Simultaneous determination of halogens (F, Cl, Br, and I) in coal

Fuel xxx (2011) xxx–xxx
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Short communication
Simultaneous determination of halogens (F, Cl, Br, and I) in coal using
pyrohydrolysis combined with ion chromatography
Bingxian Peng, Daishe Wu ⇑, Jinhu Lai, Huayun Xiao, Ping Li
Department of Environmental Science and Engineering, Nanchang University, Nanchang 330031, China
a r t i c l e
i n f o
Article history:
Received 22 May 2011
Received in revised form 4 December 2011
Accepted 8 December 2011
Available online 21 December 2011
Ion chromatography
a b s t r a c t
A method for the determination of halogens (F, Cl, Br, and I) in coal using pyrohydrolysis for sample digestion and ion chromatography is proposed. The pyrohydrolysis conditions and the types and concentrations of the absorption solutions are optimized. The limits of detection of the method are 0.045, 0.072,
0.15, and 0.25 lg g 1 for F, Cl, Br, and I, respectively. With its simplicity, precision, accuracy, and economy, the proposed method can be widely used for the routine analysis of all four halogens in coal.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Monitoring the halogen levels in coal is important because of
their effects on human health and the environment. Few methods
can be adopted to determine halogens in coal simultaneously. F
can only be determined through ion chromatography (IC) and ionselective electrode (ISE), whereas instrumental neutron activation
analysis (INAA) and inductively coupled plasma-mass spectrometry
(ICP-MS) can only analyze Cl, Br, and I [1–4]. Sample decomposition
is a critical step in halogen analysis. Halogens are volatile and readily lost when the sample is treated; furthermore, the reagents used
for sample digestion may interfere with the determination process
itself. To eliminate these drawbacks, pyrohydrolysis and microwave-induced combustion (MIC) have been proven effective and
reliable digestion methods for determining halogens in coal and
oil [2–9]. MIC combined with IC, a routine and classic analytical
method for determining halogens in water [10], has been successfully used to determine halogens simultaneously in coal [4]. However, about 15% of Chinese coal has less than 2.5 lg g 1 Br and 75%
have less than 3.0 lg g 1 I. Therefore, the limits of detections (LODs)
for Br and I (2.5 and 3.0 lg g 1, respectively) obtained using IC coupled with MIC is relatively high [4].
To lower the LODs of Br and I further, the present study establishes a quantitative method for determining F, Cl, Br, and I in coal
using the IC system after pyrohydrolysis. The pyrohydrolysis conditions, as well the types and concentrations of the absorption
⇑ Corresponding author. Tel./fax: +86 791 83969595.
E-mail address: [email protected] (D. Wu).
solutions are optimized. The method is validated using certified
reference coals (for F) or spikes (for Cl, Br, and I).
2. Experimental
2.1. Apparatus
The pyrohydrolysis apparatus was developed as mentioned in
our previous study [5]. An IC system, the 861 Advanced Compact
IC with an 838 Advanced Sample Processor (Metrohm AG, Herisau,
Switzerland), was used for analysis. A mixture of 1.8 mM Na2CO3
and 1.7 mM NaHCO3 at a flow rate of 1 mL min 1 served as the eluent. A solution of 50 mM H2SO4 was used as the regenerant. The
volume of the sample injection loop was 10 lL.
2.2. Reagents, samples, and certified reference materials
The Na2CO3 and NaHCO3 were of analytical reagent grade
(Merck, Darmstadt, Germany). Standard stock solutions containing
1000 mg L 1 F , Cl , Br , and I were prepared by dissolving an
appropriate amount of their corresponding sodium salts at 99.9%
purity (Merck, Darmstadt, Germany) in water. Ultrapure water,
with a resistance of 18.2 MX cm, was used to prepare the
The four samples were collected and prepared in accordance
with the Chinese standard method for coal preparation [11]. To
determine the accuracy of the analysis of the actual coal samples,
four Chinese soil reference materials (SRMs) for F, Cl, Br, and I
(GBW07403, GBW07404, GBW07405, and GBW07407) and three
0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Peng B et al. Simultaneous determination of halogens (F, Cl, Br, and I) in coal using pyrohydrolysis combined with ion
chromatography. Fuel (2011), doi:10.1016/j.fuel.2011.12.011
B. Peng et al. / Fuel xxx (2011) xxx–xxx
coal reference materials for F (GBW11121, GBW11122, and
GBW11123) were adopted.
