Article

pubs.acs.org/EF

Determination of Boron in Coal Using Closed-Vessel Microwave

Digestion and Inductively Coupled Plasma Mass Spectrometry (ICP-
MS)
Shifeng Dai,† Weijiao Song,† Lei Zhao,† Xiao Li,† James C. Hower,*,‡ Colin R. Ward,§ Peipei Wang,†
Tian Li,† Xin Zheng,∇ Vladimir V. Seredin,⊥,∥ Panpan Xie,† and Qingqian Li†
†
State Key Laboratory of Coal Resources and Safe Mining, China University of Mining and Technology (Beijing), Beijing 100083,
China
‡
Center for Applied Energy Research, University of Kentucky, 2540 Research Park Drive, Lexington, Kentucky 40511, United States
§
School of Biological, Earth and Environmental Sciences, University of New South Wales, Sydney, NSW 2052, Australia
∇
ThermoFisher Scientific, Beijing 10083, China
⊥
Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences, Staromonetny per.
35, Moscow 119017, Russia

ABSTRACT: Boron in coal is of great interest, mainly because it can be used as paleosalinity indicator; it is also of
environmental concern because of its toxic effects, especially on land plants. This paper describes a new method for
determination of the boron concentration in coal by inductively coupled plasma mass spectrometry (ICP-MS) after closed-vessel
microwave digestion. Samples of raw coal rather than coal ash were used for the determination to avoid the loss of volatile
organically bound boron. Addition of H3PO4 to the HNO3 and HF used as reagents in the process could also significantly
diminish boron volatilization during acid-drying after sample digestion. A 2% ammonia solution, which was injected into an ICP-
MS spray chamber to eliminate the memory effect of boron, may reduce boron signals to blank levels (within 120 s) during ICP-
MS analysis. The boron concentrations of National Institute of Standards and Technology (NIST) standard reference coal
samples obtained using the ICP-MS in high-resolution mode and with 103Rh or 115In used as online addition internal standards
are in good agreement with the certified values.

1. INTRODUCTION
Boron in coal is of interest, both because it can be used as
paleosalinity indicator for the coal’s sedimentary environ-
ment1−4 and because it may have adverse environmental
effects.5−7 For example, Goodarzi and Swaine8 successfully
used the total boron concentration to develop fresh/brackish
and brackish/marine indices of coal sedimentary environments.
Their work places the fresh/brackish and brackish/marine
boundaries at 50 and 110 μg/g B and, although this
paleosalinity indicator remains controversial,2,9,10 these values
have been widely used by others.2,4,11−13 However, an elevated
concentration of boron in coal may also be derived from
hydrothermal fluids,10 volcanic activity,2,9 and climatic
variations.9
High boron concentrations may have toxic effects on land
plants,5,6 and this may preclude the use of fly ash as a soil
ameliorant and limit disposal options.14,15 Relatively small
excesses may be detrimental, but the impact depends in part on
the mobility of the boron in the ash material. Some studies have
shown that a large fraction of the boron in fly ash is in soluble
form and it is often the most mobile trace element in coal
ash.16−20 The susceptibility to harm is also plant species-
specific,7,21 and this provides a further complication in
evaluating the environmental effects of boron in coal and its
combustion products.14 On the other hand, Yunusa et al.15
reported that boron phytotoxicity from coal ash may be
minimized in the field situation, where the soil volume is not
limited and where leaching is possible. Indeed, once the roots
extend beyond the zone of ash incorporation, the plants may be
able to regain much of the early loss in growth and actually
benefit from the ash-derived nutrients.15 A very few studies
have also shown that high boron concentrations may affect
male reproductive capabilities in animals,22 although probably
not in humans where no such negative findings have been
reported.23
Three modes of occurrence of boron in coal are commonly
recognized, namely, bound to the organic matter, associated
with clay minerals (mainly illite), and bound within the crystal
lattice of tourmaline.2,7,14,24−28 Although illite and tourmaline
may be locally important modes of occurrence, the organically
bound mode is generally considered to be the most
common.7,12,14,24
The mode of occurrence exerts dominant control on the
partitioning behavior of boron, both during coal ashing and
during coal utilization. Boron present in coal as tourmaline is
retained in ash at a temperature of 1000 °C, while organically
bound boron is easily volatilized.14 Ashing experiments have
shown a significant loss of boron, in some cases at 370 °C and,
in one case, at 150 °C during low-temperature radio frequency
Received: April 22, 2014
Revised: June 4, 2014
Published: June 23, 2014

