.9-
3 3 -
1.6
0 0 -
a
ffl
J
1 \ 1 \- 1 1 1 1 1 1
o
— 2 ! i
1.7
Q_
t 1.1) J
£1.0 -
0.7 •
0.3
0.0 -
;
, , _ ^ ^ n
0 I'D 20 30 140 50 60 70 80 90 100
PERCENT RECOVERY
HERRIN (NO. 6) COflL
1.25 1.28 1.33 1.140 1.60 2.89 >2.
SPECIFIC GRflVITY FRflCTION
HERRIN (NO.6) COflL
Fig. 53 - Arsenic in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of arsenic in
individual fractions.
27.2-
22.6-
18. 1-
13.6
9. 1 -
14.5 -
n n -
/*^^ " *X*
35 0-
30.0-
E 2S.O-
Q_
CL
20.0
CD
15.0-
10.0-
5.0 -
o.n .
10 20 30 140
PERCENT RECOVERY
DflVIS CQHL
1.28 1.29 1.31 1.140 1.60 >1.6
SPECIFIC GRflVITY FRflCTION
DflVIS COflL
Fig. 54- - Boron in specific gravity fractions of a sample from the Davis Coal Member.
Left: washability curve. Right: distribution of boron in individual fractions.
-------
3.0 -•
2.6 -.
: 2. 1 -•
' 1.7 -.
—t—
—t—
—H
30 40 50 60 70
PERCENT RECOVERY
DflVIS CQHL
80 90 100
4.7
4.0
£3.4
Q_
1.29 1.31 1.40 1.60 2.89
SPECIFIC GRRVITY FRRCTION
DflVIS CORL
Fig. 55 - Beryllium in specific gravity fractions of a sample from the Davis Coal
Member. Left: washability curve. Right: distribution of beryllium in
individual fractions.
2.0 •
1.7
1 4
1.1-
0.9
0.6 -
0.3 -
n . n .
a
•
j
I
I
B__ B_J
1 1 1 1 1 1 1 1 1 1
36 0-
30.9
£ 25.7,
o.
Q_
20.6-
a
° 15.4
10. 3-
5 1 -
n n -
„ „ 1
1 '
!
0 10 20 30 40 50 60 70 80 90
PERCENT RECOVERY
loO
1.29 1.31 1.40 1.60 2.89
SPECIFIC GRRVITY FRRCTION
DflVIS CORL
QRVIS CGRL
Fig. 56 - Cadmium in specific gravity fractions of a sample from the Davis Coal
Member. Left: washability curve. Right: distribution of cadmium in individual
fractions.
5.8 •
5.0 -
4.2 -
3.3
2.5 •
1.7 -
0.8 -
0.0 -
a
/
/
/
/
ffl/ ffl
ffi/^
^^^*
19.0-
16.3-
£ 13 6-
tL
CL
10.9-
S
5.4 -
2.7 -
n.n -
— 1 —
p ]
0 10 20 30 40 50 60
PERCENT RECOVERY
HERRIN (NO.B) CORL
90 100
1.25 1.28 1.33 1.40 1.60 > 1.6
SPECIFIC GRRVITY FRflCTION
HERRIN (NO.6) COflL
Fig. 57 - Cobalt in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of cobalt in
individual fractions.
-------
- 1*6 -
m.o-
12.0-
10. 0-
8.0 -
6.0 -
4.0 -
2.0 -
0.0-
ffl
ffl
.a— • •
— ffl^ ~
l'o 20 30 40 50 60 70 80 90 100
PERCENT RECOVERY
DflVIS COflL
70.0
60.0-
£ 50.0-
40 0-
o:
U 30.0
20.0
10.0-
0.0 -
H
1.28
— i
.29 1.31 40 .60 2.89 >2.9
SPECIFIC GRflVITY FRRCTION
DHVIS CORL
Fig. 58 - Chromium in specific gravity fractions of a sample
Left: washability curve. Right: distribution
29. 1-
214.9-
20.8-
16.6-
12.5-
8.3 -
4.2
0.0 -
/
J
/
m^_^*^
- — a — ~
10 20 30 40 50 60 70 80 90 100
PERCENT RECOVERY
COLCHESTER (NO. 2) COflL
~ 1 . 8 -
C\J
D
Si. 5 -
1.3 -
i 1 .0 -
30.8-
0.5 -
0. 3 -
0.0 -
from the Davis Coal Membe
of chromium
in individual fractions
i 1
" n n n
i .214
J
.26 1.30 .40 .60 2.89 >2.9
SPECIFIC GRRVITY FRRCTION
COLCHESTER (NO. 2} COflL
Pig. 59 - Copper in specific gravity fractions of a sample
Coal Member. Left: washability curve. Right:
3.0 -
2.6 -
2.2
1.7 -
1.3 -
0.9 -
0 14 •
0.0 •
individual fractions.
.-—-•-•
.^
a
1 1 1 1 ^ 1 1 ) 1 1
4.9 -
£ 3.5
Q_
Q_
~ 2.8
CL
°2.1 •
1.4 -
0.7 -
o n
from
the Colchester (No. 2)
distribution of copper in
— I —
— 1
( 1
30 40 50 60
PERCENT RECOVERY
DRVIS COflL
80 90 100
1.29 1.31 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRRCTION
DflVIS CORL
Fig. 60 - Gallium in specific gravity fractions of a sample from the Davis Coal Member.
Left: washability curve. Right: distribution of gallium in individual fractions.
-------
9.14 -
0.0
~\0 20 30 UD 50~
60
to-
80 90 100
PERCENT RECOVERY
DRVIS CORL
5.7 --
2.9
1 .14
0.0
1.29 1.31 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRflCTION
DflVIS COHL
Fig. 61 - Germanium in specific gravity fractions of a sample from the Davis Coal
Member. Left: washability curve. Right: distribution of germanium in
individual fractions.
0.28 -
0.214 •
0.20
0. 16
0. 12 -
0.08 -
0.014 -
n nn .
1
i
m
_ffl ,a^»^a
1 1 1 1 1 1 ( 1 1 1
3.80 -
3.26 -
£ 2.71 -
Q_
~ 2. 17 -
LD
r 1.63 -
1.09 -
0.514 •
O.DO -
n
— i
!
0 10 20 30 40 SO 60 70 80 90 100
PERCENT RECOVERY
HERRIN [NQ.61 CORL
1.25 1.28 1.33 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRRCTION
HERRIN (NO.6) CORL
Fig. 62 - Mercury in specific gravity fractions of a sample from the Herrin
(No. 6) Coal Member. Left: washability curve. Right: distribution of
mercury in individual fractions.
69.6-
59.6-
£ U9.7-
Q_
0-
~ 39.8-
*~ 29. 8-
19.9-
9.9 -
n. o -
J
s-m
- H.6 H
ru
o
2 3.9 -
_ 3.3
Q-
12.0 -
1.3 -
0.7 -
n n .
' ^ n
'
[}
10 20 30 140 50 60
PERCENT RECOVERY
HERRIN [NO. 6) CORL
80 90 100
1.25 1.28 1.33 1.140 1.60 2.89 >2.
SPECIFIC GRHVITY FRflCTION
HERRIN (NO.6) COflL
Fig. 63 - Manganese in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of manganese in
ind iv idual frac t i ons.
-------
11. S--
9.9 --
: 8 . 2
3.3 --
1.6 --
0.0
- 1*8 -
0
20 30
70~
50 60
PERCENT RECOVERY
COLCHESTER (NO.2) COflL
80 90
0.14 --
0.2 --
0.0
1.214 1.26 1.30 1.140 1.60 2.89
SPECIFIC GRRVITY FRflCTIQN
COLCHESTER (NO.2) CORL
>2.9
Pig. 6& - Molybdenum in specific gravity fractions of a sample from the Colchester
(No. 2) Coal Member. Left: washability curve. Right: distribution of
molybdenum in individual fractions.
30 5-
21.8-
17. y-
13. 1-
8. 7 •
14. y -
n n .
a
J
/
m
a — —""'^
.a- — — ~~~~~~
-11-
o
0.8 •
Q_
t 0.7 -
20.5 -
0.3 •
0.2 •
o. n •
Tin
i — -
10 20 30 140 SO 60 70 80 90
PERCENT RECOVERY
COLCHESTER (NO.2) COflL
1.26 1.30 1.140 1.60 2.89 >2.9
SPECIFIC GRRVITY FRRCTION
COLCHESTER (NO.2) CORL
Pig. 65 - Nickel in specific gravity fractions of a sample from the Colchester
(No. 2) Coal Member. Left: washability curve. Right: distribution of nickel
in individual fractions.
o
- 0.9 -
_0.8 -
X
a.
£0.5 -
0.3
0.2
o n
1
1
ffl
1 1 1 1 -1 1 1 1 1 L_— .
(r7 1 S •
O
-1.3-
1.0 -
Q_
t 0.8 -
£0.6 .
0.14 -
0.2 •
0 0 •
_ _ _ ,-, n
— i
lo 20
UO 50 60 70 80
PERCENT RECOVERY
DRVIS COflL
1.29 1.31 1.140 1.60 2.89
SPECIFIC GRRVITY FRACTION
DRVIS COflL
Fig. 66 -
Left:
Lead in specific gravity fractions of a sample from the Davis Coal Member.
washability curve. Right: distribution of lead in individual fractions.
-------
0.57 -
O.M9 -
£ 0. 140 •
Q_
O-
0.32 -
CQ
0.16-
0.08 -
n. nn -
S
/
/
ffl
^/
^___^~-
ffl-~
3.60 -
3.09 -
£2.57 -
Q_
a_
~ 2.06 -
CD
1.03 -
0.51 -
0. DO -
n
l~7~l
i — |
i — |
so no so o
PERCENT RECOVERY
ORVJS COfiL
ao 90
1.28 1.39 1.31 1.1)0 1.60 2.89
SPECIFIC GRflVITT FRflCTION
DflVIS COflL
Fig. 67 - Antimony in specific gravity fractions of a sample from the.Davis Coal
Member. Left: washability curve. Right: distribution of antimony in
individual fractions.
2.8
2.14
2.0
1.6 -
1.2 -
0.8 -
o.o.
ffl
ffl
/
ffl'
ffl B
10 ^o s'o Jo s'o e'o T'O so 90 100
PERCENT RECOVERY
HERRIN (NO. 6) CORL
21.0-
18.0-
-15.0.
Q_
Q_
12.0-
LU
"Vo -
6.0 -
3.0 -
0.0 -
[~7~i
1.25
rr
n
1
1.28 1.33 1.140 1.60 2.89 >2.9
SPECIFIC GRflVITY FRflCTION
HERRIN (NO. 6) COflL
Fig. 68 - Selenium in specific gravity fractions of a sample
from
the Herrin (No. 6)
Coal Member. Left: washability curve. Right: distribution of selenium in
15.2-
13. 1-
10.9-
8.7 -
6.5 -
14.14 -
2.2 -
0.0 -
individual fractions.
ffl - — ~~
1 1 1 1 1 1 1 1 1 1
52.0-
1414.6-
£37.1-
Q_
Q_
29.7-
22.3-
114.9-
0.0 •
n
—
—
20 30 140 50 60
PERCENT RECOVERY
COLCHESTER (NO.2) CORL
100
1.24 1.26 1.30 1.140 1.60 2.89
SPECIFIC GRflVITY FRflCTION
COLCHESTER (NO. 2} COflL
>2.9
Fig. 69 - Vanadium in specific gravity fractions of a sample from the Colchester
(No. 2) Coal Member. Left: washability curve. Right: distribution of
vanadium in individual fractions.
-------
- 50 -
o
x i^,, .
3.S •
0.
5:2.9 •
£2-2 '
1.5 •
0.7
0.0 •
•
;
i
I'D ^o ^o~~ ^40 3a eo T^i ao do 100
=T 1.5
0
X
- 1.3
„'•' '
Q-
t 0.9
5°-'-
O.U •
0.2 •
0.0
1.25 1.28 1.33 1.140 1.60 2.89 >2.9
PERCENT RECOVERY
HERRIN (NO. 6) COPL
SPECIFIC GRRVITY FRPCTION
HERRIN (NO.6) COfiL
Pig. 70 - Zinc in specific gravity fractions of a sample from the Herrin (No. 6)
Coal Member. Left: washabllity curve. Right: distribution of zinc in
individual fractions.
3.6 •
3. 1 --
: 2.6 -
' 2.1 -•
0.0
"to 20 ^0 W 50 60 70 80 90~
PERCENT RECOVERY
COLCHESTER (NO.2) CORL
20.0
17. i
: 1U.3
'll.i4
5.7 ..
2.9 ••
0.0
n
1.24 1.26 1.30 1.140 1.60 2.89
SPECIFIC GRflVITY FRflCTION
COLCHESTER (NO.2) CORL
>2.9
Fig. 71 - Zirconium in specific gravity fractions of a sample from the Colchester
(No. 2) Coal Member. Left: washability curve. Right: distribution of
zirconium in individual fractions.
-------
- 51 -
TABLE lU—AFFINITY OF ELEMENTS FOR PURE COAL AND FOR MINERAL MATTER,
AS DETERMINED FROM FLOAT-SINK DATA
Davis Coal
Clean coal - lightest B
specific gravity fraction Ge
(elements in "organic Be
combination") Ti
Ga
>
P
V
Cr
Sb
Se
Co
Cu
Ni
Mn
Zr
Mo
Cd
Mineral matter - specific Hg
gravity greater than 1 . 60 Pb
(elements in "inorganic Zn
combination" ) As
DeKoven Coal
Ge
Ga
Be
Ti
Sb
Co
P
Ni
Cu
Se
Cr
Mn
Zn
Zr
V
Cd
Mo
Pb
Hg
As
Colchester
(No. 2) Coal
Ge
B
P
Be
Sb
Ti
Co
Se
Ga
V
Ni
Pb
Cu
Hg
Zr
Cr
Mn
As
Mo
Cd
Zn
Herrin (No. 6)
Coal
Ge
B
Be
Sb
V
Mo
Ga
P
Se
Ni
Cr
Co
Cu
Ti
Zr
Pb
Mn
As
Cd
Zn
Hg
have the greatest organic affinities. These are Ge, Be, and B, which are three
of the top five elements listed by Zubovic (1966, p. 222) in similar analyses
of trace element data. At the other end of the list are the elements with the
least affinity for the organic portion of the coal. The elements Hg, Zr, Zn,
As, and Cd are near the bottom in all four coals studied, and Pb, Mn, and Mo
are near the bottom in three of the four. The remaining elements, those that
are apparently associated, to varying degrees, with both the organic and inorganic
portions of the coals can also be divided into two groups: those elements that
tend to be more generally allied to the elements with organic affinities (P, Ga,
Sb, Ti, and V), and those elements that tend to be more inorganically associated
(Co, Ni, Cr, Se, and Cu). A comparison of this summarized sequence with that
given by Zubovic (1966, p. 222) shows generally good agreement, with only a few
minor discrepancies. The elements listed in table 1 include 12 of the 15 elements
discussed by Zubovic (1966) as well as nine additional elements.
Although an element may be listed among those with the highest organic
affinities, its occurrence in inorganic combination in coals is not precluded.
Boron, which is among those found in high concentrations in the cleanest coal
fractions, is known to occur in amounts up to 200 ppm in the clay mineral illite
from Illinois coals (Bohor and Gluskoter, 1973). Similarly, a portion of those
elements usually concentrated most heavily in the high specific gravity fractions
may also be in organic combination. This dual mode of occurrence was postulated
-------
- 52 -
for the Hg content of Illinois coals by Ruch, Gluskoter, and Kennedy (l9Tl),
and mercury is included here with the elements having lower organic affinities.
The shapes of the washability curves for Mg, Na, Co, Cr, Cu, Ga, Ni, Sb, Se,
and V all suggest at least a partial organic contribution. They all have
positive slopes, showing that those elements are concentrated in the mineral
matter, but all of the curves flatten out at some distance above the base-line
and, if extrapolated to zero percent recovery, would intersect the ordinate
well above the origin. These elements all have curves which are flatter than
the LTA curve for the same set of coal samples and more nearly resemble the
washability curve for total sulfur (TOS) in the Davis Coal Member (fig. 50).
