Soil quality - Determination of organochlorine pesticides and polychlorinated biphenyls - Gas-chromatographic method with electron capture detection

This International Standard specifies a method for quantitative determination of seven polychlorinated biphenyls
and seventeen organochlorine pesticides in soil.
This International Standard is applicable to all types of soil.
Under the conditions specified in this International Standard, limits of detection of 0,1 μg/kg to 4 μg/kg (expressed
as dry matter) can be achieved.

Qualité du sol - Dosage des pesticides organochlorés et des biphényles polychlorés - Méthode par chromatographie en phase gazeuse avec détection par capture d'électrons

L'ISO 10382:2002 spécifie une méthode de dosage quantitatif de sept biphényls polychlorés et de dix-sept pesticides organochlorés dans le sol.
L'ISO 10382:2002 est applicable à tous les types de sol.
Dans les conditions spécifiées dans l'ISO 10382:2002, les limites de détection de 0,1 g/kg à 4 g/kg (exprimées en matière sèche) peuvent être obtenues.

Kakovost tal - Določevanje organoklornih pesticidov in polikloriranih bifenilov - Plinska kromatografija z detektorjem z zajemom elektronov (ECD)

Ta mednarodni standard določa metodo za kvantitativno določevanje sedmih polikloriranih bifenilov in sedemnajstih organoklornih pesticidov v tleh.
Ta mednarodni standard se uporablja za vse vrste tal.
Pod pogoji, določenimi v tem mednarodnem standardu, je mogoče doseči meje zaznavanja od 0,1 μg/kg do 4 μg/kg (izraženo kot suha snov).

General Information

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

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INTERNATIONAL ISO
STANDARD 10382
First edition
2002-10-15
Soil quality — Determination of
organochlorine pesticides and
polychlorinated biphenyls — Gas-
chromatographic method with electron
capture detection
Qualité du sol — Dosage des pesticides organochlorés et des biphényles
polychlorés — Méthode par chromatographie en phase gazeuse avec
détection par capture d'électrons
Reference number
ISO 10382:2002(E)
ISO 2002
---------------------- Page: 1 ----------------------
ISO 10382:2002(E)
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ii © ISO 2002 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 10382:2002(E)
Contents Page

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

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

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

3 Principle ......................................................................................................................................................... 1

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

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

6 Preparation of standard solutions of PCB and OCP ................................................................................. 7

7 Sampling and preservation of samples ...................................................................................................... 8

7.1 Sampling ........................................................................................................................................................ 8

7.2 Sample preservation and pretreatment ...................................................................................................... 8

8 Procedure....................................................................................................................................................... 8

8.1 Blank............................................................................................................................................................... 8

8.2 Extraction and concentration ...................................................................................................................... 8

8.3 Clean-up of the extract ................................................................................................................................. 9

8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs........... 9

8.5 Gas chromatographic analysis.................................................................................................................. 10

9 Test report.................................................................................................................................................... 14

10 Accuracy ...................................................................................................................................................... 14

Annex A (informative) Table of retention times of polychlorinated biphenyls and organochlorine

pesticides for two different capillary columns......................................................................................... 15

Annex B (informative) Scheme for the preparation of standard solutions including injection standards...... 16

Annex C (informative) Results of an interlaboratory trial carried out in the Netherlands ................................ 17

Annex D (informative) Clean-up to remove elemental sulfur and some other organic sulfur compounds..... 20

Bibliography.............................................................................................................................................................. 22

© ISO 2002 – All rights reserved iii
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ISO 10382:2002(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 3.

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 International Standard may be the subject of

patent rights. ISO shall not be held responsible for identifying any or all such patent rights.

ISO 10382 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical

methods and soil characteristics.
Annexes A, B, C and D of this International Standard are for information only.
iv © ISO 2002 – All rights reserved
---------------------- Page: 4 ----------------------
INTERNATIONAL STANDARD ISO 10382:2002(E)
Soil quality — Determination of organochlorine pesticides and
polychlorinated biphenyls — Gas-chromatographic method with
electron capture detection
1 Scope

This International Standard specifies a method for quantitative determination of seven polychlorinated biphenyls

and seventeen organochlorine pesticides in soil.
This International Standard is applicable to all types of soil.

Under the conditions specified in this International Standard, limits of detection of 0,1 µg/kg to 4 µg/kg (expressed

as dry matter) can be achieved.
2 Normative references

The following normative documents contain provisions which, through reference in this text, constitute provisions of

this International Standard. For dated references, subsequent amendments to, or revisions of, any of these

publications do not apply. However, parties to agreements based on this International Standard are encouraged to

investigate the possibility of applying the most recent editions of the normative documents indicated below. For

undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC

maintain registers of currently valid International Standards.

ISO 10381-1, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes

ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques

ISO 11465:1993, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric

method

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

3 Principle

After pretreatment, the soil test sample is extracted with a hydrocarbon solvent.

The extract is concentrated; polar compounds are removed by passing the concentrated extract through a column

filled with aluminium oxide. The eluate is concentrated.

Elemental sulfur is removed from the concentrated extract, if necessary, by treatment with tetrabutylammonium

sulfite reagent.

The extract is analysed by gas chromatography. The various compounds are separated using a capillary column

with an immobile phase of low polarity. Detection occurs with an electron-capture detector (ECD).

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are assigned and quantified by

comparison of relative retention times and relative peak heights (or peak areas) with respect to injection standards

© ISO 2002 – All rights reserved 1
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ISO 10382:2002(E)

added, with the corresponding variables of an external standard solution. The efficiency of the procedure depends

on the composition of the soil that is investigated. The described procedure does not take account of incomplete

extraction due to the structure and composition of the soil sample.

The limit of detection is dependent on the determinands, the equipment used, the quality of chemicals used for

extraction of the soil sample, and the clean-up of the extract.

NOTE 1 For confirmation of the identity of detected compounds and the concentrations found, further investigation is

necessary. Confirmation can be carried out by repeating the gas chromatographic analysis using a column of different polarity

and/or using gas chromatography/mass spectrometry (GC/MS).

NOTE 2 Other non-volatile organochlorine compounds, e.g. some chlorobenzenes, can also be identified and quantified by

this method.
4 Reagents

All reagents shall be of recognized analytical grade. The purity of the reagents used shall be checked by running a

blank determination as described in 8.1.
4.1 Petroleum ether, boiling range 40 °C to 60 °C.
4.2 Acetone.
4.3 n-Hexane.
4.4 Diethyl ether.

Diethyl ether can contain peroxides which may oxidize some of the determinands. Check for the absence of

peroxides, e.g. by shaking with a freshly prepared 10 % (mass fraction) KI solution.

4.5 Anhydrous sodium sulfate, heated for at least 6 h to 550 °C ± 20 °C, cooled to about 200 °C in a furnace

and then to ambient temperature in a desiccator containing magnesium perchlorate or a suitable alternative.

The anhydrous sodium sulfate shall be kept carefully sealed.

4.6 Aluminium oxide, basic or neutral, areic mass 200 m /g, activity Super I according to Brockmann.

4.7 Aluminium oxide, deactivated with 10 % water.

To 90 g of aluminium oxide (4.6) add 10 g of water. Shake until all lumps have disappeared. Allow the aluminium

oxide to condition before use for approximately 16 h, sealed from the air.
4.8 Silica gel, particle size 60 µm to 200 µm, deactivated with 5 % water.

Heat 95 g of silica gel for at least 24 h in an oven at 150 °C. Then allow to cool in a desiccator and add 5 g of

water. Shake until all lumps have disappeared. Allow the silica gel to condition before use for approx. 16 h, sealed

from the air.

For each new batch of aluminium oxide or silica gel, the elution pattern should be checked against a standard

solution of PCB and OCP. If necessary, the deactivation of the adsorbent should be adjusted (see 8.4).

2 © ISO 2002 – All rights reserved
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ISO 10382:2002(E)
4.9 Standards.
4.9.1 Polychlorinated biphenyls.
PCB- 28: 2,4,4'-trichlorobiphenyl CAS number : 7012-37-5
PCB- 52: 2,2',5,5'-tetrachlorobiphenyl CAS number: 35693-99-3
PCB-101: 2,2',4,5,5'-pentachlorobiphenyl CAS number: 37680-73-2
PCB-118: 2,3',4,4',5-pentachlorobiphenyl CAS number: 31508-00-6
PCB-138: 2,2',3,4,4',5'-hexachlorobiphenyl CAS number: 35065-28-2
PCB-153: 2,2',4,4',5,5'-hexachlorobiphenyl CAS number: 35065-27-1
PCB-180: 2,2',3,4,4',5,5'-heptachlorobiphenyl CAS number: 35065-29-3

NOTE The numbers 28, 52, etc. correspond with the sequential numbers of chlorobiphenyls according to the IUPAC rules

for the nomenclature of organic compounds.
4.9.2 Organochlorine pesticides.
Hexachlorobenzene (HCB) CAS number: 118-74-1
α-Hexachlorocyclohexane (α-HCH) CAS number: 319-84-6
β-Hexachlorocyclohexane (β-HCH) CAS number: 319-85-7
γ-Hexachlorocyclohexane (γ-HCH) CAS number: 58-89-9
Aldrin CAS number: 309-00-2
Dieldrin CAS number: 60-57-1
Endrin CAS number: 72-20-8
Heptachlor CAS number: 76-44-8
Heptachloro epoxide (exo-, cis- or a-isomer) CAS number: 28044-83-9
Heptachloro epoxide (endo-, trans- or b-isomer) CAS number: 1024-57-3
α-Endosulfan CAS number: 959-98-7
p,p'-DDE CAS number: 72-55-9
o,p'-DDD CAS number: 53-19-0
o,p'-DDT CAS number: 784-02-6
p,p'-DDD CAS number: 72-54-8
o,p'-DDE CAS number: 3424-82-6
p,p'-DDT CAS number: 50-29-3
1) Registration used by the Chemical Abstracts Service.
© ISO 2002 – All rights reserved 3
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ISO 10382:2002(E)
4.9.3 Injection standards.
PCB-155: 2,2',4,4',6,6'-hexachlorobiphenyl CAS number: 33979-03-2

Select a second injection standard, not interfering with the analytes, from the following substances:

PCB-143: 2,2',3,4,5,6'-hexachlorobiphenyl CAS number: 68194-15-0
PCB-207: 2,2',3,3',4,4',5,6,6'-nonachlorobiphenyl CAS number: 52663-79-3
Mirex CAS number: 2385-85-5
4.10 Tetrabutylammonium reagent (TBA sulfite reagent).

