CHARACTERIZATION OF COAL,

COAL ASH AND COAL FLY ASH

USING BORATE FUSION FOR ICP
ANALYSIS

Introduction
Coal is the most abundant fossil fuel in the world [1]. It has been used by humans for centuries and is still widely used today
to produce electricity, steel and industry materials such as cement [2].

It is essential for industries to characterize coal to fully understand its use as well as to manage the recovery of its derivative
products in order to reduce the environmental impact. Characterization also prevents damages on industrial equipment
caused by mineral deposit in furnaces and kettles [3].

The purpose of this project is to demonstrate that precision and accuracy criteria in standard methods such as ASTM D6357,
ASTM D6349 and AS 1038.14 1-2003 can be met by using borate fusion as a dissolution method for ICP-OES analysis. This
preparation step will be facilitated by using LeNeo® fusion instrument.

Method

Apparatus and Instrumental Conditions

An automatic LeNeo fusion instrument designed by Claisse was used to generate borate solutions. Its resistance-based
electric system, excellent insulation properties and preset fusion programs allow a uniform heating, thus providing repeatable
and reproducible fusion conditions and a perfect retention of volatile elements.

A Fisher Scientific Isotemp® muffle furnace was used for the LOI determinations and the preparation of ignited samples.

A Perkin Elmer® Optima® 7300 DV ICP-OES spectrometer was used to collect the data. The operating parameters used on
the spectrometer are shown in Table 1.

Table 1: Optima 7300 DV operating parameters

Nebulizer Gem Tip Cross flow

Plasma: 16 L/min
Spray chamber Scott Argon flow Nebulizer: 0.8 L/min
Auxiliary: 0.4 L/min
Injector Alumina 2 mm i.d.

RF 1500 W Sample flow rate 1.0 mL/min

Global Sample Preparation Method

Before being submitted to the fusion process, each sample was ashed in a Pt/Au crucible in the muffle furnace according to
this following ashing method:
 1. Ramp up to 500 °C for 1 hour

2. Ramp up to 750 °C for 2 hours

3. Hold at 750 °C for 2 hours

The ashes were then fused following the procedure of mixing 0.150 g of lithium nitrate (LiNO3) and 1.000 g of lithium
metaborate/1.5% lithium bromide (LiM/LiBr) flux in Pt/Au crucibles. A fully automatic LeNeo instrument was used to fuse the
samples.

The complete process of fusion and dissolution took less than 15 minutes. The resulting solutions were then diluted up to
200 mL in 10% nitric acid for subsequent analyses on a Perkin Elmer Optima 7300 DV ICP-OES.

Results
High lithium matrix can cause signal suppression or signal increase for some elements.
In order to counteract this effect, matrix matching and internal standards were used. The dilution of sample prevented any
clogging caused by a high salt matrix. The calibration solutions of each element were done in a LiM/LiBr 1.5% matrix, just
like the sample. Calibration curves were done using a concentration range close to the sample concentrations.
Sample concentrations are within the calibration range. Five points including the blank were used for each element. The
correlation of each curve was higher than 0.999.

Method Detection Limits

Method detection limits (MDLs) were based on 10 replicate measurements of a series of low diluted sample solutions. The
MDL was calculated by multiplying the standard deviation of the 10 replicate measurements by three.

MDL= 3 x S10
Table 2: Method detection limit obtained by wavelength used and type of view

Elements Wavelength (nm) View MDL (mg/L)

Al 237.313 Axial 0.07

Ba 413.065 Axial 0.006

Ca 422.673 Radial 0.1

Fe 238.863 Axial 0.02

K 766.490 Axial 0.002

Mg 279.077 Axial 0.007

Mn 293.305 Axial 0.001

Na 589.592 Radial 0.05

P 177.434 Axial 0.03

S 181.975 Axial 0.06

Si 252.851 Radial 0.07

Sr 460.733 Axial 0.002

Ti 337.279 Axial 0.002

Zn 213.857 Axial 0.003

Accuracy and Precision

The following tables show the precision and accuracy obtained in coal and fly ash with three different certified reference
materials (CRMs) (10 replicates for each CRM). The precision expresses the closeness of the results obtained in a series of
10 measurements made with the same sample while the accuracy is the proximity of measurement results to the true value.
Both were calculated based on the certified values of the following certified reference materials: EOP-12-1-02, NCS
FC28127 and VS 7177-95.

