SIST EN 15527:2009
Characterization of waste - Determination of polycyclic aromatic hydrocarbons (PAH) in waste using gas chromatography mass spectrometry (GC/MS)
Characterization of waste - Determination of polycyclic aromatic hydrocarbons (PAH) in waste using gas chromatography mass spectrometry (GC/MS)
This European Standard specifies the quantitative determination of 16 polynuclear aromatic hydrocarbons (PAH) according to the priority list of the Environmental Protection Agency (EPA, 1982). This European Standard is applicable for wastes such as contaminated soil, sludge and rubble, bitumen or waste containing bitumen. This European Standard describes a gas chromatographic method with mass spectrometric detection (GCMS). Under the conditions specified in this document, a typical lower limit of application of 0,1 mg/kg for each individual PAH can be achieved.
Charakterisierung von Abfällen - Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Abfall mittels Gaschromatographie-Massenspektrometrie (GC/MS)
Dieses Dokument legt ein Verfahren zur quantitativen Bestimmung von 16 polycyclischen aromatischen
Kohlenwasserstoffen (PAK) entsprechend der Prioritätenliste der Umweltschutzagentur (EPA, 1982) fest.
Dieses Dokument gilt für Abfälle wie kontaminierten Boden, Schlamm und Bauschutt, Bitumen oder
bitumenhaltigen Abfall.
Das vorliegende Dokument beschreibt ein gaschromatographisches Verfahren mit massenspektrometischer
Detektion (GC-MS). Unter den in diesem Dokument festgelegten Bedingungen kann eine Bestimmungsgrenze
von 0,01 mg/kg (für jeden einzelnen PAK) und von 0,1 mg/kg (Summe der 16 PAK) erzielt werden
(angegeben als Trockensubstanz).
ANMERKUNG Unter der Voraussetzung der nachgewiesenen Eignung können mit diesem Verfahren auch andere
PAK-Verbindungen analysiert werden.
Caractérisation des déchets - Dosage des hydrocarbures aromatiques polycycliques (HAP) dans les déchets par chromatographie en phase gazeuse/spectrométrie de masse (CG/SM)
La présente Norme internationale spécifie le dosage quantitatif de 16 hydrocarbures aromatiques
polynucléaires (HAP) selon la liste de polluants prioritaires établie par l’Agence de protection de
l’environnement (États-Unis) [Environmental Protection Agency (EPA), 1982]. Le présent document est
applicable aux déchets tels que sol contaminé, boues et gravats, bitume ou déchets bitumineux.
Le présent document décrit une méthode par chromatographie en phase gazeuse couplée a une détection
par spectrométrie de masse (CG-MS). Dans les conditions spécifiées dans le présent document, une limite
inférieure d’application de 0,01 mg/kg (pour chacun des HAP) et 0,1 mg/kg (somme des 16 HAP) peut etre
garantie (exprimée en matiere seche).
NOTE D’autres composés HAP peuvent etre analysés au moyen de la présente méthode, dans la mesure ou son
applicabilité a été prouvée.
Karakterizacija odpadkov - Določevanje policikličnih aromatskih ogljikovodikov (PAH) v odpadkih z uporabo plinske kromatografije z masno spektrometrijo (GC-MS)
General Information
Relations
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.JOMLNRYRGLNRY06Charakterisierung von Abfällen - Bestimmung von polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Abfall mittels Gaschromatographie-Massenspektrometrie (GC/MS)Caractérisation des déchets - Dosage des hydrocarbures aromatiques polycycliques (HAP) dans les déchets par chromatographie en phase gazeuse/spectrométrie de masse (CG/SM)Characterization of waste - Determination of polycyclic aromatic hydrocarbons (PAH) in waste using gas chromatography mass spectrometry (GC/MS)71.040.50Fizikalnokemijske analitske metodePhysicochemical methods of analysis13.030.01Odpadki na splošnoWastes in generalICS:Ta slovenski standard je istoveten z:EN 15527:2008SIST EN 15527:2009en,fr,de01-junij-2009SIST EN 15527:2009SLOVENSKI
STANDARD
SIST EN 15527:2009
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15527July 2008ICS 13.030.01; 71.040.50 English VersionCharacterization of waste - Determination of polycyclic aromatichydrocarbons (PAH) in waste using gas chromatography massspectrometry (GC/MS)Caractérisation des déchets - Dosage des hydrocarburesaromatiques polycycliques (HAP) dans les déchets parchromatographie en phase gazeuse/spectrométrie demasse (CG/SM)Charakterisierung von Abfällen - Bestimmung vonpolycyclischen aromatischen Kohlenwasserstoffen (PAK) inAbfall mittels Gaschromatographie-Massenspektrometrie(GC/MS)This European Standard was approved by CEN on 29 May 2008.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN 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 translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2008 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15527:2008: ESIST EN 15527:2009
EN 15527:2008 (E) 2 Contents Page Foreword.3 Introduction.4 1 Scope.5 2 Normative references.5 3 Terms and definitions.5 4 Principle.6 5 Reagents.6 5.1 General.6 5.2 Reagents for extraction procedures.6 5.3 Reagents for clean-up procedures.6 5.4 Reagents for gas chromatographic analysis.7 5.5 Standards.7 6 Apparatus.8 6.1 Extraction and clean-up procedures.8 6.2 Gas chromatograph.9 6.3 Capillary columns.9 6.4 Preparation of standard solutions.10 7 Hazards.11 8 Interference.12 8.1 Interference during sampling, storage and extraction.12 8.2 Interference due to co-elution.12 9 Sample conservation.12 10 Pretreatment.12 10.1 General.12 10.2 Drying.13 10.3 Particle size reduction.13 11 Procedure.13 11.1 Blank.13 11.2 Extraction.13 11.3 Addition of the internal standard solution.14 11.4 Concentration or dilution.14 11.5 Clean up of the extract.14 11.6 Addition of the injection standard.15 11.7 Gas chromatographic analysis with mass spectrometric detection.15 12 Performance characteristics.19 13 Test report.22 Annex A (informative)
