See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/13097550

Trace elements in coal. Environmental and health significance

Article  in  Biological Trace Element Research · April 1999

Source: PubMed

CITATIONS READS

77 1,509

1 author:

Robert B Finkelman
University of Texas at Dallas
338 PUBLICATIONS   13,297 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

The moon View project

Medical Geology +++ View project

All content following this page was uploaded by Robert B Finkelman on 19 November 2015.

The user has requested enhancement of the downloaded file.

9 1999 by Humana Press Inc.
All rights of any nature, whatsoever, reserved.
0163-4984/99/6703-0197 $12.00

Trace Elements in Coal

Environmental and Health Significance
ROBERT B. FINKELMAN
U.S. Geological Survey, Mail Stop 956, Reston, VA 20192
Received April 20, 1998; Accepted June 6, 1998

ABSTRACT
Trace elements can have profound adverse effects on the health
of people burning coal in homes or living near coal deposits, coal
mines, and coal-burning power plants. Trace elements such as arsenic
emitted from coal-burning power plants in Europe and Asia have
been shown to cause severe health problems. Perhaps the most wide-
spread health problems are caused by domestic coal combustion in
developing countries where millions of people suffer from fluorosis
and thousands from arsenism. Better knowledge of coal quality char-
acteristics may help to reduce some of these health problems. For
example, information on concentrations and distributions of poten-
tially toxic elements in coal may help delineate areas of a coal deposit
to be avoided. Information on the modes of occurrence of these ele-
ments and the textural relations of the minerals in coal may help to
predict the behavior of the potentially toxic trace metals during coal
cleaning, combustion, weathering, and leaching.
Index Entries: Coal combustion; health impacts; trace elements;
trace metals; coal quality.

INTRODUCTION
Trace elements in the e n v i r o n m e n t come from a variety of natural
and anthropogenic sources (1). Perhaps n o n e of the sources is as misun-
derstood as coal combustion. U n d e r certain conditions, the emission of
trace elements from coal c o m b u s t i o n can be relatively benign. U n d e r
other conditions, these emissions present a potentially d e a d l y threat that
has caused severe health problems for tens of millions of people. Ironi-
cally, the concerns over the e n v i r o n m e n t a l and h u m a n health impacts of
coal c o m b u s t i o n appear to be inversely proportional to the d a m a g e done.

Biological Trace Element Research 197 Vol. 67, 1999

198 Finkelman

Table 1
Arithmetic and Geometric Means for Chemical Elements in US Coal
Arithnaetic Geometric
Component Mean S.D. Mean S.D. Max. Num.

