SIST EN ISO 22155:2013
(Main)Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)
Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)
This International Standard specifies a static headspace method for quantitative gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected aliphatic ethers in soil. This International Standard is applicable to all types of soil. The limit of determination 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 determination apply (expressed on the basis of dry matter):
Typical limit of determination when using gas chromatography/flame ionization detection (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 determination when using gas chromatography/electron capture detection (GC/ECD):
- volatile halogenated hydrocarbons: 0,01 mg/kg to 0,2 mg/kg.
Lower limits of determination can be achieved for some compounds by using mass spectrometry (MS) with selected ion detection (see Annex D).
Bodenbeschaffenheit - Gaschromatographische Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter Ether - Statisches Dampfraum-Verfahren (ISO 22155:2011)
Diese Internationale Norm legt ein statisches Dampfraumverfahren für die gaschromatographische quanti-tative Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter aliphatischer Ether in Böden fest.
Diese Internationale Norm ist auf alle Bodenarten anwendbar.
Die Bestimmungsgrenze hängt vom angewendeten Nachweissystem und von der Qualität des für die Extraktion der Bodenprobe verwendeten Methanols ab.
Unter den in dieser Internationalen Norm festgelegten Bedingungen gelten folgende Bestimmungsgrenzen (bezogen auf Trockensubstanz):
Bei Anwendung eines Gaschromatographen mit Flammenionisationsdetektor (GC/FID) liegt die typische Bestimmungsgrenze:
- bei 0,2 mg/kg für flüchtige aromatische Kohlenwasserstoffe
- und bei 0,5 mg/kg für aliphatische Ether, wie Methyl-tert-Butylether (MTBE) und tert-Amylmethylether (TAME);
Bei Anwendung eines Gaschromatographen mit Elektroneneinfangdetektor (GC/ECD) liegt die typische Bestimmungsgrenze:
- bei 0,01 mg/kg bis 0,2 mg/kg für flüchtige Halogenkohlenwasserstoffe.
Niedrigere Bestimmungsgrenzen können durch Anwendung der Massenspektrometrie (MS) mit Einzelionen-nachweis erreicht werden (siehe Anhang D).
Qualité du sol - Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse - Méthode par espace de tête statique (ISO 22155:2011)
L'ISO 22155:2011 spécifie une méthode par espace de tête statique pour le dosage quantitatif par chromatographie en phase gazeuse des hydrocarbures aromatiques et halogénés volatils et de certains éthers aliphatiques dans le sol.
L'ISO 22155:2011 est applicable à tous les types de sol.
La limite de dosage dépend du système de détection utilisé et de la qualité de méthanol utilisé pour l'extraction de l'échantillon de sol.
Dans les conditions spécifiées dans l'ISO 22155:2011, les limites de dosage suivantes (exprimées par rapport à la matière sèche) s'appliquent.
Limite de dosage type lorsque la chromatographie en phase gazeuse avec détecteur à ionisation de flamme (CG/FID) est utilisée:
hydrocarbures aromatiques volatils: 0,2 mg/kg;
éthers aliphatiques sous forme de méthyl tert-butyl éther (MTBE) et de tert-amyl méthyl éther (TAME): 0,5 mg/kg.
Limite de dosage type lorsque la chromatographie en phase gazeuse avec détecteur à capture d'électrons (CG/ECD) est utilisée:
hydrocarbures halogénés volatils: 0,01 mg/kg à 0,2 mg/kg.
Des limites de dosage plus faibles peuvent être atteintes pour certains composés si l'on utilise la spectrométrie de masse (SM) avec détection sélective des ions.
Kakovost tal - Določevanje hlapnih aromatskih in halogeniranih ogljikovodikov in izbranih etrov s plinsko kromatografijo - Metoda s statičnim vzorčevalnikom iz plinske faze (headspace) (ISO 22155:2011)
Ta mednarodni standard določa metodo s statičnim vzorčevalnikom iz plinske faze (headspace) za določevanje hlapnih aromatskih in halogeniranih ogljikovodikov in izbranih alifatskih etrov v tleh s kvantitativno plinsko kromatografijo. Ta mednarodni standard se uporablja za vse vrste tal. Meja določevanja je odvisna od uporabljenega sistema za detekcijo in kakovosti stopnje metanola, ki se uporablja za ekstrakcijo vzorca tal. Pod pogoji, določenimi v tem mednarodnem standardu, se uporabljajo naslednje meje določevanj (izraženo na podlagi suhe snovi):
tipična meja določevanja z uporabo plinske kromatografije/plamenske ionizacijske detekcije (GC/FID):
– hlapni aromatski ogljikovodiki: 0,2 mg/kg,
- alifatski etri kot metil terc-butil eter (MTBE) in terc-amil metil eter (TAME): 0,5 mg/kg; tipična meja določevanja z uporabo plinske kromatografije/detektorja na zajetje elektronov (GC/EDC):
– hlapni halogenski ogljikovodiki: 0,01 mg/kg do 0,2 mg/kg.
Nižje meje določevanja se lahko dosežejo za nekatere zmesi z masno spektrometrijo (MS) z izbrano detekcijo iona (glej dodatek D).