Representative chromatograms.23 Annex B (informative)
Additional validation data.32 Annex C (informative)
Summary of general requirements and recommendations.36 Bibliography.37
SIST EN 15527:2009
EN 15527:2008 (E) 3 Foreword This document (EN 15527:2008) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, 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 January 2009, and conflicting national standards shall be withdrawn at the latest by January 2009. 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, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. SIST EN 15527:2009
EN 15527:2008 (E) 4
Introduction Polynuclear aromatic hydrocarbons (PAH) are ubiquitous because of the fact that they are released in appreciable quantities every year into the environment through the combustion of organic materials such as coal, fuel oils, petrol, wood, refuse and plant materials. Since some of these PAH compounds are carcinogenic or mutagenic, their presence in the environment (air, water, soil, sediment and waste) are regularly monitored and controlled. At present, the determination of PAH is carried out in these matrices in most of the routine laboratories following the preceding steps for sampling, pre-treatment, extraction, clean-up by measurement of specific PAH by means of gas chromatography in combination with mass spectrometric detection(GC-MS) or by HPLC in combination with UV-DAD- or Fluorescence-detection (HPLC-UV-DAD/FLD). However, the different matrices covered in this standard may contain a lot of contaminants. For this reason, the GC-MS method seems to be most appropriate for waste analysis. SIST EN 15527:2009
EN 15527:2008 (E) 5
1 Scope This European Standard specifies the quantitative determination of 16 polynuclear aromatic hydrocarbons (PAH) according to the priority list of the Environmental Protection Agency (EPA, 1982). This European Standard is applicable for wastes such as contaminated soil, sludge and rubble, bitumen or waste containing bitumen. This European Standard describes a gas chromatographic method with mass spectrometric detection (GC-MS). Under the conditions specified in this document, a typical lower limit of application of 0,1 mg/kg for each individual PAH can be achieved.
NOTE 1 This method may be applied to the analysis of other PAH compounds not specified in the scope provided its applicability has been proven by proper in-house validation experiments. NOTE 2 For some materials, e. g. bitumen, the lower limit of application of 0,1 mg/kg cannot be achieved due to interferences. NOTE 3 Under certain circumstances the method may be applicable to PAH concentrations lower than 0,1 mg/kg but it is in the responsibility of the laboratory to provide proper validation data for such low concentrations. 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. EN 14346, Characterization of waste — Calculation of dry matter by determination of dry residue or water content EN 15002, Characterization of waste — Preparation of test portions from the laboratory sample ISO 14507, Soil quality — Pretreatment of samples for determination of organic contaminants 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 analyte selected polynuclear aromatic hydrocarbons (PAH) with 2 to 6 condensed aromatic rings (see Table 1) 3.2 calibration standard solution of PAH prepared from a secondary standard and/or stock solutions of native PAH and deuterated PAH used to calibrate the response of the instrument 3.3 extraction standard deuterated PAH or native (unlabeled) PAH of medium volatility that are unlikely to be present in waste added to the sample before extraction and used for control of the extraction efficiency SIST EN 15527:2009
EN 15527:2008 (E) 6 3.4 internal standard deuterated PAH added to the sample after extraction and used for quantification of the concentrations of PAH in the sample 3.5 injection standard deuterated or native PAH that are unlikely to be present in waste samples added to the sample extract before injection into the GC, to monitor variability of instrument response and the recovery of the internal/extraction standards 4 Principle The PAH are extracted from the sample by use of acetone and a hexane-like solvent. If appropriate, the obtained extract is purified by adsorption column chromatography. The extract is analysed by gas chromatography with mass spectrometric detection (GC-MS) using capillary columns of low polarity. Concentrations of PAH are quantified using an internal-standard-method. 5 Reagents 5.1 General All reagents shall be of recognised analytical grade. The suitability of the reagents shall be checked by running a blank determination as described in 11.1. 5.2 Reagents for extraction procedures 5.2.1 Reagents for extraction by shaking/sonication 5.2.1.1 Acetone. 5.2.1.2 Petroleum ether (Boiling range 40 °C to 60 °C) or n-hexane or iso-hexane or cyclohexane (hexane-like solvents with a boiling range between 30 °C and 68 °C are allowed). 5.2.1.3 Sodium chloride, anhydrous. 5.2.1.4 Distilled water or water of equivalent quality. 5.2.1.5 Anhydrous sodium sulphate, heated for at least 6 h to 550 °C ± 20 °C, cooled to about 200 °C in the furnace and then to ambient temperature in a desiccator containing magnesium perchlorate or a suitable alternative. The anhydrous sodium sulphate shall be kept carefully sealed. Commercial available anhydrous sodium sulphate is also applicable. 5.2.2 Reagents for Soxhlet extraction 1:1 (v/v) mixtures of acetone/petroleum ether (boiling range 40 °C to 60 °C) or acetone/ n-hexane or acetone/iso-hexane or acetone/cyclohexane. 5.3 Reagents for clean-up procedures 5.3.1 Clean-up A – Aluminium oxide 5.3.1.1 Aluminium oxide basic or neutral, specific surface 200 m2/g, activity Super I. SIST EN 15527:2009