The total sulfur in the whole coal (raw, or unwashed) 3/8 inch by 28 mesh Davis
Coal sample is composed of 0.07 percent sulfate sulfur, 1.17 percent organic
sulfur, and 3.25 percent pyritic sulfur; thus it contains a little more than
25 percent of the sulfur in organic combination.
Concentration of an element in the heavier fractions shows that
element to be in inorganic combination. In the cases in which the final
separation was done in bromoform (2.89 s.g.), we can postulate further on the
mode of occurrence of certain elements. Si, Ti, Al, and K are all concentrated
in the gravity fraction from 1.60 to 2.89 and are less abundant in the gravity
fraction greater than 2.89- These elements are found associated with each
other in the clay minerals and not in the heavier sulfides. Fe, S, As, Hg,
Mo, Pb, Cd, and Zn are all concentrated in the heaviest gravity fractions
(s.g. > 2.89) and are very likely present as sulfide minerals.
IDENTIFICATION OF MINERAL PHASES CONTAINING TRACE ELEMENTS
During the past few years several reports which describe investigations
concerned with the origin, distribution, and mode of occurrence of mineral mat-
ter in Illinois coals have been published (Gluskoter, 1967; Gluskoter, Pierard,
and Pfefferkorn, 1970; Gluskoter and Ruch, 1971; Rao and Gluskoter, 1973; and
Gluskoter and Lindahl, 1973).
Certain of the trace elements determined in coals occur in discrete
mineral phases. The identification of those minerals is therefore important.
Identifying minerals in the low-temperature ash of coals is generally done by
X-ray diffraction analysis, but the technique may not be sufficiently sensitive
to identify very small quantities of a mineral. However, greater sensitivity
may be achieved by using a scanning electron microscope (SEM) and the nondispersive
X-ray analytical equipment that is an accessory to the SEM; in this way many of
the minerals can be identified, even if they are present in very small quantities
(pi. 1).
Plate 1 - Scanning electron photomicrographs of minerals in coals.
A. Calcite (GaCOj) from cleat filling in Herrin (No. 6) Coal Member.
B. Kaolinite (aluminosilicate} from cleat filling; in Herrin (No. 6) Coal Member.
C. Pyrite (FeS2) framboids in low-temperature ash of DeKoven Coal Member.
D. Sphalerite (ZnS, also contains cadmium) from low-temperature ash of Herrin
(No. 6) Coal Member.
E. Galena (PbS) from low-temperature ash of DeKoven Coal Member.
F. Apatite (calcium phosphate mineral) from low-temperature ash of coal sample
from Colorado.
-------
- 53 -
Plate 1
-------
Sphalerite (ZnS) has "been identified as the host mineral for Zn
and Cd in the low-temperature ash of many coal samples from "both the Illinois
Basin (Illinois, Indiana, and western Kentucky) and Missouri. The distribution
of Zn in coals of the Illinois Basin is presented in a published abstract
(Gluskoter, Hatch, and Lindahl, 1973), and a more complete article describing
the occurrence of sphalerite in coals is in preparation. The mode of occur-
rence of the cadmium in Illinois coals has also "been described recently
(Gluskoter and Lindahl, 1973). The sphalerite has been found in relatively
large, discrete grains (pi. 1, D), and as the specific gravity of sphalerite
is greater than k, the mineral could be removed if the coal were washed
(separated by specific gravity techniques).
The low-temperature ash from a coal sample from Colorado (C-17097)
that has a relatively high P content was studied to identify the mineral phase
containing the P. The mineral phase contained Ca in addition to P (pi. 1, F).
A calcium phosphate mineral was also identified in the sample of an Illinois
coal (C-15^8) which contained 1^3 ppm F, the highest concentration of fluorine
in the coals analyzed. Apatite (generally carbonate-fluorapatite) has been
reported associated with coals; therefore, it is reasonable to assume that the
mineral we have observed is apatite.
A separate phase containing lead has also been observed in the very
fine fraction (less than 7^ \m) of the low-temperature ash of a sample of the
DeKoven Coal Member (C-159UU). Although the X-radiation cannot be used to
definitely identify sulfur in the presence of Pb, the crystal structure of the
mineral and its mode of occurrence (pi. 1, E) indicate that the mineral is
galena (PbS).
Other elements which have been identified in intimate association with
pyrite (FeSa) are nickel and copper (pi. 1, C). The identification of addi-
tional chalcophile elements which are in close association with pyrite requires
more sensitive analytical equipment and improved sample preparation techniques.
SUMMARY AND CONCLUSIONS
Complete chemical analyses of 101 whole coal samples and of 32
laboratory-prepared samples, obtained by specific gravity separations of four
coals, have been made in the laboratories of the Illinois State Geological
Survey. Trace elements determined were Sb, As, Be, B, Br, Cd, Cr, Co, Cu,
F, Ga, Ge, Pb, Mn, Mo, Ni, Hg, P, Se, Sn, V, Zn, and Zr. In addition, the
following major and minor elements were also determined: Al, Ca, Cl, Fe, Mg,
K, Si, Na, S, and Ti. Standard coal analyses—proximate, ultimate, heating
value, varieties of sulfur, and ash—are also reported.
Procedures for the analytical methods used—neutron activation, optical
emission, atomic absorption, X-ray fluorescence, and ion-selective electrode—
are given in detail in the appendix.
Wherever possible, accuracy was evaluated by comparing results obtained
by the various methods from representative splits of a coal sample.
Further comparisons were made by analyzing whole coal and its low- and high-
temperature ashes, thus permitting a thorough evaluation of trace element losses
resulting from volatilization during sample preparation.
-------
- 55 -
Generally, the results of the various analytical procedures compared
favorably, although exceptions are noted, e.g., for V and F. Certain techniques
have been chosen as preferred methods for determining specific elements because
they are more accurate, their precision is superior, or they take less time for
analysis.
Eighty-two of the 101 whole coal samples were from the Illinois Basin
(Illinois, Indiana, and western Kentucky). The additional 19 samples were from
other areas of the United States. The four samples which were prepared in the
laboratory (washed) were also from the Illinois Basin.
As a first step in the statistical analyses of the more than 6,000
analytical values generated (there were as many as 50 separate determinations
done on a single coal sample), arithmetic means, standard deviations, ranges,
and linear correlation coefficients were calculated on the trace elements, major
elements, high- and low-temperature ashes, and the proximate and ultimate coal
analyses for the 101 coals tested.
On the basis of these statistical calculations and of histograms of
the element distributions, the elements can be grouped with those of similar
type. One group displays a relatively normal distribution of analytical values,
and elements within this group have small standard deviations and ranges. In-
cluded in this group are Al, F, Fe, Ga, Be, Br, B, Cr, Cu, K, Hi, Si, Ti, Se,
and V. Elements in the second group all have a skewed pattern of analytical values,
with large standard deviations and ranges. This group includes Cd, Zn, P, As,
Sb, Pb, Sn, Cl, Ge, and Hg. The first group includes many of the elements with
organic affinities and also those elements which are thought to be syngenetic
and, therefore, inherited from an early period of coal swamp formation. The
second group includes elements commonly found in coal, and in sedimentary rocks
in general, as carbonates and sulfides. These minerals are often emplaced in
coal by epigenetic mineralization.
Correlation coefficients for the various parameters determined for the
coals from the Illinois Basin and for all of the 101 coals demonstrate the
following geochemical associations:
1. The highest value for the correlation coefficients determined is
that between Zn and Cd (r = 0.93). Both Zn and Cd are present in coals in the
mineral sphalerite and probably essentially only in that form.
2. Elements commonly found in nature as sulfides are the chalcophile
elements, which include As, Co, Cu, Ni, Pb, and Sb, which are all positively
correlated with each other in the coals analyzed.
3. The lithophile elements, those commonly occurring in nature as
silicates, include K, Ti, Al, and Si, which also have mutual positive correlations
in the data reported. These elements are found in coals primarily as clay min-
erals (aluminosilicates).
^. Mn has a positive correlation of 0.63 with Ca in the coals analyzed,
and does not correlate as well with any other parameter. It is present in small
amounts and most likely is in solid solution with Ca in calcite (CaCOs).
5. Sodium and Cl have a positive correlation of 0.53 in the coals
studied.
-------
- 56 -
Several additional geochemical relationships have "been suggested by
the chemical analytical data, such as:
a. The concentrations of As, Cu, Pb, Si, and Al in the coals of
the Illinois Basin decrease from the older to the younger coals.
b. The correlation between Na and Cl increases from the older to
the younger coals in the Illinois Basin.
c. The boron concentration in the coals of the Illinois Basin also
increases from the older to the younger coals. This suggests that the Basin
was becoming more marine (increasing in salinity) during the period of time
between deposition of the older and the younger coals.
We expect that further interpretations of some of the relationships
which have been noted and further elucidation of the geological parameters that
have influenced the chemical characteristics of the coals will result from
continued analyses of the data which are currently underway. These analyses
will include areal mapping of concentrations of elements and also the mapping
of the distributions of the elements within a single coal seam.
The average concentration of an element in the earth's crust is its
clarke value. The mean value for each trace element was compared to the clarke
for that element, and only three elements were enriched by at least one order of
magnitude (present in an amount greater than 10 times the clarke) and three
depleted by at least one order of magnitude (present in an amount less than one-
tenth the clarke). Because of the large number of variables used in calculating
various clarke values, differences of less than one order of magnitude were not
considered significant. The three elements enriched in coals are Cd, Se, and
B. Boron is concentrated only in the coals of the Illinois Basin and probably
represents a higher salinity of the waters in the coal swamp or of the waters
which flooded the coal swamp there. The only three elements found to be depleted
are Mn, F, and P.
An analysis of the data from the laboratory-prepared (washed) coals
has enabled the grouping of the determined elements, on the basis of their
tendency to be concentrated with the cleanest coal or with the mineral matter.
Those elements which are most closely associated with the clean coal are those
with the highest "organic affinity" and include Ge, Be, and B. At the other end
of the scale are those elements combined primarily in the mineral matter. This
group has the least organic affinity and includes Hg, Zr, Zn, Cd, As, Pb., Mn,
and Mo. The remaining elements, which are apparently associated to varying
degrees with both the organic and inorganic fractions of the coal, can be
divided into two groups: those which are more nearly allied with the elements
with organic affinities (P, Ga, Ti, Sb, and V) and those that generally are
more inorganically combined (Co, Ni, Cr, Se, and Cu).
Many minerals have been reported from coals, including aluminosilicates,
carbonates, and sulfides; and the mode of occurrence of the elements that make
up those minerals is obvious. However, several additional elements were con-
centrated in some of the coals studied and the possibility that these elements
too may be in discrete mineral phases was investigated.
-------
- 57 -
Sphalerite (ZnS) has "been identified as the host phase for both Zn
and Cd in a number of coals , including all those which contained relatively
high concentrations of Zn (greater than 500 ppm). The phosphate mineral
apatite, more precisely a carbonate fluorapatite, was identified in the low-
temperature ashes of both the coal sample that was found to contain the largest
concentration of P and of the coal sample that contained the largest concen-
tration of F.
A separate phase, identified as galena (PbS), has been observed in
the low-temperature ash of a sample high in Pb. Both Ni and Cu have been
identified in intimate association (probably in solid solution) with pyrite
in several samples.
-------
APPENDIX
PREPARATION OF COAL SAMPLES
Low-Temperature Ashing (LTA) and Trace Element Volatility
A coal ashing technique variously identified as electronic low-
temperature ashing (LTA), radio-frequency ashing, or oxygen-plasma ashing
vas used to prepare samples in this study. Coal is ashed in commercially
available devices (LFE Corporation Model LTA600 or the International Plasma
Corporation Model 1101) in which oxygen is passed through a high-energy
electromagnetic field produced by a radio-frequency oscillator. The
oscillator tube operates at a frequency of 13-56 Mhz, in compliance with
Federal Communications Commission requirements for scientific and medical
equipment (Gleit, 1963). A discharge takes place, which produces an acti-
vated gas plasma consisting of a mixture of "atomic and ionic species as
well as electronically and vibrationally excited states" (Gleit, 1963).
As the activated oxygen passes over the coal sample, oxidation of the organic
matter occurs at relatively low temperatures. The electronics involved is dis-
cussed in articles by the developers of this technique (Gleit, 1963; Gleit
and Holland, 1962).
Coal for low-temperature ashing is ground to pass a 20-mesh sieve;
approximately 50 g is placed in Pyrex boats, dried in a vacuum desiccator,
and placed in the ashing chamber. Ashing takes place at a pressure of 1 to
3 torr at an oxygen flow rate of 50 "to 100 ml per minute. The plasma
temperature may be varied by changing the radio-frequency power level. At
a radio-frequency power of 100 watts the plasma temperature is approximately
70° C. Higher temperatures are attained in the ashing chambers as a result
of the exothermic oxidative reaction between the activated gases and the coal.
Ashing temperature, monitored with a Raynger model LTX-28 infrared remote ther-
mometer, was not allowed to exceed 150° C in this study. Prior to analysis,
low-temperature ash samples are hand ground in an agate mortar and, depending
on the analytical method used, dried at 110° C at atmospheric pressure or in a
vacuum oven.
The effects of low-temperature ashing and of the oxidizing gas stream
upon pure minerals and upon minerals in coal have been discussed in earlier
papers (Gluskoter, 1965b, 1967; Rao and Gluskoter, 1973). No oxidation of
minerals in the coal has been reported, and the only observed changes are those
to be expected at a temperature of 150° C and pressure of 1 torr. Therefore,
the major mineral constituents of coal—pyrite, kaolinite, illite, quartz, and
calcite—are unaffected by radio-frequency ashing.
Most trace elements contained in coal mineral matter are not volatilized
during low-temperature ashing; many elements thought to be present in organic
combination are also retained in the low-temperature ash.
Samples prepared by low-temperature ashing have several important
analytical advantages: (l) few trace elements are volatilized at the low ashing
temperature (150° C); (2) no chemicals (such as are required for wet-ashing
whole coal) need be added during preparation—only oxygen under a
- 59 -
-------
- 60 -
partial vacuum is introduced; (3) trace elements in the ash generally are con-
centrated "by 10 or more times their amount in whole coal; and (4) subsequent
analytical treatment is greatly simplified in most cases.
However, some of the more volatile trace elements, e.g., Hg, Br, F,
and Sb, may be at least partially lost during low-temperature ashing. In
testing for such elements, whole coal must be analyzed directly or combusted
under controlled conditions.
Because conventional high-temperature ashing at 300° to 700° C in a
muffle furnace may result in losses of Hg, Br, F, Se, Sb, As, and possibly other
trace elements, low-temperature ashing in an oxygen atmosphere was investigated
as a means of oxidizing coal organic matter without volatilization of trace
elements. The volatility of each trace element during low-temperature plasma
oxidation of coal was studied by one or more of the following procedures:
l) Volatile combustion products collected in cold-traps (-78° C)
in the vacuum train of the low-temperature asher were analyzed.
2) Whole coal, which had been subjected to neutron irradiation, was
ashed and any volatile radioisotopes collected in the cold-trap of the asher
were determined and compared with their concentrations in the original sample.
3) Trace element results obtained from the direct analysis of whole
coal were compared with results obtained from low-temperature and/or high-
temperature ashes (700° C) prepared from the same coal to determine whether
significant losses occurred during ashing. This procedure was also used to
evaluate losses from coals ashed at ^50° C.
The results of the foregoing tests show that only Hg (up to 90%), Br
(100%), and Sb (up to 50%) are lost during low-temperature ashing of coal.
Although F was not tested, it is presumed to be totally volatilized.
High-Temperature Coal Ash (HTA) and Trace Element Volatility
Analysis of low-temperature coal ash by optical emission spectroscopy
has proved to be unsatisfactory because the ash contains various kinds of
chemical compounds that behave erratically in the DC arc. High-temperature
coal ash (k^0° to 500° C), which is composed of elemental oxides, is more
amenable to analysis by optical emission. It is also more easily and rapidly
prepared than low-temperature coal ash. Thus, high-temperature ash, prepared
from -100 mesh coal, is used for both optical emission methods employed in this
study. Care is used during the ashing procedure to oxidize all carbonaceous
material. The coal ash is ground in an agate or mullite mortar and dried at
110° C prior to analysis.
