CEN/TC 19/WG 27 - Elemental analysis of petroleum and related products

This document specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the determination of sulfur content in automotive fuels. This document is applicable to:
—    gasoline containing up to 3,7 % oxygen by mass (including those blended with ethanol up to 10 % by volume) having sulfur contents in the range of 6,9 mg/kg to 56,7 mg/kg,
—    diesel fuels including those containing up to about 30 % fatty acid methyl ester (FAME) by volume, paraffinic diesel fuel, and neat FAME, having sulfur contents in the range of 5,0 mg/kg to 60,2 mg/kg.
The sulfur content in other products can be determined according to the test method specified in this document; however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this document.
For reasons of spectral overlap, this document is not applicable to leaded automotive gasoline, gasoline having a content of greater than 8 mg/kg lead or to product and feedstock containing lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the concentration of sulfur measured, or more than 10 mg/kg, whichever is the greater.

This document specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur content of the following products:
—     having sulfur contents in the range 3 mg/kg to 500 mg/kg,
—     motor gasolines containing up to 3,7 % (m/m) oxygen [including those blended with ethanol up to about 10 % (V/V)],
—     diesel fuels, including those containing up to about 30 % (V/V) fatty acid methyl ester (FAME),
—     having sulfur contents in the range of 3 mg/kg to 45 mg/kg,
—     synthetic fuels, such as hydrotreated vegetable oil (HVO) and gas to liquid (GTL).
Other products can be analysed and other sulfur contents can be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this document. Halogens interfere with this detection technique at concentrations above approximately 3 500 mg/kg.
NOTE 1  Some process catalysts used in petroleum and chemical refining can be poisoned when trace amounts of sulfur-bearing materials are contained in the feedstocks.
NOTE 2  This test method can be used to determine sulfur in process feeds and can also be used to control sulfur in effluents.
NOTE 3  For the purposes of this document, "% (m/m)" and "% (V/V)" are used to represent the mass fraction, w, and the volume fraction, φ, of a material respectively.
NOTE 4  Sulfate species in ethanol do not have the same conversion factor of organic sulfur in ethanol. Nevertheless, sulfates have a conversion factor close to that of organic sulfur.
NOTE 5  Nitrogen interference can occur, see 6.5 for further guidance.

This document specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content of liquid, homogeneous automotive fuels from 5 mg/kg to 500 mg/kg, which have a maximum oxygen content of 3,7 % (m/m). This product range covers:
—          diesel fuels containing up to about 30 % (V/V) fatty acid methyl esters (FAME),
—          motor gasolines containing up to about 10 % (V/V) ethanol,
—          synthetic fuels such as hydrotreated vegetable oil (HVO) and gas to liquid (GTL) having sulfur contents in the range of 5 mg/kg to 45 mg/kg.
Products with higher oxygen content show significant matrix effects, e.g. pure FAME used as biodiesel, nevertheless, pure FAME can be analysed when the corresponding procedures are followed (see 5.3 and 8.1).
Other products can be analysed with this test method, though precision data for products other than those mentioned have not been established for this document.
NOTE 1   Sulfur contents higher than 500 mg/kg can be determined after sample dilution, however, the precision was not established for diluted samples.
NOTE 2    For the purposes of this document, "% (m/m)" and "% (V/V)" are used to represent the mass fraction, w, and the volume fraction, φ, of a material respectively.

This European Standard specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content in ethanol (E85) automotive fuel [3], containing ethanol between 50 % (V/V) and 85 % (V/V), from 5 mg/kg to 20 mg/kg, using instruments with either monochromatic or polychromatic excitation.
NOTE 1   Sulfur contents higher than 20 mg/kg can be determined after sample dilution with an appropriate solvent. However, the precision was not established for diluted samples.
NOTE 2   For the purposes of this European Standard, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction (µ) and the volume fraction (φ) of a material respectively.
WARNING - The use of this Standard can involve hazardous materials, operations and equipment. This Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of users of this standard to take appropriate measures to ensure the safety and health of personnel prior to application of the standard, and fulfil statutory and regulatory requirements for this purpose.

