EDXRF APPLICATION NOTE

SULFUR IN BUNKER FUEL

SCOPE
The analysis of sulfur in bunker fuel and diesel as per
ASTM D4294 is demonstrated.

BACKGROUND
Sulfur content is regulated in many petroleum fuels oils,
and plays an important role in fuel quality and control
of polluting emissions. In the 1970s, the International
Maritime Organization (IMO) formed its ship pollution
rules at the International Convention on the Prevention
of Pollution from Ships, known as MARPOL 73/78.
Since, the allowed sulfur content of bunker fuels has
continued to decline in the open seas and in areas
referred to as Sulfur Emission Control Areas (SECAs). SECAs are defined protected areas in which only low
sulfur bunker fuels and marine diesels can be used. Therefore, it is critical to monitor the sulfur content to
ensure regulatory compliance and to improve air quality, affecting those utilizing as well as producing and
supplying bunker fuels. To meet the needs of the industry, Koehler offers EDX1000, a simple and versatile
benchtop EDXRF analyzer for the analysis of sulfur and other elements in a wide variety of petroleum fuels,
including bunker and diesel. EDX1000 is an important tool to meet the requirements for monitoring sulfur at
these various levels, with the ability to measure sulfur over a broad range of concentrations and into the
future as sulfur levels become even lower.

INSTRUMENTATION
Model: Koehler EDX1000
X-ray tube: 4 W Ag-anode
Detector: Semiconductor
Sample Type: Bunker Fuel & Diesel
Film: Mylar
Analysis Time: 100 sec
Environment: Air
Optional: Autosampler

SAMPLE PREPARATION
To measure a sample, gently shake the sample bottle, allow bubbles to settle and fill a 32mm XRF sample
cup 3/4 full (5g).

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1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
Sulfur in Bunker Fuel – Low Range 0.10 – 1.00% S

CALIBRATION
An empirical calibration was built using a set of commercially available certified bunker oil standards, which
is similar to crude or residual oil. Goodness-of-fit is optimized by developing separate calibration methods
for different sulfur ranges, if needed. A summary of the calibration for 0.10 – 1.00 S is shown here, using a
measurement time of 100 sec.

Correlation Plot
Element: S Std Error of Est: 0.0028
Units: % Correlation: 0.99995 S
Sample Standard Calculated 1.00
I.D. Value Value
Calculated Value

STD 1 0.10 0.098 0.75

STD 2 0.30 0.304
STD 3 0.50 0.499 0.50
STD 4 0.70 0.698
STD 5 1.00 1.001 0.25

0 0 0.00
1.1 1.1 0.00 0.25 0.50 0.75 1.00
Standard Value

REPEATABILITY
To demonstrate repeatability (precision), the select samples were chosen from the set of calibration
standards. Each sample was measured in static position for ten repeat analyses using a total analysis time
of 100 sec per measurement, with typical results shown below.

Element: S Units: %

Standard Average
Sample ID Std Dev % Relative
Value Value
STD 1 0.10 0.0994 0.001 1.0

STD 3 0.50 0.5035 0.003 0.6

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
Sulfur in Bunker Fuel – High Range 0.50 – 5.00% S

CALIBRATION
An empirical calibration was built using a set of commercially available certified bunker oil standards, which
is similar to crude or residual oil. Accuracy is optimized by developing separate calibration methods for
different sulfur ranges, if needed. A summary of the calibration for 0.50 – 5.00 S is shown here, using a
measurement time of 100 sec.

Correlation Plot
Element: S Std Error of Est: 0.0151
Units: % Correlation: 0.99995 S
5.00
Sample Standard Calculated
I.D. Value Value
4.00
Calculated Value

STD 6 0.50 0.505

STD 7 1.00 0.994 3.00
STD 8 2.50 2.488
STD 9 3.00 3.011 2.00
STD 10 4.00 4.015
STD 11 5.00 4.988 1.00

0.00
0 0
0.00 1.00 2.00 3.00 4.00 5.00
5.1 5.1
Standard Value

REPEATABILITY
To demonstrate repeatability (precision), the select samples were chosen from the set of calibration
standards. Each sample was measured in static position for ten repeat analyses using a total analysis time
of 100 sec per measurement, with typical results shown below.

Element: S Units: %

Standard Average
Sample ID Std Dev % Relative
Value Value
STD 7 1.00 0.993 0.004 0.4

STD 11 5.00 5.006 0.015 0.3

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
Sulfur in Diesel – 0.10 – 1.50% S

CALIBRATION
An empirical calibration was built using a set of commercially available #2 diesel fuel standards. A summary
of the typical high range calibration is shown here, using a measurement time of 100 sec.

Correlation Plot
Element: S Std Error of Est: 0.0054
Units: % Correlation: 0.99993 S
2.00
Sample Standard Calculated
I.D. Value Value
STD 1 0.10 0.099 Calculated Value 1.50

STD 2 0.30 0.295

STD 3 0.50 0.498 1.00
STD 4 0.70 0.708
STD 5 1.00 0.996 0.50
STD 6 1.50 1.500

0.00
0 0
0.00 0.50 1.00 1.50 2.00
5.1 5.1
Standard Value

REPEATABILITY
To demonstrate repeatability (precision), the select samples were chosen from the set of calibration
standards. Each sample was measured in static position for ten repeat analyses using a total analysis time
of 100 sec per measurement, with typical results shown below.

Element: S Units: %

Standard Average
Sample ID Std Dev % Relative
Value Value
STD 1 0.10 0.103 0.001 1.0

STD 3 0.50 0.496 0.002 0.4

STD 5 1.00 1.008 0.003 0.3

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
TYPICAL DETECTION LIMITS
To determine the Lower Limit of Detection (LLD) using the empirical method, ten repeat analyses of mineral
oil containing no S were measured and the standard deviation calculated. The LLD is then defined as three
times the standard deviation. The LLD shown here is application to bunker fuel, diesel and crude oil, over
the concentration ranges shown above.

S LLD @ 100 sec

20 ppm

INTERNATIONAL STANDARD TEST METHODS

The Koehler EDX1000 complies with the following international standards test methods for measuring sulfur
in crude, bunker fuel, diesel and other petroleum oils. Note that by weight 1 ppm = 1 mg/kg.

ASTM
ISO 20847 ISO 8754 IP 496 IP336 JIS K 2541-4
D4294
16 ppm – 5% 30 -500 mg/kg 100 mg/kg – 5% 100 mg/kg – 5% 100 mg/kg – 5% 0.01 – 5%

CONCLUSION
The performance shown here demonstrates the ability of the EDX1000 to yield excellent results for the
measurement of sulfur in bunker fuel and diesel in air, without the need for helium purge. Simple, modern
touch screen interface allows for reliable and efficient measurement protocols, and performance meets the
major international norms shown above.

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.