To determine volatility losses, a set of samples from two coals was
ashed in uncovered, used porcelain crucibles at temperatures of 300°, kOO°, 500°.
600°, and 700° C. Trace element determinations were made on each of the
10 resulting ash samples. The analyses (table A) do not exhibit trace element
losses or gains in samples ashed between 300° and 700° C except in C-16317, in
which there was an apparent overall gain in boron concentration and a possible
loss of lead at 300° C.
-------
- 61 -
TABLE A—CONCENTRATIONS OF TRACE ELEMENTS IN MOISTURE-FREE COAL (ppm)
FROM HIGH-TEMPERATURE ASH SAMPLES PREPARED AT VARIOUS
TEMPERATURES IN USED PORCELAIN CRUCIBLES
Sample number and temperature
Element
C-16317
C-16030
300°C
100°C
500°C
600°G
700°C
300°G
100°C
500°C
600°C 700°C
Sn
B
Pb
Cu
Co
Ni
Be
Or
V
Mo
Ge
1.1
62
77
21
7-9
39
2-5
21
12
12
16
< 1.2
90
61
20
-
39
2.5
19
45
13
16
< 1.2
101
61
21
8.5
36
2.6
19
36
9-3
20
< 1.2
119
65
21
8.9
39
2.6
20
10
10
17
< 1.2
106
61
22
8.1
35
2.6
20
35
7-6
21
< 2.0
23
13
17
15
11
2.1
16
37
26
9-3
< 2.0
31
19
18
19
17
2.5
17
32
19
7-5
< 2.0
31
16
17
17
^7
2.1
17
33
19
8.1
< 1.9
16
11
18
17
17
2.5
18
30
16
8.8
< 1-9
10
43
17
19
49
2.1
18
33
18
7-3
For both coals, the "boron concentrations increased with ashing at
temperatures from 300° to 600° C, and then decreased slightly between 600°
and 700° C. Williams and Vlamis (l96l) noted similar results when ashing
plant material, with added Ca(OH)2, in muffle furnaces, and when heating
Ca(OH)2 in the same furnaces in the absence of plant material. The increase
in boron concentration was greater for samples in uncovered crucibles or
dishes than for those in covered ones. Their explanation was that boron
vapor from the walls of the muffle furnace condensed in the alkaline material.
The concentration of boron increased with temperature and heating time.
To determine whether a similar change for boron takes place when
ashing coal (without addition of alkaline material), we ashed two different
coals in a Hoskins Electric Furnace, Type FD204A, in covered and uncovered
platinum crucibles at 300°, 400°, 500°, 600°, and TOO0 C for 20 hours each.
The results (table B) indicate that boron concentrations again showed an in-
creasing trend when the coal was ashed in uncovered crucibles. However, in
covered crucibles, the boron concentrations remain relatively constant until
an ashing temperature of TOO0 C is reached. It should also be noted that
the boron concentrations in the samples ashed in the covered crucibles are
higher, in most cases, than in the corresponding uncovered samples. Apparently
boron is lost from the samples in the uncovered crucibles more easily at
lower temperatures, suggesting competing reactions, a loss mechanism,
volatilization or retention on or in the crucible walls, and a reaction causing
recombination of boron with the bulk sample. The recombination reaction be-
comes more efficient than the loss mechanism at higher temperatures in the
uncovered crucibles. Loss of boron is prevented in the covered crucibles
-------
- 62 -
TABLE B—ASHING TEMPERATURE STUDY WITH PLATINUM CRUCIBLES AND COVERS*
Uncovered
Element
Sn
B
Cu
Co
rii
Be
Cr
V
Mo
Ge
Sn
B
Cu
Co
Ni
Be
Cr
V
Mo
Ge
300°C
< 1-9
30
16
15
39
2.6
19
32
11
5-1
7.1
W
16
5-2
12
5.1
23
1(4
7.2
14
400°C
4.2
32
14
15
38
2.5
17
24
7.8
5.1
7-0
53
17
1.9
12
5-5
22
36
6.2
16
500°C
2.1
41
15
13
36
2.6
15
19
5.1
5-7
6.8
64
18
4.8
13
5-1
22
33
5-3
14
600°C
< 1.6
15
17
14
37
2.5
17
18
5-5
5-3
7-1
61
29
1-5
11
5.3
20
28
4.2
16
700°C
0-17601
< 1.6
41
25
13
35
2.3
17
18
4.7
5-6
0-17215
8.0
70
33
4.4
11
5-6
20
28
4.0
18
300°C
< 2.4
39
15
14
39
2.8
15
31
11
3.4
8.4
78
22
6.4
12
6.6
23
48
9-8
18
Covered
400°C
2.9
38
15
14
37
2.5
16
24
8.4
5-9
7.0
65
17
5-0
12
5-5
21
37
6.4
14
500°C
3.6
42
15
14
37
2.5
17
21
6.2
5-5
6.7
77
17
5-3
13
6.0
21
34
6.4
17
6oo°c
2.5
43
18
13
36
2.5
17
18
5-6
5.6
5-9
72
20
4.7
11
5.3
21
27
4.7
15
700°C
2.6
52
28
13
35
2.6
18
17
4.0
5-5
7-3
93
34
4.6
10
5.6
22
26
3.7
16
* Same muffle furnace used throughout; concentrations - ppm; coal basis - moisture-free;
ashing time - 20 hr, throughout.
-------
- 63 -
when sufficient residence time is provided for the recombination reaction to
occur. A reason for the apparent increase in boron concentration in the covered
700° C ash samples is not known.
The analytical data for copper indicate that some contamination may
have resulted from the platinum crucibles, as seen from the similar concentration
trends for covered and uncovered crucibles. Vanadium and molybdenum data in-
dicated an apparent loss by volatilization during ashing as the temperature
increased.
These increasing and decreasing concentration trends do not appear
to be related to the spectrographic method used for analyses. Continuous time
vs. relative intensity curves were obtained for the iron internal standard line
and the boron, vanadium, and molybdenum analytical lines for sample C-17601
using the 300° and 700° C covered and uncovered ash samples. The resulting
curves for each spectral line were similar regardless of the sample used, and
in each case total line emission was attained within the 65 second exposure
time normally used.
Although no carbonaceous material is visible, some residual organic
material may remain in the coal ashed at 300° C. This may result in higher
concentrations for some elements (V, Pb, Mo, etc.) because of the volatility of
the organic species present. The observed differences in percent ash for LTA
(150° C) and HTA (500° C) (see table 3) indicate that samples are not completely
"ashed" at the lower temperature. (Approximately 1% carbonaceous material is
normally present in LTA.) The data for Pb (table A) may be explained on this
basis; however, results of the Mo and V determinations show a marked, continuous
decrease in concentration up to 700° C. This is attributed to increased
volatilization with increased temperature.
Evidence that the aforementioned losses of V and Pb may not be
significant from a practical standpoint is shown by the general agreement of re-
sults obtained by optical emission, X-ray fluorescence, and atomic absorption
for whole coal and low-temperature ash. The values for Mo are as yet uncon-
firmed .
The duration of the ashing period at 500° C in covered and uncovered
platinum crucibles (table C) shows no appreciable influence, with the exception,
previously noted, that there was the loss of boron from samples in uncovered
crucibles, which reached a relatively constant concentration prior to five hours.
Molybdenum and vanadium, which showed decreasing concentrations with increasing
temperature, do not exhibit any ashing time dependence.
It is recommended that ashing be conducted in covered platinum or
silica crucibles at 500° C if boron is among the elements to be determined.
Further data concerning the concentration of boron determined in whole coal,
when available, may require some changes in the coal ashing procedure used for
this element. Uncovered crucibles may be used for ashing the samples for the
other elements because small volatilization losses of vanadium and molybdenum
are not prevented by covering the crucible during ashing.
Table D contains a summary of trace element volatilization losses for
both high- and low-temperature ash. These results dictated the coal ashing
-------
TABLE C—ASHING TIME VS. TRACE ELEMENT CONCENTRATIONS (ppm)
c-17601*
Uncovered
Element
Sn
B
Cu
Co
Ni
Be
Cr
V
Mo
Ge
5 hr
1.8
39
16
13
36
2.4
17
20
6.2
5-0
10.5 hr
2.1
38
18
14
38
2.5
19
19
5-9
5-6
20.75 hr
< 1.6
35
16
14
37
2.8
19
21
6.0
5-5
5 hr
< 1-7
47
17
14
37
2.4
17
22
7-5
6.0
Covered
10.5 hr
< 1-7
42
16
14
37
2.5
17
21
6.5
6.3
20.75 hr
< 1-7
44
17
15
38
2.8
19
19
6.4
6.0
* 500° C HTA, covered and uncovered Ft crucibles, same muffle furnace.
TABLE D—VOLATILITY OF TRACE ELEMENTS IN COAL
Low-temperature ash
Retained (> 95$) Lost
Ga
Se
As
Zn
Ni
Co
Be
Cu
Pb**
V
Mn
Cr
Cd
Hg (up to 90$)
Br (100$)
Sb (up to 50$)
P (untested but
presumed lost)
High-temperature ash
Retained* Lost
Zn
Ni
Co
Cu
Pb**
B**
Cd
Mn
Cr
Be
Ge
Sn
Se
Mo**(33$)
V**( possibly up
to 25$)
(untested but
presumed retained)
* No significant losses observed in coal ash from 300° to 700° C or
between results from whole coal and low-temperature ash or high-
temperature ash (~450° C).
** See discussion on high-temperature ash (p. 60-63).
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- 65 -
method finally used for a particular trace element. Thus, determinations of
Sb, Br, Hg, and F are performed on whole coal; Ga, Se, and As are determined
in low-temperature coal ash; and the remaining elements may be determined in
the more readily prepared high-temperature coal ash.
METHODS OF ANALYSIS
During the initial 12 months of this investigation, at least
10 chemists devoted many months to the development and application of analytical
methods for the determination of trace, minor, and major elements in whole
coal and coal ash. Existing procedures for coal or ash analysis, with only
minor modifications, were found suitable for the analysis of many elements.
However, the analysis of some elements required major changes or new approaches.
Initially, accuracy and precision of analysis were emphasized rather
than spead. Where possible, results obtained from one method were critically
compared with those of another, and refinements were made where necessary.
The process was slow, and at the time of this writing, standards for the trace
element composition of coal are not yet available. Round-robin testing for
the standardization of multiple trace element concentrations in coal has been
completed jointly by the U.S. Environmental Protection Agency and the National
Bureau of Standards. The American Society for Testing and Materials, Committee
D-5 on Coal and Coke, also has a new program for the standardization of methods
for determining trace elements in coal. The Illinois State Geological Survey
has been active in both studies.
In this investigation, six independent instrumental methods were used
to analyze whole coal and coal ash. Considerable overlap occurs in the elements
determined by each method. As the investigation progressed, the procedures that
proved most precise, accurate, and convenient were used for routine analysis.
The analytical methods were developed by the following personnel in
the Survey's Analytical Chemistry Section: X-ray fluorescence (X-RF) by John
K. Kuhn, atomic absorption (AA) by Peter C. Lindahl, optical emission-direct
reading (OE-DR) by Gary B. Dreher, optical emission-photographic (OE-P) by
John A. Schleicher, neutron activation analysis (NAA) by Joyce Kennedy Frost,
Patricia M. Santoliquido, and R. R. Ruch, and ion-selective electrode (ISE) by
Josephus Thomas, Jr.
X-Ray Fluorescence Analysis of Whole Coal and Coal Ash
X-ray fluorescence determinations were made on whole coal for As, Br,
Pb, Zn, Cu, Ni, P, Cl, S, V, Mg, K, Ca, Fe, Ti, Al, Si, Mn, Co, and Cr and on
coal ash for Ni, P, V, Mg, K, Ca, Fe, Ti, Al, and Si. A Philips vacuum
spectrometer equipped with a Mark I solid-state electronic panel was used for
all analyses.
A chromium target X-ray tube was employed for the determination of
all elements except Co, Cr, and Mn; for these, a tungsten target X-ray tube was
used. Additional elements might also be determined by using equipment of more
advanced design than was available for this study. Goniometer and other
-------
- 66 -
TABLE E—X-RAY FLUORESCENCE SETTINGS FOR THE ANALYSIS OF COAL
AND COAL ASH
Pulse height
analyzer
Element
Si
Al
Ti
Fe
Ca
K
Mg
V
S
Cl
p
Ni
Cu
Zn
Pb
Br
As
Co
Or
Mn
X-ray
KL3
KL3
KL3
KL3
KL3
KL3
KL23
KL3
KL3
KL3
KL3
KL3
KLj
KL3
L3N5
KL3
KL3
KL3
KL3
KM23
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& KL2
& L2I%
& KL2
& KL2
& KL2
& KL2
20 angle
108
142
86
57
44
50
136
76
75
64
110
48
45
41
28
29
34
52
69
56
.01
.44
.12
• 51
.85
.32
.69
• 93
.24
.94
• 99
.66
.02
• 79
.24
• 97
.00
• 79
.35
.64
Background 20
111
145
89
60
47
53
139
80
78
67
113
50
49
44
31
35
37
55
72
59
.01
• 95
.12
• 51
• 95
.90
.69
• 93
.38
.94
• 99
.36
.67
.25
.24
.12
.00
• 79
.35
.64
Crystal
EDDT
EDDT
LiF
LiF
EDDT
EDDT
ADP
LiF
EDDT
EDDT
Ge
LiF
LiF
LiF
LiF
LiF
LiF
LiF
LiF
LiF
Vacuum
yes
yes
no
no
yes
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
Base
7
5
5
5
14
14
4
5
12
11
9
10
11
10
22
25
24
8
6
8
Window
17
12
18
25
30
21
8
16
18
19
15
27
28
22
28
23
23
40
28
25
instrument settings used for the analyses are listed in table E. The sample
preparation procedure follows.
Low- and High-Temperature Coal Ashes
Coal ash is composed entirely of inorganic mineral matter; whole coal
is composed primarily of organic compounds containing carbon, hydrogen, oxygen,
nitrogen, and sulfur, with only minor amounts of mineral matter. Because of the
large and variable percentages of relatively heavy elements in both low- and
high-temperature coal ashes, matrix-related problems are troublesome and, for
the determination of major and minor elements, can best be overcome by use of
a dilution technique such as that described by Rose, Adler, and Flanagan (1962)
and used extensively for geological samples. For this procedure, low-temperature
ash is dried in a vacuum oven, and high-temperature ash is dried at 105° C in
air. Ashes must be stored in a desiccator because many absorb relatively large
quantities of water in a few minutes. From the dried sample, 125 mg is weighed
into a graphite crucible containing 1.0000 g of lithium tetraborate. The sample
is placed in a depression made in the tetraborate, thereby preventing sample
contact with the crucible wall. Next, 125 mg of lanthanum oxide is added as a
heavy-element X-ray absorber, and the contents of the crucible are mixed with
a glass rod as thoroughly as possible without scraping the crucible wall or
bottom. This mixture is fused in a furnace for 15 minutes at 1000° C, removed,
-------
- 67 -
covered with a second crucible, and allowed to cool to room temperature. The
resulting fused pellet is then weighed to determine fusion loss and placed in
the grinding vial of a No. 6 "Wig-L-Bug" grinder with 2 percent by weight of
Somar mix (a commercial mixture used as a grinding and plasticizing agent).
The sample is ground for 3 minutes, transferred to a 1 1/8-inch die, and
pressed at Uo,000 psi. Samples are placed in the spectrometer and exposed to
the X-rays, and the various elements are determined in the usual fashion.
When "backed with an appropriate material, the pressed disk is at least semi-
permanent .
For calibration, each sample is compared to a group of analyzed
standards with a range of major and minor element concentrations similar to
the ranges of the unknown coal ash samples. The U.S. Geological Survey standard
silicate rock samples are convenient for this purpose.
Whole Coal
Coal is a heterogeneous mixture of organic compounds composed of
relatively light elements (H, C,N, 0, S). Of the inorganic constituents,
pyrite (iron and sulfur) exhibits considerable variation, rarely falling short
of 0.2 percent or exceeding 5-0 percent of bituminous and higher rank coals.