© 2014 American Chemical Society 4517 dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522
Energy & Fuels
ashing;29 this could be explained by the common organic
affinity of boron, and may be responsible for the high emissions
noted for this otherwise refractory element.14,29
Previous studies indicate that boron in coal has been mostly
determined by atomic emission spectroscopy (AES) or
inductively coupled plasma−atomic emission spectrometry
(ICP-AES).2,13,30−33 However, as indicated by Huggins,32 the
precision of AES or ICP-AES is not as high as other trace
element techniques, and the trace-element concentrations are
often described as being only semiquantitative. Another
disadvantage of AES or ICP-AES is the high detection limits
of these methods. Such techniques are rarely applied directly to
coal, and are usually used on high-temperature ash samples
prepared from the coal. For example, the U.S. Geological
Survey has recommended the ICP-AES method for boron
determination after the coal ash is decomposed with sodium
peroxide using a sintering process (450 °C for 30 min).31 This
method has also been adopted by others.34−36 Eskenazy et
al.2,30 used atomic emission spectroscopy for boron determi-
nation after the samples were ashed in platinum crucibles in an
open muffle furnace at 500 °C. However, as indicated above,
high-temperature ashing of coal can lead to loss of volatile
organically bound boron,14,29 and thus the boron concentration
in the coal may be underestimated.
Inductively coupled plasma mass spectrometry (ICP-MS)
has become an established method since the 1980s for
determination of multiple trace elements,37−42 including
those in coal and coal-related materials.4,26,43−46 However,
one requirement is that the sample must be dissolved
completely. ICP-MS has several advantages, including low
detection limit, high sensitivity, relatively simple spectra, wide
linearity range, and simultaneous determination of multiple
trace elements in a run.32,47 It is nevertheless clear that no one
technique is sufficiently general or precise to be universally
applicable to all trace elements in coal and coal-related
materials. Like any sensitive analytical techniques, ICP-MS
has some limitations, such as polyatomic spectral interferences
and memory effects during aspiration of the liquid sample into
the spray chamber of the ICP-MS instrument.47,48 For the
determination of boron in coal by ICP-MS, however, the major
hindrances are how to avoid the loss of volatile organically
bound boron during coal sample preparation and how to
eliminate the memory effects of boron during ICP-MS analysis.
2. EXPERIMENTAL SECTION
2.1. Instrumentation. A ThermoFisher ICP-MS (X Series II) was
used for boron determination, based on raw (unashed) coal samples.
Prior to ICP-MS analysis, the coal samples were digested using an
UltraClave microwave high-pressure reactor (Milestone). Although
closed-vessel microwave digestion is not a standard method for coal
digestion prior to trace-element analysis, numerous studies have
proved that it is a powerful method,4,13,18,27,44−47,49−51 which could
avoid the loss of trace elements during the ashing procedure required
by normal digestion techniques.
A Milli-Q A10 system (Millipore) was used to prepare ultrapure
water (18.2 MΩ cm). A DuoPUR acid purification system (Milestone)
was used for further purification of the guaranteed HNO3 reagent. The
TraceCLEAN Automatic Acid Reflux System (Milestone) was used for
vessel cleaning at a temperature of 300−350 °C for 2 h.
2.2. Standard Solutions, Reagents, Gases, and Investigated
Samples. Five concentration levels (0, 1, 10, 50, and 100 μg/L) of the
standard solution (1000 μg/mL, single-element boron standard
solution GSB 04-1716-2004, National Center of Analysis and Testing
