Soil quality - Determination of polycyclic aromatic hydrocarbons (PAH) - Gas chromatographic method with mass spectrometric detection (GC-MS)

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

Qualité du sol - Dosage des hydrocarbures aromatiques polycycliques (HAP) - Méthode par chromatographie en phase gazeuse avec détection par spectrométrie de masse (CG-SM)

L'ISO 18287:2006 spécifie le dosage quantitatif de 16 hydrocarbures aromatiques polycycliques (HAP) selon la liste de polluants prioritaires établie par l'Agence de Protection de l'Environnement (États-Unis) [Environmental Protection Agency (EPA), 1982]. L'ISO 18287:2006 est applicable à tous les types de sols (échantillons bruts prélevés sur le terrain ou échantillons ayant été soumis à un séchage chimique), couvrant une large gamme de niveaux de contamination par les HAP.
Dans les conditions spécifiées dans l'ISO 18287:2006, une limite inférieure d'application de 0,01 mg/kg (exprimée en matière sèche) peut être garantie pour chacun des HAP.

Kakovost tal - Določevanje policikličnih aromatskih ogljikovodikov (PAH) - Plinska kromatografija z masno selektivnim detektorjem (GC-MS)

Ta mednarodni standard določa kvantitativno določevanje 16 policikličnih aromatskih ogljikovodikov (PAH) v skladu s prednostnim seznamom ameriške Agencije za varstvo okolja (EPA, 1982). Ta standard se uporablja za vse vrste tal (vlažne vzorce s terena ali kemijsko posušene vzorce) in zajema široko območje ravni onesnaženja PAH.
Pod pogoji, določenimi v tem mednarodnem standardu, je spodnjo mejo uporabe 0,01 mg/kg
(izraženo kot suha snov) mogoče zagotoviti za vsak posamezen policiklični aromatski ogljikovodik.

General Information

Status
Published
Public Enquiry End Date
03-Jun-2019
Publication Date
04-Sep-2019
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
30-Aug-2019
Due Date
04-Nov-2019
Completion Date
05-Sep-2019

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INTERNATIONAL ISO
STANDARD 18287
First edition
2006-01-15
Soil quality — Determination of polycyclic
aromatic hydrocarbons (PAH) — Gas
chromatographic method with mass
spectrometric detection (GC-MS)
Qualité du sol — Dosage des hydrocarbures aromatiques polycycliques
(HAP) — Méthode par chromatographie en phase gazeuse avec
détection par spectrométrie de masse (CG-SM)
Reference number
ISO 18287:2006(E)
ISO 2006
---------------------- Page: 1 ----------------------
ISO 18287:2006(E)
PDF disclaimer

This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but

shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In

downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat

accepts no liability in this area.
Adobe is a trademark of Adobe Systems Incorporated.

Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation

parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In

the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below.

© ISO 2006

All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,

electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or

ISO's member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2006 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 18287:2006(E)
Contents Page

Foreword............................................................................................................................................................ iv

Introduction ........................................................................................................................................................ v

1 Scope ......................................................................................................................................................1

2 Normative references ............................................................................................................................1

3 Principle..................................................................................................................................................2

4 Reagents.................................................................................................................................................2

5 Apparatus ...............................................................................................................................................4

6 Sampling, preservation and pretreatment ..........................................................................................5

7 Procedure ...............................................................................................................................................5

7.1 Extraction procedure.............................................................................................................................5

7.2 Clean-up procedure...............................................................................................................................6

7.3 Gas-chromatographic analysis with mass spectrometric detection................................................6

8 Evaluation...............................................................................................................................................8

9 Performance characteristics ................................................................................................................9

10 Quality assurance..................................................................................................................................9

11 Test report ..............................................................................................................................................9

Annex A (informative) Examples of typical GC-MS chromatograms and instrument conditions.............10

Annex B (informative) Results of interlaboratory comparisons...................................................................13

Bibliography ......................................................................................................................................................17

© ISO 2006 – All rights reserved iii
---------------------- Page: 3 ----------------------
ISO 18287:2006(E)
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 18287 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical

methods and soil characteristics.
iv © ISO 2006 – All rights reserved
---------------------- Page: 4 ----------------------
ISO 18287:2006(E)
Introduction

This International Standard is principally based on the extraction method described in ISO 13877. It is

modified for the use of gas-chromatography with mass spectrometric detection and is applicable for different

PAH pollution levels of soils.

Two alternative extraction methods, A and B, are described in this International Standard.

Method A (two-step method): Extraction of the field-moist soil sample with acetone and petroleum ether,

followed by the removal of acetone by washing the extract with water as prescribed in ISO 13877.

Method B (one-step method or on-line method): Extraction of the field-moist soil sample with a mixture of

acetone, petroleum ether and water in the presence of sodium chloride. This method is preferred for soil

samples with a high content of organic matrix.

Experience has shown that these two methods are applicable with comparable results to less as well as highly

polluted soils
© ISO 2006 – All rights reserved v
---------------------- Page: 5 ----------------------
INTERNATIONAL STANDARD ISO 18287:2006(E)
Soil quality — Determination of polycyclic aromatic
hydrocarbons (PAH) — Gas chromatographic method with
mass spectrometric detection (GC-MS)

SAFETY PRECAUTIONS — Certain PAH are highly carcinogenic and must be handled with extreme

care. Contact of solid materials, solvent extracts and solutions of standard PAH with the body must

not be allowed to occur. PAH may co-distil with solvent and become deposited outside of stoppered

bottles; all containers containing solutions of PAH in solvent must therefore always be handled using

gloves which are solvent resistant and preferably disposable. PAH contamination of vessels may

detected by irradiation with 366 nm UV light. Vessels containing PAH solutions should be stored

standing in beakers to contain any spillage in the case of breakage.

Solid PAH are most dangerous and give rise to a dust hazard due to their crystals becoming

electrostatically charged. These materials must only be handled where proper facilities are available

(e.g. adequate fume hoods, protective clothing, dust masks). It is strongly advised that standard

solutions be prepared centrally in suitably equipped laboratories or are purchased from suppliers

specialized in their preparation.

Solvent solutions containing PAH must be disposed of in a manner approved for the disposal of toxic

wastes.
1 Scope

This International Standard specifies the quantitative determination of 16 polycyclic aromatic hydrocarbons

(PAH) according to the priority list of the Environmental Protection Agency, USA (EPA, 1982). This

International Standard is applicable to all types of soil (field-moist or chemically dried samples), covering a

wide range of PAH contamination levels.

Under the conditions specified in this International Standard, a lower limit of application of 0,01 mg/kg

(expressed as dry matter) can be ensured for each individual PAH.
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, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes

ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric

method

ISO 14507:2003, Soil quality — Pretreatment of samples for determination of organic contaminants

ISO 10381-8, Soil quality — Sampling — Part 8: Guidance on sampling of stockpiles

ISO 16720, Soil quality —Pretreatment of samples by freeze-drying for subsequent analysis

© ISO 2006 – All rights reserved 1
---------------------- Page: 6 ----------------------
ISO 18287:2006(E)
3 Principle

The extraction is carried out using acetone and petroleum ether. Acetone is an efficient extractant, in

particular because it is able to break down soil aggregates. Petroleum ether increases the efficiency of the

extraction and is necessary as solvent in the subsequent concentration procedure. An extraction method for

PAH should at least use 50 ml of acetone and 50 ml of petroleum ether (for a chemically dried sample). If a

wet sample is used, the amount of acetone should be increased to at least 100 ml. Different ways of extraction

can lead to the same results provided that the above recommendations are observed. If the sample contains a

large amount of water, or if water has been added, sodium chloride (NaCl) should be added to improve the

efficiency of the extraction.

Two alternative extraction methods, A and B, are described in this International Standard.

Method A (two-step method): A field moist soil sample is extracted two times with acetone, then petroleum

ether is added to the acetone extract. The extract is washed two times with water. The organic layer is dried

with anhydrous sodium sulfate.

Method B (one-step method or on-line method): A field-moist soil sample is extracted with a fixed ratio of a

mixture of acetone, petroleum ether, water and sodium chloride. An aliquot of the organic layer is dried with

anhydrous sodium sulfate.

If necessary, a clean-up step using adsorption chromatography on silica gel, as well as a concentration step,

may be included.

The extract is then analysed by capillary gas-chromatography. The identification and the quantification of the

PAH is made with mass spectrometric detection, using appropriate deuterated PAH as internal standards.

4 Reagents

All reagents used shall be of recognized analytical grade and free from PAH. A blank determination shall be

carried out to ensure that the reagents do not contain PAH in detectable concentrations.

4.1 Water, use only distilled water or water of equivalent purity.
4.2 Acetone, for residue analysis.
4.3 Petroleum ether, for residue analysis (boiling range 40 °C to 60 °C).
4.4 Cyclohexane, for residue analysis.
4.5 Isooctane, for residue analysis.
4.6 Sodium chloride, anhydrous.
4.7 Sodium sulfate, anhydrous, for residue analysis.
4.8 Magnesium perchlorate or suitable drying agent.
4.9 Silica gel 60, for column chromatography, particle size 63 µm to 200 µm.
4.10 Silica gel 60, water content: w(H O) = 10 % (mass fraction).