Concentration ranges of other major elements are less. Consequently, absorption
and enhancement effects are minimal, and the absorption characteristics of the
sample matrix are relatively constant. Effects due to matrix variations are
generally small and corrections for them are easily made.
To prepare the whole coal disk for X-ray fluorescence analysis,
2.0000 g of air-dried coal is placed in the grinding vial of a No. 6 "Wig-L-Bug"
grinder along with 10 percent by weight of Somar mix. The mixture is ground
for 3 minutes, transferred to a die and, with a suitable backing, pressed into
a disk at a pressure of ^0,000 psi. The disk is dried in vacuum to prevent
losses that could occur at higher temperatures in a drying oven. Determinations
of all major, minor, and trace elements except iron, titanium, and vanadium are
performed in vacuum to avoid X-ray scattering due to adsorption of water on the
surface of the whole coal disk.
Standards are prepared from analyzed coals by the same procedure, and
all determinations are made in order of descending potential volatility. Some
absorption-enhancement effects, primarily from iron, do occur and must be dealt
with individually for each trace element affected. One method for making such
corrections is to observe the effect of adding different amounts of iron to a
coal of known composition on the count rate for each element and to make appro-
priate adjustments.
The concentration of an element in a sample of unknown composition is
calculated by using a concentration/count "factor," which is the ratio of the
concentration of the element in chemically analyzed standards to the background-
corrected count rate for a given element (see table E for 29 angular settings).
This ratio is defined by the slope of the calibration curve obtained from a plot
of the count rate for each element in the standards vs. the element's respective
concentration. The concentration of any element in a sample being analyzed is
the product of its "factor" multiplied by the count rate.
-------
- 68 -
Effect of Whole Coal Particle Size on Precision
A set of nine whole coal samples was analyzed by X-ray fluorescence
to determine the effect of particle size upon the precision of measurement.
Representative portions of each coal were sequentially ground to pass through
60, 100, 200, 325, and UOO mesh sieves. Duplicate 2-gram samples from each
mesh size were weighed and further reduced in size by grinding for 3 minutes
in a No. 6 Wig-L-Bug. The final grinding eliminated, as nearly as possible,
any size segregation in the pressed coal disks. The disks were subsequently
prepared for analysis as previously described.
Table F shows the differences in concentrations, expressed in per-
centage or parts ptr million, between duplicate coal samples. Progressive
reduction of coal particle size from -60 to -kOO mesh resulted in better
agreement between duplicate coal samples for all trace elements determined
except Br. Most notable improvements observed were for Ni, Cu, Zn, and Pb.
In all cases, the mean of the relative differences between duplicate deter-
minations was reduced below 5 percent for coal ground to pass -200 mesh size.
The data given in table G demonstrate that for most purposes accept-
able precision can be obtained on -200 mesh coal, but not on -60 mesh coal.
Further improvement in precision may be obtained by grinding coal samples to
pass a -325 mesh screen, but such a high degree of precision is not generally
necessary except for special purpose analyses, e.g., for making standard
samples. Variation in the initial coal sampling procedure would probably
negate any small improvement in precision which might result from further
grinding.
These conclusions are based on nine coal samples and hundreds of
individual analyses and therefore represent a reasonably good statistical base.
While the accuracy of X-ray fluorescence methods for the analysis of
whole coal may suffer somewhat from lack of good standards, the precision is
at least as good as in other methods used in this study. Consequently, it is
felt that the conclusions reached are valid for any method using a 1- or 2-gram
sample for analysis.
Comparative Analyses
Table H compares the mean values for coal ash analyses made by X-ray
fluorescence at the Survey with those made by the British Coal Utilization
Research Association (Dixon et al., 196U). The latter samples were analyzed
in many laboratories by a variety of wet chemical and instrumental methods.
Results show the X-ray method to be accurate for the oxides listed. Additional
comparisons given for 25 coals (Ruch, Gluskoter, and Shimp, 1973) show that
whole coal X-ray fluorescence determinations of As, Br, V, Cu, Ni, Zn, and Pb
are in good agreement with results of coal ash analyses obtained by the other
independent methods used in that study. Further, results of X-ray fluorescence
analyses of whole coal for Si, Al, Ca, Mg, Fe, K, Ti, and P compare favorably
with fluorescent analyses of coal ash prepared from the same coals when results
are converted to a whole coal basis from the percentage of ash in the coal.
-------
- 69 -
TABLE F—DIFFERENCES BETWEEN DUPLICATE ANALYSES
OF WHOLE COAL SIZE FRACTIONS
Element
Fe
V
Ti
Al
Si
K
Ca
S
Cl
P
Mg
Ni
Gu
Zn
Pb
As
Br
-60 mesh -100 mesh
0.03 0.01
1.3 2.9
0.01 0.01
0.03 0.08
0.07 o.oi
0.004 0.003
0.015 0.017
0.02 0.02
0.001 0.003
1.3 1.6
0.012 0.012
1.9 1.7
4.8 0.8
8.5 i.o
2.8 1.9
3.0 1.4
0.8 0.4
-200 mesh
0.00
1-7
0.02
0.03
0.05
0.005
0.023
0.02
0.002
2.1
0.010
3.2
0.2
0.5
2.0
1.9
0.5
TABLE G— RANGE OF RELATIVE
DUPLICATE ANALYSES
AT THREE COAL MESH
Element -60 mesh
V 0.0 - 10.
P 2.0 - 18.
Ni 1.5 - 25.
Cu 0.8 - 20.
Zn 1.2-25.
Pb 0.4 - 23.
As 0.1 - 6.
Br 0.0 - 4.
0 0
0 2
0 0
0 0
0 1
0 1
0 0
0 0
-325 mesh
0.01
2.4
0.02
0.02
0.01
0.002
0.018
0.01
0.004
1.3
0.011
2.9
0.1
1.3
0.4
0.0
0.4
Extra-
fine
-400 mesh mesh
0.01 0.00
0.6 0.4
0.01 0.01
0.04 0.01
0.02 0.03
0.002 0.001
0.005 0.004
0.00 0.02
0.001 0.003
1.0 1.0
0.005 0-005
0.9 0.8
0.1 0.1
0.2 0.2
0.8 0.9
0.3 0.6
0,3 0.2
Concen-
tration
unit
%
ppm
%
%
%
%
%
%
%
ppm
%
ppm
ppm
ppm
ppm
ppm
ppm
DIFFERENCES (%} BETWEEN
FOR EACH TRACE ELEMENT
SIZES
-200 mesh
.3 - 5-0
.0 - 10.0
.0 - 20.0
.2 - 1.0
.2 - 12.0
-2 - 9-5
.1 - 4.0
.0 - 3.5
-325 mesh
0.3 - ^.0
1-5 - 7-5
1.5 - 8.0
0.2 - 1.0
0.1 - 6.5
0.4 - 5.0
0.0 - 1.5
0.0 - 3.0
-------
- TO -
TABLE H—COMPARISON OF ISGS X-RAY FLUORESCENCE ANALYSES OF COAL ASH
WITH BCURA* ANALYSES (in percent)
Oxide
Si02
Ti02
A1203
Fe203
MgO
CaO
K20
P2°5
BCURA
X-RF
53.28
1.65
34.11
5-83
0.66
0-73
2.45
0.48
No. 4
Reported*
53.41
1.70
33.88
5-76
0.71
0.77
2.38
0.41
BCURA
X-RF
29.27
0.65
19-73
39-02
1.18
2.47
1.94
0.14
No. 5
Reported*
29.43
0.70
19.82
39-24
1.29
2.54
1.95
0.14
BCURA No. 7
X-RF
20.01
0.26
10.03
62.16
0.58
2.31
1.38
0.17
Reported*
20.37
0.34
10-33
62.31
0.63
2.30
1-39
0.15
BCURA No. 10
X-RF
44.03
1.18
29.93
13.56
2.05
1.24
3.68
0-77
Reported*
44.49
1.19
30.02
13.82
2.00
1.29
3.71
0.77
BCURA
X-RF
51-45
0.96
28.20
6.27
2.33
7.89
?.84
0.09
Slag
Reported*
51.58
0.96
28.45
5-99
2.26
7.91
2.81
0.05
Ave .
diff.
0.25
0.04
0.19
0.17
0.06
0.04
0.03
0.03
* British Coal Utilization Research Association (Dixon et al., 1964).
Because analyses performed by the optical emission and atomic a.bsorp-
tion methods used in this study are made on high- and low-temperature ashes,
small variations from the results obtained on whole coal samples by X-ray
fluorescence are to be expected. For Zn and As, variations are larger at high
concentrations. At least some of this variation is due to differences in sample
particle size and the occurrence of discrete mineral particles in whole coal.
Precision
Relative standard deviation (l a) for X-ray fluorescence analyses of
whole coal in this study are as follows: Si - 0.35 percent, Ti - 1.9 percent,
Al - 0.9 percent, Fe - 1.2 percent, Mg - 3.3 percent, Ca - 0.1 percent,
K - O.T percent, P - 1.6 percent, V - 1.3 percent, S - 0.5 percent, Cl - h.2
percent, Ni - 8.U percent, Cu - h.O percent, Zn - 3.8 percent, Pb - 1.9 percent,
As - 1.8 percent, and Br - 2.0-percent.
Optical Emission Spectrometric Analysis
of High-Temperature Coal Ash
Trace quantities of 11 elements in high-temperature coal ash samples
containing 10 to 30 percent Fe as FeaOs were determined simultaneously arid rap-
idly with a Jarrell-Ash Model 750 direct-reading emission spectrometer, vising Fe
(2483.27 K) as a variable internal standard. As little as 20 mg of coal ash
sample sufficed for quadruplicate analyses. The elements determined by this
method in this study are B, Pb, Cu, Co, Ni, Be, Cr, V, Sn, Mo, and Ge.
Construction of Calibration Curves
Eight standard samples were prepared by adding various amounts of a
synthetic standard (1000 ppm of each of the elements to be determined) to U.S.
Geological Survey standard granite G-2 (adjusted to a SiOarAlaOa ratio of 3:1
by addition of 379 mg of spectroscopically pure A1203 to 0.50000 g of G-2).
-------
- 71 -
TABLE I—CONCENTRATIONS IN STANDARD MATERIALS OF G-2 BASE IN 3:1 Si02-Al203
MATRIX + 1000 ppm SYNTHETIC STANDARD FOR SPECTROMETRIC METHOD
Element
B
Pb
Cu
Co
Ni
Be
Cr
V
Sn
Mo
Ge
Weight
0.00
l
.00
of synthetic
G-2
4.
04
9-
standard
+ 379 m
19
19-
( mg ) added
& A1203
79
Parts
1.86
26.7
9-95
4.55
5-95
2.23
8.37
34.4
0.93
1.12
0.66
2
28
11
6
7
4
10
36
2
2
2
.84
• 5
.8
.40
• 79
.08
.2
.2
•78
• 97
• 51
5-
33.
17-
12.
13.
9-
15.
41.
8.
8.
8.
78
9
3
0
4
67
8
6
37
57
11
10.
43.
26.
21.
22.
19-
25-
50.
17-
17-
17-
7
0
6
3
6
0
0
6
7
9
5
20.
61.
45.
39-
41.
37-
43.
68.
36.
36.
36.
5
2
1
9
2
6
6
7
4
6
1
54.45
Weight of
to 0.5 g Na2Bij.OY.10H20
(mg)
133.22 535-89 6.32
per million
50.2
116
101
96.0
97-3
94.0
99-5
123
92.8
92.9
92.5
106 264 1320
220 512
206 504
202 501
203 502
200 500
205 503
226 516
199 500
199 500
199 ^99
The preparation and resulting concentrations are summarized in Table I. A
ninth standard sample composed of 0.50000 g of G-2, 379 mg of A1203, and
6.32 mg of Na2Bit07-10H20 was later prepared to increase the range of the
"boron calibration curve to 1320 ppm.
The final mixtures for all standard and coal ash samples include
40 mg of standard or coal ash, 10 mg of spectroscopically pure Ba(N03)2, and
150 mg of SP-2X graphite powder. They are combined by mixing in a plastic
vial half an inch in diameter by 1 inch high that contains two plastic balls
an eighth of an inch in diameter. One mixture is prepared for each of the
nine standards. The small amount of Ba(N03)2 is added to improve the arcing
characteristics and the reproducibility of results from replicate analyses.
Higher amounts of Ba(NOa)2 (up to 120 mg in 200 mg total mixture, 40 mg of
sample) decreased reproducibility.
The effect of varying concentrations of Fe203 in the standards was
investigated; relative intensities of analytical lines were not found to be
dependent upon the iron concentration, except in the cases of weak spectral
interference.
Internal Standardization
Because an iron line was used as the variable internal standard, the
concentration of iron in each coal ash sample was determined by X-ray fluorescence
analysis of the whole coal. A response curve for the Fe 2483.27 1 internal
-------
- 72 -
standard line was drawn. Six coal ash samples with known different
concentrations were arced under identical conditions, and the relative
intensity values of the Fe internal standard line were plotted versus
concentration on log-log graph paper. The standardized relative intensity
shown on this response curve for Fe 2483 A" was used to preset the spectrometer
for each sample arced.
Standard Conditions
The sample electrode (anode) is a thin-walled crater electrode with
an outside diameter of one-eighth of an inch and a crater one-fourth of an
inch deep (National L-3979 or equivalent). The cathode is a pointed counter
electrode one-eighth of an inch in diameter (National L-4036 or equivalent).
The analytical gap of 6 mm is surrounded by a 10 SCFH flow of gas composed of
80 percent argon and 20 percent oxygen. A short-circuit current of 15 amperes
DC is maintained for 65 seconds while arcing a sample charge of 15 mg. The
proportions in the sample mixture are 4:1:15 [sample:Ba(N03)2: graphite powder]
for standard and coal ash samples.
The wavelengths of the analytical lines used are listed in table J.
TABLE J—ANALYTICAL WAVELENGTHS AND RELATIVE STANDARD DEVIATIONS
FOR THE DETERMINATION OF TRACE ELEMENTS IN HIGH-TEMPERATURE
COAL ASH BY DIRECT READING SPECTROMETRY
Analytical Average relative Range of relative
Element wavelength (A) standard deviation (%] standard deviation (%)
B
Pb
Cu
Co
Ni
Be
Cr
V
Sn
Mo
Ge
2496.8 (second order)
2833.07
3273.96
3453.50
3414.76
2348.61
4254.35
3185.40
3034.12
3170.35
2651.18
5-2
8.6
7-5
4.8
4-7
3.6
4.0
6.6
22
6.3
16
1.0
3.8
2.9
1.1
2.4
1.2
1.0
2.8
10
2.6
3-0
- 13
- 14
- 20
- 19
- 11.2
- 8.6
- 9-1
- 11
- 73
- 22
- 42
-------
- 73 -
Comparative Analyses
Results for V, Be, Cu, Hi, Pb, Ge, Cr, B, and Co, calculated to a
whole coal basis, have been shown by Ruch, Gluskoter, and Shimp (19T3) to be
in good agreement with those obtained by atomic absorption spectrometry (LTA),
X-ray fluorescence spectrometry (whole coal), photographic optical emission
spectroscopy (HTA), and neutron activation (NAA).
Table J lists the average relative standard deviations and their
ranges for each element. Most of the coal ash samples contain Sn in concen-
trations less than the detection limit, making the precision values for Sn
meaningless. Because the analytical line for Ge is weak, a small change in
the number of Ge atoms emitting at that wavelength in the arc during the arcing
period produces a relatively large change in line intensity.
Optical Emission Spectrographic Analysis
of High-Temperature Coal Ash
Samples of coal ash ignited to 500° C were analyzed by the photographic
method of emission spectrography with a Jarrell-Ash 3.H m Ebert grating spectro-
graph. The elements so determined are: B, Mn, Cr, Ge, Pb, Be, Mo, V, Cu, Zn,
Zr, Co, and Ni. Analyses of Ag and Bi were attempted, but their concentrations
were below the respective detection limits.