EN 15527:2008 (E) 7 5.3.1.2 Preparation of deactivated aluminium oxide. Add 10 g of water to 90 g of aluminium oxide (5.3.1.1). Shake until all lumps have disappeared. Allow the aluminium oxide to equilibrate before use for some 16 h, sealed from air. Use it for a maximum of 2 weeks. 5.3.2 Clean up B- Silica gel 60
5.3.2.1 Silica gel 60, particle size 63 µm to 200 µm. 5.3.2.2 Preparation of silica gel 60 with a water content of 10 % (w/w). Silica gel 60, heated for at least 3 h at 450 °C, cooled down and stored in a desiccator containing magnesium perchlorate or another suitable drying agent. Before use, heat it once again at least for 5 h at 130 °C in a drying oven. Then allow to cool in a desiccator to ambient temperature. Transfer the silica gel to a flask and add 10 % water (w/w). Shake for 5 min intensively by hand until all lumps have disappeared and then for 2 h in a shaking machine. Store the deactivated silica gel sealed from air and use it for maximum of one week. 5.4 Reagents for gas chromatographic analysis Carrier gas for gas chromatography, e. g. helium of suitable purity. 5.5 Standards 5.5.1 Calibration standards, extraction standards and internal standards Choose internal/extraction standard substances whose physical and chemical properties (such as extraction behaviour, retention time) are similar to those of the compounds to be analysed. Deuterated PAH should be used as internal standards for the GC-MS method for evaluation of results. Verify the stability of the internal/extraction standards regularly. Table 1 contains native and a minimum number of deuterated PAH to be used for calibration of specific analytes. The use of isotope dilution (each native PAH is quantified with respect to his labelled analogue) is recommended. NOTE Certified solutions of PAH and single solid PAH substances with certified purity are commercially available. SIST EN 15527:2009
EN 15527:2008 (E) 8
Table 1 — Native PAH and deuterated PAH PAH reference substances for calibration Internal/extraction standard substances: (deuterated PAH) Naphthalene
(CAS No. 91-20-3) Naphthalene- D8 Acenaphthene
(CAS No.83-32-9) Acenaphthene-D10 Acenaphthylene
(CAS No.208-96-8)
Fluorene
(CAS No.86-73-7)
Anthracene
(CAS No.120-12-7)
Phenanthrene
(CAS No. 85-01-8) Phenanthrene-D10 (extraction standard) Fluoranthene
(CAS No.206-44-0)
Pyrene
(CAS No.129-00-0)
Benzo(a)anthracene
(CAS No.56-55-3) Benzo(a)anthracene-D12 Chrysene
(CAS.No.218-01-9)
Benzo(b)fluoranthene
(CAS No. 205-99-2)
Benzo(k)fluoranthene
(CAS No.207-08-9)
Benzo(a)pyrene
(CAS No.50-32-8) Benzo(a)pyrene-D12 Indeno(1,2,3-cd)pyrene (CAS No.193-39-5)
Dibenzo(ah)anthracene
(CAS No.53-70-3)
Benzo(ghi)perylene
(CAS No.191-24-2)
Perylene-D12
5.5.2 Injection standards A deuterated PAH is added to the final extract before GC-MS injection to check the recovery of the deuterated internal/extraction standards. Suitable injection standards are 1-methylnaphthalene-D10, benzo(e)pyrene-D10 and triphenylene-D12.
6 Apparatus 6.1 Extraction and clean-up procedures Customary laboratory glassware.
All glassware and material that comes into contact with the sample or extract shall be free of PAH and any interfering compounds. 6.1.1 Extraction procedures 6.1.1.1 Glass sample bottles of appropriate size with glass stopper or screw top and polytetrafluorethene seal (PTFE). SIST EN 15527:2009
EN 15527:2008 (E) 9 6.1.1.2 Shaking device, with horizontal movement (200 to 300 strokes per minute). 6.1.1.3 Ultrasonic bath. 6.1.1.4 Water bath, adjustable up to 100 °C. 6.1.1.5 Separatory funnels with a capacity of 1 l. 6.1.1.6 Conical flasks with a capacity of 500 ml. 6.1.1.7 Soxhlet extraction apparatus, consisting of: round bottom flask, e. g.100 ml, Soxhlet extractors and soxhlet thimbles, e. g. 27 mm x 100 mm, vertical condensers, e. g. 300 mm, water-bath or heating mantle as heating apparatus. 6.1.1.8 Evaporator, Kuderna Danish or other evaporators, e. g. a rotary evaporator, if found to be equally suitable. 6.1.1.9 5 ml volumetric flask. 6.1.2 Clean-up procedures 6.1.2.1 Quartz wool or silanized glass wool NOTE Working with quartz wool imposes a risk to health through the release of fine quartz particles. Inhalation of these should be prevented . 6.1.2.2 Boiling chips glass or porcelain beads. 6.1.2.3 Calibrated test tubes with a capacity of 10 ml to 15 ml and ground glass stopper. 6.1.2.4 Glass chromatography column, 5 mm to 10 mm internal diameter, length e. g. 600 mm. 6.2 Gas chromatograph Gas chromatograph equipped with an on-column, split/splitless or programmable temperature vaporizer (PTV) injection system, capillary column (6.3) and a mass spectrometric detector (GC-MS). 6.3 Capillary columns Low to medium polar capillary columns such as 5 % phenyl-methyl silicone stationary phase coated onto fused silica capillary column or an equivalent chemically bonded phase column may be used. Choose a capillary column that allows for sufficient resolution of the critical pairs mentioned below. The resolution between the chromatographic peaks of benzo(b)fluoranthene/ benzo(k)fluoranthene as well as of benzo(a)pyrene/benzo(e)pyrene shall be better than 0,5. The resolution is defined according to Figure 1 and Equation (1): SIST EN 15527:2009
EN 15527:2008 (E) 10
Key X
Time Y
Intensity R2R1,tt Retention times of each eluted component 1 and 2 in s b2b1,ww Peak widths of each peak at its base in s Figure 1 — Resolution of chromatographic peaks
()b2b1R1R22wwttR+−= (1) where R
is the resolution; R2R1,tt
are the retention times of each eluted component 1 and 2 in s; b2b1,ww
are the peak widths of each peak at its base in s. 6.4 Preparation of standard solutions 6.4.1 Single substance stock solution Solutions of the individual substances of native and deuterated PAH (see Table 1) in an appropriate solvent with a mass concentration of e. g. 10 µg/ml.