Use silica gel 60 (4.9), heated for at least 3 h at 450 °C, cooled down in a desiccator (5.13) and stored with

magnesium perchlorate or a suitable drying agent (4.8). Before use, heat for at least 5 h at 130 °C in a drying

oven (5.14). Then allow to cool in a desiccator and add 10 % water (mass fraction) in a flask. Shake

intensively by hand for 5 min until all lumps have disappeared and then for 2 h in a shaking machine (5.3).

2 © ISO 2006 – All rights reserved
---------------------- Page: 7 ----------------------
ISO 18287:2006(E)

Store the desactivated silica gel in the absence of air and use it for a maximum of one week.

4.11 Reference substances, internal standards

Choose as 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 the evaluation of results. Verify the stability of the

internal standards regularly. Table 1 lists native and deuterated PAH.
Table 1 — Native PAH and deuterated PAH
Deuterated PAH internal
PAH reference substances CAS No.
standard substances
91-20-3 Naphthalene-d
Naphthalene
Acenaphthene-d
83-32-9
Acenaphthene
Acenaphthylene 208-96-8
Fluorene 86-73-7
Anthracene 120-12-7
85-01-8 Phenanthrene-d
Phenanthrene
Fluoranthene 206-44-0
Pyrene 129-00-0
56-55-3 Benz[a]anthracene-d
Benz[a]anthracene
Chrysene 218-01-9
205-99-2 Benzo[e]pyrene-d
Benzo[b]fluoranthene
Benzo[k]fluoranthene 207-08-9
Benzo[a]pyrene 50-32-8
193-39-5 Perylene-d
Indeno[1,2,3-cd]pyrene
Dibenz[ah]anthracene 53-70-3
Benzo[ghi]perylene 191-24-2
4.12 Standard solutions for GC-MS

If a commercially available certified standard stock solution of the relevant PAH is used, the calibration

solutions with different levels of PAH concentrations are prepared by diluting an appropriate volume of stock

solution with cyclohexane (4.4) in volumetric flasks (5.8).
4.12.1 Single-substance stock solution

If no certified standard solutions are used, prepare single-substance stock solutions by weighing

approximately 10 mg of each of the standards “native PAH” and “deuterated PAH” (see Table 1) to the

1) Certified solutions of PAH and single solid PAH substances with certified purity are available from a limited number of

suppliers, e.g. Institute for Reference Materials and Measurements (IRMM), B-2440 Geel, Belgium. National Institute of

Science and Technology, Office of Standard Ref. Data, Washington D.C. 20234 USA, or from other commercial providers.

This information is given for the convenience of users of this International Standard and does not constitute a

endorsement by ISO of these suppliers.
© ISO 2006 – All rights reserved 3
---------------------- Page: 8 ----------------------
ISO 18287:2006(E)

nearest 0,1 mg in a 50 ml volumetric flask, dissolving them in cyclohexane (4.4) and diluting to the mark with

cyclohexane (200 µg/ml).

Store the single-substance stock solutions in a dark place at a temperature of about −15 °C to −18 °C.

4.12.2 Stock solution containing mixed PAH standards

Transfer 1 ml to 5 ml (adjust the volume for individual components according to their occurrence in soil) of the

single-substance stock solution (4.12.1) to a 100 ml volumetric flask and dilute to the mark with cyclohexane

(2 µg/ml to 10 µg/ml).
4.12.3 Stock solution containing mixed internal standards

Transfer 5 ml each of the single-substance stock solutions (4.12.1) of the deuterated PAH into a 100 ml

volumetric flask and dilute to the mark with cyclohexane (10 µg/ml).

Store the diluted standard solutions 4.12.2 and 4.12.3 at about 4 °C, protected from light and evaporation.

NOTE Stock solutions are stable for about 1 year.
4.12.4 Calibration standard solutions

Prepare a series of calibration standards over a suitable range (e.g. 0,20 µg/ml to 5,0 µg/ml) by transferring

1 ml to 5 ml of the stock solution containing mixed PAH standards (4.12.2) and 1 ml of the mixed internal

standard solution (4.12.3) to a 10 ml volumetric flask and dilute to the mark with cyclohexane. Each of the

calibration standards contains nominally 1,0 µg/ml of each of the deuterated PAH.

NOTE Calibration standard solutions are stable for about 1 year.
5 Apparatus
Usual laboratory glassware.

All glassware shall be thoroughly cleaned, preferably in a dishwasher using a customary cleaning procedure,

followed by rinsing with acetone and subsequently with petroleum ether. Heating of glassware at 450 °C for

2 h is also allowed.

5.1 Brown glass sample containers, of nominal capacity 1 l, with screw caps provided with an inlay of

polytetrafluoroethylene (PTFE).
5.2 Sample divider.
5.3 Shaking machine, with horizontal movement (200 to 300 movements per minute).
5.4 Concentration apparatus, Kuderna Danish, or rotary evaporator.
5.5 Water bath, adjustable up to 100 °C.
5.6 Stainless steel dish.

5.7 Conical flasks, of 100 ml, 500 ml and 1 000 ml capacity, with screw caps provided with an inlay of

polytetrafluoroethylene (PTFE).
5.8 Volumetric flasks, of 10 ml, 50 ml and 100 ml nominal capacity.
5.9 Separating funnels, with a capacity of 250 ml, 500 ml and 1 000 ml.
5.10 Pipettes, of 1 ml, 2 ml, 5 ml and 10 ml, and Pasteur pipettes.
4 © ISO 2006 – All rights reserved
---------------------- Page: 9 ----------------------
ISO 18287:2006(E)
5.11 Syringe, of 100 µl, graduated in microlitres.
5.12 Centrifuge, with tubes of 100 ml capacity, with screw caps.
5.13 Desiccator.
5.14 Drying oven, adjustable up to 150 °C.
5.15 Glass wool, silanized.

5.16 Chromatography column, with storage tank at the top and PTFE stopcock at the bottom, with length

250 mm and internal diameter 10 mm.

5.17 Gas chromatograph, equipped with a suitable injection system, capillary column and a mass

spectrometric detector (GC-MS).

5.18 Capillary columns: Use a fused silica capillary column with a length of 30 m and internal diameter of

0,22 mm, coated with a film of cross-linked non-polar polysiloxane or slightly polar modified polysiloxane with

an efficient separation. The column shall be suitable to seperate benzo[a]pyrene and benzo[e]pyrene.

6 Sampling, preservation and pretreatment

Carry out sampling in accordance with ISO 10381-1 and ISO 10381-8. Store field-moist samples for no longer

than 7 days in suitable containers in a dark place at a temperature below 10 °C (refrigerator). If necessary,

use the procedure for the treatment of large samples described in ISO 10381-8 to reduce the size of the

sample to 1 kg. Pretreat the obtained sample in accordance with ISO 14507:2003 (use procedure 8.4 to

obtain a pretreated field-moist sample and procedure 8.3 to obtain a chemically dried sample). If freeze-drying

of the sample is prescribed, follow ISO 16720.
Determine and record mass fractions less than 2 mm and greater than 2 mm.

Determine the content of the dry matter in the field-moist soil in accordance with ISO 11465.

7 Procedure
7.1 Extraction procedure

7.1.1 Method A (two-step method): Weigh 10 g to 25 g of the field-moist sample and place it in a conical

flask (5.7) or a screw cap centrifuge tube of 100 ml capacity (5.12). After adding 1 ml of mixed internal

standard solution (4.12.3) (10 µg of each deuterated PAH) and subsequently 50 ml of acetone (4.2) to the test

sample, close the conical flask with a screw cap provided with an inlay of polytetrafluoroethylene (PTFE) and

extract by shaking thoroughly for 1 h on a shaking machine (5.3). Add 50 ml of petroleum ether (4.3), shake

again, decant then shake with another portion of 50 ml of petroleum ether. After allowing settling, decant the

supernatant. Combine the extracts and remove the acetone and other polar comp
...

SLOVENSKI STANDARD
SIST ISO 18287:2019
01-oktober-2019

Kakovost tal - Določevanje policikličnih aromatskih ogljikovodikov (PAH) - Plinska

kromatografija z masno selektivnim detektorjem (GC-MS)
Soil quality - Determination of polycyclic aromatic hydrocarbons (PAH) - Gas
chromatographic method with mass spectrometric detection (GC-MS)

Qualité du sol - Dosage des hydrocarbures aromatiques polycycliques (HAP) - Méthode

par chromatographie en phase gazeuse avec détection par spectrométrie de masse
(CG-SM)
Ta slovenski standard je istoveten z: ISO 18287:2006
ICS:
13.080.10 Kemijske značilnosti tal Chemical characteristics of
soils
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
SIST ISO 18287:2019 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST ISO 18287:2019
---------------------- Page: 2 ----------------------
SIST ISO 18287:2019
INTERNATIONAL ISO
STANDARD 18287
First edition
2006-01-15
Soil quality — Determination of polycyclic
aromatic hydrocarbons (PAH) — Gas
chromatographic method with mass
spectrometric detection (GC-MS)
Qualité du sol — Dosage des hydrocarbures aromatiques polycycliques
(HAP) — Méthode par chromatographie en phase gazeuse avec
détection par spectrométrie de masse (CG-SM)
Reference number
ISO 18287:2006(E)
ISO 2006
---------------------- Page: 3 ----------------------
SIST ISO 18287:2019
ISO 18287:2006(E)
PDF disclaimer

This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but

shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In

downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat

accepts no liability in this area.
Adobe is a trademark of Adobe Systems Incorporated.

Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation

parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In

the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below.

© ISO 2006

All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,

electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or

ISO's member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2006 – All rights reserved
---------------------- Page: 4 ----------------------
SIST ISO 18287:2019
ISO 18287:2006(E)
Contents Page

Foreword............................................................................................................................................................ iv

Introduction ........................................................................................................................................................ v

1 Scope ......................................................................................................................................................1

2 Normative references ............................................................................................................................1

3 Principle..................................................................................................................................................2

4 Reagents.................................................................................................................................................2

5 Apparatus ...............................................................................................................................................4

6 Sampling, preservation and pretreatment ..........................................................................................5

7 Procedure ...............................................................................................................................................5

7.1 Extraction procedure.............................................................................................................................5

7.2 Clean-up procedure...............................................................................................................................6

7.3 Gas-chromatographic analysis with mass spectrometric detection................................................6

8 Evaluation...............................................................................................................................................8

9 Performance characteristics ................................................................................................................9

10 Quality assurance..................................................................................................................................9

11 Test report ..............................................................................................................................................9

Annex A (informative) Examples of typical GC-MS chromatograms and instrument conditions.............10

Annex B (informative) Results of interlaboratory comparisons...................................................................13

Bibliography ......................................................................................................................................................17

© ISO 2006 – All rights reserved iii
---------------------- Page: 5 ----------------------
SIST ISO 18287:2019
ISO 18287:2006(E)
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 18287 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical

methods and soil characteristics.
iv © ISO 2006 – All rights reserved
---------------------- Page: 6 ----------------------
SIST ISO 18287:2019
ISO 18287:2006(E)
Introduction

This International Standard is principally based on the extraction method described in ISO 13877. It is

modified for the use of gas-chromatography with mass spectrometric detection and is applicable for different

PAH pollution levels of soils.

Two alternative extraction methods, A and B, are described in this International Standard.

Method A (two-step method): Extraction of the field-moist soil sample with acetone and petroleum ether,

followed by the removal of acetone by washing the extract with water as prescribed in ISO 13877.

Method B (one-step method or on-line method): Extraction of the field-moist soil sample with a mixture of

acetone, petroleum ether and water in the presence of sodium chloride. This method is preferred for soil

samples with a high content of organic matrix.

Experience has shown that these two methods are applicable with comparable results to less as well as highly

polluted soils
© ISO 2006 – All rights reserved v
---------------------- Page: 7 ----------------------
SIST ISO 18287:2019
---------------------- Page: 8 ----------------------
SIST ISO 18287:2019
INTERNATIONAL STANDARD ISO 18287:2006(E)
Soil quality — Determination of polycyclic aromatic
hydrocarbons (PAH) — Gas chromatographic method with
mass spectrometric detection (GC-MS)

SAFETY PRECAUTIONS — Certain PAH are highly carcinogenic and must be handled with extreme

care. Contact of solid materials, solvent extracts and solutions of standard PAH with the body must

not be allowed to occur. PAH may co-distil with solvent and become deposited outside of stoppered

bottles; all containers containing solutions of PAH in solvent must therefore always be handled using

gloves which are solvent resistant and preferably disposable. PAH contamination of vessels may

detected by irradiation with 366 nm UV light. Vessels containing PAH solutions should be stored

standing in beakers to contain any spillage in the case of breakage.

Solid PAH are most dangerous and give rise to a dust hazard due to their crystals becoming

electrostatically charged. These materials must only be handled where proper facilities are available

(e.g. adequate fume hoods, protective clothing, dust masks). It is strongly advised that standard

solutions be prepared centrally in suitably equipped laboratories or are purchased from suppliers

specialized in their preparation.

Solvent solutions containing PAH must be disposed of in a manner approved for the disposal of toxic

wastes.
1 Scope

This International Standard specifies the quantitative determination of 16 polycyclic aromatic hydrocarbons

(PAH) according to the priority list of the Environmental Protection Agency, USA (EPA, 1982). This

International Standard is applicable to all types of soil (field-moist or chemically dried samples), covering a

wide range of PAH contamination levels.

Under the conditions specified in this International Standard, a lower limit of application of 0,01 mg/kg

(expressed as dry matter) can be ensured for each individual PAH.
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, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes

ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric

method

ISO 14507:2003, Soil quality — Pretreatment of samples for determination of organic contaminants

ISO 10381-8, Soil quality — Sampling — Part 8: Guidance on sampling of stockpiles

ISO 16720, Soil quality —Pretreatment of samples by freeze-drying for subsequent analysis

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ISO 18287:2006(E)
3 Principle

The extraction is carried out using acetone and petroleum ether. Acetone is an efficient extractant, in

particular because it is able to break down soil aggregates. Petroleum ether increases the efficiency of the

extraction and is necessary as solvent in the subsequent concentration procedure. An extraction method for

PAH should at least use 50 ml of acetone and 50 ml of petroleum ether (for a chemically dried sample). If a

wet sample is used, the amount of acetone should be increased to at least 100 ml. Different ways of extraction

can lead to the same results provided that the above recommendations are observed. If the sample contains a

large amount of water, or if water has been added, sodium chloride (NaCl) should be added to improve the

efficiency of the extraction.

Two alternative extraction methods, A and B, are described in this International Standard.

Method A (two-step method): A field moist soil sample is extracted two times with acetone, then petroleum

ether is added to the acetone extract. The extract is washed two times with water. The organic layer is dried

with anhydrous sodium sulfate.

Method B (one-step method or on-line method): A field-moist soil sample is extracted with a fixed ratio of a

mixture of acetone, petroleum ether, water and sodium chloride. An aliquot of the organic layer is dried with

anhydrous sodium sulfate.

If necessary, a clean-up step using adsorption chromatography on silica gel, as well as a concentration step,

may be included.

The extract is then analysed by capillary gas-chromatography. The identification and the quantification of the

PAH is made with mass spectrometric detection, using appropriate deuterated PAH as internal standards.

4 Reagents

All reagents used shall be of recognized analytical grade and free from PAH. A blank determination shall be

carried out to ensure that the reagents do not contain PAH in detectable concentrations.

4.1 Water, use only distilled water or water of equivalent purity.
4.2 Acetone, for residue analysis.
4.3 Petroleum ether, for residue analysis (boiling range 40 °C to 60 °C).
4.4 Cyclohexane, for residue analysis.
4.5 Isooctane, for residue analysis.
4.6 Sodium chloride, anhydrous.
4.7 Sodium sulfate, anhydrous, for residue analysis.
4.8 Magnesium perchlorate or suitable drying agent.
4.9 Silica gel 60, for column chromatography, particle size 63 µm to 200 µm.
4.10 Silica gel 60, water content: w(H O) = 10 % (mass fraction).

Use silica gel 60 (4.9), heated for at least 3 h at 450 °C, cooled down in a desiccator (5.13) and stored with

magnesium perchlorate or a suitable drying agent (4.8). Before use, heat for at least 5 h at 130 °C in a drying

oven (5.14). Then allow to cool in a desiccator and add 10 % water (mass fraction) in a flask. Shake

intensively by hand for 5 min until all lumps have disappeared and then for 2 h in a shaking machine (5.3).

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ISO 18287:2006(E)

Store the desactivated silica gel in the absence of air and use it for a maximum of one week.

4.11 Reference substances, internal standards

Choose as 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 the evaluation of results. Verify the stability of the

internal standards regularly. Table 1 lists native and deuterated PAH.
Table 1 — Native PAH and deuterated PAH
Deuterated PAH internal
PAH reference substances CAS No.
standard substances
91-20-3 Naphthalene-d
Naphthalene
Acenaphthene-d
83-32-9
Acenaphthene
Acenaphthylene 208-96-8
Fluorene 86-73-7
Anthracene 120-12-7
85-01-8 Phenanthrene-d
Phenanthrene
Fluoranthene 206-44-0
Pyrene 129-00-0
56-55-3 Benz[a]anthracene-d
Benz[a]anthracene
Chrysene 218-01-9
205-99-2 Benzo[e]pyrene-d
Benzo[b]fluoranthene
Benzo[k]fluoranthene 207-08-9
Benzo[a]pyrene 50-32-8
193-39-5 Perylene-d
Indeno[1,2,3-cd]pyrene
Dibenz[ah]anthracene 53-70-3
Benzo[ghi]perylene 191-24-2
4.12 Standard solutions for GC-MS

If a commercially available certified standard stock solution of the relevant PAH is used, the calibration

solutions with different levels of PAH concentrations are prepared by diluting an appropriate volume of stock

solution with cyclohexane (4.4) in volumetric flasks (5.8).
4.12.1 Single-substance stock solution

If no certified standard solutions are used, prepare single-substance stock solutions by weighing

approximately 10 mg of each of the standards “native PAH” and “deuterated PAH” (see Table 1) to the

1) Certified solutions of PAH and single solid PAH substances with certified purity are available from a limited number of

suppliers, e.g. Institute for Reference Materials and Measurements (IRMM), B-2440 Geel, Belgium. National Institute of

Science and Technology, Office of Standard Ref. Data, Washington D.C. 20234 USA, or from other commercial providers.

This information is given for the convenience of users of this International Standard and does not constitute a

endorsement by ISO of these suppliers.
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ISO 18287:2006(E)

nearest 0,1 mg in a 50 ml volumetric flask, dissolving them in cyclohexane (4.4) and diluting to the mark with

cyclohexane (200 µg/ml).