Construction of Calibration Curves
Because of the high concentrations of many trace elements in coal ash
and the inability of the photographic plate to record accurately the large amount
of light emitted, a 6 percent neutral density filter is inserted in the light
path of the spectrograph to attenuate the emitted light. Synthetic standards
containing 1, 10, 50, 100, 250, 500, and 1000 ppm of the elements to be deter-
mined are prepared (from commercially available mixtures) in a base matrix
having a 3:1 silica-to-alumina ratio. To these standards is added 10 percent
Fe203 , so that the final concentration of elements to be determined is 0.9, 9,
45, 90, 225, 1*50, and 910 ppm.
The first two standards are generally too low in concentration to be
measured; consequently, 10 mg of the higher concentration standards are mixed
in replicate with 10 mg of graphite and arced to completion plus 10 seconds
(about 150 seconds). The transmissions of the attenuated lines, as recorded on
an 8 by 10 inch Eastman Spectrum Analysis No. 1 photographic plate, are measured
on a densitometer-comparator, and the values are converted to their Seidel
transformed values.
Seidel values are plotted against concentration on semi-log paper and
the resultant curves transferred to a calculating board. After attenuation
of light from the arc, background on the photographic plate is barely dense
enough to overcome emulsion inertia; therefore no corrections are made.
-------
Standard Conditions
The sample electrode (anode) used is graphite; the counterelectrode
is one-eighth-inch tapered graphite rods rounded to a radius of one-thirty-second
of an inch at the tip. Current used is 11 amperes true at 220 volts. The
electrode spacing is k mm, and the analytical gap is surrounded by a 14- SCFH
laminar flow of 80 percent argon and 20 percent oxygen. Photographic plates
are developed in Eastman D-19 developer for 3.0 minutes, shortstopped in
11 percent acetic acid for 30 seconds, and fixed for h minutes in Eastman Fixer.
Plates are then washed in running tap water for 20 minutes, rinsed in deionized
water, and dried. Wavelengths of analytical lines used are given in table K.
TABLE K—ANALYTICAL WAVELENGTHS AND RELATIVE STANDARD
DEVIATIONS FOR THE DETERMINATION OF TRACE
ELEMENTS IN HIGH-TEMPERATURE COAL ASH
BY PHOTOGRAPHIC OPTICAL EMISSION
Element
B
Mn
Or
Ge
Pb
Bi
Be
Mo
V
Cu
Ag
Zn
Zr
Co
Ni
Analytical
wavelength (A)
24-97.7
2576.1
2677.2
2651.2
2833.1
3067.7
3130.4-
3170.4
3184-.0
324-7-5
3280.7
334-5-0
3392.0
3405.1
34-14-. 8
Relative
standard
deviation (%}
12
19
23
16
9
--
14-
22
30
18
--
--
37
25
24-
In a number of coal ash samples an extremely faint Ag line was observed,
but the amount present was too small to be accurately measured. In addition,
many ashes contained high Zn concentrations outside the analysis limitations of
this photographic method.
-------
- 75 -
Comparative Analyses
Although the precision values (table K) indicate a relatively high
error for the method, averages of replications for V, Be, Cu, Ni, Pt>, Ge, Cr,
Co, and Zn show generally good agreement with other methods of analysis when
all values are calculated to the whole coal basis (Ruch, Gluskoter, and Shimp,
1973). This agreement is particularly true for concentrations in the lower
ranges—25 ppm or less. However, at or near 100 ppm, agreement with other
methods is poor.
Atomic Absorption Analysis of Coal Ash
An atomic absorption method for the determination of Cd, Cu, Ni, Pb,
and Zn in ash from coal and coal float-sink fractions has been extensively
investigated. Both the low- and high-temperature coal ash and the low-temperature
ash from coal float-sink fractions can be readily analyzed by atomic absorption
spectrophotometry when an acid digestion bomb is used for sample treatment.
The digestion bomb technique for the decomposition of silicates
(Bernas, 1968; Langmuhr and Paus, 1968) and aluminosilicates (Buckley and
Cranston, 1971) was modified and found applicable to the decomposition of ashed
samples of coal and coal float-sink fractions.
Atomic absorption measurements were made using a Beckman Model 1301
Atomic Absorption Accessory with a Beckman DB-G Grating Spectrophotometer.
Measurements were recorded on a Beckman Model 1005 Linear-Log Ten-Inch
Potentiometric Recorder, which was coupled with a Beckman 73^90 Scale Expander.
A Beckman 100^10 Autolam Burner was used with an air-acetylene flame. Standard
single-element hollow cathode lamps were used. Corrections for background
absorption were made using a non-absorbing spectral line from either a
hydrogen-continuum source or a hollow-cathode lamp.
Reagents and Construction of Calibration Curves
All reagents used are ACS certified reagent grade chemicals, and
standard stock solutions are prepared from high-purity metals. A standard
stock solution of each element—Cd, Cu, Ni, Pb, and Zn—is prepared to give a
metal ion concentration of 100 ppm. Calibration standards prepared from
diluted stock solutions containing 1.4 percent aqua regia, 1 percent HF, and
1 percent HaPOs are made up so that the standards match the sample solutions
obtained in the decomposition method.
Sample Decomposition Procedure
The decomposition of the low-temperature ash of coal, the float-sink
fractions of coal, and the high-temperature coal ash is carried out in a Parr
^7^5 acid digestion bomb.
Approximately 0.1 g of the ashed coal material—previously ground
in an agate or mullite mortar and dried at 110° C for several hours—is
transferred to the Teflon cup of the decomposition vessel. The low-temperature
-------
- 76 -
ash sample is treated with 1.0 ml of concentrated HC1 and then heated to
dryness on a steam table. The HC1 treatment is omitted for high-temperature
ash samples. Both types of samples are then wetted with 0.7 ml of aqua regia
(1:3:1 HN03-HC1-H20), 0.5 ml of HF is added, and the acid digestion 'bomb is
closed. The "bomb is heated at 100° to 110° C for 2 hours. After it cools to
ambient temperature, the bomb is disassembled and the decomposed sample treated
with 10 ml of a HaBOa solution (0.05 g per ml) to complex the fluorine. The
dissolved sample is transferred to a 50 ml Pyrex volumetric flask, diluted to
volume with deionized water, and placed in a polyethylene bottle for storage.
Atomic Absorption Spectrophotometric Procedure
The following analytical wavelengths are used: 228.8 nm (Cd),
32^.7 nm (Cu), 232.0 nm (Ni), 283-3 nm (Pb), and 213.9 nm (Zn). Samples
analyzed for Cd, Ni, Pb, and Zn are reaspirated at a nearby nonabsorbing
hollow-cathode lamp spectral line or at the analytical line using a hydrogen
continuum source for background correction. Cation standards are prepared
with the following indicated ranges: 0.1 to 1.0 ppm for Cu, Ni, and Zn;
0.1 to 5-0 ppm for Pb; and 0.01 to 0.5 ppm for Cd. In determinations of all
elements except Zn, the sample being analyzed requires no further dilution;
for Zn an additional dilution might be necessary. Metal ion concentrations
in the samples are calculated by interpolation from a calibration curve of
absorbance vs. concentration. A new calibration curve is constructed for each
set of analyses.
Comparative Analyses
Results obtained by atomic absorption spectrophotometry for Cd, Cu,
Pb, and Ni concentrations, expressed on the whole coal basis, agree well with
results obtained by the other analytical methods used in this study; and atomic
absorption results for low- and high-temperature ashes prepared from the same
coal sample also compared well when expressed on the whole coal basis (Ruch,
Gluskoter, and Shimp, 1973). These favorable comparisons indicate that these
trace elements are not volatilized when coal is ashed at ^50° to 500° C.
The determination of Zn in the coals and coal ashes studied presented
a unique sampling problem. In a few samples, marked variations in Zn results
were observed. The Zn content of these coals is attributed primarily to the
presence of discrete particles of sphalerite (ZnS), which contributes to the
inhomogeneity of a coal sample and thus can result in significant variations
in Zn concentrations. The degree of coal grinding required to achieve
representative samples is being studied further. Decreasing the particle size
prior to the reduction in sample quantity should improve agreement among the
various methods of analysis.
Estimates of the average relative standard deviation for elements
determined by atomic absorption spectrophotometry are 10 percent or better.
-------
- 77 -
Neutron Activation
Radiochemical separations performed on low-temperature coal ash are
used for the determination of Se, As, Ga, Zn, and Cd. Whole coal is used for
the determination of Hg, Sb, and Br, which are totally or partially volatilized
during low-temperature coal oxidation. Manganese and Na are determined by
instrumental neutron activation analysis. Float-sink fractions of the coal
samples are processed in the same manner as coal samples.
All irradiations are made in the University of Illinois Advanced
TRIGA reactor, utilizing a thermal neutron flux of 1.1* x 1012 neutrons cm~2
sec" . During irradiation the samples and standards are rotated at 1 rpm to
insure equal neutron flux.
The containers used for the samples and standards in the irradiations
are two-fifths-dram polyethylene snap-cap vials previously cleaned with deionized
water and acetone.
The y-ray counting system consisted of a 3 inch by 3 inch Nal(Tl)
detector connected to a Nuclear-Chicago UOO-channel analyzer.
Chemical yields are obtained for each sample to determine losses
during radiochemical separations.
Determination of Se in Low-Temperature Coal Ash
Each sample (about 200 mg) of low-temperature coal ash is accurately
weighed into a polyethylene vial. The samples and a sealed polyethylene vial
containing a comparative standard of 1 mg Se per ml solution (prepared by
dissolving spectrograde Se metal in HNOa and HCl) are irradiated for 2 or 3
hours, and then allowed to decay for 3 days.
Each sample is quantitatively transferred to a 100-cc round-bottomed
distillation flask, and then 20 ml of concentrated HCl, 5 ml of concentrated
HNOs, 5 nil of concentrated HClOit, and 3 ml of Se carrier (containing 10 mg Se
per ml) are added. This mixture is refluxed overnight.
The mixture is distilled to a volume of about 10 ml in an air stream,
and the distillate collected in 2 ml of distilled water in a flask in an ice
bath. Ten ml of concentrated HCl and 12 ml of concentrated HBr are added to
the distilling flask and distilled. Second portions of HCl and HBr are added
and the distillation is repeated. To the combined distillate, 7 ml of 6 percent
sulfurous acid (HaSOs) is added to precipitate red amorphous Se, which is
allowed to settle.
The supernatant liquid is decanted through a Teflon-coated filtering
apparatus containing a weighed filter paper. Hot water is added to the Se in
the beaker to convert it to gray metallic Se, which is filtered, washed with
more hot water and acetone, air-dried for 2 hours, weighed, and then mounted
on cardboard.
-------
- 78 -
The Se comparative standard is diluted 1:100 with water, and 1 ml
(10 yg of Se) is transferred to a flask containing 3 ml of Se carrier. The
standard is distilled and precipitated in the same manner as the samples.
Radiochemical yields of the samples and standard are quantitative.
Samples and standard are counted for the activity of the 0.121 and
0.136 MeV gamma rays of 75Se, which has a half life of 120 days. These two
gamma rays give a single photopeak with the 3 inch by 3 inch Nal(Tl) detector
and 400-channel analyzer.
The Se concentration of the low-temperature coal ash samples is
calculated and, by using the percentage of low-temperature ash in the coal,
converted to ppm of Se in whole coal. The relative standard deviation of a
measurement is normally "better than 10 percent. Analysis of the National
Bureau of Standards (NBS) SRM-1630 for Se gave the result 2.0 ± 0.13 ppm,
which compares favorably with the provisional value of 2.1 ppm established
by the NBS.
Determination of As in Low-Temperature Ash
Each sample (about 200 mg) of low-temperature coal ash is accurately
weighed into a two-fifths-dram polyethylene vial. The samples and a sealed
polyethylene vial containing a comparative standard of 10 mg As per ml
(prepared by dissolving sodium arsenite [NaAsO;>] in water and HgOa) are
irradiated for 2 hours and allowed to decay overnight.
Each sample is quantitatively transferred to a 100-cc round-bottomed
distillation flask; and 20 ml of concentrated HC1, 5 ml of concentrated HN03,
5 ml of concentrated HClOit, and 3 ml of As carrier solution (10 mg As per ml)
are added. The mixture is refluxed overnight and distilled to a 10-ml volume
in an air stream; the distillate is collected in 30 ml of distilled water. Ten
ml of concentrated HC1 and 12 ml of concentrated HBr are added to the distil-
lation flask, and this mixture is distilled. Second portions of HC1 and HBr
are added, and the distillation is repeated. Five g of sodium hypophosphite
(NaH2P02-HaO) are added to the combined distillate, and the mixture is heated
to just below the boiling point for 2 to 3 hours until the solution clears and
the black As metal precipitate is completely digested. The As precipitate is
suction-filtered onto a weighed filter paper, washed with distilled water and
acetone, air-dried, weighed, and mounted on cardboard.
The As standard is diluted 1:250 with dilute HC1 and a 1-ml aliquot
(ko g of As) is transferred to a flask containing 3 ml of As carrier. The
standard is distilled and precipitated in the same manner as the samples.
Radiochemical yields of the sample and standard are quantitative.
The samples and standard are counted for the activity of the 0.559 MeV
y-ray photopeak of 26.5 hr 76As.
The As concentration of the low-temperature coal ash samples is cal-
culated and converted to ppm As in whole coal from the percentage of low-
temperature ash in the coal. The maximum relative standard deviation of a
measurement is 12 percent.
-------
- 79 -
Radiochemical Separation and Determination of As in Coal
with an Inorganic Exchanger (Acid Aluminum Oxide)
A carrier-free separation of arsenic "by retention on acid aluminum
oxide (AAO) ion exchange columns is a second neutron activation method developed
for the analysis of coal ash.
One hundred mg of an irradiated low-temperature ash sample, using
the same sample preparation and irradiation procedure as previously described
for As, is fused with 2 g NaOH. The melt is dissolved in 10 ml of distilled
water, and 14 ml of concentrated HNOa is added. The resultant solution, which
is ~7M HNOa, is passed through a chromatographic column (7 mm by 40 mm) filled
with acid aluminum oxide (1.6 g) and then the column is rinsed with 10 ml of
7M HN03. Arsenic-76 retained on the column is counted. The standard solution
(17 US As in 0.5 ml) is taken up in 25 ml of 7M HN03, passed through and re-
tained on an acid aluminum oxide column, and then counted. The loading capacity
of the exchanger is 1*3.5 yg As/g AAO.
Results of triplicate As determinations for the two neutron activation
methods are in excellent agreement (table L).
TABLE L—COMPARISON OF MEAN ARSENIC VALUES OBTAINED BY
INORGANIC EXCHANGER AND DISTILLATION TECHNIQUES
0 -Number
0-14970
0-15384
C -162 64
0-16317
0-14796
0-15566
Illinois
Coal Member
No.
No.
No.
No.
No.
No.
6
5
5
6
5
2
As (ppm) ± o~
AAO column
1.9 ±
7-5 ±
9-5 ±
24.4 ±
29 ±
89 ±
0.3
0.4
0.4
0.7
5
1
As (ppm)
distillation
2
7
9
24
28
93
.1
.4
.6
This method of As analysis is much faster than the distillation method
and provided a check for previous As results. An excellent separation of As from
Sb is obtained by this procedure.
Determination of Ga in Low-Temperature Coal Ash
Oven-dried LTA samples (100 mg) are weighed into two-fifths-dram snap-cap
polyethylene vials, heat-sealed, and irradiated for 2 hours along with standard
solutions prepared from pure Ga metal.
Ga (5 mg) and Zn (30 mg) carriers are added to each irradiated ash
sample, which is then fused with NaOH in a nickel crucible. (A tracer study
showed that no Ga is lost during fusion.) After the fusion melt is dissolved
in 25 to 50 ml of water and a mixed sulfide precipitate has formed, the solution
is filtered and adjusted to pH 8 with HC1, at which point Ga is coprecipitated
-------
- 80 -
with the Zn(OH)2' The hydroxide precipitate is then filtered and dissolved
in 8M HCL (15 ml), and the Ga is extracted from the resulting solution with
isopropyl ether (15 ml). Gallium is then back-extracted from the organic
fraction with 15 ml of water; extraction and back-extraction are repeated
and the combined water extracts are counted. Some 76As follows the Ga, but
there is no interference with the 0.832 MeV photopeak of lU-hr 72Ga. Radio-
chemical yields are determined by re-irradiation; they are within the h6 to
7^ percent range.