for Nonferrous Metals and Electronic Materials) were used to establish
calibration curves of boron. The standard stock solutions of 103Rh
4518
Article
(1000 μg/mL, single-element Rh standard solution GSB 04-1746-
2004, National Center of Analysis and Testing for Nonferrous Metals
and Electronic Materials), 115In (100 μg/mL, CCS4, Inorganic
Ventures), and 9Be (100 μg/mL, CCS4, Inorganic Ventures) were
used as the internal standards for online addition during ICP-MS
analysis. The standard solution (10 μg/mL, THM-TS-1, Inorganic
Ventures), containing multielements, Li, Co, In, and U, was used to
prepare the tuning solution. All standards were used without further
purification and prepared in 2% (v/v) HNO3.
Metal-oxide-semiconductor (MOS) reagent HF (40%, v/v), the
guaranteed reagents HNO3 (65%, v/v) and H3PO4 (85%, v/v) were
used for sample digestion. Ultrapure 99.999% Ar was used without
further purification as the cooling, auxiliary, and nebulizer gas.
National Institute of Standards and Technology (NIST) standard
reference coal samples, including SRM1632c, SRM2682b, and
SRM2685b, were used to evaluate the suitability of the ICP-MS
technique for boron determination, based on the unashed coal
material.
2.3. Sample Digestion. To allow for the volatile behavior of
organically bound boron,14,29 50 mg of each NIST standard coal
sample, crushed to <200 mesh (<75 μm), was digested in the closed
PTFE vessel of the UltraClave microwave high-pressure reactor. The
reagents for digestion of each 50-mg coal sample were 0.5 mL of 85%
(v/v) H3PO4, 3 mL of 65% (v/v) HNO3, and 1 mL of 40% (v/v) HF.
A different reagent assemblage (HNO3−HF) was also used for
digestion of the NIST standard coals to investigate whether and, if so,
how much boron might be volatized during the acid-drying process
after sample digestion. For the HNO3−HF tests, the reagents for each
50-mg coal sample were 3 mL of 65% (v/v) HNO3 and 3 mL of 40%
HF.
The basic load for the digestion tank of the UltraClave reactor was
composed of 330 mL of distilled H2O, 30 mL of 30% H2O2, and 2 mL
of 98% H2SO4 (analytical reagent). Initial nitrogen pressure was set at
50 bar. The highest temperature was set at 240 °C, and that was
applied for 75 min. The microwave digestion program is presented in
Table 1.
Table 1. Microwave Program for Sample Digestion
time temperature pressure microwave power
step (min) (°C) (bar) (W)
1 12 60 100 1000
2 20 125 100 1000
3 8 160 130 1000
4 15 240 160 1200
5 60 240 160 1000
cooling 60 min
time
The digested samples were transferred to polyfluoroalkoxy (PFA)
digestion cups (resistant to HF corrosion), and then subjected to
drying on an electric hot plate at 180 °C. Five mililiters (5 mL) of 65%
(V/V) HNO3 was added to the dried samples in the digestion cups,
which were then covered by the cup lids and kept at 180 °C on the
electric hot plate for 4 h. After that, the samples were cooled to room
temperature, transferred to PFA volumetric flasks, and then diluted to
100 mL with ultrapure water for ICP-MS analysis.
2.4. ICP-MS Determination Procedure. The torch position and
ion lenses of the instrument were first optimized and tested by
performing short-term stability tests in the standard mode, with a 1
μg/L tuning solution (prepared from 10 μg/mL standard solution) to
maximize ion signal and stability. The optimized parameters of the
ICP-MS are presented in Table 2. Analyses using standard- and high-
resolution modes were performed on NIST standard samples to
investigate whether the use of different resolution modes would affect
the boron determination.
Various rinse solutions (ultrapure water, 2% HNO3, 2% HNO3 +
2% mannitol, and 2% ammonia solution) were used to investigate the
dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522
Energy & Fuels Article

