SIST EN 15527:2009

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
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