APPLICATION NOTE 1145

Determination of halogens in coal using combustion

ion chromatography
Authors Introduction
Adelon Agustin1, Carl Fisher2, and Despite the emergence of alternative energy sources (e.g. natural gas, biofuel,
Mark Manahan1 wind, and solar), 40% of the world’s electricity is generated using coal.1 When
1
COSA Xentaur, Yaphank, NY, USA coal is burned, the exhaust contains halogens that can be released into the
2
Thermo Fisher Scientific, Sunnyvale, atmosphere as acid gases such as hydrogen chloride (HCl) and hydrogen
CA, USA fluoride (HF), which can harm vegetation, animals, and infrastructure directly
or cause acid rain.2 Mercury (Hg) is another toxic pollutant that is present in
Keywords coal exhaust. To reduce emissions of Hg and other toxic pollutants by coal
CIC, Dionex ICS-2100, Dionex burning power plants, the U.S. Environmental Protection Agency (U.S. EPA)
Integrion HPIC system, Dionex IonPac published the Mercury and Air Toxics Standards (MATS) rule, which established
AS15, AQF-2100H technology-based emissions limitation standards that reflected the levels
achieved by the best-performing sources in operation at that time.3 To meet
Goal these standards, power plants have had to incorporate pollutant removal
Combine automated combustion technologies into their design or retrofit existing facilities. The ability of pollution
with ion chromatography to quantify control devices to capture Hg from flue gases is enhanced in the presence
halogens in coal. of halogens. Coals with higher amounts of chloride are more likely to result in
greater concentrations of the oxidized forms of mercury, which are water soluble
and can be captured by the wet scrubbers used to reduce sulfur emissions.4
Determination of the levels of halogens in coal can be used to predict the
efficacy of a particular pollution control strategy and suggest what alterations
would be required to meet federal standards.

Because coal is a solid that is not readily solubilized, accessing and quantifying
its constituents requires some form of sample preparation prior to analysis.

1
Combustion methods have been developed that ensure gases. The combustion by-product gases, including HX
complete decomposition of solid and semi-solid samples and SO2/SO3, are passed through an aqueous absorbing
and concomitant release of halogens. These methods solution and directly injected into the IC instrument,
include the use of the Wickbold apparatus, combustion thereby eliminating the sample matrix and any associated
(oxygen) bombs, the Schöniger flask, microwave-induced interferences (Figure 1). The absorbing solution used is
combustion (MIC), and automated furnace combustion dependent on the anions of interest. Typically, deionized
systems such as the one described here.5 After the (DI) water is used for halides or an aqueous hydrogen
sample is combusted, detection can include precipitation peroxide solution if halides and sulfur are being analyzed.
with silver nitrate followed by gravimetric analysis6 or The hydrogen peroxide is required to ensure all the sulfur
measurement by ion chromatography (IC),7 coulometric anions are oxidized to sulfate prior to injection into the
titration,8 or ion selective electrodes9. IC. The fully automated process of CIC saves time and
labor, increases reproducibility, and eliminates the need to
Combustion IC (CIC) uses the thermochemical dispose of hazardous chemicals used in acid digestions or
decomposition of organic matter in the presence of oxygen back extractions.
(oxidative pyrolysis) to convert the analytes of interest to

Gas Absorption Furnace Sample Changer Process Flow

Oxygen Ar/02
5 Washing Sampling boat Injection port 1 Absorbent is sent to the absorption tube
Sampling loop

2 Sample is burned (combustion)

4
Ion Injection valve
Chromatography 3 Absorbent absorbs the combusted gas
Automatic tube wash
Absorption tube

Combustion tube
Suction
2 Sample burning 4 Absorbent is injected into the IC system
1 Absorbent H20

3 Absorbing the produced gas 5 Absorption tube is rinsed/cleaned with solution

Drain

Figure 1. Diagram of a CIC system.