Saturate a solution of tetrabutylammonium hydrogen sulfate in a mixture of equal volumes of water and 2-propanol,

c[(C H ) NHSO ] = 0,1 mol/l, with sodium sulfite.
4 9 4 4
NOTE 25 g of sodium sulfite is normally sufficient for 100 ml of solution.
4.11 n-Heptane.
5 Apparatus
5.1 Customary laboratory glassware.

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

procedure, followed by rinsing with acetone and a subsequent rinsing with petroleum ether or hexane.

5.2 Glass sample bottles, of nominal capacity 1 l, with screw top and polytetrafluoroethene seal (PTFE).

5.3 Shaking device, with horizontal movement (200 to 300 strokes per minute).
5.4 Water bath, capable of being heated to 100 °C.
5.5 Shaking funnels, with a capacity of 2 l.
5.6 Conical flasks, with a capacity of 500 ml.
5.7 Evaporator, Kuderna Danish (see Figure 1).

Other evaporators, e.g. a rotary evaporator, may be used if found to be equally suitable.

5.8 Quartz wool or silanized glass wool, rinsed with petroleum ether or hexane.

WARNING Working with quartz wool imposes a risk to health through the release of fine quartz particles.

Prevent inhalation of these by using a fume cupboard and wearing a dust mask.

5.9 Boiling chips, of glass or porcelain beads, rinsed with petroleum ether or hexane.

5.10 Calibrated test tubes, with a capacity of 15 ml and ground glass stoppers.
5.11 Chromatography tubes (see Figure 2).

5.12 Gas chromatograph, equipped with a non-discriminating injection system, capillary column and

electron-capture detector (ECD) based on Ni.
4 © ISO 2002 – All rights reserved
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ISO 10382:2002(E)

NOTE 1 Working with an encapsulated radioactive source such as that present in an ECD requires a licence in accordance

with the appropriate national regulations.

NOTE 2 Gas chromatographs equipped with two detectors and with facilities for connecting two capillary columns to the

same injection system are very well suited for this analysis; with such apparatus the confirmatory analysis can be performed

simultaneously.

5.13 Capillary column, of fused silica, with a length of 50 m and an internal diameter of about 0,25 mm coated

with a film of cross-linked polysiloxane.

Other columns can also be used, although in some cases unsatisfactory separation is obtained. A column coated

with a moderate polar phase, e.g. CP-Sil 19, OV 1701 etc., shall be used to confirm the result obtained.

NOTE The retention times for PCB and OCP on capillary columns coated with CP-Sil 8 and CP-Sil 19 are given in

annex A.
© ISO 2002 – All rights reserved 5
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ISO 10382:2002(E)
Key
1 Graduated test tube, capacity 15 ml ISO 383 29/32
2 Distillation flasks ISO 383 14/23
3 Receiver flask
4 Reflux condenser
All joints shall be in accordance with ISO 383.
Figure 1 — Example of evaporator (Kuderna Danish)
6 © ISO 2002 – All rights reserved
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ISO 10382:2002(E)
Dimensions in millimetres
Figure 2 — Example of chromatography tube
6 Preparation of standard solutions of PCB and OCP

Prepare individual concentrated primary standard solutions of mass concentration about 0,4 mg/ml in n-heptane by

weighing approx. 10 mg of each of the standards (4.9) to the nearest 0,1 mg and dissolving them in 25 ml of

n-heptane.

Check the purity of the primary standard solutions by means of a gas chromatogram of the solutions concerned.

Preferably a relatively non-specific detector, such as a flame ionization detector (FID) or a heat conductivity

detector (TCD), shall be used.

Combine small quantities (2 ml to 10 ml) of the individual primary standard solutions into a mixed standard solution

of PCB and OCP including the injection standards (see annex B). Using this solution, prepare the working standard

solutions in accordance with annex B by dilution.

Components present in mixed standard solutions should be completely separated by the gas chromatographic

columns used.

Store the primary and diluted standard solutions in a dark place at a temperature of less than 4 °C.

NOTE The solutions are stable for at least one year, provided that evaporation of solvent is negligible.

© ISO 2002 – All rights reserved 7
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ISO 10382:2002(E)
7 Sampling and preservation of samples
7.1 Sampling

Obtain representative soil samples in accordance with ISO 10381-1 using sampling apparatus in accordance with

ISO 10381-2.
7.2 Sample preservation and pretreatment

Samples shall be pretreated as soon as possible. Store the samples in a dark place at a temperature below 10 °C,

if possible in a refrigerator. For OCP testing, the storage times for field-moist soil samples shall not be longer than

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

samples if there is insufficient homogeneity for taking a representative test sample. Grinding should take place

cryogenically after chemical drying with anhydrous sodium sulfate (4.5) in accordance with ISO 14507.

It is permissible for dried samples, if kept sealed, to be stored for a longer period at room temperature

(approx. one month).
8 Procedure
8.1 Blank

Before treating the samples, perform a blank determination as described in 8.2 to 8.5 using the same amount of

reagents that are used for the extraction, clean-up and analysis of a sample. For cryogenically ground samples,

perform the blank using 8 g of sodium sulfate (4.5) and 2 g of talcum, to which all the necessary reagents are

added.

If the blank value is unreasonably high, i.e. more than 10 % of the lowest value of interest, find the cause through a

step-by-step examination of the whole procedure.

For measurements at the limit of determination, even reagents suitable for residue analyses may not fulfil this

criterion. In that case, sufficient blank determinations shall be incorporated in each series of samples.

Values obtained from analysis of blanks should be smaller than the detection limit for the analytes concerned.

8.2 Extraction and concentration
8.2.1 Cryogenically ground samples

Take 20 g of cryogenically ground sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test

sample and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether

(4.1) and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1).

Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml

of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7).

Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract.

8.2.2 Field-moist samples

Take 20 g of field-moist sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test sample

and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether (4.1)

and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1).

If the water content of the sample is greater than 25 %, increase the amount of acetone. The ratio acetone:water

should be at least 9:1. The ratio acetone:petroleum ether shall be kept constant at 1:2.

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ISO 10382:2002(E)

Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml

of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7).

Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract.

Other extraction techniques, such as ultrasonic extraction, microwave or pressurized extraction, may be suitable.

However, if using other extraction techniques, the comparability of such techniques to the method described in this

International Standard shall be proven.
8.2.3 Concentration

Add a boiling chip (5.9) to the extract and concentrate the extract to approx. 10 ml. Transfer the concentrated

extract to a calibrated test tube (5.10) and further concentrate to 1 ml using a gentle stream of nitrogen at room

temperature.

NOTE Too high temperatures and a too high flow of nitrogen may result in loss of the more volatile PCBs and OCPs.

8.3 Clean-up of the extract

Prepare an adsorption column by placing a small plug of quartz wool (5.8) in the chromatography tube (5.11) and

packing it dry with 2,0 g ± 0,1 g of aluminium oxide (4.7).

Before use, the elution pattern of each series of aluminium oxide columns and the necessary elution volume should

be verified using a standard solution of PCB and OCP.

With a pipette, transfer the extract to the dry packed adsorption column; rinse the test tube twice with 1 ml of

petroleum ether and transfer the rinsings to the column with the same pipette as soon as the liquid level reaches

the upper side of the column packing. Elute with approx. 20 ml of petroleum ether.

Divide the eluate into two equal parts and store one part for an eventual analysis of the diluted extract. Concentrate

the other part of the eluate with a gentle stream of nitrogen, without additional heating, to a final volume of about

1 ml.

NOTE 1 Commercially available disposable columns may be used as an alternative if found equally suitable.

The presence of sulfur in the extract of PCBs and non-polar OCPs can cause interferences in the chromatogram. If

elemental sulfur is expected to be present (this occurs amongst others in anaerobic soils), remove it as follows.

Add 2 ml of TBA sulfite reagent (4.10) to 1 ml of concentrated extract and shake for 1 min. Add 10 ml of water and

shake again for 1 min. Separate the organic phase from the water with a Pasteur pipette and add a few crystals of

anhydrous sodium sulfate to remove the remaining traces of water.

NOTE 2 Other methods to remove sulfur, e.g. with pyrogenic copper (see annex D), may be used as an alternative if found

equally suitable.

If no further clean-up is required, to the final extract add 10 µl of the injection standard solution containing

100 times as much of the injection standards (4.9.3) per millilitre as is present per millilitre of working standard

solution (see annex B).

8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs

In the case of very complex samples, insufficient separation may be obtained with gas chromatographic analysis.

In this case an additional chromatographic separation, using the whole concentrated extract, may overcome this

problem.

The whole concentrated extract is separated by column chromatography on silica gel (4.8) into two fractions. The

first fraction contains the PCBs and non-polar OCPs (HCB, p,p'-DDT, heptachlor, aldrin and p,p'-DDT). The second

fraction contains the rather more polar OCPs (α-HCH, β-HCH, γ-HCH, dieldrin, endrin, o,p'-DDD and α-

endosulfan). Check the elution pattern with the aid of a standard solution of PCB and OCP. If necessary, adjust the

© ISO 2002 – All rights reserved 9
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ISO 10382:2002(E)

activity of the silica gel by adding more water if the compounds referred to above from the first fraction appear in

the second fraction, or if the first fraction does not contain the compounds mentioned above. Add less water to the

silica gel if the compounds mentioned above from the second fraction appear in the first fraction.