3.2. Limits of detection
The LODs of F, Cl, Br, and I (S/N = 3) during the pyrohydrolysis
with IC determination were 0.045, 0.072, 0.15, and 0.25 lg g 1,
2.3. Procedures
A 1.0 g coal sample (100 mesh) was evenly mixed with 0.25 g
silica (20–50 mesh), placed in a porcelain boat, and then covered
with 1.5 g silica. A tube furnace was heated to preset temperatures
of 500–1100 °C. The oxygen flow rate was preset to 20–
120 mL min 1. A 15 mL absorption solution was placed into a
60 mL volumetric flask and then placed in an ice bath (<25 °C) to
absorb the halogens released from the coal samples. The charged
porcelain boat within the silica boat was gradually moved to the
center of the high-temperature zone within 10 min. The coal was
maintained in the high temperature zone for a preset time of 10–
20 min. The other operations were the same as in our previous
study [5].
2.4. Calibration and sample analysis
The standard working solutions were prepared fresh daily by
serially diluting stock standard solutions using ultrapure water.
Appropriate amounts of the standard working solution were
placed in Metrohm autosampler tubes, and filled to 10 mL with
ultrapure water. The solutions were then analyzed through IC.
The method was calibrated with standard solutions of F , Cl ,
Br , and I prior to the determinations. A 10 mL sample of the
absorption solution was pipetted into a Metrohm autosampler
tube, and then analyzed via IC.
For comparative purposes, the F content in coal was determined
by ISE. The I content in the coal was determined through catalytic
spectrophotometry (CS) [5].
3. Results and discussion
3.1. Optimization of the pyrohydrolysis conditions and the absorption
Pyrohydrolysis was adopted to digest the coal samples and separate the halogens from the sample matrix. The separation depended mainly on the variations in temperature, time, oxygen
flow rate, and the volume and concentration of the absorption
solution. The pyrohydrolysis conditions were optimized specifically as follows: pyrohydrolytic temperature of 1050 °C, pyrohydrolytic time of 25 min, and oxygen flux of 90 mL min 1.
The literature reports that a mixture of Na2CO3 and NaHCO3
solutions, tetramethyl ammonium hydroxide (TMAH), NaOH, and
Na2SO3, could be used to absorb the released halogens when the
samples were digested through pyrohydrolysis [2,4,5,12]. The effects of the species in the absorption solution on the halogen analysis are shown in Table 1. A mixture of 7.2 mM Na2CO3 and 6.8 mM
NaHCO3, a pH buffer solution (pH = 10.3), was found to be the best
absorption solution. The matrix effects were also minimized during
the IC analysis.
3.3. Accuracy and precision
The accuracy of the proposed method was evaluated by determining the Chinese SRMs with certified halogen values and analyzing the recoveries in the coal samples that had been spiked with
SRMs. The measured results are in reasonable agreement with
the certified concentrations and the F and I values determined
through ISE and CS, respectively. The recoveries ranged from
96.6–105%, 93.4–108%, 92.3–107%, and 93.6–103% for F, Cl, Br,
and I, respectively, with corresponding mean values of 102%,
98.5%, 102%, and 97.3%. The relative standard deviations of the
six repeated analyses of the four coal samples ranged from 0.30%
to 0.79% for F, with an average value of 0.51%. The values for Cl ranged from 0.18% to 0.69%, with an average value of 0.41%. The values
for Br ranged from 0.30% to 2.40%, with an average value of 1.11%.
The values for I ranged from 1.88% to 4.24%, with an average value
of 3.22%. This method is thus accurate for determining the halogen
content in coal.