In this application note, coal samples were combusted • Thermo Scientific Dionex EGC III KOH cartridge
in the Mitsubishi® AQF-2100H system and then fluoride (P/N 074532)
and chloride were accurately and precisely determined
• Thermo Scientific Dionex CR-ATC Continuously
using the Thermo Scientific Dionex ICS-2100 Ion
Regenerated Anion Trap Column (P/N 060477)
Chromatography System with a Thermo Scientific™
Dionex™ IonPac™ AS15 anion-exchange column set. • Thermo Scientific™ Dionex™ AERS™ 500 Anion
Electrolytically Regenerated Suppressor, 4 mm
Equipment (P/N 082540)
• Mitsubishi Automatic Quick Furnace AQF-2100H
− Solid Auto Sampler ASC-240S Software
• Thermo Scientific™ Dionex™ Chromeleon™
––Horizontal Furnace HF-210
Chromatography Data System (CDS) software,
- AQF-2100H Mullite Pyrolysis Set (P/N AQ3QM5) version 7.2

––Gas Absorption Unit GA-210 • Mitsubishi NSX-2100 version 2.0.2.0

––External Solution Selector ES-210 Reagents and Standards

• DI water, Type I reagent grade, 18 MΩ-cm resistivity or
• Dionex ICS-2100 Ion Chromatography System (The better
Thermo ScientificTM DionexTM IntegrionTM HPICTM system
can also be used for this application)
2
• Fisher Scientific, ACS Grade Preparation of Standards
Stock Solutions
––Sodium bromide (P/N S255)
To prepare 1000 mg/L stock solutions, accurately weigh
––Sodium chloride (P/N S271) the amounts of standard compounds listed in Table 1,
transfer to a 100 mL volumetric flask, and fill to mark with
––Sodium fluoride (P/N S299)
DI water. Mix thoroughly. Concentrated standards should
be stable for at least one month when stored at 4 °C.
Sample
Table 1. Mass of standard compound to prepare 100 mL of a
Coal samplers were obtained in powder form and were 1000 mg/L stock halide solution.
stored at room temperature.
Analyte Compound Mass (g)
IC Conditions Bromide Sodium bromide 0.129
Chloride Sodium chloride 0.164
Columns: Dionex IonPac AG15 Guard, 4 × 50 mm
Fluoride Sodium fluoride 0.221
(P/N 053942)
Dionex IonPac AS15 Separation, 4 × 250 mm
(P/N 053940) Working Standard Solutions
Prepare the highest concentration working standard
Eluent Source: Dionex EGC III KOH cartridge with Dionex
solutions [1.0 mg/L (F, Br) and 5.0 mg/L (Cl)] by pipetting
CR-ATC column
the appropriate amount of 1000 mg/L stock into a
Eluent Conc.: 38 mM KOH 100 mL volumetric flask and diluting to the mark with
Flow Rate: 1.2 mL/min DI water. Prepare the 0.1, 0.25, 0.5 mg/L (F, Br) and
0.1, 0.5, 1.0 mg/L (Cl) standard solution mixes by diluting
Column Temp.: 30 °C
the highest concentration working standards with DI
Inj. Volume: 200 µL (Full loop) water. When the standard solutions are not in use, store
Detection: Suppressed conductivity, Dionex AERS at 4 °C.
500 suppressor, 4 mm, recycle mode,
113 mA System Preparation and Configuration
Background IC System
Install, hydrate, and condition the Dionex EGC III KOH
Total Conductance: ~ 1.1 µS
eluent generator cartridge as described in the product
Noise: < 1 nS manual.10 Refer to the Dionex Integrion HPIC System
System Backpressure: ~1800 psi Operator’s Manual14 if you are using that system rather
than the Dionex ICS-2100 IC system. Install and hydrate
Combustion Conditions
the Dionex CR-ATC trap column11 and the Dionex AERS
Mass Combusted: 10–55 mg 500 suppressor.12 Finish the system setup according to
Furnace Inlet Temp.: 900 °C the product manuals and the Dionex ICS-2100 system
Furnace Outlet Temp.: 1050 °C Operator’s Manual.13 Install and condition the guard and
separation columns for 30 min prior to installing the
Argon Flow (Carrier): 200 mL/min
columns in-line with the suppressor.
Oxygen Flow (Combustion Agent): 400 mL/min
Humidified Argon Flow: 100 mL/min Combustion System
Coal, petroleum, and mineral products that contain high
Humidified Argon Pump Setting: 2
levels of alkali and alkaline earth metals (such as sodium,
Pyrolysis Tube: Ceramic insert potassium, and calcium) can cause rapid devitrification
Sample Boat: Ceramic (crystal formation causing small cracks to form) of quartz
Absorption Solution: Water components and combustion tubes requiring their
frequent replacement, resulting in higher system
Absorption Tube Size: 10 mL
maintenance costs. Additionally, accuracy and recovery of
Absorption Solution Volume: 10 mL halides and sulfur are compromised by high temperature
AQF Mode: Constant Volume combustion in a quartz pyro-tube. As a result, this
application requires the use of a ceramic (mullite)
3
 
