Application Note XRF

Precise determination of low level

Sulfur in oil according to ASTM
D2622-98
Venus
Introduction
Elemental analysis of petroleum products is a critical requirement, not
only as a quality control procedure to conform to standards, but also to
comply with the large number of environmental regulations, like sulfur
concentration levels in oils.
A test method that covers the determination of total sulfur in
petroleum products is described in ASTM D2622. This ASTM norm
specifies a procedure for analyzing low levels of sulfur using a
wavelength dispersive X-ray fluorescence (WDXRF) spectrometer.
There is a continuous trend to reduce the concentration of sulfur below
50 ppm in petroleum products. Because of this the results presented
here are focused on a low concentration range of sulfur.
The Venus 200minilab is ideally suited for many applications, one of
which is the analysis of sulfur in a range of products including crude
oil, diesel, gasoline and waste oil.
Application
Instrumentation To measure sulfur in oil according to
For this application a PANalytical Venus 200minilab WDXRF the international norm ASTM D2622
spectrometer was configured to meet the requirements of the a calibration was set up using a series
D2622-98 norm. This instrument is equipped with a scandium tube, of standards with a measurement time
operated at 50 kV and 4 mA and a helium purge facility for optimal of 200 seconds per sample.
excitation and measurement. One sample was measured 20 times
in order to illustrate the repeatability
Sample preparation of the measurement. The average
Calibration standards were prepared gravimetrically by mixing known concentration was 3.84 ppm and the
amounts of di-n-butyl sulfide and high purity mineral oil using the standard deviation was 0.38 ppm.
method described in the ASTM D2622 norm. The allowed deviation according to
Standards covering the range of 0-50 ppm were prepared, each with a ASTM D2622-98 is 3.7 ppm
maximum relative error of less than 1%. respectively.
The standards were poured into P2 "de Kat" liquid cells, using
6 micron Mylar supporting film.

Procedure
As described in the ASTM D2622, the intensities of the series of
standards were measured with the sulfur Kα line at 0.5373 nm and the
background at 0.5437 nm. Calibration samples were measured to cover
the concentration range 0 - 50 ppm. The calibration curve for sulfur
was set up by using the regression model incorporated in the Venus
software package.
Results
Element Concentration range RMS LLD
The total measuring time is 200
seconds per sample. The calibration S 0 – 50 ppm 0.32 ppm 0.8 ppm
curve, indicates an excellent
correlation between measured Table 1. Sulfur calibration details
intensity and concentration and is
shown in Figure 1. Table 1 shows
calibration data with the Element Concentration Standard deviation Deviation allowed
(ppm) (ppm) according to
concentration range and their Root ASTM D2622-98
Mean Square (RMS). (ppm)
The RMS is an indication of the
magnitude of the differences between S 3.84 0.38 3.7
the measured concentration and the
chemical concentration. Thus, a Table 2. Sulfur repeatability results
smaller RMS indicates a more
accurate calibration.
Repeatability is another important
aspect of analysis and is an inherent
characteristic of WDXRF. This is
illustrated in Figure 2 where the same
sample has been measured 20 times.
From this set of data, the average
concentration and the standard
Intensity

deviation for sulfur are calculated and

Printed in The Netherlands on 50% recycled, chlorine free paper. Data subject to alteration without notice. For reference purposes only. 9498 707 26411 PN3259
given in Table 2. The ASTM D2622
norm requires a repeatability (defined
as 0.00736 (X+0.0002)0.4) in the
range of 0.0003 - 0.093 % S (3 - 930
ppm). According to this formula, at
the level of 3.8 ppm sulfur, an
absolute deviation of 3.7 ppm is 0 5 10 15 20 25 30 35 40 45 50
allowed. Concentration S (ppm)
Conclusion
The obtained standard deviation for Figure 1. Calibration curve of sulfur in oil
the repeatability measurement at 3.8
ppm is ± 0.38 ppm, or 3.8 ppm
± 10% relative. Whereas, the ASTM 7
D2622 norm allows far much larger
variations e.g. 3.8 ppm ± 100% 6
relative. Thus it can be concluded
Concentration (ppm)

that the Venus 200minilab sequential 5

WDXRF spectrometer is able to
analyse sulfur in petroleum products 4
very precisely and is more than
capable of meeting the requirements 3
of the norm.
2

1
0 2 4 6 8 10 12 14 16 18 20
Sequence

Figure 2. Repeatability of sulfur in Oil

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