Single substance stock solutions can be prepared from pure solid PAH or purchased. These solutions are used for confirmation and identification of single PAH in the chromatogram. The single substance stock solutions and diluted standard solutions are to be stored in a dark place at about 4 °C (or less). They are stable for about 1 year. 6.4.2 Multiple substance stock solution of native PAH Dilute the multiple substance stock solution of the native PAH in an appropriate solvent to a mass concentration of e. g. 10 µg/ml for each individual PAH. SIST EN 15527:2009
EN 15527:2008 (E) 11 6.4.3 Multiple substance stock solution of deuterated PAH Multiple deuterated PAH standards for use as internal standard are commercially available as mixtures in a suitable solvent or can be prepared from pure solid PAH. The solutions should be diluted to mass concentrations of e. g. 10 µg/ml for each individual deuterated standard. NOTE The standard solutions should be prepared in the same solvent as the final extract. 6.4.4 Calibration standard solutions Prepare a series of calibration standard solutions(at least 5) covering a suitable range of concentrations by transferring different volumes of the multiple substance stock solution of native PAH standards (6.4.2) and a constant volume of the internal standard solution (6.4.3) and injection standard solution into a volumetric flask and fill up to the mark with a hexane-like solvent.
EXAMPLE
Transfer for example 500 µl of both multiple stock solutions of native and deuterated PAH into a 5 ml volumetric flask and fill up to the mark with a hexane-like solvent. For example, 1 µl of this calibration solution contains 1 ng of the respective individual native and deuterated substances. NOTE Concentrations of internal standards in sample extracts should ideally be in the same range as those of the analytes (e. g. 1 µg/ml). 6.4.5 Preparation of extraction standard solution Prepare a stock solution of a deuterated or native PAH (e. g. phenanthrene-D10) in an appropriate solvent according to 6.4.1. The concentration of the extraction standard in the final extract should be in the same range as in the calibration solutions. 6.4.6 Preparation of internal standard solution Prepare a multiple substance stock solution of deuterated PAH according to 6.4.3 which is to be added to the sample after extraction. Examples of internal standard compounds are given in Table 1. The amount of the internal standards has to be adjusted in such a way that their concentrations in the final extract correspond to those in the calibration solutions. 6.4.7 Preparation of injection standard Prepare a single substance stock solution according to 6.4.1.
NOTE A suitable injection standard is e. g. deuterated benzo(e)pyrene or other PAH, which does not interfere with the target analyte. 7 Hazards Anyone dealing with waste and sludge analysis has to be aware of the typical risks of that kind of material irrespective of the parameter to be determined. Waste and sludge samples may contain hazardous (e. g. toxic, reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction. Consequently it is recommended that these samples should be handled with special care. The gases which may be produced by microbiological or chemical activity are potentially flammable and will pressurise sealed bottles. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations should be followed with respect to all hazards associated with this method.
Certain PAH are carcinogenic and must be handled with extreme care. Skin contact with solid materials, PAH standard solutions and sample extracts must be prevented. PAH may co-evaporate with solvents and deposit on the outer walls of stoppered glass bottles and containers. Hence, all containers, which contain solutions of PAH in organic solvents or sample extracts must be handled wearing solvent resistant disposable protecting gloves. PAH contamination of containers may be detected by irradiation with 366 nm U.V. light. Vessels SIST EN 15527:2009
EN 15527:2008 (E) 12 containing PAH solutions should be stored in beakers to absorb any spillage in case of breakage. There is a particular risk by inhalation of PAH dust when working with crystalline PAH standards. Thus, these materials must only be handled where proper facilities are available (e. g. adequate fume hoods, protective clothing, dust masks etc). Solutions containing PAH must be disposed of in a manner approved for disposal of toxic wastes. NOTE Preferably, certified reference standard solutions of suppliers specialised in their preparation should be used. 8 Interference 8.1 Interference during sampling, storage and extraction Use sampling containers made up of materials (preferably of glass or stainless steel) that do not change the sample during the contact time. Do not use plastic equipments for sampling, sample storage or extraction. Keep the samples from direct sunlight and prolonged exposure to light. During storage of the samples, losses of PAH may occur due to adsorption to the walls of the containers. The extent of the losses depends on the storage time. 8.2 Interference due to co-elution There is a certain risk of co-elution of target PAH in one peak with other PAH not mentioned in the scope. . These interferences may lead to unresolved or incompletely resolved peaks and, depending on their concentration compared to the target analyte, affect the accuracy of the analytical results.
