XRF 5035

Analysis of Low Concentration Sulfur in

Automotive Fuels by Mini-Z Sulfur
Analyzer According to ASTM D2622-10
Benchtop wavelength dispersive
X-ray fluorescence
spectrometer
Mini-Z Sulfur Analyzer

fuel oil
petroleum

automotive fuels
sulfur
diesel fuel
gasoline
ASTM
benchtop

by azza-bazoo

Introduction
Recent developments in ultra low sulfur diesel (ULSD)
fuel has improved fuel efficiency and created cleaner
exhaust gas and permitted limit of sulfur in fuel oils has
been decreased 10 or 15 ppm for the limit in many
countries. There is a strong possibility that these regulations can become even more severe.
For compliance verification, X-ray fluorescence (XRF)
spectrometry is the definitive analysis tool for use at
distribution terminal, as well as mobile or stationary
testing laboratories.
This application note demonstrates that Mini-Z Sulfur
Analyzer can meet the requirements of ASTM
D2622-10.

Instrument
The Mini-Z Sulfur Analyzer (hereafter called Mini-Z S),
a benchtop single fixed-channel wavelength dispersive
X-ray fluorescence (WDXRF) spectrometer, is designed to minimize the restrictions in installation such
as cooling water, special power supply, installation
space, etc. The Mini-Z S is equipped with an air-cooled
40 W Cr-target X-ray tube and the RX-9 analyzing
crystal, optimized for sulfur analysis.
The Mini-Z S has a built-in operation control panel,
which enables simple and easy operation.

The counting time was 300 seconds for peak and

background measurements.
The path atmosphere of the Mini-Z S is helium.

Sample preparation
Four milliliter of each sample was poured into a special
liquid cell called Caplugs with analysis film of 2.5 m
Mylar film (Chemplex 100).

Standard and calibration

Number 2 diesel fuel standards and isooctane-based
standards provided by VHG Labs were used for calibration for diesel fuel and gasoline respectively. The
calibration results are listed in Table 1 and the calibration curves are shown in Figure 1.
Table 1 Calibration result for each material using Mini-Z S
(in mg/kg)
Material

Diesel fuel

Isooctane (for Gasoline)

Calibration range

0 1000

0 1000

Accuracy

1.3

2.1

LLD

0.3

The accuracy of calibration is calculated by the following formula,

XRF 5035

Accuracy =

(C

C
i

nm

Ci : calculated value of standard sample

: reference value of standard sample

C
i
n : number of standard samples
m : degree of freedom (2: linear).

The lower limit of detection (mg/kg) is calculated by the

following formula,

IB
LLD = 3 1 B = 3
m
m 1000 t

m : sensitivity of calibration (kcps/[mg/kg])

B : standard deviation of blank intensity (kcps)

IB : blank intensity (kcps)
t : counting time (s)

Analysis results
Repeatability tests were carried out using a representative sample for each material. For each sample, two
aliquots were prepared and quantified with the calibration Figure 1; this process was repeated twenty times.
The test results are tabulated in Table 2 (a) for diesel
fuel and (b) for gasoline, in which the average and the
difference of two aliquots each are shown respectively.
r represents repeatability defined by the following
formula,

Repeatability (r) = 0.1462X0.8015 mg/kg

X: total sulfur concentration (mg/kg)

(1)

in ASTM D2622-10, which states that the difference

between successive test results obtained by the same
operator with the same apparatus under constant operation conditions on identical test material would, in
the long run, in the normal and correct operation of the
test method, exceed the values calculated by Equation
(1) only in one case in twenty.
The test results shown in Table 2, where the maximum
value for each fuel is smaller than r, prove that the
performance of the Mini-Z S meets the requirement of
ASTM D2622-10 for diesel fuel and gasoline.

(a)

Intensity

Intensity

Conclusion

Standard value (ppm)

Low concentration sulfur in petroleum-based fuel can

be routinely analyzed with high accuracy and precision
on the Mini-Z Sulfur Analyzer, a benchtop single
fixed-channel WDXRF spectrometer, which does not
require external water for cooling an X-ray tube or
special power supply. This application note demonstrates that the performance of the Mini-Z Sulfur Analyzer meets the requirement of ASTM D2622-10, which
has become strict in the recent versions of ASTM
D2622.

(b)

Intensity

Intensity

Reference

Standard value (ppm)

Figure 1 Calibration curve for each material of Mini-Z S

(a) Diesel fuel
(b) Isooctane (for gasoline)

ASTM D2622-10 Standard Test Method for Sulfur in

Petroleum Products by Wavelength Dispersive X-ray
Fluorescence Spectrometry.

XRF 5035

Table 2 Repeatability test result for Mini-Z S (qualification test for ASTM D2622-10)
(a) Diesel fuel
(b) Gasoline
Run #

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Avg.

Average

Difference

(mg/kg)

(mg/kg)

9.0
8.8
9.0
9.5
9.4
9.2
9.3
9.5
9.8
9.5
9.8
10.1
9.5
9.4
9.5
9.5
9.6
9.9
9.7
9.7
9.5

0.0
0.3
0.1
0.4
0.6
0.8
0.3
0.1
0.6
0.0
0.7
0.8
0.8
0.3
0.2
0.0
0.1
0.4
0.2
0.6

Maximum
r (repeatability)

0.8
0.9

Run #

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Avg.

Average

Difference

(mg/kg)

(mg/kg)

15.7
16.2
16.0
15.7
15.6
16.0
16.2
16.1
16.4
16.4
16.4
16.3
16.0
16.3
16.9
17.1
16.7
16.6
17.0
17.0
16.3

1.0
0.1
0.3
0.3
0.2
0.6
0.2
0.0
0.5
0.5
0.6
0.8
0.1
0.5
0.7
0.2
0.6
0.4
0.4
0.4

Maximum
r (repeatability)

1.0
1.3

XRF 5035

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