Table 2. Optimized Instrumental Parameters for Inductively Table 4. Comparison of Observed Boron Concentrations
Coupled Plasma Mass Spectrometry (ICP-MS) and Relative Error (RE) between Different Reagent
Assemblages, Based on the 10B Spectral Line and Using 115In
item value/status item value/status
as an Internal Standard Solution
plasma RF power 1400 W uptake time 60 s
nebulizer gas flow 0.93 L/min washout time 120 s H3PO4−HNO3−HF HNO3−HF
a
auxiliary gas flow 0.8 L/min pole bias −4.8 V certified observed RE observed REa
cool gas flow 13.5 L/min hexapole bias −2.1 V sample value (μg/g) [B] (μg/g) (%) [B] (μg/g) (%)
sampling depth 150 steps number of main 3 SRM1632c 62 ± 2 62.1 0.09 bdlb
runs SRM2682b 39 40.6 4.10 17.5 55.24
ICP-MS interface Nickel Xt dwell time 10 ms SRM2685b 109 109.9 0.84 3.40 96.88
peristaltic pump 30 rpm acquisition peak jumping a
speed mode mode RE = (|observed − certified|/certified) × 100. bbdl = below detection
spray chamber 3 °C number of 3 limit.
temperature channels

removal of boron memory effects during aspiration of the liquid may interact to produce a more stable, nonvolatile boron-
sample into the ICP-MS (Figure 1). A washout time of 120 s was used bearing complex.52,53
to establish the baseline signal of boron for each rinse solution.
The results (Figure 1) indicated that a 2% ammonia solution
can effectively eliminate the boron memory effect and reduce
boron signals to blank levels (within 120 s), similar to analytical
results obtained by Al-Ammar et al.54 and Huang et al.55 The
boron memory effect is not attributed to the skimmer, sampler,
or other mass spectrometer components, but originates from
the tendency of boron to volatilize as boric acid from the
sample solution that covers the inside surface of the ICP-MS
spray chamber.54 The ammonia solution may neutralize the
volatile boric acid on the surface to form a nonvolatile
compound (e.g., NH4H2BO3).54
Under the optimized conditions (Table 2) and with the ICP-
MS in high-resolution mode, using 2% ammonia as a rinse
solution and with samples digested using H3PO4−HNO3−HF,
the linearity of the calibration curves was considered to be
satisfactory over the range 0−100 μg/L, having a determination
coefficient r2 > 0.999 at each run with or without the different
internal standard solutions (9Be, 103Rh, and 115In) (see Table
Figure 1. Removal of boron memory effects by different rinse 5). The method detection limits, which were calculated as three
solutions. times the standard deviation of the average from the blank
samples (n = 11), are listed in Table 5.
Table 5 also lists the observed concentrations, measured
3. RESULTS AND DISCUSSION using either the 10B or 11B spectral line, for the NIST standard
The relative standard deviations, which were obtained by 11 reference coal samples, as well as relative errors, using different
repeated measurements on NIST coal samples, were found to online additions of internal standard solutions.
be lower for the high-resolution mode than for the standard- Using different online additions of internal standard
resolution mode, respectively (Table 3), indicating that the solutions, the observed boron concentrations based on the
10
high-resolution mode is more suitable for the determination of B and 11B spectral lines are close to each other, indicating that
boron in coal. the observed boron concentrations based on the two isotope
The results showed that most of the boron volatized during spectral lines are both suitable for determination of boron in
the acid-drying process where H3PO4 was not used for sample coal.
digestion (Table 4). This is attributed to the formation of If Be is used as the internal standard, the observed boron
volatile BF3 via reaction between boron and HF. However, in concentrations (whether based on the 10B or 11B spectral line)
the H3PO4−HNO3−HF digestion system, H3PO4 and boron are not as close to the certified values as those using Rh and In
as internal standards (see Table 5), although the mass-to-charge
Table 3. Relative Standard Deviations of Boron ratio (m/z) of 9Be is closer to both 10B and 11B than those of
103
Concentration in NIST Standard Coal Samples, Based on Rh and 115In. This is probably due to the higher
10 concentration of Be, compared to those of Rh and In in the
B Spectral Line at Different Resolution Modea
9 103 115
coal samples. NIST standard reference coal SRM1632c, for
Be Rh In example, contains 1.0 μg/g Be, and the average Be
sample HR SR HR SR HR SR concentrations in world coals and in Chinese coals are 1.6
SRM1632c 2.57 3.72 3.68 3.01 0.68 3.91 μg/g56 and 2.11 μg/g,57 respectively. However, the average In
SRM2682b 2.88 6.69 2.25 5.53 3.35 7.1 concentration in world coals and Chinese coals is only 0.0047
SRM2685b 0.94 4.55 1.65 4.35 1.76 4.86 μg/g56 and 0.0031 μg/g,57 respectively. Rh is very low and is
estimated to be <0.001 μg/g in coal.58 The higher Be and lower
a
HR, high-resolution mode; SR, standard-resolution mode. Rh and In concentrations in these coals suggest that both Rh
4519 dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522
Energy & Fuels Article