This European Standard specifies a method based on inductively coupled plasma optical emission spectrometry (ICP OES) for the determination of manganese content from about 0,5 mg/l to about 7,5 mg/l and of iron content from about 1,4 mg/l to about 6,0 mg/l in unleaded petrol containing up to 3,7 % (m/m) oxygen.
WARNING - The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.
NOTE 1   Manganese as MMT and iron as ferrocene are added to petrol to increase anti-knock properties.
NOTE 2   Solutions of MMT in petrol are unstable when exposed to light. Low and erratic results are expected if petrol samples are exposed to light prior the analysis.
Iron and manganese contents higher than 6,0 mg/l and 7,5 mg/l respectively may be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been established for such a procedure. Further work regarding automotive ethanol (E85) fuel is on-going in CEN.
NOTE 3   For the purposes of this European Standard, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction (µ) and the volume fraction (φ) of a material respectively.

This European Standard specifies a method based on inductively coupled plasma optical emission spectrometry (ICP OES) for the determination of manganese content and of iron content, each from about 0,5 mg/l to about 7,0 mg/l in diesels including those containing up to about 10 % (V/V) fatty acid methylester (FAME).
WARNING — The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.
NOTE 1   Manganese and iron contents higher than 7,0 mg/l can be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been established for such a procedure.
NOTE 2   For the purposes of this European Standard, the term “% (V/V)” is used to represent the volume fraction (φ) of a material.

This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the determination of sodium, potassium, calcium, phosphorus, copper and zinc concentrations of diesel fuels, including those containing up to 30 % (V/V) fatty acid methyl ester (FAME), in the range detailed in Table 1. These six elements are considered as the most essential ash forming elements.

This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the determination of phosphorus content of Fatty Acid Methyl Esters (FAME) in the range of 2,5 mg/kg to 8,0 mg/kg.
WARNING - The use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

This European Standard specifies an ion chromatographic (IC) method for the determination of inorganic chloride content in ethanol from about 1 mg/kg to about 30 mg/kg and of sulfate content in ethanol from about 1 mg/kg to about 20 mg/kg.
NOTE   Sulfate content can be determined from 0,5 mg/kg to 1,0 mg/kg. However, the precision was not established as no samples with sulfate content in this range were included in the interlaboratory test.
WARNING - Use of this method may involve hazardous equipment, materials and operations. This method does not purport to address to all of the safety problems associated with its use, but it is the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

This European Standard specifies a method based on flame atomic absorption spectrometry (FAAS) for the determination of manganese content as methylcyclopentadienyl manganese tricarbonyl (MMT  )) in unleaded petrol from about 2 mg/l to about 8 mg/l. This test method is applicable to unleaded petrol containing up to 3,7 % (m/m) oxygen, including those with ethanol up to 10 % (V/V).
NOTE 1   Manganese as MMT is added to petrol to increase antiknock properties.
WARNING - The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.
NOTE 2   Solutions of MMT in unleaded petrol are unstable when exposed to light. Low and erratic results are expected if samples are exposed to light prior the analysis.
NOTE 3   Manganese contents higher than 8 mg/l can be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been established for such procedure.
NOTE 4   Application to the determination of other manganese compounds in unleaded petrol has not been tested.
NOTE 5   For the purposes of this European Standard, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction (µ) and the volume fraction of a material respectively.

This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the determination of nickel content in the range 4 mg/kg to 55 mg/kg and of vanadium content in the range 4 mg/kg to 150 mg/kg in fuel oils and residual fuel oils.
NOTE 1   Nickel content can be determined from 2 mg/kg to 4 mg/kg and vanadium content can be determined from 1 mg/kg to 4 mg/kg. However, the precision was not established as no samples with nickel and vanadium contents in these ranges were included in the interlaboratory test. Nickel and vanadium contents higher than those reported can be determined after sample dilution. However, the precision was not established for diluted samples.
NOTE 2   For the purposes of this European Standard, the term "% (V/V)" is used to represent the volume fraction (phi).
WARNING - The use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.

This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP-OES) method for the direct determination of elements content in ethanol, namely phosphorus in the range (0,13 to 1,90) mg/kg, copper in the range (0,050 to 0,300) mg/kg, and sulfur in the range (2,0 to 15,0) mg/kg.
WARNING - The use of this method may involve hazardous equipment, materials and operations. This method does not purport to address to all of the safety problems associated with its use, but it is the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
NOTE   For the purposes of this document, the terms "% (m/m)" and "% (V/V)" are used to represent respectively the mass fraction (w) and volume fraction (greek symbol phi).