Ash % 13.1 8.3 10.9 1.9 50.0 7976

Aluminum(A1) % 1.5 1.1 1.1 2.1 10.6 7882
Antimony(Sb) ppm 1.2 1.6 .61 3.6 35 7473
Arsenic (As) ppm 24 60 6.5 5.5 2200 7676
Barium (Ba) ppm 170 350 93 3.0 22000 7836
Beryllium(Be) ppm 2.2 4.1 1.3 3.5 330 7484
Bismuth (Bi) ppm (<1.0) n.d. n.d. n.d. 14 920
Boron (B) ppm 49 54 30 3. I 1700 7874
Bromine (Br) ppm 17 19 9.1 4.1 160 4999
Cadmium (Cd) ppm .47 4.6 .02 18 170 6150
Calcium (Ca) % .46 1.0 .23 3.3 72 7887
Carbon (C) % 63 15 62 1.3 90 7154
Cerium (Ce) ppm 21 28 5.1 7.1 700 5525
Cesium (Cs) ppm 1.1 1.1 .70 3.2 15 4972
Chlorine (C1) ppm 614 670 79 41 8800 4171
Chromium (Cr) ppm 15 15 10 2.7 250 7847
Cobalt (Co) ppm 6.1 10 3.7 2.9 500 7800
Copper (Cu) ppm 16 15 12 2.1 280 7911
Dysprosium (Dy) ppm 1.9 2.7 .008 35 28 1510
Erbium (Er) ppm 1.0 1.1 .002 73 11 1792
Europium (Eu) ppm .40 .33 .12 5.8 4.8 5268
Fluorine (F) ppm 98 160 35 15 4000 7376
Gadolinium(Gd) ppm [1.8] n.d. n.d. n.d. , 39 2376
Gallium (Ga) ppm 5.7 4.2 4.5 2.1 45 7565
Germanium (Ge) ppm 5.7 14 .59 16 780 5689
Gold (Au) ppm (<0.05) n.d. n.d. n.d. n.d. n.d.
Hafnium (Hf) ppm .73 .68 .04 38 18 5120
Holmium (I-Io)ppm [0.35] n.d. n.d. n.d. 4.5 1130
Hydrogen (H) % 5.2 .09 5.2 1.2 9.5 7155
Indium (In) ppm (<0.3) n.d. n.d. n.d. n.d. n.d.
Iodine (I) ppm (<1.0) n.d. n.d. n.d. n.d. n.d.
Iridium (I0 ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Iron (Fe) ppm 1.3 1.5 .75 2.9 24 7882
Lanthanum (La) ppm 12 16 3.9 6.0 300 6235
Lead (Pb) ppm 11 37 5.0 3.7 1900 7469
Lithium (Li) ppm 16 20 9.2 3.3 370 7848
Lutetium (Lu) ppm .14 .10 .06 4.7 1.8 5008
Magnesium(Mg) % .I 1 .12 .07 2.7 1.5 7887

Coal plays a crucial role in the world's energy mix--about 26% of all
the energy produced in the world in 1995 was derived from coal combus-
tion (2). Nearly 60% of the electricity produced in the United States is gen-
erated from coal. Forecasts for the next 20 yr suggest that coal use in the
United States will increase slightly; however, coal use in developing coun-
tries, especially China and India, should increase substantially because of
population growth and industrialization (2). One consequence of the min-
ing and combustion of coal is the mobilization of trace elements, especially
trace metals, that may have environmental and human health significance.

Biological Trace Element Research Vol. 67, 1999

Trace Elements in Coal 199

Table 1 (Continued)
Arithmetic Geometric
Component Mean S.D. Mean S.D. Max. Num.

Manganese (Mn) ppm 43 84 19 3.9 2500 7796

Mercury (Hg) ppm .17 .24 .10 3.1 10 7649
Molybdenum(Mo) ppm 3.3 5.6 1.2 6.5 280 7107
Neodymium(Nd) ppm [9.5] n.d. n.d. n.d. 230 4749
Nickel (Ni) ppm 14 15 9.0 2.8 340 7900
Niobium (Nb) ppm 2.9 3.1 1.0 7.7 70 6843
Nitrogen (N) % 1.3 0.4 1.3 1.4 13 7153
Osmium (Os) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Oxygen (O) % 16 12 12 2.0 60 7151
Palladium (Pd) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Phosphorus (P) ppm 430 1500 20 20 58000 5079
Platinum (Pt) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Potassium (K) % .18 .21 .10 3.5 2.0 7830
Praseodymium(Pr) ppm [2.4] n.d. n.d. n.d. 65 1533
Rhenium (Re) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Rhodium (Rh) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Rubidium (Rb) ppm 21 20 .62 41 140 2648
Ruthenium (Ru) ppm (<0.001) n.d. n.d. n.d. n.d. n.d.
Samarium (Sm) ppm 1.7 1.4 .35 13 18 5151
Scandium (Sc) ppm 4.2 4.4 3.0 2.3 100 7803
Selenium(Se) ppm 2.8 3.0 1.8 3.1 150 7563
Silicon (Si) % 2.7 2.4 1.9 2.4 20 7846
Silver (Ag) ppm (<0.1) .35 .01 9.1 19 5038
Sodium (Na) % .08 .12 .04 3.5 1.4 7784
Strontium (Sr) ppm 130 150 90 2.5 2800 7842
Sulfur (S) % 1.8 1.8 1.3 2.4 25 7214
Tantalum (Ta) ppm .22 .19 .02 13 1.7 4622
Tellurium (Te) ppm (<0.1) n.d. n.d. n.d. n.d. n.d.
Terbium (Tb) ppm .30 .23 .09 7.7 3.9 5024
Thallium (TI) ppm 1.2 3.4 .00004 205 52 1149
Thorium (Th) ppm 3.2 3.0 1.7 5.0 79 6866
Thulium (Tm) ppm [0.15] n.d. n.d. n.d. 1.9 365
Tin (Sn) ppm 1.3 4.3 .001 54 140 3004
Titanium (Ti) % .08 .07 .06 2.2 .74 7653
Tungsten (W) ppm 1.0 7.6 .10 14 400 4714
Uranium (U) ppm 2.1 16 1.1 3.5 1300 6923
Vanadium (V) ppm 22 20 17 2.2 370 7924
Ytterbium (Yb) ppm [0.95] n.d. n.d. n.d. 20 7522
Yttrium 0 0 ppm 8.5 6.7 6.6 2.2 170 7897
Zinc (Zn) ppm 53 440 13 3.4 19000 7908
Zirconium (Zr) ppm 27 32 19 2.4 700 7913