Table 5. Observed (Obs) and Certified (Cert) Values of Boron in NIST Standard Reference Coal Samples, as Well as Internal
Solution Recovery (Rec), Method Detection Limit (MDL), Relative Errors (RE), and Determination Coefficient (DC) of the
ICP-MS Analysis
10 11
B B
a
sample Rec (%) Cert (μg/g) Obs (μg/g) MDL (μg/L) RE (%) DC Obs (μg/g) MDL (μg/L) REa (%) DC
No Internal Standard
SRM1632c 62 47.1 0.65 24.1 0.9994 46.6 0.45 24.9 0.9994
SRM2682b 39 30.2 0.65 22.6 0.9994 30.3 0.45 22.2 0.9994
SRM2685b 109 85.1 0.65 21.9 0.9994 85.5 0.45 21.6 0.9994
9
Be Internal Standard
SRM1632c 83.75 62 54.9 0.87 11.5 0.9994 54.4 0.68 12.3 0.9995
SRM2682b 83.18 39 35.6 0.87 8.8 0.9994 35.7 0.68 8.4 0.9995
SRM2685b 83.31 109 99.9 0.87 8.3 0.9994 100.4 0.68 7.9 0.9995
103
Rh Internal Standard
SRM1632c 78.57 62 58.0 0.77 6.4 0.9995 57.4 0.62 7.4 0.9995
SRM2682b 79.74 39 36.6 0.77 6.3 0.9995 36.7 0.62 5.8 0.9995
SRM2685b 77.52 109 106.3 0.77 2.5 0.9995 106.8 0.62 2.0 0.9995
115
In Internal Standard
SRM1632c 78.62 62 57.8 0.84 6.8 0.9995 57.3 0.66 7.7 0.9995
SRM2682b 79.88 39 36.3 0.84 6.9 0.9995 36.5 0.66 6.4 0.9995
SRM2685b 77.75 109 105.7 0.84 3.1 0.9995 106.2 0.66 2.6 0.9995
a
RE = (|Obs − Cer|/Cer) × 100.

and In are better internal standards than Be, although the
former two elements have somewhat higher m/z ratios.
4. CONCLUSION
In summary, closed-vessel microwave digestion of unashed coal
combined with inductively coupled plasma mass spectrometry
(ICP-MS) analysis represents a reliable method for determi-
nation of boron concentration in coal. Closed-vessel microwave
digestion and the H3PO4−HNO3−HF reagents may avoid
boron volatilization during both the digestion and the
subsequent acid-drying processes. The use of 2% ammonia as
the rinse solution may effectively eliminate memory effects
during the ICP-MS analysis. The use of 103Rh or 115In as online
internal standards is more suitable than use of 9Be for boron
determination, because Rh and In are generally less abundant
than Be in coal.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: james.hower@uky.edu.
Notes
The authors declare no competing financial interest.
∥
Deceased.
■ ACKNOWLEDGMENTS
This research was supported by the National Key Basic
Research Program of China (No. 2014CB238900), National
Natural Science Foundation of China (No. 41272182), and
Program for Changjiang Scholars and Innovative Research
Team in University (IRT No. 13099).
■ REFERENCES
(1) Gluskoter, H. J.; Ruch, R. R.; Miller, W. G.; Cahill, R. A.; Dreher,
G. B.; Kuhn, J. K. Trace elements in coal: occurrence and distribution.
Ill. State Geol. Surv. Circ. 1977, 499, 1−154.
(2) Eskenazy, G.; Delibaltova, D.; Mincheva, E. Geochemistry of
boron in Bulgarian coals. Int. J. Coal Geol. 1994, 25, 93−110.
(3) Hower, J. C.; Ruppert, L. F.; Williams, D. A. Controls on boron
and germanium distribution in the low-sulfur Amos coal bed, Western
Kentucky coalfield, USA. Int. J. Coal Geol. 2002, 53, 27−42.
(4) Dai, S.; Zhang, W.; Ward, C. R.; Seredin, V. V.; Hower, J. C.; Li,
X.; Song, W.; Wang, X.; Kang, H.; Zheng, L.; Wang, P.; Zhou, D.
Mineralogical and geochemical anomalies of late Permian coals from
the Fusui Coalfield, Guangxi Province, southern China: influences of
terrigenous materials and hydrothermal fluids. Int. J. Coal Geol. 2013,
105, 60−84.
(5) Underwood, E. J. Trace Elements in Human and Animal Nutrition;
Academic Press: San Diego, CA, 1977; 545 pp.
(6) Valkovic, V. Trace Elements in Coal, Vol. II; CRC Press: Boca
Raton, FL, 1983; 281 pp.
(7) Swaine, D. J. Trace Elements in Coal; Butterworths: London,
1990; 278 pp.
(8) Goodarzi, F.; Swaine, D. J. Paleoenvironmental and environ-
mental implications of the boron content of coals. Geol. Surv. Can. Bull.
1994, 471, 1−46.
(9) Bouska, V.; Pesek, J. Boron in the aleuropelites of the Bohemian
massif. In 5th Meeting of the European Clay Groups, Prague, Czech
Republic, 1983; pp 147−155.
(10) Lyons, P. C.; Palmer, C. A.; Bostick, N. H.; Fletcher, J. D.;
Dulong, F. T.; Brown, F. W.; Brown, Z. A.; Krasnow, M. R.;
Romankiw, L. A. Chemistry and origin of minor and trace elements in
vitrinite concentrates from a rank series from the eastern United
States, England, and Australia. Int. J. Coal Geol. 1989, 13, 481−527.
(11) Riley, K. W.; French, D. H.; Lambropoulos, N. A.; Farrell, O. P.;
Wood, R. A.; Huggins, F. E. Origin and occurrence of selenium in
some Australian coals. Int. J. Coal Geol. 2007, 72, 72−80.
(12) Riley, K. W.; French, D. H.; Farrell, O. P.; Wood, R. A.;
Huggins, F. E. Modes of occurrence of trace and minor elements in
some Australian coals. Int. J. Coal Geol. 2012, 94, 214−224.
(13) Chen, J.; Liu, G.; Jiang, M.; Chou, C.-L.; Li, H.; Wu, B.; Zheng,
L.; Jiang, D. Geochemistry of environmentally sensitive trace elements
in Permian coals from the Huainan coalfield, Anhui, China. Int. J. Coal
Geol. 2011, 88, 41−54.
(14) Boyd, R. J. The partitioning behaviour of boron from tourmaline
during ashing of coal. Int. J. Coal Geol. 2002, 53, 43−54.
(15) Yunusa, I. A. M.; Loganathan, P.; Nissanka, S. P.; Manoharan,
V.; Burchett, M. D.; Skilbeck, C. G.; Eamus, D. Application of coal fly
ash in agriculture: A strategic perspective. Crit. Rev. Environ. Sci.
Technol. 2012, 42, 559−600.

