Fresenius J Anal Chem (1999) 364 : 705–708
O R I G I N A L PA P E R
Vít Šprta · Bohumil Knob · Pavel Janoš
X-ray fluorescence determination of total sulfur in fly ash
Received: 27 October 1998 / Revised: 5 March 1999 / Accepted: 11 March 1999
Abstract Standard addition, double dilution and stan-
dard calibration were used for x-ray fluorescence (XRF)
determinations of sulfur in fly ashes. Samples were analysed
as pellets prepared by mixing with acrylate copolymer or
with microcrystalline cellulose (in the case of the double
dilution method). Lithium sulfate was used for the stan-
dard addition method and also as standard with known
sulfur content for the double dilution method. Fly ashes
analysed by optical emission spectrometry with an induc-
tively coupled plasma (ICP-OES) were used as standards
for the standard calibration XRF method. Sulfur was de-
termined in the range of ca. 10–1–100 % S. For the fly ashes
from the North-Bohemian brown coals, the differences
between the XRF determinations and the ICP-OES deter-
minations ranged from ca. 1.4 to 10% rel. and precision
(repeatability) was better than 10% (RSD). The standard
calibration method is suitable for routine analyses of real
samples of similar nature. The methods of standard addi-
tion and double dilution are rather laborious in sample
preparation compared with the standard calibration.
Introduction
Fly ash is a solid waste produced in great quantities par-
ticularly during combustion of fossil fuels in power
plants, but also in many other industrial processes. Its pro-
duction as well as its handling and dumping causes poten-
tial hazards to plants, animals and human health [1]. On
the other hand, the utilisation of the fly ash in waste man-
agement, e.g. for wastewater sludge conditioning, is ex-
tensively studied [2]. Therefore, the contents of toxic ele-
ments such as heavy metals are usually determined to as-
sess environmental impacts.
Recently, fly ash has gained much attention as a raw
material in building industry, where it is used for cement
V. Šprta, B. Knob, P. Janoš (쾷)
Research Institute of Inorganic Chemistry, Revoluční 84,
CZ-400 01 Ústí nad Labem, Czech Republic
© Springer-Verlag 1999
production, concrete mixing, ceramics and other products.
For those applications, it is important to know the content
of the major elements, both metals (Al, Fe, Ca) as well as
non-metals (Si, S). Sulfur may cause a degradation of the
concrete and therefore its amount has to be controlled [3].
Various analytical methods have been used for an ele-
mental analysis of the fly ashes. Most of them (gravime-
try, titrimetry, photometry, AAS, ICP-OES, ICP-MS),
however, require a laborious and time consuming sample
dissolution. From the non-destructive techniques, x-ray
emission methods, such as particle-induced x-ray emis-
sion (PIXE) and x-ray fluorescence spectrometry (XRF)
have been employed most frequently for the bulk ele-
mental analyses of the fly ashes. Sixteen metals, both ma-
jor and microelements, were quantified in fly ash samples
from the coal-fired power plants in India using PIXE and
energy-dispersive XRF [4]. XRF together with instru-
mental neutron activation analysis (INAA) were used for
the determination of 23 elements in Hungarian brown
coals, fly ash, bottom ash and dust particulates [5]. Parti-
cle size/density separated fractions of the coal fly ash
were characterised by energy-dispersive XRF and other
instrumental techniques [6]. Metalic elements were in-
vestigated in [4–6] from the point of view of their envi-
ronmental impacts. Major as well as minor elements in-
cluding Si, but not sulfur, were determined by automated
XRF of the pressed fly ash pellets [7]. Sulfur together
with a number of major and trace elements were deter-
mined in a study of the elemental distribution in Greek
lignites and their ashes [8]. Direct XRF measurements
were recommended for the determinations of 22 elements
including some non-metals (Si, S) in airborne particles
[9]. Relatively little experimental details are reported on
the determination of sulfur in the above mentioned stud-
ies. Depth selective x-ray absorption fine structure spec-
trometry (XAFS), in which both the x-ray fluorescence
yield and the total electron yield are recorded concomi-
tantly, seems to be very promising for element-speciation
and element-distribution studies [10]. XAFS allows to
obtain information about the chemical state and distribu-
tion of sulfur in particles of the fractionated coal fly ash
706
[11]; this technique, however, is not commonly available
in most laboratories.