The possibility that 72Ga might be produced during irradiation by
a (n,p) reaction with 72Ge, as well as by the (n,y) reaction with 71Ga, was
investigated. Two milligrams of pure Ge metal was irradiated along with
samples of coal ash in a regular run and subsequently counted. Wo radio-
chemical separation is needed for the Ge metal, as there is no spectral
interference between Ge and Ga. Less than 0.02 yg of "apparent" Ga was
produced in Ge metal. Therefore, for every part of Ge in coal ash, the
contribution to 72Ga is less than 10"5.
The average relative standard deviation of the technique is about
8 percent for replicate samples.
Determination of Zn and Cd in Low-Temperature Coal Ash
Oven-dried LTA samples (100 mg) are weighed into two-fifths-dram
snap-cap polyethylene vials, heat-sealed, and irradiated for 2 hours along with
standard solutions prepared from pure Zn metal and pure Cd metal.
Ten mg of Zn and U mg of Cd carriers are added to the irradiated ash
sample, and are fused with NaOH (2 g) in a nickel crucible. (A tracer study
showed that no Zn or Cd is lost during fusion.) The fusion melt is dissolved
in 50 ml of distilled water, and 25 ml of 8M HC1 is added so that the resulting
solution is 2M in HC1. The solution is then loaded onto a Dowex 1 by 8
(100 to 200 mesh) anion exchange column (6 g resin) that has been pre-equilibrated
with 2M HC1 (30 ml). After the column is rinsed with 2M HC1 (20 ml), Zn and Cd
are eluted with 60 ml of distilled water in the same fraction, and Zn is deter-
mined immediately from the intensity of the 0.^38 MeV photopeak of 13.8-hr
69mZn. For Cd, a decay period of one week from the time of irradiation is re-
quired so that 13.8-hr mZn completely decays. The count rate of the 0.523 MeV
photopeak of 5^-hr 115Cd is then measured. Radiochemical yields are determined
by re-irradiation and are in the 80 to 95 percent range for Zn and are quantitativ
for Cd. The average relative standard deviation is 25 percent for Zn and better
than 10 percent for Cd.
Determination of Hg in Whole Coal
From 0.6 to 1.0 g of coal (hand-ground to 20 mesh and air-dried) is
accurately weighed into a two-fifths-dram polyethylene snap-cap vial. Hand
grinding of coal samples to -20 mesh is recommmended to avoid excessive heating
and possible loss of Hg. A 1.0 ml aliquot of a 10.3 mg per ml standard solution
of Hg++ (as nitrate) is sealed in a similar polyethylene vial. Samples and
standard are simultaneously irradiated for 2 hours; one day must be allowed for
the preferential decay of shorter-lived radioisotopes (such as 2"*Na, 31Na, and
56Mn).
-------
- 81 -
Each sample is mixed 1-to-l with 60-mesh Norton Alundum RR
transferred to a 4-inch porcelain boat (Fisher Combax, size A), and covered with
Alundum. The boat, previously impregnated with 2 mg Hg++ carrier (as nitrate),
is placed in a 1-inch-diameter Vycor tube and the contents then combusted
slowly with a Bunsen burner (~500° to 600° C). An oxygen flow of about 50 to
75 ml per minute is maintained through the tube. The gaseous and volatilized
products are bubbled through two consecutive 100 ml vacuum traps, each con-
taining 20 ml of a 3.25 pH sodium acetate-acetic acid buffer solution (Hinkle,
Leong, and Ward, 1966), kO ml of saturated bromine water, and 30 mg of Hg++
(as nitrate). The combustion process requires about 1 hour to insure controlled
burning and efficient transfer of gases to the traps. (CAUTION: Sample should
be burned very gradually, as there is danger of violent explosion.~] Approximately
250 ml of 2M HC1 is used to wash the glassware and the Vycor tube and is then
combined with the trap solutions. The resulting solution (~^50 ml) is passed
through a column 1 cm in diameter containing 3.5 ml of Dowex 2 in the chloride
form. After radioactive interferences are eluted with hO ml of water and ho ml
of 2M HC1, the resin is transferred to a 100-ml polystyrene bottle, allowed to
settle uniformly, and then counted for 197Hg (t^ = 65 hours, 66 KeV gamma ray).
A 0.10 ml aliquot of the irradiated standard is diluted to 100 ml with
2M HNOs. One ml of this solution is immediately pipetted into a porcelain boat
(already impregnated with 2 mg of inactive Hg++) and air-dried. About 1 g of
unirradiated coal is mixed with Alundum, placed in the boat, covered with Alundum,
and burned in the same manner as the irradiated samples.
Recovery of Hg in the process is 67 ± 15 percent. The amount of Hg
in a sample is calculated by comparing the height of the photopeak of the sample
to that of the standard. The average relative standard deviation of the method
is 20 percent, and the detection limit is 0.01 ppm for a 1-gram sample and
2-hour irradiation.
Comparisons of Hg values determined by this method with preferred
values from a U.S. Bureau of Mines round-robin study (Schlesinger and Schultz,
1972) are given in table M. The accuracy of this method is excellent.
Alternate Determination of Hg in Coal
The method of Rook, Gills, and LaFleur (l97l) was modified and utilized
to determine Hg during the latter stages of this investigation. The standards,
sample preparation, irradiation procedure, and combustion are essentially the
same as previously described for Hg.
This procedure differs in that combustion products (including Hg) are
collected in a cold-trap, which is cooled by dry ice. After complete combustion
of the coal sample, the cold-trap tube is warmed to room temperature and the
mercury is washed out with HNOa- A further refinement of the method consists
of the removal of 82Br by precipitation as AgBr (the HgBr2 remains soluble).
The resulting solution is decanted and counted for 197Hg. The Hg standard is
treated identically. Radiochemical yield determinations are obtained by re-
irradiation and range from 80 to 90 percent. The average relative standard
deviation is 15 percent, and the detection limit is 0.01 ppm for a 1-gram sample
and 2-hour irradiation. Analyses of the standard coal NBS-1630 using this method
give Hg values in excellent agreement with the standard value (0.13 ppm).
-------
- 82 -
TABLE M—COMPARISON OF Hg VALUES WITH PUBLISHED DATA*
Best value
Coal location
Belmont Co. , Ohio
Harrison Co., Ohio
Jefferson Co., Ohio
Kanawha Co., W. Virginia
Washington Co., Pennsylvania
Clay Co., Indiana
Muhlenberg Co., Kentucky
Rosebud Co., Montana
Henry Co., Missouri
Montrose Co., Colorado
Navajo Co. , Arizona
NBS SRM-1630 (West Virginia)
(ppm)
0
0
0
0
0
0
0
0.
0
0
0
0
• 15 ±
.41 ±
.24 ±
.07 ±
.12 ±
.07 ±
• 19 ±
061 ±
.16 ±
.05 ±
.06 ±
.13
0.
0.
0.
0.
0.
03
06
04
02
04
0.02
0.
0.
0.
0.
0.
03
007
06
01
01
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
ISGS
(ppm)
15,
45,
23,
09,
13,
08,
24,
07,
17,
05,
05,
14
0.
0.
0,
0.
0.
0.
0.
0.
0.
0.
0.
17
46
30
08
14
11
23
06
18,
05,
05,
0.19
0.05
0.07
* Schlesinger and Schultz, 1972.
Determination of Sb in Whole Coal
In a manner similar to that described in the Hg procedure, 0.6 to
1.0 g of air-dried coal is hand ground, weighed, and irradiated with a standard.
The irradiated sample, -100 mg benzoic acid, and from 10 to 30 mg of accurately
weighed SbaOa carrier are placed in a Parr combustion bomb and burned at an
oxygen pressure of 25 atmospheres. The contents of the bomb are rinsed into a
beaker with concentrated HC1, and digested on a hot plate for 1 hour, and the
mixture is filtered. The filter paper and contents are vigorously heated with
100 ml of 1M KOH and 4 ml 30 percent H20z for 2 hours and then cooled and
filtered.
The filtrates are combined and diluted to ~1000 ml, and HaS is passed
through the solution. The sulfide precipitate is filtered, dissolved in 20 ml
of aqua regia, and evaporated to dryness. The residue is then treated with 1 g
of NH2OH-HC1, dissolved in 2 ml of 4M HC1, and evaporated to dryness. The
residue is redissolved in 1 ml of 0.5M IOUSCT-2M HC1 (Hamaguchi et al. , 1969)
and loaded on a Dowex 2 column (~5 ml in SCN~ form), which is then eluted with
15 ml of 0.5M NH.tSCN-0.5M HC1 (to remove As) and 10 ml of 0.005M NH.tSCN-0.5M HC1.
Subsequently, the Sb fraction is eluted with 150 ml of 2N ^SOi*, and 50 ml of
concentrated HC1 is added to it .
The solution is counted for 122Sb (ti^ = 2.8 day, 0.56 MeV y-ray).
Radiochemical yields are determined by re-irradiation and range from 30 to 55
percent. The average relative standard deviation of the method is 20 percent.
-------
- 83 -
Determination of Br in Whole Coal
From 0.6 to 1.0 g of coal (hand-ground to 20 mesh and air-dried) is
accurately weighed into a two-fifths-dram polyethylene snap-cap vial. One ml
of a standard solution containing 111 mg of Br as NHi+Br is sealed in a similar
vial. Samples and standards are simultaneously irradiated for 2 hours, and
about 1 day is allowed for the decay of shorter-lived radioisotopes.
Each sample is mixed 1 to 1 with 60-mesh Norton Alundum RR (A1203)
and transferred to a l|-inch porcelain boat. Twenty mg Br as NHi+Br solution is
added to the boat and allowed to dry. The contents of the boat are then covered
with Alundum and the boat is placed in a 1-inch Vycor tube. Combustion of the
sample takes place slowly using a Bunsen burner (~500° to 600° C) in an oxygen-
flow system, with a flow rate of between 50 and 75 ml per minute. The gaseous
and volatilized products are bubbled through two consecutive traps containing
3M NaOH or KOH. The first trap contains 200 ml and the second 80 ml. (CAUTION:
Sample should be burned very gradually, as there is danger of violent explosion.)
After combustion, all glassware is washed with water, and the wash
liquid is combined with the alkali trap solutions. The combined solutions are
then counted for 82Br (t, = 36 hours, 0.56 MeV Y-ray).
-5
A 5-ral aliquot is re-irradiated for chemical yield determination,
which varies from ^9 to 77 percent. The average relative standard deviation
is 10 percent.
Instrumental Neutron Activation Analysis of Mn in Whole Coal
From 0.6 to 1.0 g of the coal (hand-ground and air-dried) is accurately
weighed into a two-fifths-dram polyethylene snap-cap vial. One ml of
a solution containing a known quantity of Mn++ (from 100 to 200 yg) is heat-
sealed into a similar vial. Samples and standard are simultaneously irradiated
for only 15 minutes in a thermal neutron flux of about 0.7 x 10 2 neutrons
cm~2 sec~ .
After approximately 2 hours are allowed for the preferential decay of
the shorter-lived radioisotopes (e.g., 31Si and 38Cl), the samples are transferred
to unirradiated containers, counted, and compared with the standard for 56Mn
(%, = 2.6 hours, 0.8k MeV y-ray).
The average relative standard deviation of this instrumental technique
is k percent.
Instrumental Neutron Activation Analysis of Na in Whole Coal
From 0.6 to 1.0 g of coal (hand-ground and air-dried) is accurately
weighed into a two-fifths-dram polyethylene snap-cap vial. A 1.0-ml solution
containing a known amount of Na+ (1000 yg) is heat-sealed in a similar vial.
Samples and standard are simultaneously irradiated for only 10 minutes in a
thermal neutron flux of about 0.7 x 1012 neutrons cm"2 sec"1.
After allowing overnight for the preferential decay of the shorter-
lived radioisotopes, the samples are counted for 2l*Na (ti- = 15. k hours,
1.37 MeV y-ray) and compared with the standard. Corrections are made for the
average blank contributions of Na from the vials.
The average relative standard deviation of this instrumental technique
is 5 percent.
-------
- Qh -
Ion-Selective Electrode Method for Determination of F in Whole Coal
A 1-gram coal sample, ground to pass a 100-mesh screen, is mixed with
about 0.25 g benzole acid (primary standard) arid placed in a fused quartz sample
holder within a Parr combustion bomb that contains 5 ml of IN NaOH. The bomb is
then pressurized to about 28 atmospheres with oxygen and fired. At least 15
minutes must elapse before the bomb is depressurized. The bomb contents are
then rinsed with three 5-ml aliquots of distilled water into a 50-ml plastic
beaker (plastic-ware is used for all subsequent operations in this method).
The beaker contents are magnetically stirred with a Teflon bar while
the pH is adjusted to 5.2 to 5-5 with 0.5W H2SOit. (The initial pH before
adjustment is about 7-0.) The beaker is then placed in a hot water bath for
about 10 minutes and removed, and the contents are again stirred to drive off
most of the dissolved C02. Five ml of 1M sodium citrate-citric acid buffer
(pH 6.3) containing 0.2M KNOs is added to the beaker contents. The total
volume is adjusted to 50 ml with distilled water and cooled to room temperature.
At this time, the potential is read. In some cases, about 10 minutes is re-
quired for equilibrium to be reached. The F concentration is calculated by the
known addition method (l ml of 0.01M F is added and the potential of the
solution read again).
The pH is critical for the initial potential reading; at 5-0 to 5-55
final results tend to be low because of F~ complexing with H+. Above pH 7-0,
results are high because of interference from OH~ or HCOs" at concentrations
of 1000 times that of the F.
An independent fusion method for sample preparation was used to deter-
mine whether F is lost during combustion of coal samples in a pressurized bomb.
The procedure for the alternate fusion method is as follows: 3 grams of coal is
mixed with 5 grams anhydrous WaaCOa and the mixture is placed into a platinum
crucible. Approximately 2 grams more of the Na2C03 are used to cover the mixture.
The crucible and contents are then heated in a furnace at about ^75° C for 2\
hours, followed by final heating over an air-boosted Meker burner (about 1000° C)
for 15 minutes to fuse the mixture. After cooling, the crucible contents are
extracted with hot water and the pH is reduced to 5-2 to 5-5 with IN Ha SO if. The
solution is warmed in hot water to assist in the removal of CC>2, and about 25 ml
of 1M sodium citrate-citric acid buffer (pH 6.2) is added to buffer the solution
and to release any fluoride which may have been complexed by iron, etc., at the
lower pH. The solution is made to a known volume (generally 250 ml), and an
aliquot is taken for reading the potential with the fluoride ion-selective
electrode. A known addition of standard fluoride solution is made and the poten-
tial is read again. From these readings the fluoride concentration is determined.
As determined by the fusion method, the fluoride content of NBS standard
coal sample 1630 is 86 ppm. The average value for five replicate determinations
made by the bomb combustion method on 1-g coal samples is 80 ± U ppm. Using the
bomb combustion method, the results of duplicate determinations for coal sample
C-1^796 are 113 and 111 ppm F; a single value obtained by the fusion method is
122 ppm. In addition to these comparative results, we found that F values deter-
mined by the alternate fusion procedure are in good agreement with those deter-
mined by a calorimetric-fluoride distillation method. These comparisons were
made on samples of gypsum containing about 1 percent F. Thus, it is reasonable
to conclude that F is not being lost during sample preparation by either procedure
and that the bomb-combustion ion-selective electrode procedure, which gives
reproducible results for F in coal, also provides an accurate appraisal of the
F present.
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TRACE ELEMENT DETECTION LIMITS FOR ALL METHODS
Table N gives trace element detection limits for each method used.
Whole coal detection limits are given for those methods used in the direct
analysis of raw coal. However, it is not possible to give whole coal detection
limits for those methods which require a coal ash for the analysis sample,
because the ash content of the coals directly affects the detection limit, as
calculated to the whole coal. For those methods, detection limits are given
on the ash basis.
U.S. EPA-NBS TRACE ELEMENT SYMPOSIUM
A large-scale interlaboratory comparison of trace element results for
coal, fly ash, fuel oil, and gasoline was completed by the U.S. Environmental
Protection Agency and the National Bureau of Standards. Our results for the
coal and fly ash were among those submitted by many laboratories. During the
recent Trace Element Symposium held in Research Triangle Park, North Carolina,
results from all laboratories were distributed to those persons in'attendance.