4520 dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522

Energy & Fuels
(16) Cox, J. A.; Lundquist, G. L.; Przyjazny, A.; Schmulbach, C. D.
Leaching of boron from coal ash. Environ. Sci. Technol. 1978, 12, 722−
723.
(17) James, W. D.; Graham, C. C.; Glascock, M. D.; Hanna, A. S. G.
Water-leachable boron from coal ashes. Environ. Sci. Technol. 1982, 16,
195−197.
(18) Querol, X.; Umaña, J. C.; Alastuey, A.; Ayora, C.; Lopez-Soler,
A.; Plana, F. Extraction of soluble major and trace elements from fly
ash in open and closed leaching systems. Fuel 2001, 80, 801−813.
(19) Sear, L. K. A.; Weatherley, A. J., Dawson, A. R. The
environmental impacts of using fly ashThe UK producers
perspective. Presented at the 2003 International Ash Utilization
Symposium, Lexington, KY, 2003.
(20) Izquierdo, M.; Querol, X. Leaching behaviour of elements from
coal combustion fly ash: An overview. Int. J. Coal Geol. 2012, 94, 54−
66.
(21) Schwab, A. P. Extractable and plant concentrations of metals in
amended coal ash. In Trace Elements in Coal and Coal Combustion
Residues; Keefer, R. F., Sajwan, K. S., Eds.; Lewis Publishers: Boca
Raton, FL, 1993; pp 185−211.
(22) Farhat, A.; Ahmad, F.; Arafat, H. Analytical techniques for boron
quantification supporting desalination processes: A review. Desalina-
tion 2013, 310, 9−17.
(23) Korkmaz, M.; Yenigün, M.; Bakirdere, S.; Ataman, O. Y.;
Keskin, S.; Müezzinoglu, T.; Lekili, M. Effects of chronic boron
exposure on semen profile. Biol. Trace Elem. Res. 2011, 143, 738−750.
(24) Ward, C. R. Mode of occurrence of trace elements in some
Australian coals. Coal Geol. 1980, 2, 77−98.
(25) Finkelman, R. B. Modes of occurrence of environmentally
sensitive trace elements in coal. In Environmental Aspects of Trace
Elements in Coal; Swaine, D. J., Goodarzi, F., Eds.; Kluwer Academic
Publishers: Dordrecht, The Netherlands, 1995; Chapter 3, pp 24− 50.
(26) Querol, X.; Fernández-Turiel, J. L.; López-Soler, A. Trace
elements in coal and their behaviour during combustion in a large
power station. Fuel 1995, 74, 331−343.
(27) Querol, X.; Alastuey, A.; Lopez-Soler, A.; Plana, F.; Zeng, R.;
Zhao, J.; Zhuang, X. Geological controls on the quality of coals from
the West Shandong Mining District, Eastern China. Int. J. Coal Geol.
1999, 42, 63−88.
(28) Oliveira, M. L. S.; Ward, C. R.; Sampaio, C. H.; Querol, X.;
Cutruneo, C. M. N. L.; Taffarel, S. R.; Silva, L. F. O. Partitioning of
mineralogical and inorganic geochemical components of coals from
Santa Catarina, Brazil, by industrial beneficiation processes. Int. J. Coal
Geol. 2013, 116−117, 75−92.
(29) Doolan, K. J.; Turner, K. E.; Mills, J. C.; Knott, A. C.; Ruch, R.
R. Volatilities of Inorganic Elements in Coals during Ashing. ACS Div.
Fuel Chem., Prepr. 1984, 29 (1), 127−134.
(30) Eskenazy, G.; Dai, S.; Li, X. Fluorine in Bulgarian coals. Int. J.
Coal Geol. 2013, 105, 16−23.
(31) Meier, A. L.; Lichte, F. E.; Briggs, P. H.; Bullock, J. H., Jr. Coal
ash by inductively coupled plasma-atomic emission spectrometry and
inductively coupled plasma-mass spectrometry. In Analytical Methods
Manual for the Mineral Resource Surveys Program; Arbogast, B. F., Ed.;
U.S. Geological Survey Open File 96−525, 1996; pp 109−125.
(32) Huggins, F. E. Overview of analytical methods for inorganic
constituents in coal. Int. J. Coal Geol. 2002, 50, 169−214.
(33) Low, F.; Zhang, L. Microwave digestion for the quantification of
inorganic elements in coal and coal ash using ICP-OES. Talanta 2012,
101, 346−352.
(34) Gürdal, G. Geochemistry of trace elements in Ç an coal
(Miocene), Ç anakkale, Turkey. Int. J. Coal Geol. 2008, 74, 28−40.
(35) Ž ivotić, D.; Wehner, H.; Cvetković, O.; Jovančićević, B.; Gržetić,
I.; Scheeder, G.; Vidal, A.; Šajnović, A.; Ercegovac, M.; Simić, V.
Petrological, organic geochemical and geochemical characteristics of
coal from the Soko mine, Serbia. Int. J. Coal Geol. 2008, 73, 285−306.
(36) Kalkreuth, W.; Holz, M.; Mexias, A.; Balbinot, M.; Levandowski,
J.; Willett, J.; Finkelman, R.; Burger, H. Depositional setting, petrology