Store the single-substance stock solutions in a dark place at a temperature of about −15 °C to −18 °C.

4.12.2 Stock solution containing mixed PAH standards

Transfer 1 ml to 5 ml (adjust the volume for individual components according to their occurrence in soil) of the

single-substance stock solution (4.12.1) to a 100 ml volumetric flask and dilute to the mark with cyclohexane

(2 µg/ml to 10 µg/ml).
4.12.3 Stock solution containing mixed internal standards

Transfer 5 ml each of the single-substance stock solutions (4.12.1) of the deuterated PAH into a 100 ml

volumetric flask and dilute to the mark with cyclohexane (10 µg/ml).

Store the diluted standard solutions 4.12.2 and 4.12.3 at about 4 °C, protected from light and evaporation.

NOTE Stock solutions are stable for about 1 year.
4.12.4 Calibration standard solutions

Prepare a series of calibration standards over a suitable range (e.g. 0,20 µg/ml to 5,0 µg/ml) by transferring

1 ml to 5 ml of the stock solution containing mixed PAH standards (4.12.2) and 1 ml of the mixed internal

standard solution (4.12.3) to a 10 ml volumetric flask and dilute to the mark with cyclohexane. Each of the

calibration standards contains nominally 1,0 µg/ml of each of the deuterated PAH.

NOTE Calibration standard solutions are stable for about 1 year.
5 Apparatus
Usual laboratory glassware.

All glassware shall be thoroughly cleaned, preferably in a dishwasher using a customary cleaning procedure,

followed by rinsing with acetone and subsequently with petroleum ether. Heating of glassware at 450 °C for

2 h is also allowed.

5.1 Brown glass sample containers, of nominal capacity 1 l, with screw caps provided with an inlay of

polytetrafluoroethylene (PTFE).
5.2 Sample divider.
5.3 Shaking machine, with horizontal movement (200 to 300 movements per minute).
5.4 Concentration apparatus, Kuderna Danish, or rotary evaporator.
5.5 Water bath, adjustable up to 100 °C.
5.6 Stainless steel dish.

5.7 Conical flasks, of 100 ml, 500 ml and 1 000 ml capacity, with screw caps provided with an inlay of

polytetrafluoroethylene (PTFE).
5.8 Volumetric flasks, of 10 ml, 50 ml and 100 ml nominal capacity.
5.9 Separating funnels, with a capacity of 250 ml, 500 ml and 1 000 ml.
5.10 Pipettes, of 1 ml, 2 ml, 5 ml and 10 ml, and Pasteur pipettes.
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5.11 Syringe, of 100 µl, graduated in microlitres.
5.12 Centrifuge, with tubes of 100 ml capacity, with screw caps.
5.13 Desiccator.
5.14 Drying oven, adjustable up to 150 °C.
5.15 Glass wool, silanized.

5.16 Chromatography column, with storage tank at the top and PTFE stopcock at the bottom, with length

250 mm and internal diameter 10 mm.

5.17 Gas chromatograph, equipped with a suitable injection system, capillary column and a mass

spectrometric detector (GC-MS).

5.18 Capillary columns: Use a fused silica capillary column with a length of 30 m and internal diameter of

0,22 mm, coated with a film of cross-linked non-polar polysiloxane or slightly polar modified polysiloxane with

an efficient separation. The column shall be suitable to seperate benzo[a]pyrene and benzo[e]pyrene.

6 Sampling, preservation and pretreatment

Carry out sampling in accordance with ISO 10381-1 and ISO 10381-8. Store field-moist samples for no longer

than 7 days in suitable containers in a dark place at a temperature below 10 °C (refrigerator). If necessary,

use the procedure for the treatment of large samples described in ISO 10381-8 to reduce the size of the

sample to 1 kg. Pretreat the obtained sample in accordance with ISO 14507:2003 (use procedure 8.4 to

obtain a pretreated field-moist sample and procedure 8.3 to obtain a chemically dried sample). If freeze-drying

of the sample is prescribed, follow ISO 16720.
Determine and record mass fractions less than 2 mm and greater than 2 mm.

Determine the content of the dry matter in the field-moist soil in accordance with ISO 11465.

7 Procedure
7.1 Extraction procedure

7.1.1 Method A (two-step method): Weigh 10 g to 25 g of the field-moist sample and place it in a conical

flask (5.7) or a screw cap centri
...

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Qualité du sol - Dosage des hydrocarbures aromatiques polycycliques (HAP) - Méthode par chromatographie en phase gazeuse avec détection par spectrométrie de masse (CG-SM)Soil quality - Determination of polycyclic aromatic hydrocarbons (PAH) - Gas chromatographic method with mass spectrometric detection (GC-MS)71.040.50Fizikalnokemijske analitske metodePhysicochemical methods of analysis13.080.10Chemical characteristics of soilsICS:Ta slovenski standard je istoveten z:ISO 18287:2006oSIST ISO 18287:2019en01-maj-2019oSIST ISO 18287:2019SLOVENSKI

STANDARD
oSIST ISO 18287:2019
Reference numberISO 18287:2006(E)© ISO 2006

INTERNATIONAL STANDARD ISO18287First edition2006-01-15Soil quality —Determination of polycyclic aromatic hydrocarbons (PAH) — Gas chromatographic method with mass spectrometric detection (GC-MS) Qualité du sol —Dosage des hydrocarbures aromatiques polycycliques (HAP) — Méthode par chromatographie en phase gazeuse avec détection par spectrométrie de masse (CG-SM)

oSIST ISO 18287:2019

ISO 18287:2006(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat accepts no liability in this area. Adobe is a trademark of Adobe Systems Incorporated. Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below.

ISO 2006 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO's member body in the country of the requester. ISO copyright office Case postale 56 • CH-1211 Geneva 20 Tel.

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ii © ISO 2006 – All rights reserved
oSIST ISO 18287:2019

ISO 18287:2006(E) © ISO 2006 – All rights reserved iiiContents Page Foreword............................................................................................................................................................iv Introduction........................................................................................................................................................v 1 Scope......................................................................................................................................................1 2 Normative references............................................................................................................................1 3 Principle..................................................................................................................................................2 4 Reagents.................................................................................................................................................2 5 Apparatus...............................................................................................................................................4 6 Sampling, preservation and pretreatment..........................................................................................5 7 Procedure...............................................................................................................................................5 7.1 Extraction procedure.............................................................................................................................5 7.2 Clean-up procedure...............................................................................................................................6 7.3 Gas-chromatographic analysis with mass spectrometric detection................................................6 8 Evaluation...............................................................................................................................................8 9 Performance characteristics................................................................................................................9 10 Quality assurance..................................................................................................................................9 11 Test report..............................................................................................................................................9 Annex A (informative)

Examples of typical GC-MS chromatograms and instrument conditions.............10 Annex B (informative)

Results of interlaboratory comparisons...................................................................13 Bibliography......................................................................................................................................................17

oSIST ISO 18287:2019

ISO 18287:2006(E) iv © ISO 2006 – 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 18287 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics. oSIST ISO 18287:2019

ISO 18287:2006(E) © ISO 2006 – All rights reserved vIntroduction This International Standard is principally based on the extraction method described in ISO 13877. It is modified for the use of gas-chromatography with mass spectrometric detection and is applicable for different PAH pollution levels of soils. Two alternative extraction methods, A and B, are described in this International Standard. Method A (two-step method): Extraction of the field-moist soil sample with acetone and petroleum ether, followed by the removal of acetone by washing the extract with water as prescribed in ISO 13877. Method B (one-step method or on-line method): Extraction of the field-moist soil sample with a mixture of acetone, petroleum ether and water in the presence of sodium chloride. This method is preferred for soil samples with a high content of organic matrix. Experience has shown that these two methods are applicable with comparable results to less as well as highly polluted soils

oSIST ISO 18287:2019
oSIST ISO 18287:2019

INTERNATIONAL STANDARD ISO 18287:2006(E) © ISO 2006 – All rights reserved 1Soil quality — Determination of polycyclic aromatic hydrocarbons (PAH) — Gas chromatographic method with mass spectrometric detection (GC-MS) SAFETY PRECAUTIONS — Certain PAH are highly carcinogenic and must be handled with extreme care. Contact of solid materials, solvent extracts and solutions of standard PAH with the body must not be allowed to occur. PAH may co-distil with solvent and become deposited outside of stoppered bottles; all containers containing solutions of PAH in solvent must therefore always be handled using gloves which are solvent resistant and preferably disposable. PAH contamination of vessels may detected by irradiation with 366 nm UV light. Vessels containing PAH solutions should be stored standing in beakers to contain any spillage in the case of breakage. Solid PAH are most dangerous and give rise to a dust hazard due to their crystals becoming electrostatically charged. These materials must only be handled where proper facilities are available (e.g. adequate fume hoods, protective clothing, dust masks). It is strongly advised that standard solutions be prepared centrally in suitably equipped laboratories or are purchased from suppliers specialized in their preparation.