General Information
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Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Bodenbeschaffenheit - Gaschromatographische Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter Ether - Statisches Dampfraum-Verfahren (ISO 22155:2011)Qualité du sol - Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse - Méthode par espace de tête statique (ISO 22155:2011)Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)13.080.10Chemical characteristics of soilsICS:Ta slovenski standard je istoveten z:EN ISO 22155:2013SIST EN ISO 22155:2013en,fr,de01-maj-2013SIST EN ISO 22155:2013SLOVENSKI
STANDARD
SIST EN ISO 22155:2013
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN ISO 22155
February 2013 ICS 13.080.10 English Version
Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)
Qualité du sol - Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse - Méthode par espace de tête statique (ISO 22155:2011)
Bodenbeschaffenheit - Gaschromatographische Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter Ether - Statisches Dampfraum-Verfahren (ISO 22155:2011) This European Standard was approved by CEN on 5 February 2013.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,
B-1000 Brussels © 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 22155:2013: ESIST EN ISO 22155:2013
EN ISO 22155:2013 (E) 2 Contents Page Foreword . 3
SIST EN ISO 22155:2013
EN ISO 22155:2013 (E) 3 Foreword The text of ISO 22155:2011 has been prepared by Technical Committee ISO/TC 190 “Soil quality” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 22155:2013 by Technical Committee CEN/TC 345 “Characterization of soils” the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by August 2013, and conflicting national standards shall be withdrawn at the latest by August 2013. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 22155:2011 has been approved by CEN as EN ISO 22155:2013 without any modification.
SIST EN ISO 22155:2013
SIST EN ISO 22155:2013
Reference numberISO 22155:2011(E)© ISO 2011
INTERNATIONAL STANDARD ISO22155Second edition2011-04-01Soil quality — Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers — Static headspace method Qualité du sol — Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse — Méthode par espace de tête statique
SIST EN ISO 22155:2013
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SIST EN ISO 22155:2013
ISO 22155:2011(E) © ISO 2011 – All rights reserved iii Contents Page Foreword.iv 1 Scope.1 2 Normative references.1 3 Principle.2 4 Reagents.2 5 Apparatus.5 6 Sampling, preservation and sample pretreatment.6 6.1 General.6 6.2 Sampling using vials prefilled with methanol.6 6.3 Sampling using coring tube method.7 7 Procedure.7 7.1 Blank determination.7 7.2 Extraction.7 7.3 Headspace analysis.7 7.4 Gas chromatographic analysis.8 8 Calculation.10 8.1 Calculation of the concentration of a volatile compound in the water sample.10 8.2 Calculation of the concentration of a volatile compound in the soil sample.11 9 Expression of results.11 10 Precision.11 11 Test report.11 Annex A (informative)
Relative retention times with respect to ethylbenzene-D10 of volatile aromatic hydrocarbons and volatile halogenated hydrocarbons.12 Annex B (normative)
Check on internal standards.14 Annex C (informative)
Validation (general).15 Annex D (informative)
Validation for the pathway soil/human.18 Bibliography.21
SIST EN ISO 22155:2013
ISO 22155:2011(E) iv © ISO 2011 – All rights reserved Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 22155 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics. This second edition cancels and replaces the first edition (ISO 22155:2005), which has been technically revised.
SIST EN ISO 22155:2013
INTERNATIONAL STANDARD ISO 22155:2011(E) © ISO 2011 – All rights reserved 1 Soil quality — Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers — Static headspace method 1 Scope This International Standard specifies a static headspace method for quantitative gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected aliphatic ethers in soil. This International Standard is applicable to all types of soil. The limit of determination 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 determination apply (expressed on the basis of dry matter): Typical limit of determination when using gas chromatography/flame ionization detection (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 determination when using gas chromatography/electron capture detection (GC/ECD): ⎯ volatile halogenated hydrocarbons: 0,01 mg/kg to 0,2 mg/kg. Lower limits of determination can be achieved for some compounds by using mass spectrometry (MS) with selected ion detection (see Annex D). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 10381-1:2002, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric method ISO 15680, Water quality — Gas-chromatographic determination of a number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge-and-trap and theral desorption ISO 18512, Soil quality — Guidance on long and short term storage of soil samples SIST EN ISO 22155:2013
ISO 22155:2011(E) 2 © ISO 2011 – All rights reserved ISO 22892, Soil quality — Guidelines for the identification of target compounds by gas chromatography and mass spectrometry 3 Principle Test samples are taken from an untreated field-moist soil sample. To prevent losses of the volatiles, samples are taken in as undisturbed a way as possible in the field with a tube corer or by adding methanol immediately in the field. The test sample is extracted with methanol. An aliquot of the methanol extract is transferred into a headspace vial with a defined amount of water and sealed. The temperature of the vials is stabilized in a thermostatic system to a temperature within the range 50 °C to 80 °C to achieve specified equilibrium conditions. Gas chromatographic analysis of the volatile compounds in gaseous phase in equilibrium with the water in the vials is carried out by using headspace injection and an appropriate capillary column. Volatile organic compounds are detected with appropriate detectors, such as a mass spectrometry detector (MS), flame ionization detector (FID), electron capture detector (ECD), photo ionization detector (PID) or electrolytic conductivity detector (ELCD). Identification and quantification are made by comparison of retention times and peak heights (or peak areas), comparing to the internal standard added. When using non-specific detectors, such as FID and ECD, the confirmation of the identity of the detected compounds and their concentrations should be done by repeating the gas chromatographic analysis using a column of different polarity. When using gas chromatography/mass spectrometry (GC/MS), the identity confirmation and the quantification can be done in a single run. 4 Reagents All reagents shall be of recognized analytical grade. Verify whether the reagents are applicable for this specific purpose and free of interfering compounds. 4.1 Water, free of volatile organic contaminants, showing negligible interferences in comparison with the smallest concentration to be determined. A sufficient amount of water from the same batch should be available to complete each batch of analyses, including all preparations. 4.2 Internal standard compounds 4.2.1 For the determination of volatile aromatic hydrocarbons, preferably two internal standards shall be selected. They shall not interfere with compounds present in the methanol extract. Examples of suitable internal standards are: ⎯ toluene-D8 (CAS-RN1) 2037-26-5); ⎯ ethylbenzene-D10 (CAS-RN 25837-05-2); ⎯ 2-bromofluorobenzene (CAS-RN 1072-85-1). 4.2.2 For the determination of volatile halogenated hydrocarbons, preferably two internal standards shall be selected. They shall not interfere with compounds present in the methanol extract.