Sufficient chromatographic resolution of the GC peaks for benzo(a)pyrene and benzo(e)pyrene as well as for benzo(b)fluoranthene and benzo(k)fluoranthene allowing accurate quantification of these compounds can be achieved by selecting an appropriate chromatographic column, which meets the performance criteria for separation of these critical pairs. On most capillary columns benzo(j)fluoranthene co-elutes with either benzo(b)fluoranthene or benzo(k)fluoranthene in one peak. Hence, measured concentrations of the target compounds benzo(b)fluoranthene and benzo(k)fluoranthene usually represent the sum of benzo(b)fluoranthene and benzo(j)fluoranthene or benzo(k)fluoranthene and benzo(j)fluoranthene, respectively. This co-elution shall be checked for by analysing mixtures of benzo(j)fluoranthene/benzo(b)fluoranthene and benzo(j)fluoranthene/benzo(k)fluoranthene and indicated when reporting results. The contribution of benzo(j)fluoranthene to the signal assigned to benzo(b)fluoranthene and benzo(k)fluoranthene, respectively, can neither be neglected nor estimated reliably. 9 Sample conservation In principle, samples shall be analysed as soon as possible after sampling. This applies in particular to the examination of microbiologically active solids. Field moist samples can be stored at a temperature of about 4 °C in sample containers in a dark place for a maximum of one week. If the sample cannot be processed within a week, it has to be stored at temperatures below –18 °C. Dried samples must be stored in the dark preferably at a temperature of about 4 °C. 10 Pretreatment 10.1 General The goal of a pre-treatment procedure is to prepare a test sample in which the content of PAH has not significantly changed compared to that in the laboratory sample. Sample pre-treatment is described in EN 15002. Remove parts which are not representative and typical for the material, e. g. all visible metallic components. Take care to avoid losses during pre-treatment of volatile compounds, e. g. naphthalene. SIST EN 15527:2009
EN 15527:2008 (E) 13 10.2 Drying Depending on the nature of the sample material and the extraction solvent to be used a drying step might be needed. If necessary, air-dry the entire sample or dry it in a ventilated drying oven at 40 °C or in a freeze dryer. Drying time and temperature depend on the technique chosen and the nature of the sample. Chemical drying (according to ISO 14507) is applicable. 10.3 Particle size reduction In order to achieve a homogeneous and representative test portion, one or more particle-size reduction steps might be needed. The choice of the technique depends on the nature of the sample and on the particle size required. Typically, particle-size reduction is a multi-step operation that implies the use of a sequence of different techniques like crushing, cutting or grinding.
For grinding of samples, which have a plastic or paste-like consistency, embrittlement with liquid nitrogen is inevitable. An ultra-centrifugal mill is highly recommended for plastic materials. 11 Procedure 11.1 Blank Perform a blank determination following the paragraphs of the procedure applied to samples
...
SLOVENSKI oSIST prEN 15527:2006
PREDSTANDARD
julij 2006
Karakterizacija odpadkov – Določevanje policikličnih aromatskih
ogljikovodikov (PAH) v odpadkih z uporabo plinske kromatografije z masno
spektrometrijsko detekcijo (GC-MS)
Characterization of waste - Determination of polycyclic aromatic hydrocarbons
(PAH) in waste using gas chromatography mass spectrometry (GC/MS)
ICS 13.030.01 Referenčna številka
oSIST prEN 15527:2006(en)
© Standard je založil in izdal Slovenski inštitut za standardizacijo. Razmnoževanje ali kopiranje celote ali delov tega dokumenta ni dovoljeno
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EUROPEAN STANDARD
DRAFT
prEN 15527
NORME EUROPÉENNE
EUROPÄISCHE NORM
May 2006
ICS
English Version
Characterization of waste - Determination of polycyclic aromatic
hydrocarbons (PAH) in waste using gas chromatography mass
spectrometry (GC/MS)
Caractérisation des déchets - Dosage des hydrocarbures Charakterisierung von Abfällen - Bestimmung von
aromatiques polycycliques (HAP) dans les déchets par polycyclischen aromatischen Kohlenwasserstoffen (PAK) in
chromatographie en phase gazeuse/spectrométrie de Abfall mittels Gaschromatographie-Massenspektrometrie
masse (CG/SM) (GC/MS)
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee CEN/TC 292.
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 Management Centre has the same
status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
Slovakia, Slovenia, Spain, Sweden, Switzerland 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
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 15527:2006: E
worldwide for CEN national Members.
---------------------- Page: 2 ----------------------
prEN 15527:2006 (E)
Contents Page
Foreword.3
Introduction .3
1 Scope .3
2 Normative references .3
3 Terms and definitions .4
4 Principle.4
5 Reagents.4
5.1 General.4
5.2 Reagents for extraction procedures.4
5.3 Reagents for clean-up procedures .5
5.4 Reagents for gas chromatographic analysis.5
5.5 Standards .5
6 Apparatus .6
6.1 Extraction and clean-up procedures .6
6.2 Gas chromatograph.7
6.3 Capillary columns.7
6.4 Preparation of standard solutions .8
7 Hazards .9
8 Interference .10
8.1 Interference during sampling, storage and extraction .10
8.2 Interference due to co-elution .10
9 Sample conservation.10
10 Pre-treatment.11
10.1 General.11
10.2 Drying.11
10.3 Particle size reduction.11
11 Procedure .11
11.1 Blank .11
11.2 Extraction .11
11.3 Addition of the internal standard solution .12
11.4 Concentration or dilution.12
11.5 Clean up of the extract .12
11.6 Addition of the injection standard .13
11.7 Gas chromatographic analysis with mass spectrometric detection.13
12 Test report .17
Annex A (informative) Representative chromatograms.18
Annex B (informative) Validation results .27
Annex C (informative) Summary of general requirements and recommendations.28
Bibliography .29
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Foreword
This document (prEN 15527:2006) has been prepared by Technical Committee CEN/TC 292
“Characterization of waste”, the secretariat of which is held by NEN.
This document is currently submitted to the CEN Enquiry.
Introduction
Polycyclic aromatic hydrocarbons (PAH) are ubiquitous because of the fact that they are released in
appreciable quantities every year into the environment through the combustion of organic matters such as
coal, fuel oils, petrol, wood, refuse and plant materials. Since some of these PAH compounds are
carcinogenic or mutagenic, their presence in the environment (air, water, soil, sediment and waste) are
regularly monitored and controlled. At present determination of PAH are carried out in these matrices in most
of the routine laboratories following the preceding steps for sampling, pre-treatment, extraction, clean up by
measurement of specific PAH by means of Gas chromatography in combination with mass spectrometric
detection(GC-MS) or by HPLC in combination with UV-DAD- or Fluorescence-detection (HPLC-UV-DAD/FLD).
However, the different matrices covered in this standard may contain a lot of contaminants. For this reason,
the GC-MS method seems to be most appropriate for waste analysis.