Solvent solutions containing PAH must be disposed of in a manner approved for the disposal of toxic wastes. 1 Scope This International Standard specifies the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAH) according to the priority list of the Environmental Protection Agency, USA (EPA, 1982). This International Standard is applicable to all types of soil (field-moist or chemically dried samples), covering a wide range of PAH contamination levels. Under the conditions specified in this International Standard, a lower limit of application of 0,01 mg/kg (expressed as dry matter) can be ensured for each individual PAH. 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, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric method ISO 14507:2003, Soil quality — Pretreatment of samples for determination of organic contaminants ISO 10381-8, Soil quality — Sampling — Part 8: Guidance on sampling of stockpiles ISO 16720, Soil quality —Pretreatment of samples by freeze-drying for subsequent analysis oSIST ISO 18287:2019

ISO 18287:2006(E) 2 © ISO 2006 – All rights reserved 3 Principle The extraction is carried out using acetone and petroleum ether. Acetone is an efficient extractant, in particular because it is able to break down soil aggregates. Petroleum ether increases the efficiency of the extraction and is necessary as solvent in the subsequent concentration procedure. An extraction method for PAH should at least use 50 ml of acetone and 50 ml of petroleum ether (for a chemically dried sample). If a wet sample is used, the amount of acetone should be increased to at least 100 ml. Different ways of extraction can lead to the same results provided that the above recommendations are observed. If the sample contains a large amount of water, or if water has been added, sodium chloride (NaCl) should be added to improve the efficiency of the extraction. Two alternative extraction methods, A and B, are described in this International Standard. Method A (two-step method): A field moist soil sample is extracted two times with acetone, then petroleum ether is added to the acetone extract. The extract is washed two times with water. The organic layer is dried with anhydrous sodium sulfate. Method B (one-step method or on-line method): A field-moist soil sample is extracted with a fixed ratio of a mixture of acetone, petroleum ether, water and sodium chloride. An aliquot of the organic layer is dried with anhydrous sodium sulfate. If necessary, a clean-up step using adsorption chromatography on silica gel, as well as a concentration step, may be included. The extract is then analysed by capillary gas-chromatography. The identification and the quantification of the PAH is made with mass spectrometric detection, using appropriate deuterated PAH as internal standards. 4 Reagents All reagents used shall be of recognized analytical grade and free from PAH. A blank determination shall be carried out to ensure that the reagents do not contain PAH in detectable concentrations. 4.1 Water, use only distilled water or water of equivalent purity. 4.2 Acetone, for residue analysis. 4.3 Petroleum ether, for residue analysis (boiling range 40 °C to 60 °C). 4.4 Cyclohexane, for residue analysis. 4.5 Isooctane, for residue analysis. 4.6 Sodium chloride, anhydrous. 4.7 Sodium sulfate, anhydrous, for residue analysis. 4.8 Magnesium perchlorate or suitable drying agent. 4.9 Silica gel 60, for column chromatography, particle size 63 µm to 200 µm. 4.10 Silica gel 60, water content: w(H2O) = 10 % (mass fraction).

Use silica gel 60 (4.9), heated for at least 3 h at 450 °C, cooled down in a desiccator (5.13) and stored with magnesium perchlorate or a suitable drying agent (4.8). Before use, heat for at least 5 h at 130 °C in a drying oven (5.14). Then allow to cool in a desiccator and add 10 % water (mass fraction) in a flask. Shake intensively by hand for 5 min until all lumps have disappeared and then for 2 h in a shaking machine (5.3).

oSIST ISO 18287:2019

ISO 18287:2006(E) © ISO 2006 – All rights reserved 3Store the desactivated silica gel in the absence of air and use it for a maximum of one week. 4.11 Reference substances, internal standards Choose as 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 the evaluation of results. Verify the stability of the internal standards regularly. Table 1 lists native and deuterated PAH.1)

Table 1 — Native PAH and deuterated PAH PAH reference substances CAS No. Deuterated PAH internal standard substances Naphthalene 91-20-3 Naphthalene-d8 Acenaphthene 83-32-9 Acenaphthene-d10 Acenaphthylene 208-96-8

Fluorene 86-73-7
Anthracene 120-12-7
Phenanthrene 85-01-8 Phenanthrene-d8 Fluoranthene 206-44-0
Pyrene 129-00-0
Benz[a]anthracene 56-55-3 Benz[a]anthracene-d12 Chrysene 218-01-9
Benzo[b]fluoranthene 205-99-2 Benzo[e]pyrene-d12 Benzo[k]fluoranthene 207-08-9
Benzo[a]pyrene 50-32-8
Indeno[1,2,3-cd]pyrene 193-39-5 Perylene-d12 Dibenz[ah]anthracene 53-70-3
Benzo[ghi]perylene 191-24-2

4.12 Standard solutions for GC-MS If a commercially available certified standard stock solution of the relevant PAH is used, the calibration solutions with different levels of PAH concentrations are prepared by diluting an appropriate volume of stock solution with cyclohexane (4.4) in volumetric flasks (5.8). 4.12.1 Single-substance stock solution If no certified standard solutions are used, prepare single-substance stock solutions by weighing approximately 10 mg of each of the standards “native PAH” and “deuterated PAH” (see Table 1) to the

1) Certified solutions of PAH and single solid PAH substances with certified purity are available from a limited number of suppliers, e.g. Institute for Reference Materials and Measurements (IRMM), B-2440 Geel, Belgium. National Institute of Science and Technology, Office of Standard Ref. Data, Washington D.C. 20234 USA, or from other commercial providers. This information is given for the convenience of users of this International Standard and does not constitute a endorsement by ISO of these suppliers. oSIST ISO 18287:2019

ISO 18287:2006(E) 4 © ISO 2006 – All rights reserved nearest 0,1 mg in a 50 ml volumetric flask, dissolving them in cyclohexane (4.4) and diluting to the mark with cyclohexane (200 µg/ml). Store the single-substance stock solutions in a dark place at a temperature of about −15 °C to −18 °C.

4.12.2 Stock solution containing mixed PAH standards Transfer 1 ml to 5 ml (adjust the volume for individual components according to their occurrence in soil) of the single-substance stock solution (4.12.1) to a 100 ml volumetric flask and dilute to the mark with cyclohexane (2 µg/ml to 10 µg/ml). 4.12.3 Stock solution containing mixed internal standards

Transfer 5 ml each of the single-substance stock solutions (4.12.1) of the deuterated PAH into a 100 ml volumetric flask and dilute to the mark with cyclohexane (10 µg/ml). Store the diluted standard solutions 4.12.2 and 4.12.3 at about 4 °C, protected from light and evaporation.

NOTE Stock solutions are stable for about 1 year. 4.12.4 Calibration standard solutions Prepare a series of calibration standards over a suitable range (e.g. 0,20 µg/ml to 5,0 µg/ml) by transferring 1 ml to 5 ml of the stock solution containing mixed PAH standards (4.12.2) and 1 ml of the mixed internal standard solution (4.12.3) to a 10 ml volumetric flask and dilute to the mark with cyclohexane. Each of the calibration standards contains nominally 1,0 µg/ml of each of the deuterated PAH. NOTE Calibration standard solutions are stable for about 1 year. 5 Apparatus Usual laboratory glassware. All glassware shall be thoroughly cleaned, preferably in a dishwasher using a customary cleaning procedure, followed by rinsing with acetone and subsequently with petroleum ether. Heating of glassware at 450 °C for 2 h is also allowed. 5.1 Brown glass sample containers, of nominal capacity 1 l, with screw caps provided with an inlay of polytetrafluoroethylene (PTFE). 5.2 Sample divider. 5.3 Shaking machine, with horizontal movement (200 to 300 movements per minute). 5.4 Concentration apparatus, Kuderna Danish, or rotary evaporator. 5.5 Water bath, adjustable up to 100 °C. 5.6 Stainless steel dish. 5.7 Conical flasks, of 100 ml, 500 ml and 1 000 ml capacity, with screw caps provided with an inlay of polytetrafluoroethylene (PTFE). 5.8 Volumetric flasks, of 10 ml, 50 ml and 100 ml nominal capacity. 5.9 Separating funnels, with a capacity of 250 ml, 500 ml and 1 000 ml. 5.10 Pipettes, of 1 ml, 2 ml, 5 ml and 10 ml, and Pasteur pipettes. oSIST ISO 18287:2019

ISO 18287:2006(E) © ISO 2006 – All rights reserved 55.11 Syringe, of 100 µl, graduated in microlitres. 5.12 Centrifuge, with tubes of 100 ml capacity, with screw caps. 5.13 Desiccator. 5.14 Drying oven, adjustable up to 150 °C. 5.15 Glass wool, silanized. 5.16 Chromatography column, with storage tank at the top and PTFE stopcock at the bottom, with length 250 mm and internal diameter 10 mm. 5.17 Gas chromatograph, equipped with a suitable injection system, capillary column and a mass spectrometric detector (GC-MS). 5.18 Capillary columns: Use a fused silica capillary column with a length of 30 m and internal diameter of 0,22 mm, coated with a film of cross-linked non-polar polysiloxane or slightly polar modified polysiloxane with an efficient separation. The column shall be suitable to seperate benzo[a]pyrene and benzo[e]pyrene. 6 Sampling, preservation and pretreatment Carry out sampling in accordance with ISO 10381-1 and ISO 10381-8. Store field-moist samples for no longer than 7 days in suitable containers in a dark place at a temperature below 10 °C (refrigerator). If necessary, use the procedure for the treatment of large samples described in ISO 10381-8 to reduce the size of the sample to 1 kg. Pretreat the obtained sample in accordance with ISO 14507:2003 (use procedure 8.4 to obtain a pretreated field-moist sample and procedure 8.3 to obtain a chemically dried sample). If freeze-drying of the sample is prescribed, follow ISO 16720. Determine and record mass fractions less than 2 mm and greater than 2 mm. Determine the content of the dry matter in the field-moist soil in accordance with ISO 11465. 7 Procedure 7.1 Extraction procedure 7.1.1 Method A (two-step method): Weigh 10 g to 2

...