1) CAS-RN: Chemical Abstracts System Registry Number SIST EN ISO 22155:2013
ISO 22155:2011(E) © ISO 2011 – All rights reserved 3 Examples of suitable internal standards are: ⎯ 1,4-dichlorobutane (CAS-RN 110-56-5); ⎯ α,α,α-trifluorotoluene (CAS-RN 98-08-8); ⎯ 2-bromofluorobenzene (CAS-RN 1072-85-1). 4.3 Volatile aromatic hydrocarbons Compound CAS-RNBenzene
71-43-2Toluene 108-88-3Ethylbenzene 100-41-4o-Xylene 95-47-6m-Xylene 108-38-3p-Xylene 106-42-3Styrene 100-42-5Naphthalene 91-20-34.4 Volatile halogenated hydrocarbons Compound CAS-RNDichloromethane 75-09-2Trichloromethane 67-66-3Tetrachloromethane 56-23-51,1-Dichloroethane 75-34-31,2-Dichloroethane 107-06-21,1,1-Trichloroethane 79-01-61,1,2-Trichloroethane 79-00-51,2-Dichloropropane 78-87-51,2,3-Trichloropropane 98-18-4cis-1,3-Dichloropropene 10061-01-5trans-1,3-Dichloropropene 10061-02-6cis-1,2-Dichloroethene 156-59-2trans-1,2-Dichloroethene 156-60-53-Chloropropene 107-05-1Trichloroethene 79-01-6Tetrachloroethene 127-18-4Monochlorobenzene 108-90-71,2-Dichlorobenzene 95-50-1SIST EN ISO 22155:2013
ISO 22155:2011(E) 4 © ISO 2011 – All rights reserved 4.5 Aliphatic ethers Compound CAS-RNMethyl tert-butyl ether (MTBE) 1634-04-4tert-Amyl methyl ether (TAME) 994-05-8NOTE This method can also be used for volatile organic compounds not included in this International Standard, provided it has been validated for each new compound. 4.6 Methanol (CAS-RN 67-56-1), as a solvent for the extraction of soil samples and for the preparation of standard solutions. NOTE Other solvents which are readily soluble in water and do not interfere with the analytical process can be used as well, for example dimethylformamide (DMF) and dimethylsulfoxide (DMSO). 4.7 Carrier gases for gas chromatography, helium, nitrogen or argon-methane ultrapure mixture. Other gases for gas chromatography shall be used in accordance with the instrument manufacturer's instructions. 4.8 Standard solutions 4.8.1 Standard stock solutions for the volatile compounds in methanol Prepare the stock solutions by adding defined amounts (e.g. 100 µl) of each standard compound (4.3, 4.4 and 4.5) with a microlitre syringe. Immerse the tip of the needle in the methanol solvent and weigh with an accuracy of 0,1 mg. NOTE 1 A convenient concentration (4 mg/ml) of the standard stock solution is obtained by weighing 100 mg of the standard substance and dissolving it in 25 ml of the solvent. The stock solution is stable for about 6 months when stored at −18 °C. NOTE 2 For practical reasons, mixed standard stock solutions can also be prepared. 4.8.2 Internal standard stock solutions in methanol Prepare the internal standard stock solutions with the individual internal standard compounds (4.2.1 and 4.2.2) with the same procedure as in 4.8.1. The containers containing the solutions shall be weighed so that any evaporation losses of the solvent may be recognized. The solutions shall be stored at a temperature of 4 °C ± 2 °C in the dark. Prior to use, they shall be brought to ambient temperature. 4.8.3 Intermediate mixed standard solutions Prepare intermediate mixed standard solutions by mixing a defined volume of each individual standard stock solution or a mixed standard stock solution and dilute with methanol. NOTE A typical concentration is 40 µg/ml. Store the intermediate mixed standard solutions at 4 °C ± 2 °C for not longer than 3 months. 4.8.4 Working standard solutions Prepare at least five different concentrations (e.g. from 0,2 µg/ml to 3,2 µg/ml) by suitable dilutions of the intermediate mixed standard solutions, adding 50 µl to 500 µl of these concentrations to methanol (10 ml) using a microlitre syringe. SIST EN ISO 22155:2013
ISO 22155:2011(E) © ISO 2011 – All rights reserved 5 4.8.5 Working internal standard solutions Prepare the internal standard solutions of defined concentration (e.g. 0,4 µg/ml) as described in 4.8.3 and 4.8.4. 4.8.6 Aqueous calibration standard solutions Prepare the calibration solutions (see Table 1) by adding a defined amount (e.g. 50 µl) of working standard solutions and internal standard solutions to a defined volume (e.g. 10 ml) of water in an appropriate headspace vial. Use a syringe and immerse the top of the needle in the water. Seal the vial tightly with a crimp cap fitted with a polytetrafluoroethylene (PTFE) coated septum. The total volume of the methanol used for calibration shall be the same as will be taken for the methanol extract of the soil sample (see 7.3). Make sure that the content of the organic solvent in the final aqueous calibration standard solution does not exceed the volume fraction of 2 %. Table 1 — Example for the preparation of calibration solutions Calibration solution Working standard solution (4.8.4) Working standard internal solution (4.8.5) Concentration in working standard solution Quantity in calibration solution of 10 ml (sample) water Concentration in aqueous calibration solution