This document specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur content of ethanol from 5 mg/kg to 20 mg/kg. Other products may be analysed and higher sulfur contents may be determined according to this test method, however, no precision data for products other than ethanol and for results outside the specified range have been established for this document. Halogens interfere with this detection technique at concentrations above approximately 3 500 mg/kg.
NOTE   For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fraction and the volume fraction of a material respectively.
WARNING — The use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.

This standard specifies a procedure for the determination of copper content in ethanol from 0,07 mg/kg to 0,20 mg/kg using graphite furnace atomic absorption spectrometry.
NOTE   For the purpose of this document, the terms “% (m/m)” and "% (V/V)" are used to represent the mass fraction, respectively the volume fraction of a material.
WARNING — Use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.

This document specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content of ethanol from 7 mg/kg to 20 mg/kg.
NOTE   For the purposes of this European Standard, the term "% (m/m)" is used to represent the mass fraction of a material.

This standard specifies a potentiometric method for the determination of inorganic chloride content in ethanol from 4 mg/l to 30 mg/l. The chloride content is determined in aqueous solution after dissolution of the evaporation residue of the ethanol sample.
WARNING — Use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.
NOTE   For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction and the volume fraction.

This standard specifies a procedure for the determination of phosphorus content measured as orthophosphate, in ethanol from 0,15 mg/l to 1,50 mg/l by ammonium molybdate spectrometric method. The phosphorus content is determined in aqueous solution after dissolution of the evaporation residue of the ethanol sample.
WARNING — Use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.

This European Standard specifies a method for the direct determination of water in ethanol to be used in gasoline blends. It is applicable to ethanol having water contents in the range 0,039 % (m/m) to 0,500 % (m/m).
NOTE   For the purposes of this document, the term “% (m/m)” is used to represent the mass fraction.
WARNING — Use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

This document specifies a procedure for the direct determination of the soap building elements Calcium (Ca), Magnesium (Mg), Sodium (Na) and Potassium (K) in fatty acid methyl esters (FAME) by ICP OES at levels of about 1 mg/kg to 10 mg/kg.

This Technical Report summarises the activity carried out by CEN/TC 19 to define the precision of new test methods for the determination of low sulfur content in automotive fuels. The full description of the activity can be found in the Working Group Report completed in August 2002, which is an internal CEN/TC 19 document.

The method is directly applicable to the determination of low concentrations (2 mg/kg to 100 mg/kg) of organic halogen in petroleum products such as gasolines, middle distillates and residual fuels. Except for fluorine (F); the organic halogens chlorine (C), bromine (Br) and iodine (J) that may be present in the sample are determined quantitatively. The halogen is reported as the equivalent number of chloride ions. A procedure is described for the removal of inorganic halides from residual fluids.

This European Standard specifies a method for the determination of nickel and vanadium by atomic absorption spectrometry in liquid petroleum products with nickel and vanadium contents greater than 5 mg/kg. NOTE: For the purposes of this European Standard, the term "% (m/m)" is used to represent the mass fraction. WARNING: The use of this European Standard can involve hazardous materials, operations and equipment. This Standard does not purport to address all of the safety problems associated with its use.

This document specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content in ethanol (E85) automotive fuel [3], containing ethanol between 50 % (V/V) and 85 % (V/V), from 5 mg/kg to 20 mg/kg, using instruments with either monochromatic or polychromatic excitation.
NOTE 1   Sulfur contents higher than 20 mg/kg can be determined after sample dilution with an appropriate solvent. However, the precision was not established for diluted samples.
NOTE 2   For the purposes of this document, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction (µ) and the volume fraction (φ) of a material respectively.
WARNING - The use of this document can involve hazardous materials, operations and equipment. This document does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this document to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

This document specifies a procedure for the direct determination of the content of the soap building elements Calcium (Ca), Magnesium (Mg), Sodium (Na) and Potassium (K) as well as Phosphorus (P) in fatty acid methyl esters (FAME) by ICP OES.
The concentrations of each component or the combinations of some to which this method is applicable are given in Table 1.
WARNING - The use of this document can involve hazardous materials, operations and equipment. This document does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this document to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
NOTE   For the purposes of this document, the term "% (V/V)" is used to represent the volume fraction, φ, of a material.