In the present work, XRF was used to determine the to-
tal sulfur content in fly ash. Various sample preparation
methods were applied to several kinds of fly ashes and
various methods of calibration and data evaluation were
compared.
Experimental
Fly ashes, chemicals
Samples of the fly ashes were collected from electrostatic precipi-
tators in various power plants fuelled with North-Bohemian brown
coals. The samples were dried at 60 °C for 5 h and then ho-
mogenised in a ball mill with corundum balls for 5 h. The CW3
sample was prepared in the Joint Research Centre, Ispra, Italy, as a
candidate reference material from incinerated chemical waste col-
lected in Germany and represents the ash produced in a specialised
incineration plant.
For the standard addition measurements, 10 g of the sample
was mixed with 5 mL of a solution of lithium sulfate of known
concentration, the mixture was homogenised by stirring and dried
at 60 °C. The dry mixture was mixed with acrylate copolymer,
dried at 60 °C again, ground and pressed in an Al dish (160 MPa).
For standard calibration measurements, the samples were treated
in a similar way without addition of lithium sulfate.
Microcrystalline cellulose was used as an inert diluent for dou-
ble dilution measurements. Two pellets containing 60 and 30% of
fly ash were prepared as follows: the fly ash was mixed with cel-
lulose at ratios 6 : 4 and 3 : 7, respectively. The mixtures were
ground, homogenised and pressed in an Al dish (160 MPa).
Lithium sulfate LiSO4 · H2O served as a standard with a known
content of sulfur – it was treated in the same way as the fly ash.
Conditions of the x-ray measurements are given in Table 1. A spe-
cial glass U4 (2THETA, Český Těšín, Czech Republic) containing
1.44% S was used as an internal standard to determine the relative
intensities of the spectral lines. ICP-OES was used as reference
method for the sulfur determination. The measurements were per-
formed with the Optima 3000, Perkin-Elmer, spectrometer at the
emission line 180.669 nm.
Results and discussion
Standard addition method
Several samples with various amounts of lithium sulfate
(as suggested by Chinchón et. al. [3]) were prepared as
described in the experimental section. The intensities of
Table 1 Apparatus and conditions of measurements
X-ray spectrometer: PHILIPS PW 1404, Rh lamp, 3 kV
Spectral line: Kα
Voltage: 40 kV
Current: 75 mA
Collimator: Fine
Crystal: GE
Angle: 110.665°
Detector: FL
Time of measurement: 30 or 60 s
Software: X40, X44
Fig. 1 Determination of sulfur by multiple addition – relative in-
tensity vs. sulfur addition
the Kα spectral lines were measured at the maximum
(Imax) and at the baseline (Ibas). Simultaneously with the
sample, the instrumental standard was measured (Ist). The
relative intensity was calculated according to the equa-
tion:
Irel = (Imax – Ibas)/Ist (1)
This procedure was applied to fly ashes from the North-
Bohemian brown coal (P4, P6, P9) and to the CW3 ash, af-
ter additions ranging from 0.053 to 1.53% S. The relative
intensities were plotted against the added amount of sulfur
and the concentration of sulfur in the original sample was
obtained from the intersection of an extension of the
straight line (relative intensity vs. addition of sulfur) with
the x-axis (Fig. 1). As can be seen from this figure, a lin-
ear dependence is obtained only up to ca. 1% S. The
points besides the linear range were not taken into account
during the evaluation of the measurements. In addition to
the graphical evaluation presented in Fig. 1 also a numer-
ical approach was applied utilising the least-square
method. Correlation coefficients were typically 0.994–
0.996, except for the P4 sample (0.978). The results of
the determinations are listed in Table 2 together with esti-
mated standard deviations and together with the results
obtained by other methods.
Double dilution method
In dilution methods, a sample is mixed with an inert elu-
ent containing no analyte. Two intensity measurements at
two different concentrations of the sample permit correc-
tions of the measured intensities for absorption-enhance-
ment effects. The standard with a known concentration of
the analyte is diluted in the same way as the sample (for a
more detailed discussion see [12, 13]).