µl µl µg/ml ng µg/l 1 50 50 (methanol) 0 0 0 2 50 50 0,2 10 1 3 50 50 0,4 20 2 4 50 50 0,8 40 4 5 50 50 1,6 80 8 6 50 50 3,2 160 16
5 Apparatus Use ordinary laboratory glassware, free of interfering compounds. All glassware shall be cleaned according to the usual procedures for this type of analysis. 5.1 Glass vials with suitable septum Glass vials (50 ml to 100 ml) and screw cap, fitted with a PTFE-coated septum for field-moist soil samples taken in the field. Glass vials (10 ml for 5 ml water and 22 ml for 10 ml water) with a PTFE-coated septum and crimped metallic cap, compatible with the headspace system connected to an appropriate gas chromatographic system. The vials shall be capable of being hermetically sealed in the field, as well as at elevated temperatures. 5.2 Crimping pliers 5.3 Headspace system This method was developed for using a totally automated equilibrium headspace analyser available from several commercial sources. The system used shall meet the following specifications. The system shall be capable of keeping the vials at a constant temperature (between 50 °C and 80 °C). SIST EN ISO 22155:2013
ISO 22155:2011(E) 6 © ISO 2011 – All rights reserved The system shall be capable of accurately transferring a representative portion of the headspace into a gas chromatograph fitted with capillary columns. 5.4 Shaking machine A shaking machine with horizontal movement (200 to 300 movements per minute). 5.5 Capillary columns Fused silica capillary columns with a non-polar or semi-polar stationary phase allowing sufficient separation of the compounds of interest. A thick film of stationary phase increases the efficiency of the separation of more volatile compounds. Examples are given in 7.4. 5.6 Gas chromatograph A gas chromatograph equipped with one or two appropriate detectors. Detectors like flame ionization detector (FID), electron capture detector (ECD), photo ionization detector (PID) or electrolytic conductivity detector (ELCD) and mass spectrometer (MS) can be used, depending on the substances to be analysed and their target level of contamination. The mass spectrometer should be able to operate over the total mass range of interest and being equipped with a data system capable of quantifying ions using selected m/z values. 5.7 Electronic integrator or computer with chromatographic software 5.8 Syringe, of volume 5 µl, 10 µl, 50 µl, 100 µl, 250 µl and 500 µl 6 Sampling, preservation and sample pretreatment 6.1 General Sampling shall be carried out in accordance with ISO 10381-1 using equipment in accordance with ISO 10381-2 after coordination with the analytical laboratory. Samples shall be analysed as soon as possible. Samples shall be stored cool in accordance with ISO 18512. Samples are not pretreated. Exposure of samples to air, even during sampling, shall be avoided as far as possible. Sampling for volatile compounds can be carried out with several techniques. It is strongly recommended to use one of the procedures described in 6.2 and 6.3 in order to prevent losses by volatilization. Determine the dry matter content of the field-moist sample in accordance with ISO 11465. In case the sampling method in 6.2 is used, a separate sample should be delivered to the laboratory for determination of the dry matter. 6.2 Sampling using vials prefilled with methanol Transfer a defined volume of soil using an appropriate device into a preweighed vial which is filled with a defined volume of methanol (4.6). Prevent leakages by cleaning the top of the vessel before sealing. The soil samples should be taken from undisturbed material using an appropriate sample cutter of known volume, e.g. a modified 20 ml disposable plastic syringe with the tip cut off. The soil sample should be collected immediately after exposing a fresh soil surface of the drilling core, e.g. of an open window sampler or the trial pit wall. The incorporation of material like roots or stones should be avoided as far as possible. Make sure that the sample is completely covered with methanol (4.6). Then close the cap of the PTFE-coated septum. At least one blank sample on every site shall be prepared in the field by opening the prepared vial for the same time period as necessary for filling with the soil sample. Add methanol (4.6) and close the cap of the vial. SIST EN ISO 22155:2013
ISO 22155:2011(E) © ISO 2011 – All rights reserved 7 The sampling vials should be kept dark in a cooler (before and after sampling) throughout the whole transportation. For details see ISO 18512.