NORME ISO
INTERNATIONALE 18287
Première édition
2006-01-15
Qualité du sol — Dosage des
hydrocarbures aromatiques
polycycliques (HAP) — Méthode par
chromatographie en phase gazeuse avec
détection par spectrométrie de masse
(CG-SM)
Soil quality — Determination of polycyclic aromatic hydrocarbons
(PAH) — Gas chromatographic method with mass spectrometric
detection (GC-MS)
Numéro de référence
ISO 18287:2006(F)
ISO 2006
---------------------- Page: 1 ----------------------
ISO 18287:2006(F)
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ISO 18287:2006(F)
Sommaire Page

Avant-propos..................................................................................................................................................... iv

Introduction ........................................................................................................................................................ v

1 Domaine d'application...........................................................................................................................1

2 Références normatives.........................................................................................................................1

3 Principe...................................................................................................................................................2

4 Réactifs...................................................................................................................................................2

5 Appareillage...........................................................................................................................................4

6 Échantillonnage, conservation et prétraitement ................................................................................5

7 Mode opératoire.....................................................................................................................................6

7.1 Mode opératoire d’extraction ...............................................................................................................6

7.2 Mode opératoire de purification...........................................................................................................6

7.3 Analyse de chromatographie en phase gazeuse avec détection par spectrométrie

de masse.................................................................................................................................................7

8 Évaluation...............................................................................................................................................9

9 Caractéristiques de performance.......................................................................................................10

10 Assurance de la qualité.......................................................................................................................10

11 Rapport d'essai ....................................................................................................................................10

Annexe A (informative) Exemples de chromatogrammes types de CG-SM et de conditions

instrumentales .....................................................................................................................................11

Annexe B (informative) Résultats d'une comparaison interlaboratoires effectuée en Allemagne...........14

Bibliographie .....................................................................................................................................................18

© ISO 2006 – Tous droits réservés iii
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ISO 18287:2006(F)
Avant-propos

L'ISO (Organisation internationale de normalisation) est une fédération mondiale d'organismes nationaux de

normalisation (comités membres de l'ISO). L'élaboration des Normes internationales est en général confiée

aux comités techniques de l'ISO. Chaque comité membre intéressé par une étude a le droit de faire partie du

comité technique créé à cet effet. Les organisations internationales, gouvernementales et non

gouvernementales, en liaison avec l'ISO participent également aux travaux. L'ISO collabore étroitement avec

la Commission électrotechnique internationale (CEI) en ce qui concerne la normalisation électrotechnique.

Les Normes internationales sont rédigées conformément aux règles données dans les Directives ISO/CEI,

Partie 2.

La tâche principale des comités techniques est d'élaborer les Normes internationales. Les projets de Normes

internationales adoptés par les comités techniques sont soumis aux comités membres pour vote. Leur

publication comme Normes internationales requiert l'approbation de 75 % au moins des comités membres

votants.

L'attention est appelée sur le fait que certains des éléments du présent document peuvent faire l'objet de

droits de propriété intellectuelle ou de droits analogues. L'ISO ne saurait être tenue pour responsable de ne

pas avoir identifié de tels droits de propriété et averti de leur existence.

L'ISO 18287 a été élaborée par le comité technique ISO/TC 190, Qualité du sol, sous-comité SC 3, Méthodes

chimiques et caractéristiques du sol.
iv © ISO 2006 – Tous droits réservés
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ISO 18287:2006(F)
Introduction

La présente Norme Internationale repose principalement sur la méthode d’extraction décrite dans l’ISO 13877.

Cette méthode est modifiée pour permettre la mise en œuvre de la chromatographie en phase gazeuse avec

détection par spectrométrie de masse et elle est applicable aux différents degrés de pollution des sols par les

HAP.

La présente Norme Internationale décrit deux méthodes d’extraction différentes, appelées méthode A et

méthode B.

Méthode A (méthode en deux étapes): extraction d’un échantillon brut prélevé sur le terrain, avec de l’acétone

et de l’éther de pétrole, suivie de l’élimination de l’acétone par lavage de l’extrait avec de l’eau comme

spécifié dans l’ISO 13877.

Méthode B (méthode en une étape ou en ligne): extraction de l’échantillon brut prélevé sur le terrain avec un

mélange d’acétone, d’éther de pétrole et d’eau en présence de chlorure de sodium. Il est préférable d’utiliser

cette méthode avec des échantillons de sol ayant une forte teneur en matrice organique.

L’expérience a montré que ces deux méthodes sont applicables à des sols peu ou très pollués, tout en

donnant des résultats comparables.
© ISO 2006 – Tous droits réservés v
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NORME INTERNATIONALE ISO 18287:2006(F)
Qualité du sol — Dosage des hydrocarbures aromatiques
polycycliques (HAP) — Méthode par chromatographie en phase
gazeuse avec détection par spectrométrie de masse (CG-SM)

PRÉCAUTIONS DE SÉCURITÉ — Certains HAP sont extrêmement cancérigènes; les manipuler avec la

plus grande précaution. Éviter tout contact corporel avec des substances solides, des extraits de

solvants et des solutions étalons de HAP. Il peut se produire une codistillation lorsque les HAP

entrent en contact avec un solvant et ils peuvent alors se déposer à l’extérieur des flacons bouchés.

En conséquence, manipuler tous les conteneurs remplis de solutions de HAP dans des solvants avec

des gants résistants aux solvants, de préférence jetables. Il est possible de détecter la contamination

des récipients par des HAP en exposant ceux-ci à un rayonnement UV à 366 nm. Il convient de stocker

les récipients contenant des solutions de HAP en position verticale dans des béchers, afin d’éviter

toute dispersion en cas de bris.

Les HAP solides sont extrêmement dangereux en raison du risque de dispersion des poudres par

effet électrostatique. Ne manipuler ces substances que si l’on dispose du matériel adéquat (tel que

des hottes aspirantes, des vêtements de protection, des masques à poussière, etc.). Il est vivement

recommandé de centraliser la préparation des solutions étalons dans des laboratoires disposant d’un

équipement adapté ou de se procurer lesdites solutions auprès de fournisseurs spécialisés dans leur

préparation.

Éliminer les solutions avec solvants contenant des HAP conformément aux prescriptions concernant

les déchets toxiques.
1 Domaine d'application

La présente Norme internationale spécifie le dosage quantitatif de 16 hydrocarbures aromatiques

polycycliques (HAP) selon la liste de polluants prioritaires établie par l’Agence de protection de

l’environnement (États-Unis) [Environmental Protection Agency (EPA), 1982]. La présente Norme

internationale est applicable à tous les types de sols (échantillons bruts prélevés sur le terrain ou échantillons

ayant été soumis à un séchage chimique), couvrant une large gamme de niveaux de contamination par les

HAP.

Dans les conditions spécifiées dans la présente Norme internationale, une limite inférieure d’application

de 0,01 mg/kg (exprimée en matière sèche) peut être garantie pour chacun des HAP.

2 Références normatives

Les documents de référence suivants sont indispensables pour l'application du présent document. Pour les

références datées, seule l'édition citée s'applique. Pour les références non datées, la dernière édition du

document de référence s'applique (y compris les éventuels amendements).

ISO 10381-1, Qualité du sol — Échantillonnage — Partie 1: Lignes directrices pour l'établissement des

programmes d'échantillonnage

ISO 11465, Qualité du sol — Détermination de la teneur pondérale en matière sèche et en eau — Méthode

gravimétrique
© ISO 2006 – Tous droits réservés 1
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ISO 18287:2006(F)

ISO 14507:2003, Qualité du sol — Prétraitement des échantillons pour la détermination des contaminants

organiques

ISO 10381-8, Qualité du sol — Échantillonnage — Partie 8: Lignes directrices pour l'échantillonnage des

stocks de réserve

ISO 16720, Qualité du sol — Prétraitement des échantillons par lyophilisation pour analyse subséquente

3 Principe

L’extraction est effectuée en utilisant de l’acétone et de l’éther de pétrole. L’acétone est un extractant efficace,

notamment parce qu’elle est capable de disloquer les agrégats de sol. L’éther de pétrole accroît l’efficacité de

l’extraction et son utilisation comme solvant est nécessaire lors de la procédure de concentration qui suit. Il

convient que toute méthode d’extraction des HAP utilise au moins 50 ml d’acétone et 50 ml d’éther de pétrole

(pour un échantillon ayant été soumis à un séchage chimique). Si l’échantillon utilisé est humide, il convient

d’augmenter la quantité d’acétone jusqu’à au moins 100 ml. Différentes méthodes d’extraction peuvent

conduire aux mêmes résultats, à condition qu’elles respectent les recommandations susmentionnées. Si

l’échantillon contient une grande quantité d’eau ou si l’on a ajouté de l’eau, il convient d’ajouter du chlorure de

sodium (NaCl) pour augmenter l’efficacité de l’extraction.

La présente Norme décrit deux méthodes d’extraction différentes, appelées A et B.