Table 0 compares the trace element values obtained for the coal by the methods
previously described with those obtained by the National Bureau of Standards,
and with the mean values of the trace element concentrations from all other
participating laboratories. Our results for F, As, Be, Cd, Cr, Hg, Mn, Ni, Pb,
and Se in the interlaboratory coal sample agreed exceptionally well with the
NBS certified* values.
During the symposium, the need for reliable methods and for analytical
chemists experienced in trace element methodology was repeatedly emphasized.
In particular, the lack of agreement of cadmium results for coal was cited; none
of the methods used by the participating laboratories could be classified as
suitable. Further, little or no data were reported for the trace elements F,
Co, Sn, Ge, Ga, Sb, Mo, B, Br, Tl, or Bi.
PREFERRED ANALYTICAL PROCEDURES
Table P summarizes the method or combination of methods used for
determining our recommended or best values for whole coal reported in table 1.
For most elements, results from two or more methods were available. As
previously discussed, extensive inter- and intra-laboratory check analyses
were made, and the ultimate choice of the best technigue(s) was made on the
basis of consistent achievement of accuracy and precision. Where more than
one method is listed in table P, results from these were averaged.
Similarly, table Q indicates the choice of analytical method for the
recommended values reported for the float-sink samples (table 10). Because
data had to be consistent within a series of specific-gravity fractions for
washability calculations, only one analytical method was used instead of a
multiple approach and averaging.
* Although still subject to change, especially in the cases of Ni and Mn, these certified
values will probably be the values given when this coal sample is offered by NBS as
a standard reference material.
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- 86 -
Element
TABLE N— SUMMARY OF DETECTION LIMITS FOR METHODS USED
IN THIS INVESTIGATION
ppm in coal ash
ppm in whole coal
Atomic
absorption
Neutron
activation
Optical
emission-
photographic
Optical
emission-
spectrometric
Neutron
activation
X-ray
fluorescence
Ag
Al
As
B
Be
Br
Ca
Cd
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
Hg
K
Mg
Mn
Mo
Na
Ni
P
Pb
S
Sb
Sn
Se
Si
Ti
V
Sn
Zr
M-.O
300
1.2 2
25 2
1 1
1 1.
12
2.5 50
36
20 3
U5 1.5
20 4 1.5
Detection limit for F by ion-selective electrode = 10 ppm in whole coal.
36
1
4-0 1.5
0.01
9
25
2
25 3
0.5
20 71 3.
20
20 30 5 2.
72
0.1
3
1.8
21]- 0
27
if-5 5 0.
20 80 4
5
5
5
5
5
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- 87 -
TABLE 0—COMPARATIVE RESULTS FOR EPA-NBS INTERLABORATORY TRACE ELEMENT STUDY
Element
As
Cd
Cr
Cu
Hg
Mn
Ni
Pb
Se
Tl
Th
U
V
Zn
Pe
Be
P
S
NBS 1632
probable
certified
values
5.9 + 0.6
0.19 ± 0.03
20.2 ± 0.5
18 ± 2
0.12 ± 0.02
40 ± 3
15 ± 1
30 ± 9
2.9 ± 0.3
0.59 ± °-3
(3)
1.4 ± 0.1
35 ± 3
37 ± ^
8700 ±300
(1.5)
Parts per million in moisture-free coal
Illinois State Geological Survey*
All labs Atomic
grand Neutron absorption Optical X-ray Ion
mean activation LTA HTA emission fluor. elec .
6.24 5.7
0.9** < 0.4 < 0.4
22.7 24 22 22
18 23 28 22
0.22 0.18
41.3 39
19.0 16 16 26 22
30.4 22 32 24 26
4.6 2.8
1-7
34-9 5^
29.5** 40 38 49
1.12
1-75 1-72
83.5** 80.4
1.28$ 1.26
( ) - Information value only.
* - Average of at least four or more determinations.
** - Questionable mean; wide scatter or limited data.
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- 88 -
TABLE P—ANALYTICAL PROCEDURES USED TO DETERMINE
RECOMMENDED TRACE ELEMENT VALUES
Element Procedure
Hg, Sb, Se, As, Ga, Mn, Na NAA
Fe, Ti, Al, Si, K, Ca, S, Cl, Mg, Br, P X-RP
Be, Ge, Co, Or OE-DR,
OE-P
Cd, Zn AA
Pb, Cu AA, OE-DR
Ni OE-DR, AA,
OE-P, X-RP
F ISE
Zr OE-P
V OE-DR,
OE-P, X-RF
Mo, Sn, B OE-DR
TABLE Q—ANALYTICAL PROCEDURES USED FOR RECOMMENDED
VALUES FOR FLOAT-SINK SAMPLES
Element Procedure
Hg, Sb, Se, As, Ga, Mn, na
Pe, Ti, Al, Si, K, Ca, S, Cl, Mg, Br,
Cd, Zn, Pb, Cu, Ni
Be, Ge, Co, Cr, V, Mo, B
Na NAA
X-RP
Ni AA
B OE-DR
Zr OE-P
-------
SUMMARY OF ANALYTICAL METHODS USED FOR THE
DETERMINATION OF TRACE ELEMENTS*
Antimony (Sb)
To better establish the accuracy of the neutron activation radio-
chemical procedure developed for whole coal, a sample was analyzed for Sb by an
independent instrumental neutron activation method. Results obtained by the two
methods are in good agreement. Results for Sb determined in low-temperature coal
ash by yet another radiochemical procedure also compared favorably with those
obtained by the whole coal radiochemical separation method described herein.
Volatilization studies show that significant amounts of Sb were lost
from one coal during low-temperature ashing. The radiochemical method for whole
coal eliminates the possibility of unpredictable Sb losses.
Arsenic (As)
Two methods, neutron activation analysis of LTA and X-ray fluorescence
analysis of whole coal, are used for the determination of As. Neutron activation
results, calculated to the whole coal basis, compare well with X-ray fluorescence
values at the higher concentrations. However, the latter method frequently
exhibits a high bias for low As concentrations. The recommended values for As
given in table 1 are those determined by the neutron activation method.
Beryllium (Be)
Direct reading and photographic optical emission methods give comparable
results for Be in high-temperature coal ash. The recommended whole coal values
in table 1 are an average of results from both methods.
Bromine (Br)
The neutron activation and X-ray fluorescence results obtained for Br
in whole coal have been shown to be in good agreement. However, the X-ray
fluorescence procedure is much more rapid and has good precision. The Br results
reported in table 1 were determined by this procedure.
Cadmium (Cd)
Cadmium determinations of low-temperature coal ash samples made by
using atomic absorption and neutron activation methods are in good agreement.
Determinations by the University of Illinois Environmental Analytical Laboratory
performed by an anodic-stripping voltammetry procedure agree very well with atomic
absorption determinations of Cd in coal ash. Our recommended values, calculated
to the whole coal basis, are those determined by atomic absorption.
* In this summary, frequent reference is made to comparison of results obtained by two or
more analytical methods. Because of the huge number of analyses involved, these data
were not included in table 1, which records only recommended values. However, all
comparisons for 25 coals were reported in Ruch, Gluskoter, and Shimp (1973).
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- 90 -
Chromium (Cr)
Recommended values for Cr, calculated to the whole coal basis, are the
means of results from direct reading and photographic optical emission methods.
Atomic absorption results for Cr also agree well with those obtained by these
two methods.
Cobalt (Co)
Good agreement for cobalt concentrations determined in coal ash by
three analytical methods—photographic and direct-reading optical emission and
neutron activation—was obtained, although photographic optical emission values
tend to be higher for samples having low concentrations. Recommended values in
table 1 are the mean concentrations, expressed on the whole coal basis, as
determined by the photographic and direct-reading optical emission methods.
Copper (Cu)
X-ray fluorescence, atomic absorption, and direct-reading and photo-
graphic optical emission results compare well for Cu in whole coal, although
X-ray fluorescence values tend to be higher and those for photographic optical
emission lower. The Cu values reported in table 1 are the means of atomic
absorption results from the analyses of low-temperature ash and direct-reading
optical emission results from the analyses of high-temperature ash.
Fluorine (F)
Fluorine determinations were performed by a commercial laboratory
and by the Illinois State Geological Survey. The F results of the commercial
laboratory's distillation-colorimetric method are generally higher than those
determined in our laboratories using the ion-selective electrode procedure.
Extensive checking of our results with those of other laboratories and the use
of independent methods of analysis show that results obtained by the ion-
selective electrode technique are more accurate. Thus, the recommended values
given in table 1 were determined by the ion-selective electrode method.
Gallium (Ga)
Results obtained for Ga by the radiochemical procedure developed
for low-temperature coal ash agree with data given by Zubovic, Stadnichenko,
and Sheffey (196^). Our average for Illinois coal is 3.6 ppm, and their
average value is k.I ppm. The literature values for U.S. Geological Survey
standard rock W-l range from 16 to 20 ppm (Fleisher, 1969); our value is 21 ppm.
Germanium (Ge)
Photographic and direct-reading optical emission results for Ge in
high-temperature coal ash are in good agreement. The recommended values in
table 1 are the mean values of whole coal concentrations determined by both
methods.
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- 91 -
Lead (Pb)
X-ray fluorescence, atomic absorption, and photographic and direct-
reading optical emission results for Pb are in good agreement, although the
direct X-ray fluorescence analysis of whole coal tends to give higher results
than the other methods, which require coal ash for analysis. The recommended
values in table 1 are means of atomic absorption and direct-reading optical
emission spectrometric results.
Mercury (Hg)
Mercury results from the radiochemical procedure previously developed
(Ruch, Gluskoter, and Kennedy, 1971) are in good agreement with those re-
ported in the 1971 U.S. Bureau of Mines round-robin study (table M). The values
obtained by this method are being reported without further independent checks.
The NBS method (Rook, Gills, and LaFleur, 1971) is used interchangeably.
Nickel (Hi)
Determinations of Ni by X-ray fluorescence, atomic absorption, and
direct-reading and photgraphic optical emission methods have shown that all
results are in good agreement when the values are calculated to the whole coal
basis. The recommended values in table 1 are means of results from all of these
methods.
Selenium (Se)
The neutron activation radiochemical separation technique for low-
temperature coal ash yields precise values on replicate samples. When cal-
culated to the whole coal basis, our value of 2.0 ppm Se compares very well with
the provisional value for NBS-SRM-1630 coal standard (Se = 2.1 ppm). Comparison
of our results with those of the previously mentioned National Bureau of Standards-
U.S. Environmental Protection Agency round-robin indicate that this method is
accurate for the analysis of coal.
Vanadium (V)
Vanadium determinations made by X-ray fluorescence analysis of whole
coal and by both direct-reading and photographic optical emission analyses of
high-temperature ash sometimes exhibit a wide scatter. Our recommended values,
expressed as concentrations in whole coal, are the means of selected values
determined by all three methods, with very high or low individual results being
deleted.
Zinc (Zn)
X-ray fluorescence, atomic absorption, and photographic optical
emission methods of analyses all yield acceptable results for Zn when values are
-------
- 92 -
given on the whole coal basis. Photographic optical emission values tend to
"be slightly lower than those of other methods. As previously mentioned, in-
consistent results for high levels of Zn are associated with localized
mineralization and sample inhomogeneity (see also the discussion of the scanning
electron microscope). Finer grinding (-325 mesh) of coal samples should improve
the analytical precision for very high concentrations of Zn. The recommended
values in table 1 are those determined by atomic absorption.
Phosphorus (P), Boron (B), Zirconium (Zr),
Molybdenum (Mo), and Tin (Sn)
Each of these elements has been determined by a single method only,
without further confirmation of the values. Phosphorus was determined by
X-ray fluorescence analysis of whole coal; B, Zr, Mo,'and Sn were determined
in coal ash by optical emission spectrescopy. The Mo values are suspected of
being biased low.
SUMMARY OF ANALYTICAL METHODS USED FOR THE
DETERMINATION OF MAJOR AND MINOR CONSTITUENTS
The results in tables 2, 3, and k give X-ray fluorescence values
(percent of moisture-free whole coal) for Si, Ti, Al, Fe, Ca, K, Mg, S, and
Cl; neutron activation values for Na; and gravimetric values for the percentage
of low- and high-temperature ashes in coal. Concentrations of each element
have been determined in both whole coal samples and samples of low- and high-
temperature ash prepared from splits of the coal sample, and good agreement
among results has been obtained for the three different coal sample preparation
techniques when all values are expressed as concentrations in whole coal. The
reported values given in table 1 for these constituents were all obtained from
direct analysis of whole coal. In addition, the X-ray fluorescence results
for S and Cl agree well with the corresponding values obtained by wet-chemical
(ASTM) methods.
-------
- 93 -
REFERENCES
Abernethy, R. P., M. I. Peterson, and F. H. Gibson, 1969, Spectrochemical analyses of coal
ash for trace elements: U.S. Bur. Mines Rept. Inv. 7281, 30 p.
American Society for Testing and Materials, 1973, 1973 book of ASTM standards with related
material, Part 19 Gaseous fuels; coal and coke: Philadelphia: ASTM, p. 10, 372,
and 380.
Attari, Andrew, 1973, Fate of trace constituents of coal during gasification: Institute
of Gas Technology, Chicago, IL 60616, EPA-650/2-73-004, 31 p.
Bernas, Bedrich, 1968, A new method for decomposition and comprehensive analysis of silicates
by atomic absorption spectrometry: Anal. Chemistry, v. 40, no. 11, p. 1682-1686.
Bohor, B. P., and H. J. Gluskoter, 1973, Boron in illite as a paleosalinity indicator of
Illinois coals: Jour. Sed. Petrology, v. 43, no. 4, p. 945-956.
Buckley, D. E., and R. E. Cranston, 1971, Atomic absorption analyses of eighteen elements
from a single decomposition of aluminosilicate: Chem. Geology, v. 7, no. 4,
p. 273-284.
Capes, C. E., A. E. Mcllhinney, D. S. Russell, and A. F. Sirianni, 1974, Rejection of
trace metals from coal during beneficiation by agglomeration: Envir. Sci. and Tech.,
v. 8, no. 1, p. 35-38.
Clarke, F. W., and H. S. Washington, 192*1, The composition of the earth's crust: U.S.
Geol. Survey Prof. Paper 127, H? P-
Deul, M., and C. S. Annell, 1956, The occurrence of minor elements in ash of low-rank
coal from Texas, Colorado, North Dakota, and South Dakota: U.S. Geol. Survey
Bull. 1036-H, 18 p.
Dixon, K., A. H. Edwards, D. Flint, and R. G. James, 1964, The analysis of a bank of
standard ashes: Fuel, v. 43, no. 5, p. 331-347-
Fleisher, Michael, 1969, U.S. Geological Survey Standards - I. Additional data on rocks
G-l and W-l, 1965-1967: Geochim. et Cosmochim. Acta, v. 33, no. 1, p. 65-79.
Forney, A. J., W. P. Haynes, S. J. Gasior, G. E. Johnson, and J. P. Strakey, Jr., 1974,
Analyses of tars, chars, gases, and water found in effluents from the synthane
process: U.S. Bur. Mines Technical Progress Report 76, 9 P-
Francis, Wilfrid, 1961, Coal, its formation and composition: London: Edward Arnold,
Ltd., 806 p.
Gleit, C. E., 1963, Electronic apparatus for ashing biologic specimens: Am. Jour. Medical
Electronics, v. 2, p. 112-118.
Gleit, C. E., and W. D. Holland, 1962, Use of electrically excited oxygen for the low
temperature decomposition of organic substances: Anal, Chemistry, v. 34, no. 11,
p. 1454-1457.
Gluskoter, H. J., 19653, Composition of ground water associated with coal in Illinois and
Indiana: Econ. Geology, v. 60, p. 614-620.
Gluskoter, H. J., 1965b, Electronic low-temperature ashing of bituminous coal: Fuel, v. 44,
no. 4, p. 285-291.
-------
- 94 -
Gluskoter, H. J., 1967, Clay minerals in Illinois coals: Jour. Sed. Petrology, v. 37,
no. 1, p. 205-214.