6.3 Sampling using coring tube method This method, by taking an undisturbed sample, greatly reduces or eliminates common losses (e.g. due to evaporation, diffusion, sorption onto plastics). This method involves a stainless-steel coring tube of minimal volume 200 ml which is filled in situ, retrieved and capped with a non-permeable material, e.g. stainless steel, aluminium foil. The tube should be filled totally. NOTE This method is not suitable for very stony soils. Store in cool conditions at a temperature of 2 °C to 8 °C for no longer than 4 d; see ISO 18512. In the laboratory during sub-sampling, take care that no volatile compounds are lost. Start as soon as possible with the cooled sample. Use the whole content of the coring tube or take a sub-sample with a suitable instrument, e.g. an apple corer, and put it directly into the vial (see 7.2). 7 Procedure 7.1 Blank determination For each series of samples, a solvent blank determination shall be carried out by adding 10 µl to 100 µl of methanol (4.6) to 5 ml to 10 ml of water (4.1), as is done with a sample. Ensure that no contamination occurs from the laboratory atmosphere. 7.2 Extraction Using the sampling procedure in 6.2, the extraction is carried out in the field; if using sampling procedure 6.3, the extraction is carried out in the laboratory. Add a defined amount of test sample (25 g to 50 g), collected as described during sampling (Clause 6) with a sampling device into a preweighed vial (50 ml to 100 ml) (see 6.2) filled with a defined amount of methanol (25 ml to 50 ml) and screw-cap the vial with PTFE-coated septum. Weigh and place the vials on the horizontal shaking machine (5.4) and shake for 30 min. Take the tube out of the shaking machine and allow it to stand for 10 min to 15 min for the settling of solid materials. If there is no settling of solid materials on standing, centrifuge for 10 min at a rotation frequency that results in a radial acceleration of 2 000 g. 7.3 Headspace analysis Transfer a defined volume of water (5 ml to 10 ml) into a headspace vial. Inject 10 µl to 100 µl of the methanol extract, obtained according to 7.2, to the bottom of the vial and seal tightly with a crimp cap fitted with a PTFE-coated septum. Then, after preparing the spiked water samples, proceed to the analysis in a very similar way to water analysis. Prepare the calibration samples in the same way with the same volume 10 µl to 100 µl of the calibration solutions (4.8.6). Take the tube out of the shaking machine and allow it to stand for 10 min to 15 min for settling of solid materials. If there is no settling of solid materials on standing, place it in the centrifuge. Centrifuge for 10 min at a rotation frequency that results in a radial acceleration of 2 000 g. NOTE 1 A lower detection limit could be achieved by addition of sodium chloride, NaCl (e.g. 3 g per 10 ml). Place the vials of water samples in the thermostated tray of the headspace system at a fixed temperature in the range from 50 °C to 80 °C, for at least 30 min and for the same time for all vials. SIST EN ISO 22155:2013
ISO 22155:2011(E) 8 © ISO 2011 – All rights reserved NOTE 2 For specific equipment working at equilibrium, the time required to reach equilibrium can vary, depending on the volatile organic substance and the volume of the vials used. Experience has shown that at least 30 min is necessary. 7.4 Gas
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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.[Not translated]Bodenbeschaffenheit - Gaschromatographische Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter Ether - Statisches Dampfraum-Verfahren (ISO 22155:2011)Qualité du sol - Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse - Méthode par espace de tête statique (ISO 22155:2011)Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)13.080.10Chemical characteristics of soilsICS:Ta slovenski standard je istoveten z:FprEN ISO 22155kSIST FprEN ISO 22155:2012en,fr,de01-december-2012kSIST FprEN ISO 22155:2012SLOVENSKI
STANDARD
kSIST FprEN ISO 22155:2012
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
FINAL DRAFT
FprEN ISO 22155
August 2012 ICS 13.080.10 English Version
Soil quality - Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers - Static headspace method (ISO 22155:2011)
Qualité du sol - Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse - Méthode par espace de tête statique (ISO 22155:2011)
Bodenbeschaffenheit - Gaschromatographische Bestimmung flüchtiger aromatischer Kohlenwasserstoffe, Halogenkohlenwasserstoffe und ausgewählter Ether - Statisches Dampfraum-Verfahren (ISO 22155:2011) This draft European Standard is submitted to CEN members for unique acceptance procedure. It has been drawn up by the Technical Committee CEN/TC 345.
If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.
This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to provide supporting documentation.
Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
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FprEN ISO 22155:2012 (E) 2 Contents Page Foreword .3 kSIST FprEN ISO 22155:2012
FprEN ISO 22155:2012 (E) 3 Foreword The text of ISO 22155:2011 has been prepared by Technical Committee ISO/TC 190 “Soil quality” of the International Organization for Standardization (ISO) and has been taken over as FprEN ISO 22155:2012 by Technical Committee CEN/TC 345 “Characterization of soils” the secretariat of which is held by NEN. This document is currently submitted to the Unique Acceptance Procedure. Endorsement notice The text of ISO 22155:2011 has been approved by CEN as a FprEN ISO 22155:2012 without any modification. kSIST FprEN ISO 22155:2012
kSIST FprEN ISO 22155:2012
Reference numberISO 22155:2011(E)© ISO 2011
INTERNATIONAL STANDARD ISO22155Second edition2011-04-01Soil quality — Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers — Static headspace method Qualité du sol — Dosage des hydrocarbures aromatiques et halogénés volatils et de certains éthers par chromatographie en phase gazeuse — Méthode par espace de tête statique
kSIST FprEN ISO 22155:2012
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kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) © ISO 2011 – All rights reserved iii Contents Page Foreword.iv 1 Scope.1 2 Normative references.1 3 Principle.2 4 Reagents.2 5 Apparatus.5 6 Sampling, preservation and sample pretreatment.6 6.1 General.6 6.2 Sampling using vials prefilled with methanol.6 6.3 Sampling using coring tube method.7 7 Procedure.7 7.1 Blank determination.7 7.2 Extraction.7 7.3 Headspace analysis.7 7.4 Gas chromatographic analysis.8 8 Calculation.10 8.1 Calculation of the concentration of a volatile compound in the water sample.10 8.2 Calculation of the concentration of a volatile compound in the soil sample.11 9 Expression of results.11 10 Precision.11 11 Test report.11 Annex A (informative)
Relative retention times with respect to ethylbenzene-D10 of volatile aromatic hydrocarbons and volatile halogenated hydrocarbons.12 Annex B (normative)
Check on internal standards.14 Annex C (informative)
Validation (general).15 Annex D (informative)
Validation for the pathway soil/human.18 Bibliography.21
kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) iv © ISO 2011 – All rights reserved Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 22155 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics. This second edition cancels and replaces the first edition (ISO 22155:2005), which has been technically revised.