Méthode A (méthode en deux étapes): Un échantillon brut prélevé sur le terrain est extrait à deux reprises

avec de l’acétone, puis on ajoute de l’éther de pétrole à l’extrait d’acétone. L’extrait est lavé deux fois à l’eau

puis la phase organique est déshydratée avec du sulfate de sodium anhydre.

Méthode B (méthode en une étape ou en ligne): Un échantillon brut prélevé sur le terrain est extrait avec un

mélange d’acétone, d’éther de pétrole, d’eau et de chlorure de sodium, en proportions définies. Une aliquote

de la phase organique est déshydratée avec du sulfate de sodium anhydre.

Si nécessaire, une étape de purification par chromatographie par adsorption sur gel de silice, ainsi qu’une

étape de concentration, peuvent être ajoutées.

L’extrait est ensuite analysé par chromatographie capillaire en phase gazeuse. L’identification et la

quantification des HAP sont effectuées par détection par spectrométrie de masse, en utilisant des HAP

deutérés appropriés comme étalons internes.
4 Réactifs

Au cours de l'analyse, utiliser uniquement des réactifs de qualité analytique reconnue et exempts de HAP. Un

dosage à blanc doit être réalisé afin de s’assurer que les réactifs ne contiennent pas de HAP en

concentrations détectables.

4.1 Eau, utiliser uniquement de l’eau distillée ou de l'eau de pureté équivalente.

4.2 Acétone, pour analyse des résidus.

4.3 Éther de pétrole, pour analyse des résidus (domaine d’ébullition de 40 °C à 60 °C).

4.4 Cyclohexane, pour analyse des résidus.
4.5 Isooctane, pour analyse des résidus.
4.6 Chlorure de sodium, anhydre.
4.7 Sulfate de sodium, anhydre, pour analyse des résidus.
2 © ISO 2006 – Tous droits réservés
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ISO 18287:2006(F)
4.8 Perchlorate de magnésium ou produit desséchant approprié.

4.9 Gel de silice 60, pour colonne de chromatographie, grosseur de particules de 63 µm à 200 µm.

4.10 Gel de silice 60, teneur en eau: w(H O) = 10 % (en masse).

Préparation: chauffer du gel de silice 60 (4.9) pendant au moins 3 h à 450 °C, refroidir dans un dessicateur

(5.13) et conserver avec du perchlorate de magnésium ou un produit desséchant approprié (4.8). Avant

utilisation, chauffer pendant au moins 5 h à 130 °C dans une étuve de séchage (5.14). Ensuite, faire refroidir

dans un dessicateur et ajouter 10 % d’eau (fraction massique) dans un ballon. Agiter énergiquement à la main

pendant 5 min jusqu’à disparition de tous les grumeaux, puis pendant 2 h dans un agitateur (5.3).

Stocker le gel de silice désactivé à l’abri de l’air et l’utiliser dans la semaine.

4.11 Substances de référence, étalons internes

Choisir des substances étalons internes ayant des propriétés physiques et chimiques (telles que leur

comportement à l’extraction et leur temps de rétention) similaires à celles des composés à analyser. Il

convient d’utiliser des HAP deutérés comme étalons internes pour l’évaluation des résultats dans le cadre de

la méthode de CG-SM utilisée dans la présente Norme internationale. Vérifier régulièrement la stabilité des

étalons internes. Le Tableau 1 contient des HAP naturels et des HAP deutérés.
Tableau 1 — HAP naturels et HAP deutérés
HAP — Substances HAP deutérés — Substances
N° CAS
de référence étalons internes
91-20-3 Naphthalène-d
Naphthalène
83-32-9 Acénaphthène-d
Acénaphthène
Acénaphthylène 208-96-8
Fluorène 86-73-7
Anthracène 120-12-7
85-01-8 Phénanthrène-d
Phénanthrène
Fluoranthène 206-44-0
Pyrène 129-00-0
56-55-3 Benz[a]anthracène-d
Benz[a]anthracène
Chrysène 218-01-9
205-99-2 Benzo[e]pyrène-d
Benzo[b]fluoranthène
Benzo[k]fluoranthène
207-08-9
Benzo[a]pyrène 50-32-8
193-39-5 Pérylène-d
Indéno[1,2,3-cd]pyrène
Dibenz[ah]anthracène 53-70-3
Benzo[ghi]pérylène

1) Il est possible de se procurer des solutions certifiées de HAP et des HAP individuels solides de pureté certifiée auprès

d'un nombre limité de fournisseurs, par exemple Institute of Reference Materials and Measurements (IRMM) B-2440 Geel,

Belgique et National Institute of Science and Technology, Office of Standard Ref. Data, Washington D.C. 20234 États-

Unis; il existe d'autres fournisseurs. Cette information est donnée à l'intention des utilisateurs de la présente Norme

internationale et ne saurait constituer un engagement de l'ISO à l'égard des fournisseurs mentionnés ci-dessus.

© ISO 2006 – Tous droits réservés 3
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ISO 18287:2006(F)
4.12 Solutions étalons pour CG-SM

Si l’on utilise une solution mère étalon certifiée du HAP recherché, disponible dans le commerce, on prépare

les solutions d’étalonnage avec différents niveaux de concentration de HAP, en diluant dans des fioles

jaugées (5.8) un volume approprié de solution mère avec du cyclohexane (4.4).
4.12.1 Solution mère monosubstance

Si l’on n’utilise pas de solutions étalons certifiées, préparer des solutions mères de chaque substance en

pesant approximativement 10 mg de chacun des étalons de «HAP naturels» et de «HAP deutérés» (voir

Tableau 1), à 0,1 mg près, dans une fiole jaugée de 50 ml, puis en les dissolvant dans du cyclohexane. Diluer

au trait de jauge avec du cyclohexane (200 µg/ml).

Conserver les solutions mères monosubstances à l’abri de la lumière, à une température d’environ − 15 °C à

− 18 °C.
4.12.2 Solution mère contenant plusieurs HAP

Transférer de 1 ml à 5 ml (volume ajusté pour chacun des composés en fonction de leur occurrence dans le

sol) de chaque solution mère monosubstance (4.12.1) dans une fiole jaugée de 100 ml et compléter au trait

de jauge avec du cyclohexane (de 2 µg/ml à 10 µg/ml).
4.12.3 Solution mère contenant plusieurs étalons internes

Transférer 5 ml de chacune des solutions mères monosubstances (4.12.1) de HAP deutérés dans une fiole

jaugée de 100 ml et compléter au trait de jauge avec du cyclohexane (10 µg/ml).

Conserver les solutions diluées 4.12.2 et 4.12.3 à environ + 4 °C, à l’abri de la lumière et de toute évaporation.

NOTE Les solutions mères restent stables pendant une année environ.
4.12.4 Solutions d’étalonnage

Préparer une gamme appropriée de solutions d’étalonnage (par exemple de 0,20 µg/ml à 5,0 µg/ml) en

transférant de 1 ml à 5 ml de solution mère contenant plusieurs HAP (4.12.2) et 1 ml de la solution mère

contenant plusieurs étalons internes (4.12.3) dans une fiole jaugée de 10 ml et compléter au trait de jauge

avec du cyclohexane. Chaque solution d’étalonnage ainsi préparée contient donc nominalement 1,0 µg/ml de

chaque HAP deutéré.
NOTE Les solutions d’étalonnage restent stables pendant une année environ.
5 Appareillage
Matériel et verrerie de laboratoire courants.

Toute la verrerie doit être soigneusement nettoyée, de préférence au lave-vaisselle, en utilisant un

programme de lavage ordinaire suivi d’un rinçage à l’acétone, puis à l’éther de pétrole. Il est également

autorisé de chauffer les récipients en verre à 450 °C pendant 2 h.

5.1 Récipients d’échantillonnage, en verre brun, de 1 l de capacité nominale, à capuchons vissés avec

joint en polytétrafluoroéthylène (PTFE).
5.2 Diviseur d’échantillons.

5.3 Agitateur, à mouvement horizontal (de 200 mouvements à 300 mouvements par min).

5.4 Concentrateur, Kuderna Danish, ou évaporateur rotatif.
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ISO 18287:2006(F)
5.5 Bain-marie, réglable jusqu’à 100 °C.
5.6 Capsule, en acier inoxydable.

5.7 Fioles coniques, de 100 ml, 500 ml et 1 000 ml de capacité, à capuchons vissés avec joint en

polytétrafluoroéthylène (PTFE).
5.8 Fioles jaugées, d’une capacité nominale de 10 ml, 50 ml et 100 ml.
5.9 Ampoules à décanter, d’une capacité de 250 ml, 500 ml et 1 000 ml.
5.10 Pipettes graduées, de 1 ml, 2 ml, 5 ml et 10 ml et pipettes Pasteur.
5.11 Seringue, de 100 µl, graduée en microlitres.
5.12 Centrifugeuse, avec tubes de 100 ml, à capuchon vissé.
5.13 Dessicateur.
5.14 Étuve de séchage, réglable jusqu'à 150 °C.
5.15 Laine de verre, silylée.

5.16 Colonne de chromatographie, avec réservoir de stockage supérieur, robinet inférieur en PTFE,

de 250 mm de longueur et de 10 mm de diamètre intérieur.

5.17 Appareil de chromatographie en phase gazeuse, équipé d’un système d’injection approprié, d’une

colonne capillaire et d’un détecteur par spectrométrie de masse (CG-SM).