1 Scope
This document specifies the quantitative determination of 16 polynuclear aromatic hydrocarbons (PAH)
according to the priority list of the Environmental Protection Agency (EPA, 1982). This document is applicable
for wastes such as contaminated soil, sludge and rubble, bitumen or waste containing bitumen.
This document describes a gas chromatographic method with mass spectrometric detection (GC-MS). Under
the conditions specified in this document, a lower limit of application of 0,01 mg/kg (for each individual PAH)
and 0,1 mg/kg (sum of 16 PAH) can be ensured (expressed as dry matter).
NOTE With this method also other PAH compounds can be analysed providing suitability is proven.
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.
prEN 14346, Characterization of waste — Calculation of dry matter by determination of dry residue and water
content
EN 15002, Characterization of waste — Preparation of test portions from the laboratory sample
ISO 14507, Soil quality — Pretreatment of samples for determination of organic contaminants
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3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
analyte
selected polycyclic aromatic hydrocarbons (PAH) with 2 to 6 condensed aromatic rings (see table 1)
3.2
calibration standard
solution of PAH prepared from a secondary standard and/or stock solutions of native PAH and deuterated
PAH used to calibrate the response of the instrument
3.3
extraction standard
deuterated PAH of medium volatility added to the sample before extraction and used for control of the
extraction efficiency
3.4
internal standard
deuterated PAH added to the sample after extraction and used for quantification of the concentrations of PAH
in the sample
3.5
injection standard
deuterated or unlabeled PAH that are unlikely to be present in waste samples added to the sample extract
before injection into the GC, to monitor the recovery of the internal standards
4 Principle
The PAH are extracted from the sample by use of acetone and hexane-like solvents. If appropriate, the extract
is purified by column chromatography.
The extract is analysed by GC-MS using a capillary column with an immobile phase of low polarity. PAH are
identified with GC-MS. PAH are quantified using an internal-standard-method.
5 Reagents
5.1 General
All reagents shall be of recognised analytical grade. The suitability of the reagents shall be checked by
running a blank determination as described in 11.1.
5.2 Reagents for extraction procedures
5.2.1 Reagents for extraction by shaking/sonification
5.2.1.1 Acetone
5.2.1.2 Petroleum ether (Boiling range 40 °C to 60 °C) or n-hexane or iso-hexane or cyclohexane
5.2.1.3 Sodium chloride, anhydrous
5.2.1.4 Distilled water or water of equivalent quality
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5.2.1.5 Anhydrous sodium sulphate
Heated for at least 6 h to 550 °C ± 20 °C, cooled to about 200 °C in the furnace and then to ambient
temperature in a desiccator containing magnesium perchlorate or a suitable alternative. The anhydrous
sodium sulphate shall be kept carefully sealed.
5.2.2 Reagents for Soxhlet extraction
5.2.2.1 mixture of acetone and petroleum ether (boiling range 40 °C to 60 °C) or n-hexane or iso-hexane
or cyclohexane 1:1 (v/v)
5.3 Reagents for clean-up procedures
5.3.1 Clean-up A – Aluminium oxide
2
5.3.1.1 Aluminium oxide Basic or neutral, specific surface 200 m /g, activity Super I
5.3.1.2 Deactivated aluminium oxide. Add 10 g of water to 90 g of aluminium oxide (5.3.1.1). Shake until
all lumps have disappeared. Allow the aluminium oxide to condition before use for some 16 h, sealed from the
air.
5.3.2 Clean up B- Silica gel 60 for column chromatography
5.3.2.1 Silica gel 60, particle size 63 µm to 200 µm
5.3.2.2 Silica gel 60, water content: mass fraction w(H2O) = 10 %. Silica gel 60, heated for at least 3 h at
450 °C, cooled down in a desiccator and stored containing magnesium perchlorate or a suitable drying agent.
Before use heat at least for 5 h at 130 °C in a drying oven. Then allow to cool in a desiccator and add 10 %
water (w/w) in a flask. Shake for 5 min intensively by hand until all lumps have disappeared and then for 2 h in
a shaking machine. Store the deactivated silica gel in the absence of air, use it for maximum of one week.
5.4 Reagents for gas chromatographic analysis
5.4.1 Carrier gas for gas chromatography - MS, helium or hydrogen of suitable purity
5.5 Standards
5.5.1 Calibration standards, extraction standards and internal standards
Choose the internal standards substances whose physical and chemical properties (such as extraction
behaviour, retention time) are similar to those of the compounds to be analysed. Deuterated PAH should be
used as internal standards for the GC-MS method for evaluation of results. Verify the stability of the internal
standards regularly. Table 1 contains native and a minimum number of deuterated PAH to be used for
calibration of specific analyte. The use of isotope dilution (each native PAH is quantified with respect to his
labelled analogue) is recommended.
NOTE Certified solutions of PAH, and single solid PAH substances with certified purity are available.
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Table 1 — Native PAH and deuterated PAH
PAH reference substances Internal standard substances:
(deuterated PAH)
Naphthalene (CAS No. 91-20-3) Naphthalene- D
8
Acenaphthene (CAS No.83-32-9) Acenaphthene-D
10
Acenaphthylene (CAS No.208-96-8)
Fluorene (CAS No.86-73-7)
Anthracene (CAS No.120-12-7)
Phenanthrene (CAS No. 85-01-8) Phenanthrene-D (extraction standard)
10
Fluoranthene (CAS No.206-44-0)
Pyrene (CAS No.129-00-0)
Benz(a)anthracene (CAS No.56-55-3) Benz(a)anthracene-D
12
Chrysene (CAS.No.218-01-9)
Benzo(b)fluoranthene (CAS No. 205-99-2)
Benzo(k)fluoranthene (CAS No.207-08-9)
Benzo(a)pyrene (CAS No.50-32-8) Benzo(a)pyrene-D
12
Indeno(1,2,3-cd)pyrene (CAS No.193-39-5)
Dibenz(ah)anthracene (CAS No.53-70-3)
Benzo(ghi)perylene (CAS No.191-24-2)
Perylene-D
12
5.5.2 Injection standards
A deuterated PAH is added to the final extract before GC-MS injection to check the recovery of the deuterated
internal standards. Suitable injection standards are D -1-methylnaphthalene, D -benzo(e)pyrene and D —
10 10 12
triphenylene.