kSIST FprEN ISO 22155:2012
INTERNATIONAL STANDARD ISO 22155:2011(E) © ISO 2011 – All rights reserved 1 Soil quality — Gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected ethers — Static headspace method 1 Scope This International Standard specifies a static headspace method for quantitative gas chromatographic determination of volatile aromatic and halogenated hydrocarbons and selected aliphatic ethers in soil. This International Standard is applicable to all types of soil. The limit of determination 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 determination apply (expressed on the basis of dry matter): Typical limit of determination when using gas chromatography/flame ionization detection (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 determination when using gas chromatography/electron capture detection (GC/ECD): ⎯ volatile halogenated hydrocarbons: 0,01 mg/kg to 0,2 mg/kg. Lower limits of determination can be achieved for some compounds by using mass spectrometry (MS) with selected ion detection (see Annex D). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 10381-1:2002, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric method ISO 15680, Water quality — Gas-chromatographic determination of a number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge-and-trap and theral desorption ISO 18512, Soil quality — Guidance on long and short term storage of soil samples kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) 2 © ISO 2011 – All rights reserved ISO 22892, Soil quality — Guidelines for the identification of target compounds by gas chromatography and mass spectrometry 3 Principle Test samples are taken from an untreated field-moist soil sample. To prevent losses of the volatiles, samples are taken in as undisturbed a way as possible in the field with a tube corer or by adding methanol immediately in the field. The test sample is extracted with methanol. An aliquot of the methanol extract is transferred into a headspace vial with a defined amount of water and sealed. The temperature of the vials is stabilized in a thermostatic system to a temperature within the range 50 °C to 80 °C to achieve specified equilibrium conditions. Gas chromatographic analysis of the volatile compounds in gaseous phase in equilibrium with the water in the vials is carried out by using headspace injection and an appropriate capillary column. Volatile organic compounds are detected with appropriate detectors, such as a mass spectrometry detector (MS), flame ionization detector (FID), electron capture detector (ECD), photo ionization detector (PID) or electrolytic conductivity detector (ELCD). Identification and quantification are made by comparison of retention times and peak heights (or peak areas), comparing to the internal standard added. When using non-specific detectors, such as FID and ECD, the confirmation of the identity of the detected compounds and their concentrations should be done by repeating the gas chromatographic analysis using a column of different polarity. When using gas chromatography/mass spectrometry (GC/MS), the identity confirmation and the quantification can be done in a single run. 4 Reagents All reagents shall be of recognized analytical grade. Verify whether the reagents are applicable for this specific purpose and free of interfering compounds. 4.1 Water, free of volatile organic contaminants, showing negligible interferences in comparison with the smallest concentration to be determined. A sufficient amount of water from the same batch should be available to complete each batch of analyses, including all preparations. 4.2 Internal standard compounds 4.2.1 For the determination of volatile aromatic hydrocarbons, preferably two internal standards shall be selected. They shall not interfere with compounds present in the methanol extract. Examples of suitable internal standards are: ⎯ toluene-D8 (CAS-RN1) 2037-26-5); ⎯ ethylbenzene-D10 (CAS-RN 25837-05-2); ⎯ 2-bromofluorobenzene (CAS-RN 1072-85-1). 4.2.2 For the determination of volatile halogenated hydrocarbons, preferably two internal standards shall be selected. They shall not interfere with compounds present in the methanol extract.
1) CAS-RN: Chemical Abstracts System Registry Number kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) © ISO 2011 – All rights reserved 3 Examples of suitable internal standards are: ⎯ 1,4-dichlorobutane (CAS-RN 110-56-5); ⎯ α,α,α-trifluorotoluene (CAS-RN 98-08-8); ⎯ 2-bromofluorobenzene (CAS-RN 1072-85-1). 4.3 Volatile aromatic hydrocarbons Compound CAS-RNBenzene
71-43-2Toluene 108-88-3Ethylbenzene 100-41-4o-Xylene 95-47-6m-Xylene 108-38-3p-Xylene 106-42-3Styrene 100-42-5Naphthalene 91-20-34.4 Volatile halogenated hydrocarbons Compound CAS-RNDichloromethane 75-09-2Trichloromethane 67-66-3Tetrachloromethane 56-23-51,1-Dichloroethane 75-34-31,2-Dichloroethane 107-06-21,1,1-Trichloroethane 79-01-61,1,2-Trichloroethane 79-00-51,2-Dichloropropane 78-87-51,2,3-Trichloropropane 98-18-4cis-1,3-Dichloropropene 10061-01-5trans-1,3-Dichloropropene 10061-02-6cis-1,2-Dichloroethene 156-59-2trans-1,2-Dichloroethene 156-60-53-Chloropropene 107-05-1Trichloroethene 79-01-6Tetrachloroethene 127-18-4Monochlorobenzene 108-90-71,2-Dichlorobenzene 95-50-1kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) 4 © ISO 2011 – All rights reserved 4.5 Aliphatic ethers Compound CAS-RNMethyl tert-butyl ether (MTBE) 1634-04-4tert-Amyl methyl ether (TAME) 994-05-8NOTE This method can also be used for volatile organic compounds not included in this International Standard, provided it has been validated for each new compound. 4.6 Methanol (CAS-RN 67-56-1), as a solvent for the extraction of soil samples and for the preparation of standard solutions. NOTE Other solvents which are readily soluble in water and do not interfere with the analytical process can be used as well, for example dimethylformamide (DMF) and dimethylsulfoxide (DMSO). 