and chemistry of Permian coals from the Paraná Basin: 2. South Santa
Catarina Coalfield, Brazil. Int. J. Coal Geol. 2010, 84, 213−236.
4521
Article
(37) Ammann, A. A. Inductively coupled plasma mass spectrometry
(ICP MS): A versatile tool. J. Mass Spectrom. 2007, 42, 419−427.
(38) Dufailly, V.; Noël, L.; Guérin, T. Determination of chromium,
iron and selenium in foodstuffs of animal origin by collision cell
technology, inductively coupled plasma mass spectrometry (ICP-MS),
after closed vessel microwave digestion. Anal. Chim. Acta 2006, 565,
214−221.
(39) Dufailly, V.; Noël, L.; Guérin, T. Optimisation and critical
evaluation of a collision cell technology ICP-MS system for the
determination of arsenic in foodstuffs of animal origin. Anal. Chim.
Acta 2008, 611, 134−142.
(40) Houk, R. S.; Fassel, V. A.; Flesch, G. D.; Svec, H. J.; Gray, A. L.;
Taylor, C. E. Inductively coupled argon plasma as an ion source for
mass spectrometric determination of trace elements. Anal. Chem.
1980, 52, 2283−2289.
(41) Papaefthymiou, H.; Papatheodorou, G.; Christodoulou, D.;
Geraga, M.; Moustakli, A.; Kapolos, J. Elemental concentrations in
sediments of the Patras Harbour, Greece, using INAA, ICP-MS and
AAS. Microchem. J. 2010, 96, 269−276.
(42) Phan-Thien, K. Y.; Wright, G. C.; Lee, N. A. Inductively coupled
plasma−mass spectrometry (ICP-MS) and -optical emission spectros-
copy (ICP−OES) for determination of essential minerals in closed
acid digestates of peanuts (Arachis hypogaea L.). Food Chem. 2012,
134, 453−460.
(43) Jarvis, I.; Jarvis, K. E. Plasma spectrometry in the earth sciences:
Techniques, applications and future trends. Chem. Geol. 1992, 95, 1−
33.
(44) Sia, S.-G.; Abdullah, W. H. Enrichment of arsenic, lead, and
antimony in Balingian coal from Sarawak, Malaysia: Modes of
occurrence, origin, and partitioning behaviour during coal combustion.
Int. J. Coal Geol. 2012, 101, 1−15.
(45) Swanson, S. M.; Engle, M. A.; Ruppert, L. F.; Affolter, R. H.;
Jones, K. B. Partitioning of selected trace elements in coal combustion
products from two coal-burning power plants in the United States. Int.
J. Coal Geol. 2013, 113, 116−126.
(46) Wagner, N. J.; Tlotleng, M. T. Distribution of selected trace
elements in density fractionated Waterberg coals from South Africa.
Int. J. Coal Geol. 2012, 94, 225−237.
(47) Li, X.; Dai, S.; Zhang, W.; Li, T.; Zheng, X.; Chen, W.
Determination of As and Se in coal and coal combustion products
using closed vessel microwave digestion and collision/reaction cell
technology (CCT) of inductively coupled plasma mass spectrometry
(ICP-MS). Int. J. Coal Geol. 2014, 124, 1−4.
(48) Kadar, A.; Noël, L.; Chekri, R.; Vastel, C.; Millour, S.; Guérin, T.
Optimisation of ICP-MS collision/reaction cell conditions for the
determination of elements likely to be interfered (V, Cr, Fe, Co, Ni, As
and Se) in foodstuffs. Talanta 2011, 85, 2605−2613.
(49) Fadda, S.; Rivoldini, A.; Cau, I. ICP-MS determinaiton of 45
trace elements in whole coal using microwave oven acid digestion for
sample preparation. Geostand. Newsl. 1995, 19, 41−54.
(50) Tozsin, G. Hazardous elements in soil and coal from the Oltu
coal mine district, Turkey. Int. J. Coal Geol. 2014, 131, 1−6 (DOI:
10.1016/j.coal.2014.05.011).
(51) Dai, S.; Li, T.; Seredin, V. V.; Ward, C. R.; Hower, J. C.; Zhou,
Y.; Zhang, M.; Song, X.; Song, W.; Zhao, C. Origin of minerals and
elements in the Late Permian coals, tonsteins, and host rocks of the
Xinde Mine, Xuanwei, eastern Yunnan, China. Int. J. Coal Geol. 2014,
121, 53−78.
(52) Shi, S.; Wen, H.; Li, B.; He, H.; Lv, C. Determination of carbon
and sulfur in geological samples by high frequency IR-adsorption
spectrometry method. Rock Miner. Anal. 2001, 20, 267−271 (in Chin.
with Engl. abstract).
(53) Li, B.; Ma, X.; Yang, H.; He, H. Determination of boron, arsenic
and sulfur in geological samples by inductively coupled plasma atomic
emission spectrometry with sample treatment by pressurized
decomposition. Rock Miner. Anal. 2003, 22, 241−247 (in Chin. with
Engl. abstract).
dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522
Energy & Fuels Article