Separate the extract as follows. Place a small plug of quartz wool in the chromatography tube. Pack it dry with

(1,5 ± 0,1) g of silica gel (4.8) and top it with 1 cm of sodium sulfate (4.5). With a pipette, transfer the concentrated

extract to the dry packed column. Rinse the test tube twice with 1 ml of hexane. Transfer the rinsings with the same

pipette to the column as soon as the liquid level just reaches the upper edge of the column packing. Elute by

adding to the column in succession 25 ml of hexane (fraction 1) and 25 ml of a mixture of hexane and diethyl ether

(volume ratio 75:25) (fraction 2).

NOTE Commercially available disposable columns may be used as an alternative if found equally suitable.

Divide each of the two eluates into two equal parts, and for each eluate store one part for a possible repetition of

the analysis in a dilution of the extract. Evaporate the other two separate fractions in test tubes to 1 ml volume.

Add 10 µl of the injection standard solution to each of the two fractions, containing 100 times as much of the

injection standards (4.9.3) per millilitre as is present per millilitre of working standard solution (see annex B).

8.5 Gas chromatographic analysis
8.5.1 Optimizing the gas chromatograph

Optimize the gas chromatograph (5.12) in such a way that optimum separation is achieved. The plate number and

capacity factor for component PCB-138 shall be greater than 6 × 10 and 6 respectively at 220 °C. The

chromatographic peaks of PCB-28 and PCB-31 shall be resolved sufficiently (resolution at least 0,5) for integrating

the PCB-28 peak.

The following settings may be used to start the optimization of the gas chromatograph:

Injection temperature (applicable only with splitless injection): 210 °C
Oven temperature: 80 °C for 4 min; 4 °C/min up to 300 °C
Detector temperature: 300 °C
Carrier gas: Helium
Gas flow: 20 cm/s to 30 cm/s
8.5.2 Calibration
8.5.2.1 General

Two types of calibration are distinguished: the initial calibration (8.5.2.2) and the daily calibration (validity check of

the initial calibration); the latter is called recalibration (8.5.2.3).

The initial calibration serves to establish the linear working range of the calibration curve. This calibration is

performed when the method is used for the first time and after maintenance and/or repair of the equipment.

The recalibration checks the validity of the linear working range of the initial calibration curve and is performed

before each series of samples.

NOTE Non-linear calibration methods are allowed, provided that they are validated.

10 © ISO 2002 – All rights reserved
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ISO 10382:2002(E)
8.5.2.2 Initial calibration

Take a gas chromatogram of a series of at least five standard solutions with equidistant concentrations as given in

annex B, including the solvent blank (see annex B). Identify the peaks by consulting annex A and if necessary the

gas chromatograms of the individual compounds. Prepare a calibration graph for each compound.

In general, the use of peak heights instead of peak areas is recommended.

Calculate by linear regression a straight line for the whole range of the calibration solutions. If the origin falls within

the 95 % confidence limits of the calculated line, recalculate by linear regression the line through the origin. This

line is called the initial calibration line.
If the origin does not fall within the 95 % confidence limits, omit the h
...

SLOVENSKI STANDARD
SIST ISO 10382:2019
01-oktober-2019

Kakovost tal - Določevanje organoklornih pesticidov in polikloriranih bifenilov -

Plinska kromatografija z detektorjem z zajemom elektronov (ECD)

Soil quality - Determination of organochlorine pesticides and polychlorinated biphenyls -

Gas-chromatographic method with electron capture detection

Qualité du sol - Dosage des pesticides organochlorés et des biphényles polychlorés -

Méthode par chromatographie en phase gazeuse avec détection par capture d'électrons

Ta slovenski standard je istoveten z: ISO 10382:2002
ICS:
13.080.10 Kemijske značilnosti tal Chemical characteristics of
soils
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
SIST ISO 10382:2019 en

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

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SIST ISO 10382:2019
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SIST ISO 10382:2019
INTERNATIONAL ISO
STANDARD 10382
First edition
2002-10-15
Soil quality — Determination of
organochlorine pesticides and
polychlorinated biphenyls — Gas-
chromatographic method with electron
capture detection
Qualité du sol — Dosage des pesticides organochlorés et des biphényles
polychlorés — Méthode par chromatographie en phase gazeuse avec
détection par capture d'électrons
Reference number
ISO 10382:2002(E)
ISO 2002
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SIST ISO 10382:2019
ISO 10382:2002(E)
PDF disclaimer

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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

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© ISO 2002

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
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Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.ch
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Printed in Switzerland
ii © ISO 2002 – All rights reserved
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Contents Page

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

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

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

3 Principle ......................................................................................................................................................... 1

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

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

6 Preparation of standard solutions of PCB and OCP ................................................................................. 7

7 Sampling and preservation of samples ...................................................................................................... 8

7.1 Sampling ........................................................................................................................................................ 8

7.2 Sample preservation and pretreatment ...................................................................................................... 8

8 Procedure....................................................................................................................................................... 8

8.1 Blank............................................................................................................................................................... 8

8.2 Extraction and concentration ...................................................................................................................... 8

8.3 Clean-up of the extract ................................................................................................................................. 9

8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs........... 9

8.5 Gas chromatographic analysis.................................................................................................................. 10

9 Test report.................................................................................................................................................... 14

10 Accuracy ...................................................................................................................................................... 14

Annex A (informative) Table of retention times of polychlorinated biphenyls and organochlorine

pesticides for two different capillary columns......................................................................................... 15

Annex B (informative) Scheme for the preparation of standard solutions including injection standards...... 16

Annex C (informative) Results of an interlaboratory trial carried out in the Netherlands ................................ 17

Annex D (informative) Clean-up to remove elemental sulfur and some other organic sulfur compounds..... 20

Bibliography.............................................................................................................................................................. 22

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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 3.

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 International Standard may be the subject of

patent rights. ISO shall not be held responsible for identifying any or all such patent rights.

ISO 10382 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical

methods and soil characteristics.
Annexes A, B, C and D of this International Standard are for information only.
iv © ISO 2002 – All rights reserved
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SIST ISO 10382:2019
INTERNATIONAL STANDARD ISO 10382:2002(E)
Soil quality — Determination of organochlorine pesticides and
polychlorinated biphenyls — Gas-chromatographic method with
electron capture detection
1 Scope

This International Standard specifies a method for quantitative determination of seven polychlorinated biphenyls

and seventeen organochlorine pesticides in soil.
This International Standard is applicable to all types of soil.

Under the conditions specified in this International Standard, limits of detection of 0,1 µg/kg to 4 µg/kg (expressed

as dry matter) can be achieved.
2 Normative references

The following normative documents contain provisions which, through reference in this text, constitute provisions of

this International Standard. For dated references, subsequent amendments to, or revisions of, any of these

publications do not apply. However, parties to agreements based on this International Standard are encouraged to

investigate the possibility of applying the most recent editions of the normative documents indicated below. For

undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC

maintain registers of currently valid International Standards.

ISO 10381-1, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes

ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques

ISO 11465:1993, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric

method

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

3 Principle

After pretreatment, the soil test sample is extracted with a hydrocarbon solvent.

The extract is concentrated; polar compounds are removed by passing the concentrated extract through a column

filled with aluminium oxide. The eluate is concentrated.

Elemental sulfur is removed from the concentrated extract, if necessary, by treatment with tetrabutylammonium

sulfite reagent.

The extract is analysed by gas chromatography. The various compounds are separated using a capillary column

with an immobile phase of low polarity. Detection occurs with an electron-capture detector (ECD).

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are assigned and quantified by

comparison of relative retention times and relative peak heights (or peak areas) with respect to injection standards

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added, with the corresponding variables of an external standard solution. The efficiency of the procedure depends

on the composition of the soil that is investigated. The described procedure does not take account of incomplete

extraction due to the structure and composition of the soil sample.

The limit of detection is dependent on the determinands, the equipment used, the quality of chemicals used for

extraction of the soil sample, and the clean-up of the extract.

NOTE 1 For confirmation of the identity of detected compounds and the concentrations found, further investigation is

necessary. Confirmation can be carried out by repeating the gas chromatographic analysis using a column of different polarity

and/or using gas chromatography/mass spectrometry (GC/MS).

NOTE 2 Other non-volatile organochlorine compounds, e.g. some chlorobenzenes, can also be identified and quantified by

this method.
4 Reagents

All reagents shall be of recognized analytical grade. The purity of the reagents used shall be checked by running a

blank determination as described in 8.1.
4.1 Petroleum ether, boiling range 40 °C to 60 °C.
4.2 Acetone.
4.3 n-Hexane.
4.4 Diethyl ether.

Diethyl ether can contain peroxides which may oxidize some of the determinands. Check for the absence of

peroxides, e.g. by shaking with a freshly prepared 10 % (mass fraction) KI solution.

4.5 Anhydrous sodium sulfate, heated for at least 6 h to 550 °C ± 20 °C, cooled to about 200 °C in a furnace

and then to ambient temperature in a desiccator containing magnesium perchlorate or a suitable alternative.

The anhydrous sodium sulfate shall be kept carefully sealed.

4.6 Aluminium oxide, basic or neutral, areic mass 200 m /g, activity Super I according to Brockmann.

4.7 Aluminium oxide, deactivated with 10 % water.

To 90 g of aluminium oxide (4.6) add 10 g of water. Shake until all lumps have disappeared. Allow the aluminium

oxide to condition before use for approximately 16 h, sealed from the air.
4.8 Silica gel, particle size 60 µm to 200 µm, deactivated with 5 % water.

Heat 95 g of silica gel for at least 24 h in an oven at 150 °C. Then allow to cool in a desiccator and add 5 g of

water. Shake until all lumps have disappeared. Allow the silica gel to condition before use for approx. 16 h, sealed

from the air.