Table 3: Precision and accuracy in brown coal fly ash with reference material EOP 12-1-02

Precision Accuracy RSD

Elements Certified values (%) Experimental values (%)
t0,975 ; 9 (%) (%) (%)

Al 16.1 16.3 0.1 98.7 0.5

Ca 1.49 1.44 0.04 96.5 3.9

Fe 5.17 5.21 0.02 99.2 0.5

K 0.651 0.630 0.011 96.7 2.4

Mg 0.581 0.623 0.002 93.0 0.5

Na 0.361 0.37 0.01 97.6 3.5

Si 22.9 23.8 0.4 96.3 3.7

Ti 3.61 3.44 0.01 95.3 0.5

Table 4: Precision and accuracy in coal ash with reference material NCS FC28127

Precision Accuracy RSD

Elements Certified values (%) Experimental values (%)
t0,975 ; 9 (%) (%) (%)

Al 3.47 3.37 0.03 97.1 1.2

Ca 1.88 1.89 0.04 99.3 2.8

Fe 1.02 1.05 0.01 97.4 1.0

K 0.29 0.281 0.005 97.0 2.5

Mg 0.28 0.294 0.002 94.7 0.8

Na 0.052 0.052 0.001 99.6 2.2

Si 5.61 6.05 0.06 92.2 1.3

Ti 0.18 0.173 0.002 96.4 1.4

Table 5: Precision and accuracy in coal with reference material VS 7177-95

Accuracy RSD
Elements Certified values (%)* Experimental values (%) n=10 Precision t0,975;9 (%)
(%) %)

Al 14.33 14.0 0.1 97.7 1.3

Ca 3.49 3.70 0.06 94.0 2.4

Fe 3.83 3.73 0.03 97.3 1.0

K 0.49 3.73 0.006 91.0 1.9

Mg 0.893 0.874 0.009 97.9 1.5

Na 0.10 0.11 0.01 97.6 3.1

Si 27.43 28.6 0.4 95.7 2.1

Ti 0.36 0.357 0.003 99.3 1.2

*Measured as Al but reported as Al2O3 on the certificate of analysis provided with material

Recovery
Table 6 shows the recovery values obtained in different matrixes. Recovery was calculated on five replicates in each of the
certified reference materials used.
Table 6: Recovery obtained in coal, ash and fly ash
EOP 12-1-02 NCS FC28127 VS 7177-95
(Brown coal fly ash) (Coal ash) (Coal)

Elements
Spiked values Spiked values Spiked values
Recovery RSD Recovery RSD Recovery RSD
(%) (%) (%) (%) (%) (%)
(mg/L) (mg/L) (mg/L)

Ba 1 102 0.4 1 102 1 1 103 0.2

of this information and we shall not be liable for errors contained herein or for damages in connection with the use of this material. Malvern Panalytical reserves the right to change the content in this material at any time without notice.
K 3 91 3 5 102 2 3 91 4

Disclaimer: Although diligent care has been used to ensure that the information in this material is accurate, nothing herein can be construed to imply any representation or warranty as to the accuracy, correctness or completeness
Mn 1 102 1 5 100 0.7 1 104 0.6

P 1 99 1 1 103 1 1 101 3

Copyright: © 2023 Malvern Panalytical. This publication or any portion thereof may not be copied or transmitted without our express written permission. anclaisse20150220coalcoalashboratefusion-EN
1 97 3 5 100 1 1 96 3

Sr 1 96 1 1 100 0.9 1 98 3

Zn 1 100 0.7 1 101 0.9 1 101 1

Conclusions
The results presented in the previous tables indicate that sample preparation by borate fusion followed by ICP-OES analysis
is an effective method to analyse coal and fly ash. The accuracy obtained (between 91.0 and 99.6%) combined with an
excellent recovery (100% ± 3% for most elements with a relative standard deviation below 3% for all elements, except for two
of them) show that the method is highly efficient. The method also showed good precision, thus proving its receptivity. This
demonstrates that the use of LeNeo fusion instrument leads to reproducible and efficient methods, despite the sample
dissolution to reduce its salt content.

References
[ 1 ] Coal Association of Canada. “About Coal”. Retrieved from the Website www.coal.ca. Calgary, Alberta. 2015.
[ 2 ] Coal Association of Canada. “Module 1: Coal Evolution”. Retrieved from the official Website at http://www.coal.ca/wp-
content/uploads/2012/04/module1_evolution.pdf. Calgary, Alberta. 2003. 12pp.
[ 3 ] PITRE, J. and BÉDARD, M. “Characterization of Coal and its By-products Using Borate Fusion and ICP-OES Analysis”.
ICP-OES application note. 2014.
.

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