6 Apparatus
6.1 Extraction and clean-up procedures
Customary laboratory glassware. All glassware and material that comes into contact with the sample or
extract shall be thoroughly cleaned.
6.1.1 Extraction procedures
6.1.1.1 Glass sample bottles of appropriate size with glass stopper or screw top and polytetrafluorethene
seal (PTFE).
6.1.1.2 Shaking device, with horizontal movement (200 to 300 strokes per minute).
6.1.1.3 Ultrasonic bath
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6.1.1.4 Water bath, adjustable up to 100 °C.
6.1.1.5 Separatory funnels with a capacity of 1 l.
6.1.1.6 Conical flasks with a capacity of 500 ml.
6.1.1.7 Soxhlet extraction apparatus, consisting of: round bottom flask e. g.100 ml, Soxhlet extractors
and soxhlet thimbles e. g. 27*100 mm, vertical condensers e. g. 300 mm, water-bath or heating mantle as
heating apparatus.
6.1.1.8 Evaporator, Kuderna Danish or other evaporators, e. g. a rotary evaporator, if found to be equally
suitable.
6.1.2 Clean-up procedures
6.1.2.1 Quartz wool or silanized glass wool
NOTE Working with quartz wool imposes a risk to health through the release of fine quartz particles. Inhalation of these
should be prevented by using a fume cupboard and wearing a dust mask.
6.1.2.2 Boiling chips glass or porcelain beads.
6.1.2.3 Calibrated test tubes with a capacity of 10 ml to 15 ml and ground glass stopper.
6.1.2.4 Chromatography tubes, Chromatography column of glass, 5 mm to 10 mm internal diameter,
length e. g. 600 mm.
6.2 Gas chromatograph
Gas chromatograph equipped with an on-column, split/splitless or programmable temperature vaporizer (PTV)
injection system, capillary column (6.3) and a mass spectrometric detector (GC-MS).
6.3 Capillary columns
Each comprising a 5% phenyl-methyl silicone stationary phase coated onto fused silica capillary column or an
equivalent chemically bonded phase column. The dimensions should be sufficient to separate the critical pairs
mentioned below (e.g. column length of 50 m, internal diameter of 0,25 mm and film thickness of 0,2 µm).
Sufficient resolution between the chromatographic peaks of critical pairs benzo(b)fluoranthene /
benzo(k)fluoranthene as well as of benzo(a)pyrene / benzo(e)pyrene is to be set as quality criteria for the
capillary column. The resolution is defined according to figure (1) and equation (1):
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Key
X Time
Y Intensity
Figure 1 — Resolution of chromatographic peaks
()t − t
R2 R1
R = 2 (1)
w + w
b1 b2
Where:
R is the resolution;
t ,t are the retention times of each eluted component 1 and 2;
R1 R2
w ,w are the peak widths of each peak at its base.
b1 b2
The resolution should be better than 0,5 for the benzo(b)fluoranthene/benzo(k)fluoranthene critical pair. The
separation should be complete for the benzo(a)pyrene/benzo(e)pyrene critical pair.
6.4 Preparation of standard solutions
6.4.1 General
Because of the toxicity of the PAH, commercially available - preferably certified - standard solutions should be
used. Avoid skin contact.
6.4.2 Single substance stock solution
Solutions of the individual substances of native and deuterated PAH (see table 1) in a non-polar solvent with a
mass concentration of e. g. 10 µg/ml. The solutions can be prepared from pure solid PAH or purchased as
solution. These solutions are used for confirmation and identification of single PAH in the chromatogram. The
single substance stock solutions are to be stored in a dark place at about 4 °C. Store the diluted standard
solutions at about 4 °C protected from light and evaporation. They are stable for about 1 year.
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6.4.3 Multiple substance stock solution of native PAH
Dilute the solution of the native PAH in a non-polar solvent to a mass concentration of e. g. 10 µg/ml for each
individual PAH.
6.4.4 Multiple substance stock solution of deuterated PAH
Multiple deuterated PAH standards for use as internal standard are commercially available as mixtures in a
suitable solvent or can be prepared from pure solid PAH. The solutions can be diluted to the same mass
concentration of e. g. 10 µg/ml for each individual deuterated standard.
NOTE The standard solutions should be in the same solvent as the extract.
6.4.5 Calibration standard solutions
Prepare a series of calibration standard solutions(at least 5) covering a suitable range of concentrations by
transferring different volumes of the multiple substance stock solution of native PAH standards (6.4.3) and a
constant volume of the internal standard solution (6.4.4) and injection standard solution into a volumetric flask
and fill up to the mark with non-polar solvent. Transfer for example 500 µl of both multiple stock solutions of
native and deuterated PAH into a volumetric 5 ml flask and fill up to the mark with cyclohexane. 1 µl of this
calibration solution contains 1 ng of the respective individual native and deuterated substances.
NOTE Concentration of internal standards in the sample extract should ideally be of the same magnitude as that of
the analyte (e. g. 1 µg/ml).
6.4.6 Preparation of extraction standard solution
Prepare a stock solution of deuterated PAH (e. g. Phenanthrene-D ) according to 6.4.2 in a non-polar solvent.
10
The amount of the extraction standard has to be adjusted so that the concentration in the final extract for GC-
MS is the same as that in the calibration solutions.
6.4.7 Preparation of internal standard solution
Multiple substance stock solution of deuterated PAH (6.4.4) are used for spiking to the sample after extraction.
