ISO/TC 190/SC 3/WG 6 - Organic analysis

This document specifies a method for determining of perchlorate in soil and soil-like materials using liquid chromatography connected to a tandem mass spectrometry (LC-MS/MS). It defines pretreatment (including drying and sieving) of sample, extraction, clean-up, analysis using LC-MS/MS, and calculation of perchlorate content in dry soil. Under the conditions specified in this document, the limit of quantitation (LOQ) is approximately 4,6 μg/kg-dry soil.

This document specifies a method for quantitative determination of organochlorine pesticides (OCPs) and semi-volatile chlorobenzenes in soil and sediment, using GC-MS and GC-ECD. The limit of detection and the limit of application depends on the determinants, the sample intake, the equipment used, the quality of chemicals used for the extraction of the sample and the clean-up of the extract. Under the conditions specified in this document, lower limits of application from 1 μg/kg (expressed as dry matter) for soils to 10 μg/kg (expressed as dry matter) for sediments can be achieved. The necessity to achieve these lower limits of application depends on the analyses order and the current limit values. Soils and sediments can differ in properties as well as in the expected contamination levels of OCPs and the presence of interfering substances. These differences make it impossible to describe one general procedure. Based on the properties of the samples, this document contains decision tables regarding drying-, extraction- and clean-up procedures. This method is performance based. The method can be modified if all performance criteria given in this method are met. The method can be applied to the analysis of other chlorinated compounds not specified in the scope in cases where suitability has been proven by proper in-house validation experiments. NOTE The validation data are shown in Annex A. This document is validated only for α-HCH, β-HCH, γ-HCH, δ-HCH, o,p′-DDE, p,p′-DDE, o,p′-DDD, p,p′-DDD, o,p′-DDT and p,p′-DDT. For sediments, data are displayed measured using an ECD detection. The comparability of ECD and MS data in terms of the approach of this document was demonstrated on additional matrices.

This document specifies the measurement of explosives and related nitrocompounds (as given in Table 1) in soil and soil materials. This document is intended for the trace analysis of explosives and related compounds by liquid chromatography–tandem mass spectrometry (LC-MS/MS). Generally, LC-MS/MS measurement shows the lower LOQ (limit of quantification) for each compound in Table 1 than using high-performance liquid chromatography (HPLC) with UV-detection (see Annex B and Annex C). Under the conditions specified in this document, concentrations as low as 0,005 mg/kg to 0,014 mg/kg-dry matter can be determined, depending on the substance. Similar compounds, in particular various nitroaromatics, by-products and degradation products of explosive compounds can be analysed using this method provided that the applicability is checked on a case-by-case basis.

This document specifies a gas-chromatographic method for the identification and quantification of organotin compounds (OTCs) in soils as specified in Table 1. This document is also applicable to samples from sediments, sludges and wastes (soil-like materials). The working range depends on the detection technique used and the amount of sample taken for analysis. The limit of quantification for each compound is about 10 µg/kg.

This document specifies a method for the determination of perchlorate in soil and soil materials. Under the conditions specified in this document, a concentration as low as 0,1 mg/kg can be determined. The working range is restricted by the ion-exchange capacity of the separator column. Dilution of the water extracts to the working range can be necessary.

ISO 15009:2016 specifies a method for quantitative gas-chromatographic determination of volatile aromatic hydrocarbons, naphthalene and volatile halogenated hydrocarbons in soil. This International Standard is applicable to all types of soil. NOTE In the case of unsaturated peaty soils, absorption of the extraction solution may occur. The lower limit of quantification is dependent on the equipment used and the quality of the methanol grade used for the extraction of the soil sample. Under the conditions specified in this International Standard the following limits of quantification apply (expressed on basis of dry matter): Typical limit of quantification when using GC-FID: - Volatile aromatic hydrocarbons: 0,1 mg/kg Typical limit of quantification when using GC-ECD: - Volatile halogenated hydrocarbons: 0,01 mg/kg Lower limits of quantification for some compounds can be achieved by using mass spectrometry (MS) with selected ion detection.