4.7 Carrier gases for gas chromatography, helium, nitrogen or argon-methane ultrapure mixture. Other gases for gas chromatography shall be used in accordance with the instrument manufacturer's instructions. 4.8 Standard solutions 4.8.1 Standard stock solutions for the volatile compounds in methanol Prepare the stock solutions by adding defined amounts (e.g. 100 µl) of each standard compound (4.3, 4.4 and 4.5) with a microlitre syringe. Immerse the tip of the needle in the methanol solvent and weigh with an accuracy of 0,1 mg. NOTE 1 A convenient concentration (4 mg/ml) of the standard stock solution is obtained by weighing 100 mg of the standard substance and dissolving it in 25 ml of the solvent. The stock solution is stable for about 6 months when stored at −18 °C. NOTE 2 For practical reasons, mixed standard stock solutions can also be prepared. 4.8.2 Internal standard stock solutions in methanol Prepare the internal standard stock solutions with the individual internal standard compounds (4.2.1 and 4.2.2) with the same procedure as in 4.8.1. The containers containing the solutions shall be weighed so that any evaporation losses of the solvent may be recognized. The solutions shall be stored at a temperature of 4 °C ± 2 °C in the dark. Prior to use, they shall be brought to ambient temperature. 4.8.3 Intermediate mixed standard solutions Prepare intermediate mixed standard solutions by mixing a defined volume of each individual standard stock solution or a mixed standard stock solution and dilute with methanol. NOTE A typical concentration is 40 µg/ml. Store the intermediate mixed standard solutions at 4 °C ± 2 °C for not longer than 3 months. 4.8.4 Working standard solutions Prepare at least five different concentrations (e.g. from 0,2 µg/ml to 3,2 µg/ml) by suitable dilutions of the intermediate mixed standard solutions, adding 50 µl to 500 µl of these concentrations to methanol (10 ml) using a microlitre syringe. kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) © ISO 2011 – All rights reserved 5 4.8.5 Working internal standard solutions Prepare the internal standard solutions of defined concentration (e.g. 0,4 µg/ml) as described in 4.8.3 and 4.8.4. 4.8.6 Aqueous calibration standard solutions Prepare the calibration solutions (see Table 1) by adding a defined amount (e.g. 50 µl) of working standard solutions and internal standard solutions to a defined volume (e.g. 10 ml) of water in an appropriate headspace vial. Use a syringe and immerse the top of the needle in the water. Seal the vial tightly with a crimp cap fitted with a polytetrafluoroethylene (PTFE) coated septum. The total volume of the methanol used for calibration shall be the same as will be taken for the methanol extract of the soil sample (see 7.3). Make sure that the content of the organic solvent in the final aqueous calibration standard solution does not exceed the volume fraction of 2 %. Table 1 — Example for the preparation of calibration solutions Calibration solution Working standard solution (4.8.4) Working standard internal solution (4.8.5) Concentration in working standard solution Quantity in calibration solution of 10 ml (sample) water Concentration in aqueous calibration solution
µl µl µg/ml ng µg/l 1 50 50 (methanol) 0 0 0 2 50 50 0,2 10 1 3 50 50 0,4 20 2 4 50 50 0,8 40 4 5 50 50 1,6 80 8 6 50 50 3,2 160 16
5 Apparatus Use ordinary laboratory glassware, free of interfering compounds. All glassware shall be cleaned according to the usual procedures for this type of analysis. 5.1 Glass vials with suitable septum Glass vials (50 ml to 100 ml) and screw cap, fitted with a PTFE-coated septum for field-moist soil samples taken in the field. Glass vials (10 ml for 5 ml water and 22 ml for 10 ml water) with a PTFE-coated septum and crimped metallic cap, compatible with the headspace system connected to an appropriate gas chromatographic system. The vials shall be capable of being hermetically sealed in the field, as well as at elevated temperatures. 5.2 Crimping pliers 5.3 Headspace system This method was developed for using a totally automated equilibrium headspace analyser available from several commercial sources. The system used shall meet the following specifications. The system shall be capable of keeping the vials at a constant temperature (between 50 °C and 80 °C). kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) 6 © ISO 2011 – All rights reserved The system shall be capable of accurately transferring a representative portion of the headspace into a gas chromatograph fitted with capillary columns. 5.4 Shaking machine A shaking machine with horizontal movement (200 to 300 movements per minute). 5.5 Capillary columns Fused silica capillary columns with a non-polar or semi-polar stationary phase allowing sufficient separation of the compounds of interest. A thick film of stationary phase increases the efficiency of the separation of more volatile compounds. Examples are given in 7.4. 5.6 Gas chromatograph A gas chromatograph equipped with one or two appropriate detectors. Detectors like flame ionization detector (FID), electron capture detector (ECD), photo ionization detector (PID) or electrolytic conductivity detector (ELCD) and mass spectrometer (MS) can be used, depending on the substances to be analysed and their target level of contamination. The mass spectrometer should be able to operate over the total mass range of interest and being equipped with a data system capable of quantifying ions using selected m/z values. 