(54) Al-Ammar, A.; Gupta, R. K.; Barnes, R. M. Elimination of boron

memory effect in inductively coupled plasma-mass spectrometry by
addition of ammonia. Spectrochim. Acta, Part B 1999, 54, 1077−1084.
(55) Huang, G.; Dou, Y.; Zhang, J.; Zhang, P.; Gao, X. Simultaneous
determination of boron, bromine, and iodine in groundwater samples
by inductively coupled plasma-mass spectrometry. Rock Miner. Anal.
2008, 27, 25−28 (in Chin. with Engl. abstract).
(56) Ketris, M. P.; Yudovich, Y. E. Estimations of Clarkes for
carbonaceous biolithes: world average for trace element contents in
black shales and coals. Int. J. Coal Geol. 2009, 78, 135−148.
(57) Dai, S.; Ren, D.; Chou, C.-L.; Finkelman, R. B.; Seredin, V. V.;
Zhou, Y. Geochemistry of trace elements in Chinese coals: A review of
abundances, genetic types, impacts on human health, and industrial
utilization. Int. J. Coal Geol. 2012, 94, 3−21.
(58) Finkelman, R. B. Trace and minor elements in coal. In Organic
Geochemistry: Principles and Applications; Engel, M. H., Macko, S. A.,
Eds.; Plenum Press: New York, 1993; pp 593−607.

■ NOTE ADDED AFTER ASAP PUBLICATION

The caption of Figure 1, the Acknowledgments paragraph, and
reference 58 were modified in the version of this paper
published June 27, 2014. The correct version published July 1,
2014.

4522 dx.doi.org/10.1021/ef500912a | Energy Fuels 2014, 28, 4517−4522