ISO 22155:2016 specifies a static headspace method for quantitative gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected aliphatic ethers in soil. ISO 22155:2016 is applicable to all types of soil. The limit of quantification is dependent on the detection system used and the quality of the methanol grade used for the extraction of the soil sample. Under the conditions specified in this International Standard, the following limits of quantifications apply (expressed on basis of dry matter). Typical limit of quantification when using GC-FID: - volatile aromatic hydrocarbons: 0,2 mg/kg; - aliphatic ethers as methyl tert.-butyl ether(MTBE) and tert.-amyl methyl ether (TAME): 0,5 mg/kg. Typical limit of quantification when using GC-ECD: - volatile halogenated hydrocarbons: 0,01 mg/kg to 0,2 mg/kg. Lower limits of quantification for some compounds can be achieved by using mass spectrometry (MS) with selected ion detection (see Annex D).

ISO 16558-1:2015 specifies a method for the quantitative determination of the total extractable volatile, the volatile aliphatic, and aromatic fractions of petroleum hydrocarbon content in field moist soil samples by gas chromatography with mass spectrometric detection. The aromatic fractions are determined by the sum of individual aromatic compounds. The sum of the volatile aliphatic (C5 to C10) and aromatic (C6 to C10) fractions can be referred to as "volatile oil". The results of the test carried out can be used for risk assessment studies related to contaminations with petroleum hydrocarbons. ISO 16558-1:2015 provides a method applicable to petroleum hydrocarbon contents from about 5 mg/kg soil expressed as dry matter for the whole aliphatic fraction C5 to C10 and about 5 mg/kg soil expressed as dry matter for the aromatic fraction in the boiling range of C6 to C10. With this method, all hydrocarbons with a boiling range of 36 °C to 184 °C, n-alkanes between C5H12 to C10H22, isoalkanes, cycloalkanes, BTEX, and di- and tri-alkyl benzenes compounds are determined as total volatile petroleum hydrocarbons C5 to C10. In addition, volatile aliphatic and aromatic fractions are specified. For the determination of semi-volatile aliphatic and aromatic fractions of petroleum hydrocarbons in soil samples, see ISO/TS 16558-2. NOTE The sub-fractions proposed in this part of ISO 16558 have shown to be suitable for risk assessment studies. However, other sub-fractions between C5H12 to C10H22 can be determined in conformity with this part of ISO 16558. On the basis of the peak pattern of the gas chromatogram and of the boiling points of the individual n-alkanes listed in Annex A, the approximate boiling range of the mineral oil and some qualitative information on the composition of the contamination can be achieved.

ISO/TS 16558-2:2015 specifies a method for the quantitative determination of the total extractable semi-volatile, aliphatic, and aromatic fractions of petroleum hydrocarbon content in field moist soil samples by gas chromatography. The results of the test carried out can be used for risk assessment studies related to contaminations with petroleum hydrocarbons. ISO/TS 16558-2:2015 provides a method applicable to petroleum hydrocarbon contents from about 100 mg/kg soil expressed as dry matter for the whole aliphatic fraction C10 to C40, as well as the aromatic fraction C10 to C40. For sub-fractions, lower limits of determination can be reached. If lower detection limits are required, large volume injection can be used or concentration of the final extract can be carried out. NOTE 1 Low concentrations of aliphatic and aromatic compounds can be found in natural uncontaminated organic rich soils like peat soils.

ISO/TS 17182:2014 describes the gas chromatographic determination of phenols, methyl phenols, di-methylphenols and tri-methylphenols (see Table 1) and selected chlorophenols (see Table 2) by using mass spectrometric detection in soil samples. This method can also be used for other solid samples, such as sediments and solid wastes. This International Standard describes an acidic liquid extraction of soil, followed by acetylation and then liquid/liquid extraction. Determination takes place by gas chromatography and mass spectrometric detection. With this method, phenols and chlorophenols can be determined at the lowest of mass concentrations ranging from approximately 0,01 mg/kg to 0,1 mg/kg depending on the component sensitivity and the quantity of sample used. In some cases, complete separation of isomers cannot be achieved. Then the sum is reported. NOTE With this method, other higher methylated phenols can also be analysed provided that the suitability and the validity of the method is proven.

ISO 13913:2014 specifies a method for the determination of selected phthalates in sludge, treated biowaste, and soil, after extraction and gas chromatographic analysis with mass spectrometric detection. The method is applicable for the determination of selected phthalates at the lowest mass content of 0,1 mg/kg to 0,5 mg/kg (expressed as dry matter), depending on the individual substance. The applicability of the method to other phthalates is not excluded except the isomeric mixtures, e.g. DiNP (Di-isononylphthalate), but is to be verified in each case.