Gluskoter, H. J., 1974, Mineral matter and trace elements in coal; _ln Babu, S. P., [ed.],
Advances in Chemistry Series: Washington, DC: American Chemical Society, in
preparation.
Gluskoter, H. J., J. R. Hatch, and P. C. Lindahl, 1973, Zinc in coals of the Illinois
Basin: Geol. Soc. America, Abstracts with Programs, v. 5, no. 7, p. 637.
Gluskoter, H. J., and P. C. Lindahl, 1973, Cadmium: Mode of occurrence in Illinois
coals: Science, v. l8l, no. 4-096, p. 264-266.
Gluskoter, H. J., Louis Pierard, and Hermann Pfefferkorn, 1970, Apatite petrifactions in
Pennsylvanian shales of Illinois: Jour. Sed. Petrology, v. 40, no. 4, p. 1363-1366.
Gluskoter, H. J., and 0. W. Rees, 1964, Chlorine in Illinois coal: Illinois Geol. Survey
Circ. 372, 23 p.
Gluskoter, H. J., and R. R. Ruch, 1971, Chlorine and sodium in Illinois coals as deter-
mined by neutron activation analyses: Fuel, v. 50, no. 1, p. 65-76.
Goldschmidt, V. M., 1935, Rare elements in coal ashes: Indus, and Eng. Chemistry, v. 27,
no. 9, p. 1100-1102.
Goldschmidt, V. M., 1937. The principles of distribution of chemical elements in minerals
and rocks: Jour. Chem. Soc., p. 655-673-
Hamaguchi, H., N. Onuma, Y. Hirao, H. Yokahama, S. Bando, and M. Furukawa, 1969, The
abundance of As, Sn, Sb, in chondritic meteorites: Geochim. et Cosmochim. Acta,
v. 33, no. 4, p. 507-518.
Helfinstine, R. J., N. F. Shimp, J. A. Simon, and M. E. Hopkins, 1971, Sulfur reduction
of Illinois coals Washabllity studies. Part 1: Illinois Geol. Survey Circ. 462,
44 p.
Helfinstine, R. J., N. F. Shimp, M. E. Hopkins, and J. A. Simon, 1974, Sulfur reduction
of Illinois coals Washability studies. Part 2: Illinois Geol. Survey Circ. 484,
32 p.
Helfinstine, R. J., J. A. Simon, N. F. Shimp, and M. E. Hopkins, 1970, Sulfur reduction
of Illinois coals Washability tests: Illinois Geol. Survey Environmental Geology
Note 34, 12 p.
Hinkle, Margaret, K. W. Leong, and F. N. Ward, 1966, Field determination of nanograit
quantities of mercury in soils and rocks: U.S. Geol. Survey Prof. Paper 550-E,
p. 135-137-
Holmes, J. A., 1918, The sampling of coal in the mine: U.S. Bur. Mines Tech. Paper 1,
22 p. (revised).
IBM Corporation, 1970, System/360 Scientific Subroutine Package, Version III, Programers
manual, Program number 360A-CM-03X, Manual number GH20-0205-4: White Plains, NY:
IBM Corporation, 454 p.
Kalb, G. W., and C. Baldeck, 1973, The determination of a mercury mass balance at a coal
fired power plant: TraDet Laboratories, Columbus, OH 43212.
Klein, D. H., and P. Russell, 1973, Heavy metals: Fallout around a power plant: Erivir.
Sci. and Tech., v. 7, no. 4, p. 357-358.
-------
- 95 -
Langmuhr, F. J., and P. E. Paus, 1968, The analysis of inorganic siliceous materials by
atomic absorption spectrophotometry and the hydrofluoric acid decomposition
technique: Anal. Chim. Acta, v. 4-3, p. ^97-508.
Magee, E. M., H. J. Hall, and G. M. Varga, Jr., 1973, Potential pollutants in fossil
fuels: Esso Res. and Eng. Co., Linden, NJ 07036, EPA-R2-73-2^9, 291 p.
Natusch, D. F. S., J. R. Wallace, and C. A. Evans, Jr., 1971, Toxic trace elements:
Preferential concentration in respirable particles: Science, v. 183, p. 202-20*1.
Nicholls, G. D., 1968, The geochemistry of coal-bearing strata, _in Murehison, D. G.,
and T. S. Westoll [eds. ] Coal and coal-bearing strata: Edinburgh and London:
Oliver and Boyd, p. 269-307.
Oak Ridge National Laboratory, 1973, Trace element measurements at the coal-fired Allen
steam plant, progress report June 1971 - January 1973: Oak Ridge National Laboratory,
Oak Ridge, Tennessee 37830, ORNL-NSF-EP-U3, 83 p.
Ode, W. H., 1963, Coal analyses and mineral matter, in H. H. Lowry [ed. ], Chemistry of
coal utilization: New York: John Wiley and Sons, supp. vol., p. 202-231-
O'Gorman, J. V., and P. L. Walker, Jr., 1972, Mineral matter and trace elements in
U.S. coals: The Pennsylvania State University, College of Earth and Mineral
Sciences, Research and Development Report No. 6l, Interim Report Mo. 2, 183 p.
Rao, C. P., and H. J. Gluskoter, 1973, Occurrence and distribution of minerals in
Illinois coals: Illinois Geol. Survey Circ. ^76, 56 p.
Rook, H. L., T. E. Gills, and P. D. LaFleur, 1971, Method for determination of mercury
in biological materials by neutron activation analysis: Anal. Chemistry, v. *J4,
no. 7, p. 11111-1117.
Rose, H. J., Isidore Adler, and F. J. Flanagan, 1962, Use of La20-2 as a heavy absorber
in the X-ray fluorescence analysis of silicate rocks: U.S. Geol. Survey Prof.
Paper ^50, p. B80-83.
Ruch, R. R., H. J. Gluskoter, and E. J. Kennedy, 1971> Mercury content of Illinois coals:
Illinois Geol. Survey Environmental Geology Note ^3, 15 P-
Ruch, R. R., H. J. Gluskoter, and N. F. Shimp, 1973, Occurrence and distribution of
potentially volatile trace elements in coal: An interim report: Illinois Geol.
Survey Environmental Geology Note 6l, 4-3 p.
Schlesinger, M. D., and Hyman Schultz, 1972, An evaluation of the methods for detecting
mercury in some U.S. coals: U.S. Bur. Mines Rept. Inv. 7609, 11 p.
Taylor, S. R., 1964-, Abundance of chemical elements in the continental crust: A new
table: Geochim. et Cosmochim. Acta, v. 28, no. 8, p. 1273-1285.
von Lehmden, D. J., R. H. Jungers, and R. E. Lee, Jr., 197^, Determination of trace
elements in coal, fly ash, fuel oil, and gasoline a preliminary comparison of
selected analytical techniques: Anal. Chem. , v. ^6, no. 2, p. 239-2tt-5-
Watt, J. D., 1968, The physical and chemical behaviour of the mineral matter in coal
under the conditions met in combustion plant; Part 1, The occurrence, origin,
identity, distribution and estimation of the mineral species in British coals:
British Coal Utilization Research Assoc., Leatherhead, Surrey, England, 121 p.
-------
- 96 -
Williams, D. E., and J. Vlamis, 1961, Boron analysis of plant tissue: Soil Science,
v. 92, p. 161-165.
Zubovic, Peter, 1966, Physiochemical properties of certain minor elements as controlling
factors of their distribution in coal: in Gould, R. P. [ed. ], Coal Science:
Advances in Chemistry Series, no. 55: Washington, DC: American Chemical Society
Publications, p. 221-216.
Zubovic, Peter, N. B. Sheffey, and Taisia Stadnichenko, 1967, Distribution of minor
elements in some coals in the western and southwestern regions of the Interior
Coal Province: U.S. Geol. Survey Bull. 1117-D, 33 p.
Zubovic, Peter, Taisia Stadnichenko, and N. B. Sheffey, 1961, Geochemistry of minor
elements in coals of the Northern Great Plains coal province: U.S. Geol. Survey
Bull. 1117-A, 58 p.
Zubovic, Peter, Taisia Stadnichenko, and N. B. Sheffey, 1964-, Distribution of minor
elements in coal beds of the Eastern Interior region: U.S. Geol. Survey Bull.
1117-B, 41 p.
Zubovic, Peter, Taisia Stadnichenko, and N. B. Sheffey, 1966, Distribution of minor
elements in coals of the Appalachian region: U.S. Geol. Survey Bull. 1117-C,
37 P.
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TECHNICAL REPORT DATA
(I'lcasc read Instructions on the rcvmc be/ore completing)
1. REPORT NO.
EPA-650/2-74-054
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Occurrence and Distribution of Potentially Volatile
Trace Elements in Coal
5. REPORT DATE
July 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R.R. Ruch, H.J. Gluskoter, and N. F. Shimp
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Illinois State Geological Survey
Urbana, Illinois 61801
10. PROGRAM ELEMENT NO.
1AB013; ROAP 21ADD-072
11. CONTRACT/GRANT NO.
68-02-0246
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The report gives results of complete chemical analyses of 101 whole coal samples
and of 32 separate fractions of four laboratory prepared (washed) coals. Trace
elements determined were: Sb, As, Be, B, Br, Cd, Cr, Co, Cu, F, Ga, Ge, Pb,
Mn, Mo, Ni, Hg, P, Se, Sn, V, Zn, and Zr. In addition, the following major and
minor elements were determined: Al, Ca, Cl, Fe, Mg, K, Si, Na, S, and Ti.
Standard coal analyses--proximate, ultimate, heating value, sulfur varieties, and
ash—are also reported. Wherever possible, accuracy was evaluated by comparing
results obtained by the various methods with results from splits of the same coal
samples. Analytical procedures given in detail include: neutron activation, optical
emission, atomic absorption, X-ray fluorescence, and ion-selective electrode.
Certain techniques were chosen for determining specific elements because they are
more accurate, their precision is superior, or they take less time for analysis.
Further comparisons, based on analyzing whole coal and its low- and high-tempera-
ture ashes , permitted a thorough evaluation of trace-element losses resulting from
volatilization during sample preparation.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI 1'ield/Group
Air Pollution
Coal
Trace Elements
Chemical Analysis
Air Pollution Control
Potential Pollutants
Analytical Techniques
13B
08G, 21D
06F
07B, 07D
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (Tills Report)
Unclassified
21. NO. OF PAGES
107
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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ENVIRONMENTAL GEOLOGY NOTES SERIES
(Exclusive of Lake Michigan Bottom Studies)
* 1. Controlled Drilling Program in Northeastern Illinois. 1965.
* 2. Data from Controlled Drilling Program in Du Page County, Illinois. 1965.
* 3. Activities in Environmental Geology in Northeastern Illinois. 19&5-
* 4. Geological and Geophysical Investigations for a Ground-Water Supply at Macomb, Illinois. 1965-
* 5. Problems in Providing Minerals for an Expanding Population. 1965.
* 6. Data from Controlled Drilling Program in Kane, Kendall, and De Kalb Counties, Illinois. 1965.
* 7. Data from Controlled Drilling Program in McHenry County, Illinois. 1965.
* 8. An Application of Geologic Information to Land Use in the Chicago Metropolitan Region. 1966.
* 9. Data from Controlled Drilling Program in Lake County and the Northern Part of Cook County, Illinois. 1966.
*10. Data from Controlled Drilling Program in Will and Southern Cook Counties, Illinois. 1966.
*11. Ground-Water Supplies Along the Interstate Highway System in Illinois. 1966.
*12. Effects of a Soap, a Detergent, and a Water Softener on the Plasticity of Earth Materials. 1966.
*13. Geologic Factors in Dam and Reservoir Planning. 1966-
*14. Geologic Studies as an Aid to Ground-Water Management. 19&7-
*15. Hydrogeology at Shelbyville, Illinois—A Basis for Water Resources Planning. 196?.
*l6. Urban Expansion—An Opportunity and a Challenge to Industrial Mineral Producers. 1967.
17. Selection of Refuse Disposal Sites in Northeastern Illinois. 19&J.
*l8. Geological Information for Managing the Environment. 19&7-
*19. Geology and Engineering Characteristics of Some Surface Materials in McHenry County, Illinois. 1968.
Illinois. 1968.
*20. Disposal of Wastes: Scientific and Administrative Considerations. 1968
*21. Mineralogy and Petrography of Carbonate Rocks Related to Control of Sulfur Dioxide in Flue
Gases—A Preliminary Report. 1968.
*22. Geologic Factors in Community Development at Naperville, Illinois. 1968.
23. Effects of Waste Effluents on the Plasticity of Earth Materials. 1968.
24. Notes on the Earthquake of November 9, 1968, in Southern Illinois. 1968.
*2J. Preliminary Geological Evaluation of Dam and Reservoir Sites in McHenry County, Illinois. 1969.
*26. Hydrogeologic Data from Four Landfills in Northeastern Illinois. 1969.
27. Evaluating Sanitary Landfill Sites in Illinois. 1969.
*28. Radiocarbon Dating at the Illinois State Geological Survey. 1969.
*29. Coordinated Mapping of Geology and Soils for Land-Use Planning. 1969.
*31. Geologic Investigation of the Site for an Environmental Pollution Study. 1970.
*33. Geology for Planning in De Kalb County, Illinois. 1970.
34. Sulfur Reduction of Illinois Coals—Washability Tests. 1970.
*36. Geology for Planning at Crescent City, Illinois. 1970.
*38. Petrographic and Mineralogical Characteristics of Carbonate Rocks Related to Sorption of
Sulfur Oxides in Flue Gases. 1970.
*40. Power and the Environment—A Potential Crisis in Energy Supply. 1970.
42. A Geologist Views the Environment. 1971.
43. Mercury Content of Illinois Coals. 1971.
45. Summary of Findings on Solid Waste Disposal Sites in Northeastern Illinois. 1971.
46. Land-Use Problems in Illinois. 1971.
48. Landslides Along the Illinois River Valley South and West of La Salle and Peru, Illinois. 1971.
49. Environmental Quality Control and Minerals. 1971.
50. Petrographic Properties of Carbonate Rocks Related to Their Sorption of Sulfur Dioxide. 1971.
51. Hydrogeologic Considerations in the Siting and Design of Landfills. 1972.
52. Preliminary Geologic Investigations of Rock Tunnel Sites for Flood and Pollution Control in
the Greater Chicago Area. 1972.
53. Data from Controlled Drilling Program in Du Page, Kane, and Kendall Counties, Illinois. 1972.
55. Use of Carbonate Rocks for Control of Sulfur Dioxide in Flue Gases. Part 1. Petrographic
Characteristics and Physical Properties of Marls, Shells, and Their Calcines. 1972.
56. Trace Elements in Bottom Sediments from Upper Peoria Lake, Middle Illinois River—A Pilot Project. 1972.
57. Geology, Soils, and Hydrogeology of Volo Bog and Vicinity, Lake County, Illinois. 1972.
59. Notes on the Earthquake of September 15, 1972, in Northern Illinois. 1972.
60. Major, Minor, and Trace Elements in Sediments of Late Pleistocene Lake Saline Compared with Those in Lake
Michigan Sediments. 1973.
6l. Occurrence and Distribution of Potentially Volatile Trace Elements in Coal: An Interim Report. 1973.
62. Energy Supply Problems for the 1970s and Beyond. 1973.
63. Sedimentology of a Beach Ridge Complex and its Significance in Land-Use Planning. 1973.
64. The U.S. Energy Dilemma: The Gap Between Today's Requirements and Tomorrow's Potential. 1973.
65. Survey of Illinois Crude Oils for Trace Concentrations of Mercury and Selenium. 1973.
66. Comparison of Oxidation and Reduction Methods in the Determination of Forms of Sulfur in Coal. 1973-
67. Sediment Distribution in a Beach Ridge Complex and its Application to Artificial Beach Replenishment. 1974.
68. Lake Marls, Chalks, and Other Carbonate Rocks with High Dissolution Rates in SOo-Scrubbing Liquors. 1974.
70. Land Resource — Its Use and Analysis. 1974.
71. Data from Controlled Drilling Program in Lee and Ogle Counties, Illinois. 1974.
*0ut of print.
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