For each new batch of aluminium oxide or silica gel, the elution pattern should be checked against a standard

solution of PCB and OCP. If necessary, the deactivation of the adsorbent should be adjusted (see 8.4).

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4.9 Standards.
4.9.1 Polychlorinated biphenyls.
PCB- 28: 2,4,4'-trichlorobiphenyl CAS number : 7012-37-5
PCB- 52: 2,2',5,5'-tetrachlorobiphenyl CAS number: 35693-99-3
PCB-101: 2,2',4,5,5'-pentachlorobiphenyl CAS number: 37680-73-2
PCB-118: 2,3',4,4',5-pentachlorobiphenyl CAS number: 31508-00-6
PCB-138: 2,2',3,4,4',5'-hexachlorobiphenyl CAS number: 35065-28-2
PCB-153: 2,2',4,4',5,5'-hexachlorobiphenyl CAS number: 35065-27-1
PCB-180: 2,2',3,4,4',5,5'-heptachlorobiphenyl CAS number: 35065-29-3

NOTE The numbers 28, 52, etc. correspond with the sequential numbers of chlorobiphenyls according to the IUPAC rules

for the nomenclature of organic compounds.
4.9.2 Organochlorine pesticides.
Hexachlorobenzene (HCB) CAS number: 118-74-1
α-Hexachlorocyclohexane (α-HCH) CAS number: 319-84-6
β-Hexachlorocyclohexane (β-HCH) CAS number: 319-85-7
γ-Hexachlorocyclohexane (γ-HCH) CAS number: 58-89-9
Aldrin CAS number: 309-00-2
Dieldrin CAS number: 60-57-1
Endrin CAS number: 72-20-8
Heptachlor CAS number: 76-44-8
Heptachloro epoxide (exo-, cis- or a-isomer) CAS number: 28044-83-9
Heptachloro epoxide (endo-, trans- or b-isomer) CAS number: 1024-57-3
α-Endosulfan CAS number: 959-98-7
p,p'-DDE CAS number: 72-55-9
o,p'-DDD CAS number: 53-19-0
o,p'-DDT CAS number: 784-02-6
p,p'-DDD CAS number: 72-54-8
o,p'-DDE CAS number: 3424-82-6
p,p'-DDT CAS number: 50-29-3
1) Registration used by the Chemical Abstracts Service.
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4.9.3 Injection standards.
PCB-155: 2,2',4,4',6,6'-hexachlorobiphenyl CAS number: 33979-03-2

Select a second injection standard, not interfering with the analytes, from the following substances:

PCB-143: 2,2',3,4,5,6'-hexachlorobiphenyl CAS number: 68194-15-0
PCB-207: 2,2',3,3',4,4',5,6,6'-nonachlorobiphenyl CAS number: 52663-79-3
Mirex CAS number: 2385-85-5
4.10 Tetrabutylammonium reagent (TBA sulfite reagent).

Saturate a solution of tetrabutylammonium hydrogen sulfate in a mixture of equal volumes of water and 2-propanol,

c[(C H ) NHSO ] = 0,1 mol/l, with sodium sulfite.
4 9 4 4
NOTE 25 g of sodium sulfite is normally sufficient for 100 ml of solution.
4.11 n-Heptane.
5 Apparatus
5.1 Customary laboratory glassware.

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

procedure, followed by rinsing with acetone and a subsequent rinsing with petroleum ether or hexane.

5.2 Glass sample bottles, of nominal capacity 1 l, with screw top and polytetrafluoroethene seal (PTFE).

5.3 Shaking device, with horizontal movement (200 to 300 strokes per minute).
5.4 Water bath, capable of being heated to 100 °C.
5.5 Shaking funnels, with a capacity of 2 l.
5.6 Conical flasks, with a capacity of 500 ml.
5.7 Evaporator, Kuderna Danish (see Figure 1).

Other evaporators, e.g. a rotary evaporator, may be used if found to be equally suitable.

5.8 Quartz wool or silanized glass wool, rinsed with petroleum ether or hexane.

WARNING Working with quartz wool imposes a risk to health through the release of fine quartz particles.

Prevent inhalation of these by using a fume cupboard and wearing a dust mask.

5.9 Boiling chips, of glass or porcelain beads, rinsed with petroleum ether or hexane.

5.10 Calibrated test tubes, with a capacity of 15 ml and ground glass stoppers.
5.11 Chromatography tubes (see Figure 2).

5.12 Gas chromatograph, equipped with a non-discriminating injection system, capillary column and

electron-capture detector (ECD) based on Ni.
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NOTE 1 Working with an encapsulated radioactive source such as that present in an ECD requires a licence in accordance

with the appropriate national regulations.

NOTE 2 Gas chromatographs equipped with two detectors and with facilities for connecting two capillary columns to the

same injection system are very well suited for this analysis; with such apparatus the confirmatory analysis can be performed

simultaneously.

5.13 Capillary column, of fused silica, with a length of 50 m and an internal diameter of about 0,25 mm coated

with a film of cross-linked polysiloxane.

Other columns can also be used, although in some cases unsatisfactory separation is obtained. A column coated

with a moderate polar phase, e.g. CP-Sil 19, OV 1701 etc., shall be used to confirm the result obtained.

NOTE The retention times for PCB and OCP on capillary columns coated with CP-Sil 8 and CP-Sil 19 are given in

annex A.
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Key
1 Graduated test tube, capacity 15 ml ISO 383 29/32
2 Distillation flasks ISO 383 14/23
3 Receiver flask
4 Reflux condenser
All joints shall be in accordance with ISO 383.
Figure 1 — Example of evaporator (Kuderna Danish)
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Dimensions in millimetres
Figure 2 — Example of chromatography tube
6 Preparation of standard solutions of PCB and OCP

Prepare individual concentrated primary standard solutions of mass concentration about 0,4 mg/ml in n-heptane by

weighing approx. 10 mg of each of the standards (4.9) to the nearest 0,1 mg and dissolving them in 25 ml of

n-heptane.

Check the purity of the primary standard solutions by means of a gas chromatogram of the solutions concerned.

Preferably a relatively non-specific detector, such as a flame ionization detector (FID) or a heat conductivity

detector (TCD), shall be used.

Combine small quantities (2 ml to 10 ml) of the individual primary standard solutions into a mixed standard solution

of PCB and OCP including the injection standards (see annex B). Using this solution, prepare the working standard

solutions in accordance with annex B by dilution.

Components present in mixed standard solutions should be completely separated by the gas chromatographic

columns used.

Store the primary and diluted standard solutions in a dark place at a temperature of less than 4 °C.

NOTE The solutions are stable for at least one year, provided that evaporation of solvent is negligible.

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7 Sampling and preservation of samples
7.1 Sampling

Obtain representative soil samples in accordance with ISO 10381-1 using sampling apparatus in accordance with

ISO 10381-2.
7.2 Sample preservation and pretreatment

Samples shall be pretreated as soon as possible. Store the samples in a dark place at a temperature below 10 °C,

if possible in a refrigerator. For OCP testing, the storage times for field-moist soil samples shall not be longer than

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

samples if there is insufficient homogeneity for taking a representative test sample. Grinding should take place

cryogenically after chemical drying with anhydrous sodium sulfate (4.5) in accordance with ISO 14507.

It is permissible for dried samples, if kept sealed, to be stored for a longer period at room temperature

(approx. one month).
8 Procedure
8.1 Blank

Before treating the samples, perform a blank determination as described in 8.2 to 8.5 using the same amount of

reagents that are used for the extraction, clean-up and analysis of a sample. For cryogenically ground samples,

perform the blank using 8 g of sodium sulfate (4.5) and 2 g of talcum, to which all the necessary reagents are

added.

If the blank value is unreasonably high, i.e. more than 10 % of the lowest value of interest, find the cause through a

step-by-step examination of the whole procedure.

For measurements at the limit of determination, even reagents suitable for residue analyses may not fulfil this

criterion. In that case, sufficient blank determinations shall be incorporated in each series of samples.

Values obtained from analysis of blanks should be smaller than the detection limit for the analytes concerned.

8.2 Extraction and concentration
8.2.1 Cryogenically ground samples

Take 20 g of cryogenically ground sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test

sample and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether

(4.1) and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1).

Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml

of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7).

Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract.

8.2.2 Field-moist samples

Take 20 g of field-moist sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test sample

and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether (4.1)

and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1).

If the water content of the sample is greater than 25 %, increase the amount of acetone. The ratio acetone:water

should be at least 9:1. The ratio acetone:petroleum ether shall be kept constant at 1:2.

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Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml

of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7).

Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract.

Other extraction techniques, such as ultrasonic extraction, microwave or pressurized extraction, may be suitable.

However, if using other extraction techniques, the comparability of such techniques to the method described in this

International Standard shall be proven.
8.2.3 Concentration

Add a boiling chip (5.9) to the extract and concentrate the extract to approx. 10 ml. Transfer the concentrated

extract to a calibrated test tube (5.10) and further concentrate to 1 ml using a gentle stream of nitrogen at room

temperature.

NOTE Too high temperatures and a too high flow of nitrogen may result in loss of the more volatile PCBs and OCPs.

8.3 Clean-up of the extract

Prepare an adsorption column by placing a small plug of quartz wool (5.8) in the chromatography tube (5.11) and

packing it dry with 2,0 g ± 0,1 g of aluminium oxide (4.7).

Before use, the elution pattern of each series of aluminium oxide columns and the necessary elution volume should

be verified using a standard solution of PCB and OCP.

With a pipette, transfer the extract to the dry packed adsorption column; rinse the test tube twice with 1 ml of

petroleum ether and transfer the rinsings to the column with the same pipette as soon as the liquid level reaches

the upper side of the column packing. Elute with approx. 20 ml of petroleum ether.