Note: All values are on a coal basis. Data are exclusively from the U.S. Geological
Survey (USGS) except for estimated values in parenthesis, which are based on USGS
and literature data. Values in brackets are calculated from cerium and lanthanum data
and assuming a chondrite normalized rare earth element distribution pattern. (n.d. = no
data; S.D. = standard deviation; Max. = maximum; Num. = n u m b e r of samples).

Coal contains detectable concentrations of virtually every element in

the periodic table (Table 1). Many of these elements, including many
potentially toxic metals, are enriched in coal (some by several orders of

Biological Trace Element Research Vol. 67, 1999

200 Finkelman

magnitude) relative to their concentrations in the Earth's surface. Ele-

ments in coal can be released into the environment by a variety of pro-
cesses such as the following:
9 Leaching of in-ground coal by ground water
9 Ground or surface water leaching of coal exposed by mining
9 Leaching of coal in storage piles by precipitation
9 Atmospheric emissions from utility, industrial, and domestic
coal combustion
9 Combustion of coal storage or waste piles
9 Natural combustion of coal beds at or near the Earth's surface
9 Leaching from buried coal combustion products or from
construction materials made from coal combustion residues
The environmental and human health impacts of most of these
processes are not fully understood and deserve further attention. For most
of these processes, the impacts will be local or, at most, regional. Coal
combustion, however, can have international and even global impacts, as
air masses transport emissions across the globe. This article describes sev-
eral examples of how trace elements, mobilized by coal combustion, have
affected the health of people in Asia and Eastern Europe.

TRACE ELEMENTS IN COAL

Concerns have been expressed in the United States (3) and elsewhere
(4) over the release of As, Be, Cd, Co, Cr, F, Hg, Ni, Pb, Sb, Se, U, and
other trace elements during the burning of coal. Trace elements such as
arsenic, emitted from coal-burning power plants in Europe, have been
shown to cause severe health problems. Bencko and Symon (5) studied
10-yr-old boys living in the vicinity of a power plant in Slovakia that
burned high-arsenic lignite (900-1500 ppm As on a dry basis). They
found significant hearing loss and attributed it to arsenic poisoning from
the power plant emissions. Bencko (6) also found a significant increase
of skin basalioma cancer in the region nearest the power plant. Bencko
and others (7) also suggested that immunological changes detected in
people living near a coal-burning power plant may be the result of beryl-
lium mobilized by coal combustion.
Recent risk assessment calculations from the U.S. Environmental
Protection Agency (8) indicate that trace element emissions from power
plants using coal having relatively low to moderate trace element con-
centrations or having efficient pollution control devices may not present
a significant health risk. This report indicates that the risk of trace ele-
ments causing cancer from inhalation in a population near a power plant
is less than 1 in a million. Nevertheless, there are other situations in
which trace elements emitted from coal combustion can cause serious
health problems. Perhaps the most widespread health problems are