!





pyro-tube insert. Refer to the Mitsubishi AQF-2100H
instruction manual for complete system setup.15




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Calculation of Analyte Concentration in Coal 2:+49
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Because the IC is calibrated by direct injection of liquid
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the concentration of analytes that were present in the coal /4:9+8


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prior to combustion. To determine the dilution, make an


Figure 2. Separation of anion standards.
aqueous 2–5 mg/L phosphate standard and compare the
area counts of the peak via direct injection to that from To determine the linear calibration ranges, the peak
dilution into the absorption tube of the gas absorption responses to concentration were determined using
unit (GA-210). Multiply this peak area ratio by the triplicate injections of calibration standards over a 10- or
dispense volume of the absorption solution (set in the 50-fold dilution range (Table 2). Plotting peak area versus
(Weight Before Drying) – (Weight After Drying)
GA parameters)
% Moisture = to get the final volume of the absorption concentration demonstrated linearity for the
Weight Before Drying
solution before injection into the IC. Multiply the final concentration ranges used, as exemplified by the fluoride
volume by 1000 when the combustion sample size is calibration curve (Figure 3). Coefficients of determination
in mg. (r2) ranged from 0.9987 to 0.9995.

Table 2. Anion calibration ranges and coefficients of determination.

Dilution = ( (Area of Dilute Injection)
(
(Area of Direct Injection)
)
) * (Absorption Solution Volume) * 1000
Concentration
Analyte r2
(mg/L)
Bromide 0.1–1.0 0.9987
Dry Coal Calculations
(Weight Before Drying) – (Weight After Drying) Chloride 0.1–5.0 0.9999
Because
% Moisture =coal powder readily absorbs moisture from the
atmosphere, which WeighttoBefore
adds
Concentration
Drying the analyte values
its mass, 
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Fluoride 0.1–1.0 0.9998

determined
Concentrationby
= CIC
( 100 –are referred to as wet unless it has
Dry
been dried. To determine
% Moisture
)
100 dry values, weigh coal into a 

heat resistant container and then dry in an oven at
>100 °C for ~1.5 h. Reweigh the sample and calculate 

the
Dilution = ( (
moisture
(Areacontent and dry) concentration:
of Direct Injection)
(Absorption Solution Volume) 1000
(Area of Dilute Injection)
* ) *


(Weight Before Drying) – (Weight After Drying)

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% Moisture = 7


Weight Before Drying


Concentration


Dry Concentration = 100 – % Moisture
(100
)


Results ( (Area of Direct Injection)

Dilution = ( and Discussion ) * (Absorption Solution Volume)
(Area of Dilute Injection) )* 1000 

Method Linear Calibration Ranges 






Because National Institute of Standards and Technology 54)+497'9/54

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(NIST)-certified coal samples were not available with a
Figure 3. Fluoride calibration curve.
suitable range of analyte concentrations for calibration by
combustion, standard halide solutions were prepared in
Concentration
Dry Concentration
DI water and =directly
100 – %injected
Moisture into the IC system
( )
100required calibration curves.
(Figure 2) to obtain the

4
Confirmation of Calibration Good precision was achieved as evidenced by the relative
To confirm the validity of the IC calibration, fluoride was standard deviation (RSD) values calculated from the three
determined in triplicate 50 mg aliquots of National replicates (0.2–5.5). In addition to fluoride and chloride,
Institute of Standards and Technology (NIST) standard peaks were detected at 7.3 and 8.2 min. These were likely
reference material 163516 (subbituminous coal) (Table 3). sulfite and sulfate, respectively. The amount of sulfur
The 27.6 mg/kg (2.1% RSD) value was in agreement with present in CIC samples can be determined by adding
that of the certified reference material (25.9 ± 3.3 mg/kg). hydrogen peroxide (H2O2) to the absorption solution at a
Chloride and bromide were detected in this material, but concentration that is high enough to ensure complete
they were not certified. oxidation of sulfite to sulfate. Caution: g/kg sulfur can be
typically found in coal, which would require the use of an
Determination of Halogens in Coal absorbent containing H2O2 in molar excess ( ≥ 900 mg/L).
Because the moisture content was not determined, the Using H2O2 at this concentration can result in the
concentrations reported here are the wet values. Coal appearance of contaminants that interfere with fluoride
samples contained 60–200 mg/kg fluorine, while chlorine determination and could damage the column and other
was generally present at higher levels and had a broader instrument components. Because water (with no H2O2)
range (30–1400 mg/kg; Figure 4 and Table 3). Bromine was was used as the absorbent for the data presented here,
detected in some of the coal samples but the multiple peaks corresponding to the sulfur-containing
concentrations were below the lowest level standard species were observed.
(0.1 mg/L).
Conclusion