Divide the eluate into two equal parts and store one part for an eventual analysis of the diluted extract. Concentrate

the other part of the eluate with a gentle stream of nitrogen, without additional heating, to a final volume of about

1 ml.

NOTE 1 Commercially available disposable columns may be used as an alternative if found equally suitable.

The presence of sulfur in the extract of PCBs and non-polar OCPs can cause interferences in the chromatogram. If

elemental sulfur is expected to be present (this occurs amongst others in anaerobic soils), remove it as follows.

Add 2 ml of TBA sulfite reagent (4.10) to 1 ml of concentrated extract and shake for 1 min. Add 10 ml of water and

shake again for 1 min. Separate the organic phase from the water with a Pasteur pipette and add a few crystals of

anhydrous sodium sulfate to remove the remaining traces of water.

NOTE 2 Other methods to remove sulfur, e.g. with pyrogenic copper (see annex D), may be used as an alternative if found

equally suitable.

If no further clean-up is required, to the final extract add 10 µl of the injection standard solution containing

100 times as much of the injection standards (4.9.3) per millilitre as is present per millilitre of working standard

solution (see annex B).

8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs

In the case of very complex samples, insufficient separation may be obtained with gas chromatographic analysis.

In this case an additional chromatographic separation, using the whole concentrated extract, may overcome this

problem.

The whole concentrated extract is separated by column chromatography on silica gel (4.8) into two fractions. The

first fraction contains the PCBs and non-polar OCPs (HCB, p,p'-DDT, heptachlor, aldrin and p,p'-DDT). The second

fraction contains the rather more polar OCPs (α-HCH, β-HCH, γ-HCH, dieldrin, endrin, o,p'-DDD and α-

endosulfan). Check the elution pattern with the aid of a standard solution of PCB and OCP. If necessary, adjust the

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activity of the silica gel by adding more water if the compounds referred to above from the first fraction appear in

the second fraction, or if the first fraction does not contain the compounds mentioned above. Add less water to the

silica gel if the compounds mentioned above from the second fraction appear in the first fraction.

Separate the extract as follows. Place a small plug of quartz wool in the chromatography tube. Pack it dry with

(1,5 ± 0,1) g of silica gel (4.8) and top it with 1 cm of sodium sulfate (4.5). With a pipette, transfer the concentrated

extract to the dry packed column. Rinse the test tube twice with 1 ml of hexane. Transfer the rinsings with the same

pipette to the column as soon as the liquid level just reaches the upper edge of the column packing. Elute by

adding to the column in succession 25 ml of hexane (fraction 1) and 25 ml of a mixture of hexane and diethyl ether

(volume ratio 75:25) (fraction 2).

NOTE Commercially available disposable columns may be used as an alternative if found equally suitable.

Divide each of the two eluates into two equal parts, and for each eluate store one part for a possible repetition of

the analysis in a dilution of the extract. Evaporate the other two separate fractions in test tubes to 1 ml volume.

Add 10 µl of the injection standard solution to each of the two fractions, containing 100 times as much of the

injection standards (4.9.3) per millilitre as is present per millilitre of working standard solution (see annex B).

8.5 Gas chromatographic analysis
8.5.1 Optimizing the gas chromatograph

Optimize the gas chromatograph (5.12) in such a way that optimum separation is achieved. The plate number and

capacity factor for component PCB-138 shall be greater than 6 × 10 and 6 respectively at 220 °C. The

chromatographic peaks of PCB-28 and PCB-31 shall be resolved sufficiently (resolution at least 0,5) for integrating

the PCB-28 peak.

The following settings may be used to start the optimization of the gas chromatograph:

Injection temperature (applicable only with splitless injection): 210 °C
Oven temperature: 80 °C for 4 min; 4 °C/min up to 300 °C
Detector temperature: 300 °C
Carrier gas: Helium
Gas flow: 20 cm/s to 30 cm/s
8.5.2 Calibration
8.5.2.1 General

Two types of calibration are distinguished: the initial calibration (8.5.2.2) and the daily calibration (validity check of

the initial calibration); the latter is called recalibration (8.5.2.3).
The initial calibration serves to establish the linear working range of the cal
...

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Qualité du sol - Dosage des pesticides organochlorés et des biphényles polychlorés - Méthode par chromatographie en phase gazeuse avec détection par capture d'électronsSoil quality - Determination of organochlorine pesticides and polychlorinated biphenyls - Gas-chromatographic method with electron capture detection71.040.50Fizikalnokemijske analitske metodePhysicochemical methods of analysis13.080.10Chemical characteristics of soilsICS:Ta slovenski standard je istoveten z:ISO 10382:2002oSIST ISO 10382:2019en01-maj-2019oSIST ISO 10382:2019SLOVENSKI

STANDARD
oSIST ISO 10382:2019
Reference numberISO 10382:2002(E)© ISO 2002

INTERNATIONAL STANDARD ISO10382First edition2002-10-15Soil quality — Determination of organochlorine pesticides and polychlorinated biphenyls — Gas-chromatographic method with electron capture detection Qualité du sol — Dosage des pesticides organochlorés et des biphényles polychlorés — Méthode par chromatographie en phase gazeuse avec détection par capture d'électrons

oSIST ISO 10382:2019

ISO 10382:2002(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 2002 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.ch Web
www.iso.ch Printed in Switzerland
ii © ISO 2002 – All rights reserved
oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved iii Contents Page Foreword....................................................................................................................................................................iv 1 Scope..............................................................................................................................................................1 2 Normative references....................................................................................................................................1 3 Principle.........................................................................................................................................................1 4 Reagents........................................................................................................................................................2 5 Apparatus.......................................................................................................................................................4 6 Preparation of standard solutions of PCB and OCP.................................................................................7 7 Sampling and preservation of samples......................................................................................................8 7.1 Sampling........................................................................................................................................................8 7.2 Sample preservation and pretreatment......................................................................................................8 8 Procedure.......................................................................................................................................................8 8.1 Blank...............................................................................................................................................................8 8.2 Extraction and concentration......................................................................................................................8 8.3 Clean-up of the extract.................................................................................................................................9 8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs...........9 8.5 Gas chromatographic analysis..................................................................................................................10 9 Test report....................................................................................................................................................14 10 Accuracy......................................................................................................................................................14 Annex A (informative)

Table of retention times of polychlorinated biphenyls and organochlorine pesticides for two different capillary columns.........................................................................................15 Annex B (informative)

Scheme for the preparation of standard solutions including injection standards......16 Annex C (informative)

Results of an interlaboratory trial carried out in the Netherlands................................17 Annex D (informative)

Clean-up to remove elemental sulfur and some other organic sulfur compounds.....20 Bibliography..............................................................................................................................................................22

oSIST ISO 10382:2019

ISO 10382:2002(E) iv © ISO 2002 – 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 3. 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 International Standard may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 10382 was prepared by Technical Committee ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics. Annexes A, B, C and D of this International Standard are for information only.

oSIST ISO 10382:2019

INTERNATIONAL STANDARD ISO 10382:2002(E) © ISO 2002 – All rights reserved 1 Soil quality — Determination of organochlorine pesticides and polychlorinated biphenyls — Gas-chromatographic method with electron capture detection 1 Scope This International Standard specifies a method for quantitative determination of seven polychlorinated biphenyls and seventeen organochlorine pesticides in soil. This International Standard is applicable to all types of soil. Under the conditions specified in this International Standard, limits of detection of 0,1 µg/kg to 4 µg/kg (expressed as dry matter) can be achieved. 2 Normative references The following normative documents contain provisions which, through reference in this text, constitute provisions of this International Standard. For dated references, subsequent amendments to, or revisions of, any of these publications do not apply. However, parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most recent editions of the normative documents indicated below. For undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC maintain registers of currently valid International Standards. ISO 10381-1, Soil quality — Sampling — Part 1: Guidance on the design of sampling programmes ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques ISO 11465:1993, Soil quality — Determination of dry matter and water content on a mass basis — Gravimetric method ISO 14507, Soil quality — Pretreatment of samples for the determination of organic contaminants 3 Principle After pretreatment, the soil test sample is extracted with a hydrocarbon solvent. The extract is concentrated; polar compounds are removed by passing the concentrated extract through a column filled with aluminium oxide. The eluate is concentrated. Elemental sulfur is removed from the concentrated extract, if necessary, by treatment with tetrabutylammonium sulfite reagent. The extract is analysed by gas chromatography. The various compounds are separated using a capillary column with an immobile phase of low polarity. Detection occurs with an electron-capture detector (ECD). Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are assigned and quantified by comparison of relative retention times and relative peak heights (or peak areas) with respect to injection standards oSIST ISO 10382:2019