This European Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the determination of the sulfur content of automotive gasolines, including those containing up to 5 % (m/m) oxygen, and of automotive diesel fuels, including those containing up to 10 % (V/V) fatty acid methylester (FAME), having sulfur contents in the range 2 mg/kg to 50 mg/kg.
Other products may be analysed and other sulfur contents may be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this standard. For reasons of spectral overlap, this standard is not applicable to leaded automotive gasolines, lead replacement gasolines containing greater than 8 mg/kg lead, or to products and feedstocks containing lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.

This CEN Report describes a method of test which can be used for the determination of polycyclic aromatic hydrocarbons (and compounds of similar structure) in diesel fuels and petroleum distillates in the concentration range 1 g/l to 40 g/l. The method described is applicable to all hydrocarbon mixtures that are completely soluble in cyclohexane and is not restricted to a particular boiling range.

This CEN Report describes a method of test which can be used for the determination of the aromaticity of petroleum products. The method described is applicable to all hydrocarbon mixtures that are completely soluble in chloroform, including kerosines, middle distillates, gas oils, coal liquids and other distillate mineral oil fractions, and is not restricted to a particular boiling range. The lower detection limit for aromaticity by the method is typically in the region of 0,5 %.

ISO 20846:2011 specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur content of motor gasolines containing up to 3,7 % (m/m) oxygen [including those blended with ethanol up to about 10 % (V/V)], and of diesel fuels, including those containing up to about 10 % (V/V) fatty acid methylester (FAME), having sulfur contents in the range 3 mg/kg to 500 mg/kg. Other products can be analysed and other sulfur contents can be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for ISO 20846:2011. Halogens interfere with this detection technique at concentrations above approximately 3 500 mg/kg.

ISO 20884:2011 specifies a wavelength-dispersive X-ray fluorescence (WDXRF) test method for the determination of the sulfur content of liquid, homogeneous automotive fuels from 5 mg/kg to 500 mg/kg, which have a maximum oxygen content of 3,7 % (m/m). This product range covers diesel fuels containing up to about 10 % (V/V) fatty acid methyl ester (FAME) and motor gasolines containing up to about 10 % (V/V) ethanol.
Products with higher oxygen content show significant matrix effects, e.g. FAME used as biodiesel. Nevertheless, FAME may be analysed when the corresponding procedures are followed.
Other products may be analysed with this test method. However, precision data for products other than those mentioned have not been established for ISO 20884:2011.

This European Standard specifies a method based on inductively coupled plasma optical emission spectrometry (ICP OES) for the determination of manganese content as methylcyclopentadienyl manganese tricarbonyl (MMT  )) in unleaded petrol from about 2 mg/l to about 8 mg/l. This test method is applicable to unleaded petrol containing up to 3,7 % (m/m) oxygen, including those with ethanol up to 10 % (V/V).
NOTE 1   Manganese as MMT is added to petrol to increase anti-knock properties.
WARNING - The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.
NOTE 2   Solutions of MMT in petrol are unstable when exposed to light. Low and erratic results are expected if petrol samples are exposed to light prior the analysis.
NOTE 3   Manganese contents higher than 8 mg/l can be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been established for such a procedure.
NOTE 4   Application of the test method to the determination of other manganese compounds in petrol has not been tested.
NOTE 5   For the purposes of this European Standard, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction (µ) and the volume fraction of a material respectively.

This European Standard specifies an ion chromatographic (IC) method for the determination of the inorganic chloride content in ethanol from 2,0 mg/l to 25,0 mg/l and of the sulfate content in ethanol from 0,9 mg/l to 15,0 mg/l.
NOTE   Inorganic chloride content can be determined from 0,8 mg/l to 2,0 mg/l and sulfate content can be determined from 0,4 mg/l to 0,9 mg/l. However, the precision was not established as no samples with chloride and sulfate contents in these ranges where included in the interlaboratory test.
WARNING Use of this method may involve hazardous equipment, materials and operations. This method does not purport to address to all of the safety problems associated with its use, but it is the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

This European Standard specifies an ion chromatographic (IC) method for the determination of inorganic chloride and of sulfate content in ethanol. The precision of the method was established for chloride content from 4 mg/l to 30 mg/l. However, the precision of the method for sulfate content was not established yet.
NOTE   Preliminary measurements showed that sulfate content can be determined from (4 to 10) mg/kg.
WARNING: Use of this method may involve hazardous equipment, materials and operations. This method does not purport to address to all of the safety problems associated with its use, but it is the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.