For the determination of sulfur in fly ashes, microcrys-
talline cellulose and lithium sulfate were used as a diluent
and standard, respectively (see experimental section). The
relative intensities measured in a similar way as stated
above were used for the calculations of the sulfur con-
tents; results are listed in Table 2. Double dilution was not
 707

Table 2 Determination of sul-

fur in fly ashes by various Sample XRF – standard XRF – double XRF – standard ICP-OES
XRF techniques, comparison addition dilution calibration
with ICP-OES. Content of S
in % P4 0.21 ± 0.01 – 0.10 ± 0.03 0.11 ± 0.02
P6 0.75 ± 0.02 0.92 ± 0.04 0.65 ± 0.05 0.67 ± 0.04
Confidence interval (α = 0.05)
estimated from at least 3 deter- P9 1.69 ± 0.07 1.85 ± 0.11 1.46 ± 0.09 1.48 ± 0.08
minations according to Dean – CW3 2.36 ± 0.08 2.02 ± 0.07 2.24 ± 0.18 1.82 ± 0.14
Dixon: x ± Kn R

Table 3 Precision of the measurement and repeatability of the ple. The repeatability of the whole procedure including
XRF determination sample preparation was tested for the calibration stan-
Precision of Repeatability – Repeatability – dards with the lowest (level 1) and the highest (level 2)
measurement level 1 level 2 concentration of sulfur (Table 3).
(n = 10) (n = 10) (n = 10) The results of the sulfur determination in the P4, P6,
Average (%S) 0.652 0.116 1.410 P9 and CW3 samples are listed in Table 2.
Standard deviation 0.002 0.009 0.035
(%S)
Conclusions

applied to the P4 fly ash, due to the low concentration of
sulfur in the original sample, so that a sufficient precision
under the given conditions cannot be obtained.
Standard calibration method
The standard calibration method is most suitable for rou-
tine analyses provided that the analytical function can be
determined by means of materials with a matrix identical
to that of the real samples. Unfortunately, there is a lack of
reference materials (fly ashes) with certified values of the
sulfur content in a sufficient range of concentrations. Of-
ten, the sulfur content in the fly ash reference materials is
indicated as an “information value” only. Sets of samples
previously analysed by other analytical methods, such as
AAS or ICP-OES, are frequently used for the calibration
of the XRF method, especially in environmental analysis
[14]. In this work, a series of the fly ashes was analysed
by ICP-OES after microwave digestion and these results
were used for the calibration of the XRF method. The re-
liability of the ICP-OES determinations was confirmed by
comparison with other methods and a small-scale inter-
laboratory comparison [15].
The calibration standards as well as samples for the
XRF measurements were prepared as described in the ex-
perimental section and the respective intensities of the Kα
spectral line were measured. Parameters of the calibration
line
y=Ex+D
were: E = 0.2765, D = –0.00723. The limit of detection
(LOD) was calculated from the following equation [16]
–D/ E
LOD = 3000 E
10 t
where t is the measuring time. LOD was 8 mg/kg for t =
30 s. The precision of the XRF measurements was deter-
mined from 10 repetitive measurements on the same sam-
The results of the sulfur determinations with various XRF
methods are summarised in Table 2 and compared with
the results of the ICP-OES determinations. The best
agreement between the XRF and ICP-OES analyses was
found for the method of standard calibration. This is quite
understandable, because the XRF standard calibration
method was calibrated using fly ashes of a similar compo-
sition previously analysed by ICP-OES. An exception is
the CW3 sample, in which the sulfur content is above the
upper limit of the calibration range (an extrapolation of
the calibration line was necessary). Moreover, the origin
and to a certain degree also the matrix of the CW3 sample
was different from those of other samples and calibration
standards, which caused a lower accuracy of the determi-
nation.
The methods of standard calibration and standard addi-
tion can be applied to fly ashes with sulfur contents from
ca. 0.1% to ca 1.5–2%. The double dilution method can-
not be applied to samples with a low sulfur content, be-
cause the intensities of the spectral line are poorly de-
tectable for the diluted samples. The critical step for the
standard addition as well as for the double dilution meth-
ods is the sample preparation: mixing/homogenisation
with additive or diluent. The precision obtained for the
determination of sulfur in fly ashes is comparable to that
achieved by XRF determination of sulfur in sulfide-con-
taining rocks [17].
During all the XRF measurements, no decrease of the
signal intensity with time (testifying the presence of ele-
mental sulfur [18]) was observed. It is supposed that sul-
(2) fur is present as sulfate (mainly in the surface layer), or
minor (residual) as sulfide in the bulk [11].
Acknowledgements This work was supported by the INCO-
COPERNICUS Program, project ERB-IC15-CT96-0811. Finan-
(3) cial support from the Czech Ministry of Education (grant No. OK
296) is also gratefully acknowledged.
708
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