Biological Trace Element Research Vol. 67, 1999

Trace Elements in Coal 201

caused by domestic coal combustion in developing countries. Millions of

people in China suffer from fluorosis (9) and thousands suffer from
arsenism (10) caused by coal combustion in China. Selenium (11) and mer-
cury poisoning have also been attributed to domestic coal combustion.
Zheng and Huang (9) have demonstrated that adsorption of fluorine
by corn dried over unvented ovens burning high (> 200 ppm in the coal)
fluorine coal is the probable cause of extensive dental and skeletal fluor-
osis in southwest China. The problem is compounded by the use of clay
as a binder for making briquettes. The clay used is a high-fluorine (about
900 ppm) residue from the intense leaching of the limestone substrate.
The occurrence of arsenic poisoning in southwest China may have a
similar etiology (10). The primary source of arsenic may be from chili
peppers dried over unvented ovens burning high-arsenic coal. One coal
sample analyzed at the U.S. Geological Survey laboratory had 35,000 ppm
arsenic on an as-analyzed basis! The fresh chili peppers have less than
1 ppm arsenic. The chili peppers dried over the high-arsenic coal fires
have more than 500 ppm arsenic (12). Ingestion of the chili peppers
tainted with arsenic from the mineralized coal has caused thousands of
cases of arsenosis, producing severe skin cancers (12).
Zheng and others (11) report nearly 500 cases of human selenosis in
southwest China that are attributed to the use of selenium-rich carbona-
ceous shales known locally as "stone coal." The stone coals have as much
as 8390 ppm selenium (whole-rock basis). The selenosis is attributed to
the practice of using combustion ash as a soil amendment. This process
introduced large amounts of selenium into the soil and resulted in sele-
nium uptake by crops.
There is also considerable concern about the health effects of mer-
cury and the proportion of anthropogenic mercury in the environment
(13). So far, there is no direct evidence of health problems caused by mer-
cury released from coal, but there are circumstances where poisoning
from mercury released from coal combustion may be occurring. Zhou
and Liu (14) reported on chronic thallium poisoning in Guizhou
Province, China, where the source of the thallium poisoning appears to
be from vegetables grown on a mercury/thallium-rich mining slag. Most
symptoms, such as hair loss, are typical of thallium poisoning. However,
loss of vision in several patients from this region was considered to be
unique (15). Mineralogical analysis of the coal being used in the homes
of patients having visual impairment revealed abundant mercury miner-
als. Chemical analysis of a coal sample being used in Guizhou Province,
China indicates a mercury concentration of 55 ppm, which is more than
300 times the average mercury concentration in US coals.
Iron concentrations in coal are generally in the percent range; thus,
iron is not truly a trace constituent. Nevertheless, it is worthwhile not-
ing that iron may act as an intermediary in causing common lung dis-
orders of coal minors. Huang and co-workers (16) have suggested that
acid-soluble ferrous iron may cause lung tissue damage leading to

Biological Trace Element Research Vol. 67, 1999

202 Finkelman

emphysema. The impact of the acid-soluble ferrous iron is tempered by

the presence of carbonate minerals in the coal that neutralize the acids
and allow the oxidation of the ferrous iron to benign ferric iron.