3.4. Analysis of coals with very low bromine and iodine levels
The proposed method is accurate for the determination of F and
Cl in all coal samples and for the determination of Br and I in most
coal samples. However, in a fraction of coal samples, the levels of
Br and I were too low (Br < 0.15 lg g 1, I < 0.25 lg g 1) to be detected by the proposed method. For these samples, 5.0 g was collected to improve the concentration of the final solution. The
results show that even relatively low Br levels in coal can be accurately determined via IC combined with pyrohydrolysis using larger samples. The concentration of the final solution for I in coal
with low sulfur (S) content can also be improved by increasing
the mass of the sample. Considering the SO24 peak is just in front
of the I peak in the chromatogram, this may interfere with the
I peak in certain coal that have high S levels. The I content of these
coals, the I content of which is less than 0.25 lg g 1 and with the
SO24 peak overlapping the I peak in the chromatogram, can be
determined using CS, which can be adopted for analyzing coals
with I levels as low as 0.04 lg g 1 [13].
3.5. A comparison of the proposed method with other methods for
simultaneously determining halogens in coal
A comparison of the methods for simultaneously determining
halogens in coal is shown in Table 2. The LODs for the halogens
in the proposed method are lower than that of the method that
uses MIC digestion combined with IC. The LODs for Br and I in
the proposed method using IC are comparable those using NAA
Table 1
Determination of F, Cl, Br, and I in Chinese SRM GBW07404 through IC using various absorption solutions after pyrohydrolysis (n = 6; uncertainties are standard deviations).
Determined value (lg g
Certified value (lg g
0.05 M NaOH
50 lg mL
502 ± 2.5
30.0 ± 0.1
541 ± 3.1
35.0 ± 0.2
3.20 ± 0.35
0.5% (v/v) TMAH
Mixture of 7.2 mM Na2CO3 and 6.8 mM NaHCO3
565 ± 2.9
37 ± 0.2
543 ± 2.7
40 ± 0.2
3.80 ± 0.42
9.00 ± 0.30
540 ± 25
4.0 ± 0.7
9.4 ± 1.1
Informed value.
nd: Not determined.
Please cite this article in press as: Peng B et al. Simultaneous determination of halogens (F, Cl, Br, and I) in coal using pyrohydrolysis combined with ion
chromatography. Fuel (2011), doi:10.1016/j.fuel.2011.12.011
B. Peng et al. / Fuel xxx (2011) xxx–xxx
Table 2
Comparison of methods for simultaneously determining halogens in coal.
Literature sources
Sample mass (g)
Digestion technique
Absorbing solution
LODs (lg g 1)
Flores et al., 2008 [4]
Landsberger et al., 1989 [1]
Bettinelli et al., 2002 [2]
This work
6 mL of 50 mM
Epithermal NAA
20 mL of 1.8 mM Na2CO3/1.7 mM
15 mL of 7.2 mM Na2CO3/6.8 mM
Determined by IC.
Determined by ICP-MS.
and ICP-MS. IC is more accessible and more economical compared
with the nuclear reactor required for NAA and ICP-MS.
4. Conclusions
A method that combines pyrohydrolysis digestion with IC has
been developed to simultaneously determine F, Cl, Br, and I in coal.
Better LODs, which were 0.045, 0.072, 0.15, and 0.25 lg g 1 for F,
Cl, Br, and I respectively, were achieved, which met the analytical
requirements for quantifying trace halogens in most coal types.
The lower Br and I levels in some coal can be determined by increasing their mass (with the exception of I in certain coal that have high S
content). The proposed method was confirmed to be accurate and
precise. An additional advantage of this method is that it employs
instrumentation, which can be acquired and maintained at lower
costs compared with those used in INAA and ICP-MS.
This work was sponsored by the National Natural Science Foundation of China (Grant Nos. 40973080 and 41173115).
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Please cite this article in press as: Peng B et al. Simultaneous determination of halogens (F, Cl, Br, and I) in coal using pyrohydrolysis combined with ion
chromatography. Fuel (2011), doi:10.1016/j.fuel.2011.12.011