ICP-OES APPLICATION

Characterization of Coal, Coal Ash and Coal Fly Ash Using Borate Fusion for ICP Analysis
Authors: Mlanie BDARD, Janice PITRE and Philippe DAIGLE | Claisse

INTRODUCTION

Global Sample Preparation Method

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].

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:

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.

Ramp up to 500C for 1 hour

Ramp up to 750C for 2 hours
Hold at 750C 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

METHOD

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.

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.

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

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

1.
2.
3.

Gem Tip Cross flow

Spray chamber

Scott

Injector

Alumina 2 mm i.d.

RF

1500 W

Argon flow

Sample flow rate

Plasma: 16 L/min
Nebulizer: 0.8 L/min
Auxiliary: 0.4 L/min

1.0 mL/min

TABLE 2: Method detection limit obtained by wavelength used and type of view
Elements

Wavelength
(nm)

View

MDL
(mg/L)

Elements

Wavelength
(nm)

View

MDL
(mg/L)

Al

237.313

Axial

0.07

Na

589.592

Radial

0.05

Ba

413.065

Axial

0.006

177.434

Axial

0.03

Ca

422.673

Radial

0.1

181.975

Axial

0.06

Fe

238.863

Axial

0.02

Si

252.851

Radial

0.07

766.490

Axial

0.002

Sr

460.733

Axial

0.002

337.279

Axial

0.002

213.857

Axial

0.003

Mg

279.077

Axial

0.007

Ti

Mn

293.305

Axial

0.001

Zn

ICP-OES APPLICATION

Accuracy and Precision

Recovery

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 6 shows the recovery values obtained in different matrixes. Recovery was calculated
on five replicates in each of the certified reference materials used.

Certified values
(%)

Experimental values
(%) n=10

Precision t0,975;9
(%)

Accuracy
(%)

RSD
(%)

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

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
Elements

Certified values
(%)

Experimental values
(%) n=10

Precision t0,975;9
(%)

Accuracy
(%)

RSD
(%)

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

0.29

0.281

0.005

97.0

2.5

Mg

0.28

0.294

0.002

94.7

0.8

Na
Si

0.052
5.61

0.052
6.05

0.001
0.06

99.6
92.2

2.2
1.3

Ti

0.18

0.173

0.002

96.4

1.4

NCS FC28127
(Coal ash)

VS 7177-95
(Coal)

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

Ba

102

0.4

102

103

91

102

91

Mn

102

100

0.7

104

0.6

99

103

101

97

100

96

Sr

96

100

0.9

98

Zn

100

0.7

101

0.9

101

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.

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

Elements

Certified values
(%)*

Experimental values
(%) n=10

Precision t0,975;9
(%)

Accuracy
(%)

RSD
(%)

Al
Ca
Fe
K
Mg
Na
Si
Ti

14.33
3.49
3.83
0.49
0.893
0.10
27.43
0.36

14.0
3.70
3.73
0.446
0.874
0.11
28.6
0.357

0.1
0.06
0.03
0.006
0.009
0.01
0.4
0.003

97.7
94.0
97.3
91.0
97.9
97.6
95.7
99.3

1.3
2.4
1.0
1.9
1.5
3.1
2.1
1.2

[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 BDARD, M. Characterization of Coal and its By-products Using Borate Fusion and ICP-OES
Analysis. ICP-OES application note. 2014.

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

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other application notes

V1-R1

Elements

Elements

EOP 12-1-02
(Brown coal fly ash)

Claisse, 2015, All rights reserved. The following trade marks are owned by Claisse : Claisse, Claisse Fluxer, Claisse (design), The First and Finest in fusion and LeNeo.

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

TABLE 6: Recovery obtained in coal, ash and fly ash