COAL CHARACTERIZATION
Determining the concentration of the elements in coal is complicated
by the fact that coal contains virtually every element in the periodic table
and by the wide range in element concentrations (from percent to parts
per billion). The situation is further complicated by the wide range in
properties, such as volatility, of the elements. To achieve a comprehen-
sive chemical characterization of coal, several analytical techniques are
generally employed. The most commonly used multielement techniques
are inductively coupled plasma-mass spectroscopy and inductively cou-
pled plasma-atomic emission spectroscopy. Instrumental neutron acti-
vation analysis has been successfully applied to coal characterization for
many years because it can be used on whole coal, thus avoiding prob-
lems of volatilization. For the highly volatile elements, element-specific
methods are employed: mercury and selenium are commonly deter-
mined by coal vapor and hydride generation atomic absorption spectro-
scopy, respectively, and fluorine and chlorine by selective ion electrode
analysis. Other analytical techniques applied to coal include X-ray fluor-
escence spectroscopy and atomic absorption spectroscopy. For a recent
discussion of chemical analysis of coal, see ref. 17.
The concentration of an element in coal has been used as a gauge of
the element's potential environmental and health impacts. Clearly, know-
ing the concentration of a potentially toxic element in coal will help
determine if use of the coal might present a health risk. Furthermore,
knowing the vertical and lateral distribution of the element in a coal
deposit will allow for intelligent decisions regarding mining all or parts
of the deposit.
However, the concentration of an element by itself provides only a
partial measure of the element's potential impacts. The modes of occur-
rence and textural relations of the element are important parameters that
may help in designing procedures to reduce human exposure to the ele-
ment. The element's modes of occurrence (chemical form) may help to
predict the element's behavior during coal cleaning, combustion, weath-
ering, and leaching (18). For example, arsenic associated with sulfide
minerals in coal may be retained in the fly ash and bottom ash of the
combusted coal, whereas organically bound arsenic may be preferentially
volatilized (19). In addition, modes of occurrence information are neces-
sary for developing efficient procedures for physically removing toxic
elements prior to coal combustion (20).
The low concentrations and the dispersed nature of many trace ele-
ments in coal makes determining their modes of occurrence a challenge.

Biological Trace Element Research Vol. 67, 1999

Trace Elements in Coal 203

The modes of occurrence of an element can be inferred from indirect

evidence, such as from the analysis of density separates. It is assumed
that those elements associated with the inorganic constituents (minerals)
will be concentrated in the heavier-specific-gravity fractions and those
elements associated with the organic constituents (macerals) will be con-
centrated in the lighter-specific-gravity fractions. Other indirect evi-
dence includes statistical correlation with other elements and behavior
of an element during heating and leaching experiments (21). Preferably,
the modes of occurrence of elements in coal should be determined
directly, using microbeam instruments such as scanning electron
microscopy with energy dispersive detectors, electron microprobe ana-
lyzers, X-ray mineralogical analysis (21), and X-ray absorption fine-
structure spectroscopy (22).

CONCLUSIONS
A better knowledge of coal quality characteristics may help to min-
imize some of the health problems caused by coal. Information on the
concentrations and distributions of potentially toxic elements in coal will
help to avoid those coal deposits or zones within coal deposits having
undesirably high concentrations of toxic compounds. Information on the
modes of occurrence of potentially toxic elements and the textural rela-
tions of the minerals and the organic components in which they occur
may help to anticipate the behavior of the potentially toxic components
during coal cleaning, combustion, weathering, and leaching. Coal qual-
ity characterization, therefore, offers coal scientists and biomedical
researchers opportunities to contribute to improve public health in many
parts of the world.

REFERENCES
1. D. C. Adriano, Trace Elements in the Terrestrial Environment, Springer-Verlag, New
York (1986).
2. Energy Information Agency, Coal [online]. Available at http://www.eia.doe.gov/oiaf/
ieo97/coal.html (file last modified 5/1/97).
3. U.S. Statutes at Large, Public Law 101-549, Provisions for attainment and mainte-
nance of national ambient air quality standards, 101st Congress, 2nd Session, 104,
Part 4, pp. 2353-3358 (1990).
4. P. Singh-Mahendra, R. M. Singh, and D. Chandra, Environmental and health prob-
lems due to geochemical alterations associated with trace elements in coals, Ghugus
Coalfield, Wardha Valley, Maharashtra, Quart. J. Geol. Min. Metall. Soc. India 57,
99-103 (1987).
5. V. Bencko and K. Symon, Health aspects of burning coal with a high arsenic content.
II. Hearing aspects of burning coal with a high arsenic content, Environ. Res. 13,
386-395 (1977).
6. V. Bencko, Health aspects of burning coal with a high arsenic content: the Central
Slovakia experience, in Arsenic: Exposure and Health Effects, C. O. Abernathy and R. L.
Calderon, eds., Chapman & Hall, New York, pp. 84-92 (1997).