ISO 13859:2014 specifies the quantitative determination of 16 PAH in sludge, soil, and treated biowaste using GC-MS and HPLC-UV-DAD/FLD covering a wide range of PAH contamination levels. When using fluorescence detection, acenaphthylene cannot be measured. The limit of detection depends on the determinants, the equipment used, the quality of chemicals used for the extraction of the sample, and the clean-up of the extract. Typically, a lower limit of application of 0,01 mg/kg (expressed as dry matter) can be ensured for each individual PAH. Sludge, soil, and treated biowaste can differ in properties and also in the expected contamination levels of PAH and presence of interfering substances. These differences make it impossible to describe one general procedure. ISO 13859:2014 contains decision tables based on the properties of the sample and the extraction and clean-up procedure to be used. Two general lines are followed, an agitation procedure (shaking) or use of Soxhlet/pressurized liquid extraction.

ISO 11916-1:2013 specifies the measurement of explosive and related nitrocompounds in soils and soil materials. ISO 11916-1:2013 is intended for the trace analysis of explosives and related compounds by high-performance liquid chromatography (HPLC) using an ultraviolet (UV) detector. Under the conditions specified in ISO 11916-1:2013, concentrations as low as 0,1 mg/kg to 1 mg/kg dry matter can be determined, depending on the substance. Similar compounds, in particular various nitroaromatics, by-products and degradation products of explosive compounds may be analysed using this method. However, the applicability should be checked on a case-by-case basis.

ISO 11916-2:2013 specifies the measurement of explosive and related compounds (nitroaromatics and nitroamines) in soils and soil materials. ISO 11916-2:2013 is intended for the trace analysis of explosives and related compounds by gas chromatography (GC) using electron capture detector(s) (ECD) or a mass spectrometer (MS) as detector. ISO 11916-2:2013 can be used when reliable and specific identification of the compounds at low detection levels is required, e.g. for the evaluation of the toxic potential of soils contaminated with 2,6-DNT. Under the conditions specified in ISO 11916-2:2013, concentrations as low as 0,05 mg/kg dry matter can be determined, depending on the substance. Similar compounds may be analysed using this method. This is, however, to be verified experimentally. This method is not suitable for the analysis of hexogen (RDX), octogen (HMX), hexyl, tetryl and nitropenta (PETN).

ISO/TS 13907:2012 specifies a method for the determination of nonylphenols (NP), nonylphenol-monoethoxylates (NP1EO) and nonylphenol-diethoxylates (NP2EO) in sludge, treated biowaste and soil using GC-MS. For sludge, a limit of detection of 0,1 mg/kg and for soil and treated biowaste of 0,02 mg/kg (expressed as dry matter) may be achieved.

ISO/TS 13896:2012 specifies a method for the determination of linear alkylbenzene sulfonate (LAS) in sludge, treated biowaste and soil using high-performance liquid chromatography (HPLC) with a fluorescence detector (FLD) or a mass selective detector (MSD). ISO/TS 13896:2012 specifies the determination of the sum of LAS. Under the conditions specified in ISO/TS 13896:2012, typically a limit of detection of 20 mg/kg (expressed as dry matter) for sludge and of 0,2 mg/kg to 0,5 mg/kg for soil and treated biowaste may be achieved. Lower limits of detection may be achieved by concentrating the extract by solvent evaporation.

ISO 22892:2006 gives criteria for gas chromatography and mass spectrometry (GC-MS) identification of target compounds in soil samples. ISO 22892:2006 is intended for use with standards developed for the determination of specific compounds. The identification criteria are based on the comparison of retention times followed by interpretation of the electron ionization mass spectra, or if necessary, additional mass spectrometric techniques and other relevant factors.

ISO 18287:2006 specifies the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAH) according to the priority list of the Environmental Protection Agency, USA (EPA, 1982). ISO 18287:2006 is applicable to all types of soil (field-moist or chemically dried samples), covering a wide range of PAH contamination levels. Under the conditions specified in ISO 18287:2006, a lower limit of application of 0,01 mg/kg (expressed as dry matter) can be ensured for each individual PAH.

ISO 11264:2005 specifies a high-performance liquid chromatography (HPLC) method for qualitative and quantitative determination of herbicides of various substance classes in soils. This method covers triazines including their related metabolites, phenyl urea compounds and other herbicides. Compounds are identified and quantified with UV-detection.