ISO 10382:2002(E) 2 © ISO 2002 – All rights reserved added, with the corresponding variables of an external standard solution. The efficiency of the procedure depends on the composition of the soil that is investigated. The described procedure does not take account of incomplete extraction due to the structure and composition of the soil sample. The limit of detection is dependent on the determinands, the equipment used, the quality of chemicals used for extraction of the soil sample, and the clean-up of the extract. NOTE 1 For confirmation of the identity of detected compounds and the concentrations found, further investigation is necessary. Confirmation can be carried out by repeating the gas chromatographic analysis using a column of different polarity and/or using gas chromatography/mass spectrometry (GC/MS). NOTE 2 Other non-volatile organochlorine compounds, e.g. some chlorobenzenes, can also be identified and quantified by this method. 4 Reagents All reagents shall be of recognized analytical grade. The purity of the reagents used shall be checked by running a blank determination as described in 8.1. 4.1 Petroleum ether, boiling range 40 °C to 60 °C. 4.2 Acetone. 4.3 n-Hexane. 4.4 Diethyl ether. Diethyl ether can contain peroxides which may oxidize some of the determinands. Check for the absence of peroxides, e.g. by shaking with a freshly prepared 10 % (mass fraction) KI solution. 4.5 Anhydrous sodium sulfate, heated for at least 6 h to 550 °C ± 20 °C, cooled to about 200 °C in a furnace and then to ambient temperature in a desiccator containing magnesium perchlorate or a suitable alternative. The anhydrous sodium sulfate shall be kept carefully sealed. 4.6 Aluminium oxide, basic or neutral, areic mass 200 m2/g, activity Super I according to Brockmann. 4.7 Aluminium oxide, deactivated with 10 % water. To 90 g of aluminium oxide (4.6) add 10 g of water. Shake until all lumps have disappeared. Allow the aluminium oxide to condition before use for approximately 16 h, sealed from the air. 4.8 Silica gel, particle size 60 µm to 200 µm, deactivated with 5 % water. Heat 95 g of silica gel for at least 24 h in an oven at 150 °C. Then allow to cool in a desiccator and add 5 g of water. Shake until all lumps have disappeared. Allow the silica gel to condition before use for approx. 16 h, sealed from the air. For each new batch of aluminium oxide or silica gel, the elution pattern should be checked against a standard solution of PCB and OCP. If necessary, the deactivation of the adsorbent should be adjusted (see 8.4). oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved 3 4.9 Standards. 4.9.1 Polychlorinated biphenyls. PCB- 28: 2,4,4'-trichlorobiphenyl CAS number1): 7012-37-5 PCB- 52: 2,2',5,5'-tetrachlorobiphenyl CAS number: 35693-99-3 PCB-101: 2,2',4,5,5'-pentachlorobiphenyl

CAS number: 37680-73-2 PCB-118: 2,3',4,4',5-pentachlorobiphenyl
CAS number: 31508-00-6 PCB-138: 2,2',3,4,4',5'-hexachlorobiphenyl
CAS number: 35065-28-2 PCB-153: 2,2',4,4',5,5'-hexachlorobiphenyl
CAS number: 35065-27-1 PCB-180: 2,2',3,4,4',5,5'-heptachlorobiphenyl

CAS number: 35065-29-3 NOTE The numbers 28, 52, etc. correspond with the sequential numbers of chlorobiphenyls according to the IUPAC rules for the nomenclature of organic compounds. 4.9.2 Organochlorine pesticides. Hexachlorobenzene (HCB) CAS number: 118-74-1 α-Hexachlorocyclohexane (α-HCH) CAS number: 319-84-6 β-Hexachlorocyclohexane (β-HCH) CAS number: 319-85-7 γ-Hexachlorocyclohexane (γ-HCH) CAS number: 58-89-9 Aldrin CAS number: 309-00-2 Dieldrin CAS number: 60-57-1 Endrin CAS number: 72-20-8 Heptachlor CAS number: 76-44-8 Heptachloro epoxide (exo-, cis- or a-isomer) CAS number: 28044-83-9 Heptachloro epoxide (endo-, trans- or b-isomer) CAS number: 1024-57-3 α-Endosulfan CAS number: 959-98-7 p,p'-DDE CAS number: 72-55-9 o,p'-DDD CAS number: 53-19-0 o,p'-DDT CAS number: 784-02-6 p,p'-DDD CAS number: 72-54-8 o,p'-DDE CAS number: 3424-82-6 p,p'-DDT CAS number: 50-29-3

1) Registration used by the Chemical Abstracts Service. oSIST ISO 10382:2019

ISO 10382:2002(E) 4 © ISO 2002 – All rights reserved 4.9.3 Injection standards. PCB-155: 2,2',4,4',6,6'-hexachlorobiphenyl CAS number: 33979-03-2 Select a second injection standard, not interfering with the analytes, from the following substances: PCB-143: 2,2',3,4,5,6'-hexachlorobiphenyl CAS number: 68194-15-0 PCB-207: 2,2',3,3',4,4',5,6,6'-nonachlorobiphenyl CAS number: 52663-79-3 Mirex CAS number: 2385-85-5 4.10 Tetrabutylammonium reagent (TBA sulfite reagent). Saturate a solution of tetrabutylammonium hydrogen sulfate in a mixture of equal volumes of water and 2-propanol, c[(C4H9)4NHSO4] = 0,1 mol/l, with sodium sulfite. NOTE 25 g of sodium sulfite is normally sufficient for 100 ml of solution. 4.11 n-Heptane. 5 Apparatus 5.1 Customary laboratory glassware. All glassware to be used shall be thoroughly cleaned, preferably in a dishwasher using a customary cleaning procedure, followed by rinsing with acetone and a subsequent rinsing with petroleum ether or hexane. 5.2 Glass sample bottles, of nominal capacity 1 l, with screw top and polytetrafluoroethene seal (PTFE). 5.3 Shaking device, with horizontal movement (200 to 300 strokes per minute). 5.4 Water bath, capable of being heated to 100 °C. 5.5 Shaking funnels, with a capacity of 2 l. 5.6 Conical flasks, with a capacity of 500 ml. 5.7 Evaporator,

Kuderna Danish (see Figure 1). Other evaporators, e.g. a rotary evaporator, may be used if found to be equally suitable. 5.8 Quartz wool or silanized glass wool, rinsed with petroleum ether or hexane. WARNING Working with quartz wool imposes a risk to health through the release of fine quartz particles. Prevent inhalation of these by using a fume cupboard and wearing a dust mask. 5.9 Boiling chips, of glass or porcelain beads, rinsed with petroleum ether or hexane. 5.10 Calibrated test tubes, with a capacity of 15 ml and ground glass stoppers. 5.11 Chromatography tubes (see Figure 2). 5.12 Gas chromatograph, equipped with a non-discriminating injection system, capillary column and electron-capture detector (ECD) based on 63Ni. oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved 5 NOTE 1 Working with an encapsulated radioactive source such as that present in an ECD requires a licence in accordance with the appropriate national regulations. NOTE 2 Gas chromatographs equipped with two detectors and with facilities for connecting two capillary columns to the same injection system are very well suited for this analysis; with such apparatus the confirmatory analysis can be performed simultaneously. 5.13 Capillary column, of fused silica, with a length of 50 m and an internal diameter of about 0,25 mm coated with a film of cross-linked polysiloxane. Other columns can also be used, although in some cases unsatisfactory separation is obtained. A column coated with a moderate polar phase, e.g. CP-Sil 19, OV 1701 etc., shall be used to confirm the result obtained. NOTE The retention times for PCB and OCP on capillary columns coated with CP-Sil 8 and CP-Sil 19 are given in annex A. oSIST ISO 10382:2019

ISO 10382:2002(E) 6 © ISO 2002 – All rights reserved

Key 1 Graduated test tube, capacity 15 ml a ISO 383 29/32 2 Distillation flasks b ISO 383 14/23 3 Receiver flask 4 Reflux condenser All joints shall be in accordance with ISO 383. Figure 1 — Example of evaporator (Kuderna Danish) oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved 7 Dimensions in millimetres

Figure 2 — Example of chromatography tube 6 Preparation of standard solutions of PCB and OCP Prepare individual concentrated primary standard solutions of mass concentration about 0,4 mg/ml in n-heptane by weighing approx. 10 mg of each of the standards (4.9) to the nearest 0,1 mg and dissolving them in 25 ml of n-heptane. Check the purity of the primary standard solutions by means of a gas chromatogram of the solutions concerned. Preferably a relatively non-specific detector, such as a flame ionization detector (FID) or a heat conductivity detector (TCD), shall be used. Combine small quantities (2 ml to 10 ml) of the individual primary standard solutions into a mixed standard solution of PCB and OCP including the injection standards (see annex B). Using this solution, prepare the working standard solutions in accordance with annex B by dilution. Components present in mixed standard solutions should be completely separated by the gas chromatographic columns used. Store the primary and diluted standard solutions in a dark place at a temperature of less than 4 °C. NOTE The solutions are stable for at least one year, provided that evaporation of solvent is negligible. oSIST ISO 10382:2019