5.18 Colonnes capillaires: il convient d’utiliser une colonne capillaire en silice fondue ayant une longueur

de 30 m et un diamètre intérieur de 0,22 mm, revêtue d’un film de polysiloxane réticulé non polaire ou de

polysiloxane modifié légèrement polaire permettant d’obtenir une séparation satisfaisante. La colonne doit

permettre de séparer du benzo[a]pyrène et du benzo[e]pyrène.
6 Échantillonnage, conservation et prétraitement

Réaliser l’échantillonnage conformément à l’ISO 10381-1 et à l’ISO 10381-8. Les échantillons bruts prélevés

sur le terrain doivent être conservés dans des récipients appropriés (5.1), à l’abri de la lumière, à une

température inférieure à 10 °C (réfrigérateur) et pendant une durée maximale de 7 j. Si nécessaire, procéder

au traitement des échantillons de grande taille conformément à la description donnée dans l’ISO 10381-8

pour ramener la taille de l’échantillon à 1 kg. Prétraiter l’échantillon obtenu conformément à l’ISO 14507:2003

(appliquer le mode opératoire 8.4 pour obtenir un échantillon brut prétraité et le mode opératoire 8.3 pour

obtenir un échantillon soumis à un séchage chimique). S’il est choisi de lyophiliser l’échantillon, appliquer

l’ISO 16720.

Déterminer et enregistrer les pourcentages en masse des fractions inférieures à 2 mm et supérieures à 2 mm.

Déterminer la teneur en matière sèche de l’échantillon brut conformément à l’ISO 11465.

© ISO 2006 – Tous droits réservés 5
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ISO 18287:2006(F)
7 Mode opératoire
7.1 Mode opératoire d’extraction

7.1.1 Méthode A (méthode en deux étapes): Peser de 10 g à 25 g d’échantillon brut et les introduire dans

une fiole conique (5.7) ou dans un tube à centrifuger (5.12) à capuchon vissé, de 100 ml de capacité.

Ajouter 1 ml de la solution mère contenant plusieurs étalons internes (4.12.3) (10 µg de chacun des HAP

deutérés), puis 50 ml d’acétone (4.2) à l’échantillon pour essai, obturer la fiole à l’aide d’un capuchon vissé

muni d’un joint en polytétrafluoroéthylène (PTFE) et procéder à l’extraction en agitant vigoureusement

pendant 1 h sur l’agitateur (5.3). Ajouter 50 ml d’éther de pétrole (4.3), de nouveau agiter, décanter, agiter

avec une nouvelle quantité de 50 ml d’éther de pétrole. Après décantation, recueillir le surnageant. Combiner

les extraits et éliminer l’acétone ainsi que les autres composés polaires en agitant à deux reprises

avec 400 ml d’eau (4.1). Éliminer l’eau.

Sécher la phase organique sur du sulfate de sodium anhydre (4.7), transférer l’extrait sec dans le

concentrateur (5.4) et ajouter 100 µl d’isooctane (4.5) comme solvant de garde.

Concentrer au bain-marie (5.5) à 40 °C jusqu’à environ 10 ml au moyen du concentrateur (5.4) à pression

réduite. La dernière étape de concentration peut se dérouler sous un léger courant d’azote à température

ambiante. La solution alors appropriée à l’analyse de CG-SM contient nominalement 1 µg/ml de chacun des

HAP deutérés.

NOTE Avec les échantillons de sol très pollués, les étapes de purification et de concentration peuvent ne pas être

nécessaires.

Il est également possible d’appliquer d’autres techniques d’extraction telles que l’extraction aux ultrasons,

l’extraction assistée par micro-ondes ou l’extraction par fluide sous pression. Néanmoins, dans ce cas, il est

nécessaire de démontrer que la technique utilisée est comparable à celle décrite dans la présente Norme

Internationale.

7.1.2 Méthode B (méthode en une étape ou en ligne): Peser de 10 g à 25 g d’échantillon brut et les

introduire dans une fiole conique (5.7) de 500 ml. Ajouter 1 ml de la solution mère contenant plusieurs étalons

internes (4.12.3) (10 µg de chacun des HAP deutérés), puis 50 ml d’eau (4.1), 40 g de chlorure de sodium

(4.6), 100 ml d’acétone (4.2) et 50 ml d’éther de pétrole (4.3) à l’échantillon pour essai, obturer la fiole à l’aide

d’un capuchon vissé muni d’un joint en polytétrafluoroéthylène (PTFE) et procéder à l’extraction en agitant

vigoureusement pendant au moins 6 h sur l’agitateur (5.2). Après décantation, transvaser le surnageant

(phase organique) dans une fiole conique et sécher l’extrait sur du sulfate de sodium anhydre (4.7)

pendant 1 h. Une centrifugeuse (5.12) peut être utilisée pour séparer la phase organique. Transférer une

aliquote (par exemple 30 ml) de l’extrait séché dans le concentrateur (5.4), ajouter 100 µl d’isooctane (4.5)

comme solvant de garde.

Concentrer au bain-marie (5.5) à 40 °C jusqu’à environ 2 ml au moyen d’un concentrateur (5.4) à pression

réduite. La dernière étape de concentration peut se dérouler sous un léger courant d’azote à température

ambiante. La solution alors appropriée à l’analyse de CG-SM contient nominalement 1 µg/ml de chacun des

HAP deutérés.

NOTE Avec les échantillons de sol très pollués, les étapes de purification et de concentration peuvent ne pas être

nécessaires.
7.2 Mode opératoire de purification

La purification doit être mise en œuvre s'il existe des composés susceptibles d'interférer avec les HAP

recherchés. En l'absence de substances interférentes ou si leur quantité est négligeable, la purification n'est

pas nécessaire mais seulement facultative. Différents modes opératoires de purification sont utilisables, en

fonction des substances à éliminer. Avant de soumettre des échantillons réels à la purification, le laboratoire

doit s'assurer que les taux de récupération après mise en œuvre de la purification sont d'au moins 80 % pour

tous les HAP concernés (y compris les étalons internes).
6 © ISO 2006 – Tous droits réservés
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ISO 18287:2006(F)

À titre d'exemple, la purification de l’extrait par chromatographie par adsorption sur gel de silice peut être

réalisée de la façon suivante:

Préparer une colonne d’adsorption en plaçant un petit tampon de laine de verre (5.15) au fond du tube de

chromatographie et la garnir avec 4 g de gel de silice (4.10). Ajouter environ 1 cm de sulfate de sodium

anhydre (4.7) jusqu’en haut de la colonne. Éluer la colonne avec 10 ml d’éther de pétrole (4.3) pour la

conditionner. Dès que le solvant d’élution atteint le haut du garnissage de la colonne, transférer l’extrait

concentré (2 ml) à la partie supérieure de la colonne à l’aide d’une pipette Pasteur (5.10). Rincer le

concentrateur (5.4) à deux reprises avec 1 ml de solvant d’élution et le transférer également en haut de la

colonne. Éluer avec approximativement 70 ml d’éther de pétrole (4.3) et recueillir l’éluat dans un tube à fond

conique calibré. Ajouter 100 µl d’isooctane (4.5) et concentrer à la température ambiante sous un léger

courant d’azote jusqu’à réduction du volume à environ 0,5 ml. Ajouter une quantité appropriée de cyclohexane

(4.4) pour obtenir un volume défini (par exemple 2 ml) de solution finale. Cette solution finale appropriée à la

CG-SM contient nominalement 1 µg/ml de chacun des HAP deutérés comme étalon interne.

NOTE 1 Il est également permis d’utiliser des cartouches disponibles dans le commerce.

NOTE 2 La purification de l'extrait en utilisant de l'oxyde d'aluminium est efficace s'il faut éliminer un grand nombre de

composés polaires perturbateurs.
7.3 Analyse de chromatographie en phase gazeuse avec détection par spectrométrie
de masse
7.3.1 Réglage du chromatographe pour l’analyse en phase gazeuse

Régler le chromatographe (5.17) de manière à obtenir une séparation optimale des HAP. Par exemple, régler

au mieux l’appareil à partir des conditions suivantes:

Colonne de séparation: Colonne capillaire, phase stationnaire de polarité nulle à moyenne,

épaisseur du film: 0,25 µm, longueur de 30 m, diamètre intérieur
de 0,25 mm.
Programme de température de l’étuve: 60 °C, 2 min
30 °C/min jusqu’à 120 °C
5 °C/min jusqu’à 300 °C
300 °C, 15 min
Température d’injection: 260 °C
Injection sans division: 1 µl, maintenir la fuite de division fermée 1,8 min
Gaz vecteur: Hélium, de 0,8 ml/min à 1 ml/min
7.3.2 Conditions de spectrométrie de masse
Température de l’interface de SM: 295 °C
Filament sous tension: 6 min

Choix des masses des ions de quantification: les ions de masses suivantes (voir Tableau 2) peuvent être

utilisés lors de l’analyse quantitative en courant d’ions sélectionné.
© ISO 2006 – Tous droits réservés 7
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ISO 18287:2006(F)

Tableau 2 — Masses des ions sélectionnées pour les hydrocarbures aromatiques polycycliques

Masse
Composé
Unité de masse
atomique (uma)
Naphthalène-d (étalon interne) 136
Naphthalène 128 (129)
Acénaphthylène 152 (151)
Acénaphthène-d (étalon in
...

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