The amount of the internal standards has to be adjusted so that their concentration in the final extract for GC-
MS is the same as that in the calibration solutions.
6.4.8 Preparation of injection standard
This is needed to check the recovery of the deuterated internal standards. A single substance stock solution
(6.4.2) e. g. deuterated benzo(e)pyrene or other PAH which is not interfering with the target analyte can be
used.
A deuterated PAH not mentioned in the scope is added before injection into the GC, to monitor variability of
the instrument response, the so called injection standard. The recovery of the internal standards throughout
the whole method can be calculated on the basis of the response of the internal standard relative to the
injection standard.
7 Hazards
Anyone dealing with waste and sludge analysis has to be aware of the typical risks of that kind of material
irrespective of the parameter to be determined. Waste and sludge samples may contain hazardous (e. g. toxic,
reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction.
Consequently it is recommended that these samples should be handled with special care. The gases which
may be produced by microbiological or chemical activity are potentially flammable and will pressurise sealed
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bottles. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations
should be followed with respect to all hazards associated with this method.
Certain PAH are carcinogenic and must be handled with extreme care. Skin contact with solid materials, PAH
standard solutions and sample extracts must prevented. PAH may co-evaporate with solvents and deposit on
the outer walls of stoppered glass bottles and containers. Hence, all containers containing solutions of PAH in
organic solvents or sample extracts must be handled wearing solvent resistant disposable protecting gloves.
PAH contamination of containers may be detected by irradiation with 366 nm U.V. light. Vessels containing
PAH solutions should be stored in beakers to absorb any spillage in case of breakage. There is a particular
risk by inhalation of PAH dust when working with crystalline PAH standards. Thus, these materials must only
be handled where proper facilities are available (e. g. adequate fume hoods, protective clothing, dust masks
etc). Solvent solutions containing PAH must be disposed of in a manner approved for disposal of toxic wastes.
NOTE Preferably, certified reference standard solutions of suppliers specialised in their preparation should be used.
8 Interference
8.1 Interference during sampling, storage and extraction
Use sampling containers of materials (preferably of steel or glass) that do not change the sample during the
contact time. Avoid plastics and other organic materials during sampling, sample storage or extraction. Keep
the samples from direct sunlight and prolonged exposure to light.
During storage of the samples, losses of PAH may occur due to adsorption on the walls of the containers. The
extent of the losses depends on the storage time.
8.2 Interference due to co-elution
There is a certain risk of co-elution of target PAH in one peak with other PAH not mentioned in the scope
which can interfere with quantification. These interferences may lead to unresolved or incompletely resolved
peaks and, depending on their magnitude, affect accuracy and precision of the analytical results.
Chromatographic separation of dibenzo(ah)anthracene and indeno(1,2,3-cd)pyrene can be critical under
certain circumstances. But due to their differences in molecular masses, they can be quantified accurately.
Sufficient chromatographic resolution of the GC peaks for benzo(a)pyrene and benzo(e)pyrene as well as for
benzo(b)fluoranthene and benzo(k)fluoranthene allowing accurate quantification of these compounds can be
achieved by selecting an appropriate chromatographic column, which meets the performance criteria for
separation of these critical pairs.
On most capillary columns benzo[j]fluoranthene (B[j]F) co-elutes with either benzo[b]fluoranthene (B[b]F) or
benzo[k]fluoranthene (B[k]F) in one peak. Hence, measured concentrations of the target compounds B[b]F
and B[k]F usually represent the sum of B[b]F and B[j]F and B[k]F and B[j]F, respectively. This co-elution shall
be checked for by analysing mixtures of B[j]F / B[b]F and B[j]F / B[k]F and indicated when reporting results.
The contribution of B[j]F to the signal assigned to B[b]F and B[k]F, respectively, can neither be neglected nor
estimated reliably.
9 Sample conservation
In principle, the samples shall be analysed as soon as possible after sampling. This applies in particular to the
examination of microbiologically active solids. Field moist samples can be stored at a temperature of
(4 ± 2) °C in sample containers in a dark place for a maximum of one week. If the sample cannot be
processed within a week, it has to be stored at temperatures below –18 °C. In order to prevent the
degradation of the analytes, dried samples must be stored in the dark preferably at a temperature of about
4 °C.
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10 Pre-treatment
10.1 General
The goal of a pre-treatment procedure is to prepare a test sample in which the content is not significantly
changed due to the process. Sample pre-treatment is described in EN 15002. Remove parts which are not
representative and typical for the material, e. g. all visible metallic components.
NOTE Take care to avoid losses during pre-treatment of volatile compounds, e. g. naphthalene.
10.2 Drying
Depending on the nature of the sample material and the extraction solvent to be used a drying step might be
needed. If it is necessary, dry the complete sample in the air or in a ventilated drying oven from which the
moist air has been removed or in a freeze dryer. The drying time and temperature depend on the technique
chosen and the nature of the sample. Chemical drying (according to ISO 14507) is applicable.
10.3 Particle size reduction
In order to achieve a homogeneous and representative test portion, one or more particle-size reduction steps
might be needed. The choice of the technique depends on the nature of the sample and on the particle size
needed. Typically, particle-size reduction is a multi-step operation that implies the use of a sequence of
different techniques like crushing, cutting or grinding.
For grinding of samples which have a plastic or paste-like consistency, embrittlement with liquid nitrogen is
inevitable. An ultra centrifugal mill is highly recommended for plastic materials.
11 Procedure
11.1 Blank
Perform a blank determination following paragraphs for the procedure applied to samples(selected extraction
and clean-up). Use the same amount of reagents that are used for the pretreatment, extraction, clean up and
analysis of a sample.
Blank values should be smaller than the detection limit for analytes concerned.
11.2 Extraction
11.2.1 Extraction by shaking or sonif
...
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