ISO 10382:2002(E) 8 © ISO 2002 – All rights reserved 7 Sampling and preservation of samples 7.1 Sampling Obtain representative soil samples in accordance with ISO 10381-1 using sampling apparatus in accordance with ISO 10381-2. 7.2 Sample preservation and pretreatment Samples shall be pretreated as soon as possible. Store the samples in a dark place at a temperature below 10 °C, if possible in a refrigerator. For OCP testing, the storage times for field-moist soil samples shall not be longer than 7 days. Determine the content of dry matter in the field-moist soil in accordance with to ISO 11465. Grind the samples if there is insufficient homogeneity for taking a representative test sample. Grinding should take place cryogenically after chemical drying with anhydrous sodium sulfate (4.5) in accordance with ISO 14507. It is permissible for dried samples, if kept sealed, to be stored for a longer period at room temperature (approx. one month). 8 Procedure 8.1 Blank Before treating the samples, perform a blank determination as described in 8.2 to 8.5 using the same amount of reagents that are used for the extraction, clean-up and analysis of a sample. For cryogenically ground samples, perform the blank using 8 g of sodium sulfate (4.5) and 2 g of talcum, to which all the necessary reagents are added. If the blank value is unreasonably high, i.e. more than 10 % of the lowest value of interest, find the cause through a step-by-step examination of the whole procedure. For measurements at the limit of determination, even reagents suitable for residue analyses may not fulfil this criterion. In that case, sufficient blank determinations shall be incorporated in each series of samples. Values obtained from analysis of blanks should be smaller than the detection limit for the analytes concerned. 8.2 Extraction and concentration 8.2.1 Cryogenically ground samples Take 20 g of cryogenically ground sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test sample and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether (4.1) and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1). Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7). Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract. 8.2.2 Field-moist samples Take 20 g of field-moist sample and place it in a conical flask (5.6). Add 50 ml of acetone (4.2) to the test sample and extract by shaking thoroughly for 15 min on a shaking device (5.3). Then add 50 ml of petroleum ether (4.1) and shake again thoroughly during 15 min. Repeat the extraction again with 50 ml of petroleum ether (4.1). If the water content of the sample is greater than 25 %, increase the amount of acetone. The ratio acetone:water should be at least 9:1. The ratio acetone:petroleum ether shall be kept constant at 1:2. oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved 9 Collect the extracts in a separating funnel of 2 litre capacity and remove the acetone by shaking twice with 500 ml of water. Dry the extract over anhydrous sodium sulfate and transfer the dried extract to the concentrator (5.7). Rinse the sodium sulfate three times with 10 ml of petroleum ether and add the rinsings to the extract. Other extraction techniques, such as ultrasonic extraction, microwave or pressurized extraction, may be suitable. However, if using other extraction techniques, the comparability of such techniques to the method described in this International Standard shall be proven. 8.2.3 Concentration Add a boiling chip (5.9) to the extract and concentrate the extract to approx. 10 ml. Transfer the concentrated extract to a calibrated test tube (5.10) and further concentrate to 1 ml using a gentle stream of nitrogen at room temperature. NOTE Too high temperatures and a too high flow of nitrogen may result in loss of the more volatile PCBs and OCPs. 8.3 Clean-up of the extract Prepare an adsorption column by placing a small plug of quartz wool (5.8) in the chromatography tube (5.11) and packing it dry with 2,0 g ± 0,1 g of aluminium oxide (4.7). Before use, the elution pattern of each series of aluminium oxide columns and the necessary elution volume should be verified using a standard solution of PCB and OCP. With a pipette, transfer the extract to the dry packed adsorption column; rinse the test tube twice with 1 ml of petroleum ether and transfer the rinsings to the column with the same pipette as soon as the liquid level reaches the upper side of the column packing. Elute with approx. 20 ml of petroleum ether. Divide the eluate into two equal parts and store one part for an eventual analysis of the diluted extract. Concentrate the other part of the eluate with a gentle stream of nitrogen, without additional heating, to a final volume of about 1 ml. NOTE 1 Commercially available disposable columns may be used as an alternative if found equally suitable. The presence of sulfur in the extract of PCBs and non-polar OCPs can cause interferences in the chromatogram. If elemental sulfur is expected to be present (this occurs amongst others in anaerobic soils), remove it as follows. Add 2 ml of TBA sulfite reagent (4.10) to 1 ml of concentrated extract and shake for 1 min. Add 10 ml of water and shake again for 1 min. Separate the organic phase from the water with a Pasteur pipette and add a few crystals of anhydrous sodium sulfate to remove the remaining traces of water. NOTE 2 Other methods to remove sulfur, e.g. with pyrogenic copper (see annex D), may be used as an alternative if found equally suitable. If no further clean-up is required, to the final extract add 10 µl of the injection standard solution containing 100 times as much of the injection standards (4.9.3) per millilitre as is present per millilitre of working standard solution (see annex B). 8.4 Column-chromatographic separation of PCBs and non-polar OCPs from several polar OCPs In the case of very complex samples, insufficient separation may be obtained with gas chromatographic analysis. In this case an additional chromatographic separation, using the whole concentrated extract, may overcome this problem. The whole concentrated extract is separated by column chromatography on silica gel (4.8) into two fractions. The first fraction contains the PCBs and non-polar OCPs (HCB, p,p'-DDT, heptachlor, aldrin and p,p'-DDT). The second fraction contains the rather more polar OCPs (α-HCH, β-HCH, γ-HCH, dieldrin, endrin, o,p'-DDD and α-endosulfan). Check the elution pattern with the aid of a standard solution of PCB and OCP. If necessary, adjust the oSIST ISO 10382:2019

ISO 10382:2002(E) 10 © ISO 2002 – All rights reserved activity of the silica gel by adding more water if the compounds referred to above from the first fraction appear in the second fraction, or if the first fraction does not contain the compounds mentioned above. Add less water to the silica gel if the compounds mentioned above from the second fraction appear in the first fraction. Separate the extract as follows. Place a small plug of quartz wool in the chromatography tube. Pack it dry with (1,5 ± 0,1) g of silica gel (4.8) and top it with 1 cm of sodium sulfate (4.5). With a pipette, transfer the concentrated extract to the dry packed column. Rinse the test tube twice with 1 ml of hexane. Transfer the rinsings with the same pipette to the column as soon as the liquid level just reaches the upper edge of the column packing. Elute by adding to the column in succession 25 ml of hexane (fraction 1) and 25 ml of a mixture of hexane and diethyl ether (volume ratio 75:25) (fraction 2). NOTE Commercially available disposable columns may be used as an alternative if found equally suitable. Divide each of the two eluates into two equal parts, and for each eluate store one part for a possible repetition of the analysis in a dilution of the extract. Evaporate the other two separate fractions in test tubes to 1 ml volume. Add 10 µl of the injection standard solution to each of the two fractions, containing 100 times as much of the injection standards (4.9.3) per millilitre as is present per millilitre of working standard solution (see annex B). 8.5 Gas chromatographic analysis 8.5.1 Optimizing the gas chromatograph Optimize the gas chromatograph (5.12) in such a way that optimum separation is achieved. The plate number and capacity factor for component PCB-138 shall be greater than 6 × 104 and 6 respectively at 220 °C. The chromatographic peaks of PCB-28 and PCB-31 shall be resolved sufficiently (resolution at least 0,5) for integrating the PCB-28 peak. The following settings may be used to start the optimization of the gas chromatograph: Injection temperature (applicable only with splitless injection): 210 °C Oven temperature: 80 °C for 4 min; 4 °C/min up to 300 °C Detector temperature: 300 °C Carrier gas: Helium Gas flow: 20 cm/s to 30 cm/s 8.5.2 Calibration 8.5.2.1 General Two types of calibration are distinguished: the initial calibration (8.5.2.2) and the daily calibration (validity check of the initial calibration); the latter is called recalibration (8.5.2.3). The initial calibration serves to establish the linear working range of the calibration curve. This calibration is performed when the method is used for the first time and after maintenance and/or repair of the equipment. The recalibration checks the validity of the linear working range of the initial calibration curve and is performed before each series of samples. NOTE Non-linear calibration methods are allowed, provided that they are validated. oSIST ISO 10382:2019

ISO 10382:2002(E) © ISO 2002 – All rights reserved 11 8.5.2.2 Initial calibration Take a gas chromatogram of a series of at least five standard solutions with equidistant concentrations as given in annex B, including the solvent blank (see annex B). Identify the peaks by consulting annex A and if necessary the gas chromatograms of the individual compounds. Prepare a calibration graph for each compound. In general, the use of peak heights instead of peak areas is recommended. Calculate by linear regression a straight line for the whole range of the calibration solutions. If the origin falls within the 95 % confidence limits of the calculated line, recalculate by linear regression the line through the origin. This line is called the initial calibration line. If the origin does not fall within the 95 % confidence limits, omit the highest concentration and repeat the calculation. Determine the deviations between the measured values and the initial calibration line. When the deviation for the highest concentration is less than 5 %, assume linearity exists for the whole range. When this deviation i

...

NORME ISO
INTERNATIONALE 10382
Première édition
2002-10-15
Qualité du sol — Dosage des pesticides
organochlorés et des biphényles
polychlorés — Méthode par
chromatographie en phase gazeuse avec
détection par capture d'électrons
Soil quality — Determination of organochlorine pesticides and
polychlorinated biphenyls — Gas-chromatographic method with electron
capture detection
Numéro de référence
ISO 10382:2002(F)
ISO 2002
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ISO 10382:2002(F)
PDF – Exonération de responsabilité

Le présent fichier PDF peut contenir des polices de caractères intégrées. Conformément aux conditions de licence d'Adobe, ce fichier peut

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© ISO 2002

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forme que ce soit et par aucun procédé, électronique ou mécanique, y compris la photocopie et les microfilms, sans l'accord écrit de l’ISO à

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ii © ISO 2002 – Tous droits réservés
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ISO 10382:2002(F)
Sommaire Page

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

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

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

3 Principe .......................................................................................................................................................... 1

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

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

6 Préparation des solutions étalons de PCB et de POC ..............................................................................7

7 Échantillonnage et conservation des échantillons ................................................................................... 8

7.1 Échantillonnage............................................................................................................................................. 8

7.2 Conservation et prétraitement des échantillons........................................................................................ 8

8 Mode opératoire ............................................................................................................................................ 8

8.1 Essai à blanc.................................................................................................................................................. 8

8.2 Extraction et concentration.......................................................................................................................... 8

8.3 Purification de l’extrait.................................................................................................................................. 9

8.4 Séparation par chromatographie en colonnes entre PCB et POC non polaires d’une part et

plusieurs POC polaires d’autre part.......................................................................................................... 10

8.5 Analyse par chromatographie en phase gazeuse ................................................................................... 10

9 Rapport d'essai............................................................................................................................................ 14

10 Exactitude .................................................................................................................................................... 15

Annexe A (informative) Tableau des temps de rétention de biphényles polychlorés et de pesticides

organochlorés pour deux colonnes capillaires différentes.................................................................... 16

Annexe B (informative) Schéma de préparation de solutions étalons comprenant les étalons internes ....... 17

Annexe C (informative) Résultats d'un essai interlaboratoires réalisé aux Pays-Bas ...................................... 18

Annexe D (informative) Élimination du soufre élémentaire et de certains autres composés soufrés

organiques ................................................................................................................................................... 21

Bibliographie............................................................................................................................................................. 23

© ISO 2002 – Tous droits réservés iii
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ISO 10382:2002(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 3.

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 de la présente Norme internationale 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 10382 a été élaborée par le comité technique ISO/TC 190, Qualité du sol, sous-comité SC 3, Méthodes

chimiques et caractéristiques du sol.