Biological Trace Element Research Vol. 67, 1999

 204 Finkelman

7. V. Bencko, E. V. Vasilieva, and K. Symon, Immunological aspects of exposure to emis-

sions from burning coal of high beryllium content, Environ. Res. 22, 439-449 (1980).
8. U.S. EPA, Study of hazardous air pollutant emissions from electric utility steam gen-
erating units--Interim final report, EPA-453/R-96-013a (1996).
9. B. Zheng, and R. Huang, Human fluorosis and environmental geochemistry in south-
west China, in Developments in Geoscience, Contributions to 28th International Geologic
Congress, 1989, Washington, D.C., Science Press, Beijing, pp. 171-176 (1989).
10. B. Zheng, X. Yu, J. Zhand, and D. Zhou, Environmental geochemistry of coal and
endemic arsenism in southwest Guizhou, R R. China, 30th International Geologic Con-
gress Abstracts, 1996, Vol. 3, p. 410.
11. B. Zheng, Y. Hong, W. Zhao, H. Zhou, W. Xia, H. Su, et al., The Se-rich carbonaceous
siliceous rock and endemic selenosis in southwest Hubei, China, Chin. Sci. Bull. 37,
1725-1729 (1992).
12. B. Zheng, personal communication (1996).
13. R Chu and D. B. Porcella, Mercury stack emissions from U. S. electric utility power
plants, in Mercury as a Global Pollutant, D. B. Porcella, J. W. Huckabee, and B. Wheat-
ley, eds., Kluwer, Dordecht, pp. 135-144 (1995).
14. D. Zhou and D. Liu, Chronic thallium poisoning in a rural area of Guizhou Province,
China, ]. Environ. Health 48, 14-18 (1985).
15. R. Dart, personal communication (1996).
16. X. Huang, R. Zalma, and H. Pezerat, Factors that influence the formation and stabil-
ity of hydrated ferrous sulfate in coal dusts. Possible relation to the emphasyma of
coal miners, Chem. Res. ToxicoI. 7, 451-457 (1994).
17. C. A. Palmer, ed., The chemical analysis of Argonne premium coal samples, U.S. Geo-
logical Survey Bulletin 2144 (1997).
18. R. B. Finkelman, Hazardous elements in coal: can we rely on modes of occurrence
information to predict their removal.) 10th Ann. Int. Pittsburgh Coal Conf. Proc.,
S.-H. Chang, ed., 1993, pp. 311-313.
19. L. S. Dale, J. F. Chapman, and S. A. Lavrencic, Trace element partitioning in stack
emissions from coal-fired power stations, in Coal Science, Vol. II, J. A. Pajares and
J. M. D. Tascon, eds., Elsevier, Amsterdam, pp. 1975-1977 (1995).
20. D.J. Akers, HAPS-Rx: Precombustion removal of hazardous air pollutant precursors,
U. S. Dept. Energy Joint Power & Fuels Syst. Contr. Conf., 1997.
21. R. B. Finkelman, Modes of occurrence of potentially hazardous elements in coal: level
of confidence, Fuel Process. Technol. 39, 21-34 (1994).
22. F. E. Huggins, N. Shah, J. Zhao, F. Lu, and G. R Huffman, Nondestructive determi-
nation of trace element speciation in coal and ash by XAFS spectroscopy, Energy Fuels
5, 574-581 (1993).

Biological Trace Element Research Vol. 67, 1999

View publication stats