ISO 14154:2005 describes the gas chromatographic determination of 15 chlorophenols (2,3-, 2,4- 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol; 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trichlorophenol, 2,3,4,5- and 2,3,4,6-tetrachlorophenol and pentachlorophenol) in soil samples. This method can also be applied to other solid samples such as sediments and solid wastes. ISO 14154:2005 describes an acid-base liquid extraction, followed by acetylation and then liquid/liquid extraction. Determination of mass concentrationis then carried out by gas chromatography and electron-capture detection. This method is applicable to chlorophenols at the lowest mass concentrations ranging from approximately 0,01 mg/kg to 0,05 mg/kg depending on the component sensitivity and the quantity of sample used. In some cases complete separation of isomers cannot be achieved, in which case the sum is reported (for instance 2,4- and 2,5-dichlorophenols).

ISO 16703:2004 specifies a method for the quantitative determination of the mineral oil (hydrocarbon) content in field-moist soil samples by gas chromatography. The method is applicable to mineral oil contents (mass fraction) between 100 mg/kg and 10 000 mg/kg soil, expressed as dry matter, and can be adapted to lower detection limits. ISO 16703:2004 is applicable to the determination of all hydrocarbons with a boiling range of 175 °C to 525 °C, n-alkanes from C10H22 to C40H82, isoalkanes, cycloalkanes, alkylbenzenes, alkylnaphthalenes and polycyclic aromatic compounds, provided that they are not absorbed on the specified column during the clean-up procedure. ISO 16703:2004 is not applicable to the quantitative determination of hydrocarbons 10 originating from gasolines. On the basis of the peak pattern of the gas chromatogram obtained, and of the boiling points of the individual n-alkanes listed in Annex B, the approximate boiling range of the mineral oil and some qualitative information on the composition of the contamination can be achieved.

ISO 14507:2003 specifies three methods for the pretreatment of soil samples in the laboratory prior to the determination of organic contaminants: if volatile organic compounds are to be measured; if moderately volatile to non-volatile organic compounds are to be measured, if the result of the subsequent analysis must be accurate and reproducible, and if the sample contains particles larger than 2 mm and/or the contaminant is heterogeneously distributed; if non-volatile organic compounds are to be measured and the extraction procedure prescribes a field-moist sample, or if the largest particles of the sample are smaller than 2 mm and the contaminant is homogeneously distributed. This procedure is also applicable if reduced accuracy and repeatability are acceptable. The pretreatment described in ISO 14507:2003 is used in combination with an extraction procedure in which the contaminant is available for the extraction liquid. NOTE For the pretreatment of soil samples for the purposes of determining non-volatile inorganic compounds and physico-chemical soil characteristics, see ISO 11464.

ISO 13914:2013 specifies a method for quantitative determination of 17 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in sludge, treated biowaste, and soil using liquid column chromatographic clean-up methods and GC/HRMS.

ISO 13876:2013 specifies a method for quantitative determination of seven selected polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) in sludge, treated biowaste, and soil using GC-MS and GC-ECD.

ISO 15009:2002 specifies a method for quantitative gas-chromatographic determination of volatile hydrocarbons, naphthalene and volatile halogenated hydrocarbons in soil. ISO 15009:2002 is applicable to all types of soil. Under the conditions specified in ISO 15009:2002, the following limits of determinations apply (expressed on basis of dry matter): volatile hydrocarbons and naphthalene: 0,1 mg/kg; volatile halogenated hydrocarbons: 0,01 mg/kg. The lower limit of determination is dependent on the equipment used and the quality of the methanol grade used for the extraction of the soil sample.

ISO 10382:2002 specifies a method for quantitative determination of seven polychlorinated biphenyls and seventeen organochlorine pesticides in soil. ISO 10382:2002 is applicable to all types of soil. Under the conditions specified in ISO 10382:2002, limits of detection of 0,1 micrograms per kilogram to 4 micrograms per kilogram (expressed as dry matter) can be achieved.

Specifies two methods for the quantitative determination of mineral oil content in soil by IR spectrometry (method A) and gas chromatography (method B). Method A is applicable to mineral oil contents above 20 mg/kg on a dry matter basis, method B to those above 100 mg/kg. Petrol cannot be determined quantitatively with these methods, due to loss of volatile compounds during sample pretreatment. Weak polar compounds of recent biogenic origin may be determined as mineral oil. Relatively high contents of polar compounds give interferences in the determination. Halogenated hydrocarbons also may interfere.