This application note demonstrates that chlorine and
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coal using combustion ion chromatography. Analysis was




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References































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3-
1. American Coal Foundation. Fast Facts About Coal, http://teachcoal.org/fast-facts-

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'7(54'9+
$:2,/9+
$:2,'9+

about-coal (accessed Sept. 28, 2015).
2. Environmental Health and Engineering, Inc. Emissions of Hazardous Air Pollutants
Figure 4. Separation of anions in absorption solution from coal from Coal-Fired Power Plants, Needham, MA, 2011.
combustion.Analyte concentrations have not been adjusted for the
3. U.S. Environmental Protection Agency. Mercury and Air Toxics Standards (MATS).
mass and dilution (see Table 3 for these values).
http://www3.epa.gov/mats/ (accessed Sept. 28, 2015).
4. United States Geological Survey. Mercury and Halogens in Coal—Their Role in
Determining Mercury Emissions From Coal Combustion. Fact Sheet 2012–3122,
Table 3. Fluorine and chlorine results in coal samples. Reston, VA, 2012.
5. Mello, P.A., Barin, J.S., Duarte, F.A., Bizzi, C.A., Diehl, L.O., Muller, E.I., and
Fluorine Chlorine Flores, E.M. Analytical Methods for the Determination of Halogens in Bioanalytical
Sample
mg/kg RSD mg/kg RSD Sciences: a Review. Anal. Bioanal. Chem., 2013, 405, 7615-7642.
6. ASTM D808-11. Standard Test Method for Chlorine in New and Used Petroleum
NIST 1635 27.6 2.1 -- --
Products (High Pressure Decomposition Device Method), 2011.
1 187 1.5 723 2.5 7. Zhang, S., Zhao, T., Wang, J., Qu, X, Chen, W. and Han, Y. Determination of
2 221 0.23 28.6 0.42 Fluorine, Chlorine and Bromine in Household Products by means of Oxygen Bomb
Combustion and Ion Chromatography.
3 75.9 3.2 1420 3.3 J Chromatogr. Sci., 2013, 51, 65-69.
4 77.5 1.2 211 0.4 8. ASTM D6721 - 01(2015). Standard Test Method for Determination of Chlorine in
5 56.5 5.0 1230 1.2 Coal by Oxidative Hydrolysis Microcoulometry, 2001.
9. ASTM D5987 - 96(2007). Standard Test Method for Total Fluorine in Coal and
6 195 3.3 81.7 5.5
Coke by Pyrohydrolytic Extraction and Ion Selective Electrode or Ion Chromatograph
n=3 Methods, 1996.
10. Thermo Fisher Scientific. Product Manual for Eluent Generator Cartridges. Doc. No.
065018-05, Sunnyvale, CA, 2014.
11. Thermo Fisher Scientific. Product Manual for CR-ATC. Doc. No. 031910-03,
Sunnyvale, CA, 2010.
12. Thermo Fisher Scientific. Product Manual for the Dionex ERS 500 Suppressor. Doc.
No. 031956-09, Sunnyvale, CA, 2013.
13. Thermo Fisher Scientific. Dionex ICS-2100 Ion Chromatography System Operator’s
Manual. Doc. No. 065291, Sunnyvale, CA, 2012.
14. Thermo Fisher Scientific. Dionex Integrion HPIC System Operator’s Manual. Doc.
No. 22153-97003 Sunnyvale, CA 2016
15. Mitsubishi Chemical Analytech, Co., Ltd.
Instruction Manual for Automatic Quick Furnace AQF-2100H. Doc. No.
ZN2AQHE-00, Chigasaki, Kanagawa Prefecture, Japan, 2010.
16. National Institute of Standards and Technology. Certificate of Analysis, Standard
Reference Material 1635, Trace Elements in Coal (Subbituminous), Gaithersburg,
MD, 2000.

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