5.7 Electronic integrator or computer with chromatographic software 5.8 Syringe, of volume 5 µl, 10 µl, 50 µl, 100 µl, 250 µl and 500 µl 6 Sampling, preservation and sample pretreatment 6.1 General Sampling shall be carried out in accordance with ISO 10381-1 using equipment in accordance with ISO 10381-2 after coordination with the analytical laboratory. Samples shall be analysed as soon as possible. Samples shall be stored cool in accordance with ISO 18512. Samples are not pretreated. Exposure of samples to air, even during sampling, shall be avoided as far as possible. Sampling for volatile compounds can be carried out with several techniques. It is strongly recommended to use one of the procedures described in 6.2 and 6.3 in order to prevent losses by volatilization. Determine the dry matter content of the field-moist sample in accordance with ISO 11465. In case the sampling method in 6.2 is used, a separate sample should be delivered to the laboratory for determination of the dry matter. 6.2 Sampling using vials prefilled with methanol Transfer a defined volume of soil using an appropriate device into a preweighed vial which is filled with a defined volume of methanol (4.6). Prevent leakages by cleaning the top of the vessel before sealing. The soil samples should be taken from undisturbed material using an appropriate sample cutter of known volume, e.g. a modified 20 ml disposable plastic syringe with the tip cut off. The soil sample should be collected immediately after exposing a fresh soil surface of the drilling core, e.g. of an open window sampler or the trial pit wall. The incorporation of material like roots or stones should be avoided as far as possible. Make sure that the sample is completely covered with methanol (4.6). Then close the cap of the PTFE-coated septum. At least one blank sample on every site shall be prepared in the field by opening the prepared vial for the same time period as necessary for filling with the soil sample. Add methanol (4.6) and close the cap of the vial. kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) © ISO 2011 – All rights reserved 7 The sampling vials should be kept dark in a cooler (before and after sampling) throughout the whole transportation. For details see ISO 18512.
6.3 Sampling using coring tube method This method, by taking an undisturbed sample, greatly reduces or eliminates common losses (e.g. due to evaporation, diffusion, sorption onto plastics). This method involves a stainless-steel coring tube of minimal volume 200 ml which is filled in situ, retrieved and capped with a non-permeable material, e.g. stainless steel, aluminium foil. The tube should be filled totally. NOTE This method is not suitable for very stony soils. Store in cool conditions at a temperature of 2 °C to 8 °C for no longer than 4 d; see ISO 18512. In the laboratory during sub-sampling, take care that no volatile compounds are lost. Start as soon as possible with the cooled sample. Use the whole content of the coring tube or take a sub-sample with a suitable instrument, e.g. an apple corer, and put it directly into the vial (see 7.2). 7 Procedure 7.1 Blank determination For each series of samples, a solvent blank determination shall be carried out by adding 10 µl to 100 µl of methanol (4.6) to 5 ml to 10 ml of water (4.1), as is done with a sample. Ensure that no contamination occurs from the laboratory atmosphere. 7.2 Extraction Using the sampling procedure in 6.2, the extraction is carried out in the field; if using sampling procedure 6.3, the extraction is carried out in the laboratory. Add a defined amount of test sample (25 g to 50 g), collected as described during sampling (Clause 6) with a sampling device into a preweighed vial (50 ml to 100 ml) (see 6.2) filled with a defined amount of methanol (25 ml to 50 ml) and screw-cap the vial with PTFE-coated septum. Weigh and place the vials on the horizontal shaking machine (5.4) and shake for 30 min. Take the tube out of the shaking machine and allow it to stand for 10 min to 15 min for the settling of solid materials. If there is no settling of solid materials on standing, centrifuge for 10 min at a rotation frequency that results in a radial acceleration of 2 000 g. 7.3 Headspace analysis Transfer a defined volume of water (5 ml to 10 ml) into a headspace vial. Inject 10 µl to 100 µl of the methanol extract, obtained according to 7.2, to the bottom of the vial and seal tightly with a crimp cap fitted with a PTFE-coated septum. Then, after preparing the spiked water samples, proceed to the analysis in a very similar way to water analysis. Prepare the calibration samples in the same way with the same volume 10 µl to 100 µl of the calibration solutions (4.8.6). Take the tube out of the shaking machine and allow it to stand for 10 min to 15 min for settling of solid materials. If there is no settling of solid materials on standing, place it in the centrifuge. Centrifuge for 10 min at a rotation frequency that results in a radial acceleration of 2 000 g. NOTE 1 A lower detection limit could be achieved by addition of sodium chloride, NaCl (e.g. 3 g per 10 ml). Place the vials of water samples in the thermostated tray of the headspace system at a fixed temperature in the range from 50 °C to 80 °C, for at least 30 min and for the same time for all vials. kSIST FprEN ISO 22155:2012
ISO 22155:2011(E) 8 © ISO 2011 – All rights reserved NOTE 2 For specific equipment working at equilibrium, the time required to reach equilibrium can vary, depending on the volatile organic substance and the volume of the vials used. Experience has shown that at least 30 min is necessary. 7.4 Gas chromatographic analysis 7.4.1 General Example of gas chromatographic conditions for this analysis: Stationary phase: low polarity, e.g. DB 5, DB 624, DB 1701 Restek2) volatiles, Film thickness: 1 µm to 3 µm Column length: 50 m to 60 m Internal diameter: 0,25 mm to 0,32 mm Oven temperature: 40 °C for 4 min
4 °C/min up to 200 °C
200 °C for 10 min Detector temperature: 300 °C (FID) Carrier gas: Helium Gas flow: 20 cm/s to 30 cm/s In
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