Les annexes A, B, C et D de la présente Norme internationale sont données uniquement à titre d’information.

iv © ISO 2002 – Tous droits réservés
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NORME INTERNATIONALE ISO 10382:2002(F)
Qualité du sol — Dosage des pesticides organochlorés et des
biphényles polychlorés — Méthode par chromatographie en phase
gazeuse avec détection par capture d'électrons
1 Domaine d'application

La présente Norme internationale spécifie une méthode de dosage quantitatif de sept biphényles polychlorés et de

dix-sept pesticides organochlorés dans le sol.
La présente Norme internationale est applicable à tous les types de sol.

Dans les conditions spécifiées dans la présente Norme internationale, les limites de détection de 0,1 µg/kg à

4 µg/kg (exprimées en matières sèches) peuvent être obtenues.
2 Références normatives

Les documents normatifs suivants contiennent des dispositions qui, par suite de la référence qui y est faite,

constituent des dispositions valables pour la présente Norme internationale. Pour les références datées, les

amendements ultérieurs ou les révisions de ces publications ne s’appliquent pas. Toutefois, les parties prenantes

aux accords fondés sur la présente Norme internationale sont invitées à rechercher la possibilité d'appliquer les

éditions les plus récentes des documents normatifs indiqués ci-après. Pour les références non datées, la dernière

édition du document normatif en référence s’applique. Les membres de l'ISO et de la CEI possèdent le registre des

Normes internationales en vigueur.

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

programmes d’échantillonnage

ISO 10381-2, Qualité du sol ― Échantillonnage ― Partie 2: Lignes directrices pour les techniques

d’échantillonnage

ISO 11465:1993, Qualité du sol ― Détermination de la teneur pondérale en matière sèche et en eau ― Méthode

gravimétrique

ISO 14507, Qualité du sol ― Prétraitement des échantillons pour la détermination des contaminants organiques

3 Principe

L'échantillon pour essai est extrait avec un solvant hydrocarboné après un prétraitement.

L'extrait est concentré, puis les composés polaires sont éliminés en faisant passer l'extrait concentré à travers une

colonne remplie d'oxyde d'aluminium. L'éluat est concentré.

Le soufre élémentaire est retiré de l'extrait concentré par un traitement avec un réactif tétrabutylammonium sulfite.

© ISO 2002 – Tous droits réservés 1
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ISO 10382:2002(F)

L'extrait est analysé par chromatographie en phase gazeuse. Les différents composés sont séparés à l'aide d'une

colonne capillaire avec une phase stationnaire de faible polarité. La détection est réalisée avec un détecteur à

capture d'électrons (ECD).

Les biphényles polychlorés (PCB) et les pesticides organochlorés (POC) sont identifiés et quantifiés en comparant

les temps de rétention relatifs et les hauteurs de pics (ou aires de pics) relatives des étalons internes ajoutés aux

variables correspondantes d’une solution d’étalons externes. L'efficacité de la procédure dépend de la composition

du sol examiné. La procédure décrite ne tient pas compte de l'extraction incomplète causée par la structure et la

composition de l'échantillon de sol.

La limite de détection dépend des substances à doser, des équipements utilisés, de la qualité des produits

chimiques utilisés pour l’extraction de l’échantillon de sol et pour la purification de l’extrait.

NOTE 1 Pour confirmer l'identité de composés détectés et leur concentration, il est nécessaire de procéder à un examen

plus approfondi. Cette confirmation peut être réalisée en procédant à une nouvelle analyse par chromatographie en phase

gazeuse au moyen d'une colonne de polarité différente et/ou par chromatographie en phase gazeuse couplée avec une

spectrométrie de masse (CG-SM).

NOTE 2 D'autres composés organochlorés non volatils, par exemple des chlorobenzènes, peuvent également être identifiés

et quantifiés par cette méthode.
4 Réactifs

Tous les réactifs doivent être de qualité analytique reconnue. La pureté des réactifs utilisés doit être vérifiée en

procédant à un essai à blanc tel que spécifié en 8.1.
4.1 Éther de pétrole, domaine d'ébullition de 40 °C à 60 °C.
4.2 Acétone.
4.3 n-Hexane.
4.4 Éther diéthylique.

L'éther diéthylique peut contenir des peroxydes qui risquent d'oxyder certaines substances à doser. Vérifier

l'absence de peroxydes, par exemple en agitant l’éther diéthylique avec une solution fraîchement préparée à 10 %

(fraction massique) de Kl.

4.5 Sulfate de sodium anhydre, chauffé pendant au moins 6 h à 550 °C ± 20 °C, refroidir à environ 200 °C au

four et ensuite à température ambiante dans un dessiccateur contenant du perchlorate de magnésium ou

équivalent.

Le sulfate de sodium anhydre doit être conservé dans un récipient rigoureusement hermétique.

4.6 Oxyde d'aluminium, alcalin ou neutre, surface spécifique de 200 m /g, activité Super I d'après Brockmann.

4.7 Oxyde d'aluminium, désactivé avec 10 % d'eau.

Ajouter 10 g d'eau à 90 g d'oxyde d'aluminium (voir 4.6). Agiter jusqu'à ce que tous les morceaux aient disparu.

Laisser reposer l'oxyde d'aluminium avant utilisation pendant environ 16 h, dans un récipient hermétique à l'air.

4.8 Gel de silice, taille des particules 60 µm à 200 µm, désactivé avec 5 % d'eau.

Chauffer 95 g de gel de silice pendant au moins 24 h dans un four à 150 °C. Puis laisser refroidir dans un

dessiccateur et ajouter 5 g d'eau. Agiter jusqu'à ce que tous les morceaux aient disparu. Laisser reposer le gel de

silice avant utilisation pendant environ 16 h, dans un récipient hermétique à l'air.

Pour chaque nouveau lot d'oxyde d'aluminium ou de gel de silice, il convient de vérifier le modèle d'élution par

rapport à une solution étalon de PCB et de POC. Si nécessaire, il convient de régler la désactivation de l'adsorbant

(voir 8.4).
2 © ISO 2002 – Tous droits réservés
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ISO 10382:2002(F)
4.9 Étalons.
4.9.1 Biphényles polychlorés.
PCB- 28: Trichloro-2,4,4' biphényle numéro CAS : 7012-37-5
PCB- 52: Tétrachloro -2,2',5,5' biphényle numéro CAS: 35693-99-3
PCB-101: Pentachloro-2,2',4,5,5' biphényle numéro CAS: 37680-73-2
PCB-118: Pentachloro-2,3',4,4',5 biphényle numéro CAS: 31508-00-6
PCB-138: Hexachloro-2,2',3,4,4',5' biphényle numéro CAS: 35065-28-2
PCB-153: Hexachloro-2,2',4,4',5,5' biphényle numéro CAS: 35065-27-1
PCB-180: Heptachloro-2,2',3,4,4',5,5' biphényle numéro CAS: 35065-29-3

NOTE Les numéros 28, 52, etc. correspondent aux numéros séquentiels des chlorobiphényles d'après les règles de

I’UICPA pour la nomenclature des composés organiques.
4.9.2 Pesticides organochlorés.
Hexachlorobenzène (HCB) numéro CAS: 118-74-1
α-Hexachlorocyclohexane (α-HCH) numéro CAS: 319-84-6
β-Hexachlorocyclohexane (β-HCH) numéro CAS: 319-85-7
γ-Hexachlorocyclohexane (γ-HCH) numéro CAS: 58-89-9
Aldrine numéro CAS: 309-00-2
Dieldrine numéro CAS: 60-57-1
Endrine numéro CAS: 72-20-8
Heptachlore numéro CAS: 76-44-8
Heptachlore époxide (exo-, cis- ou isomère-a) numéro CAS: 28044-83-9
Heptachlore époxide (endo-, trans- ou isomère-b) numéro CAS: 1024-57-3
α-Endosulfan numéro CAS: 959-98-7
p,p'-DDE numéro CAS: 72-55-9
o,p'-DDD numéro CAS: 53-19-0
o,p'-DDT numéro CAS: 784-02-6
p,p'-DDD numéro CAS: 72-54-8
o,p'-DDE numéro CAS: 3424-82-6
p,p'-DDT numéro CAS: 50-29-3
1) Enregistrement utilisé par le Chemical Abstracts Service.
© ISO 2002 – Tous droits réservés 3
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ISO 10382:2002(F)
4.9.3 Étalons internes.
PCB-155: Hexachloro-2,2',4,4',6,6' biphényle numéro CAS: 33979-03-2

Sélectionner un deuxième étalon interne, ne perturbant pas les analytes, parmi les substances suivantes:

PCB-143: Hexachloro-2,2',3,4,5,6' biphényle numéro CAS: 68194-15-0
PCB-207: Nonachloro-2,2',3,3',4,4',5,6,6' biphényle numéro CAS: 52663-79-3
Mirex numéro CAS: 2385-85-5
4.10 Réactif de tétrabutylammonium (réactif TBA sulfite).

Saturer avec du sulfite de sodium une solution d'hydrogénosulfate de tétrabutylammonium dans un mélange

composé d'un volume équivalent d'eau et d'alcool isopropylique, c[(C H ) NHSO ] = 0,1 mol/l.

4 9 4 4
NOTE 25 g de sulfite de sodium devraient suffire pour 100 ml de solution.
4.11 n-Heptane.
5 Appareillage
5.1 Verrerie courante de laboratoire.

L'ensemble de la verrerie à utiliser doit être soigneusement nettoyée, de préférence dans un lave-vaisselle pendant

un cycle de lavage habituel, suivi d'un rinçage à l'acétone et d'un autre rinçage à l'éther de pétrole ou à l'hexane.

5.2 Flacons d'échantillonnage en verre, de capacité nominale 1 l, avec une extrémité filetée et un bouchon

revêtu de polytétrafluoroéthène (PTFE).
5.3 Agitateur mécanique, à mouvement horizontal (200 à 300 coups par minute).
5.4 Bain d'eau, réglable jusqu'à 100 °C.
5.5 Ampoules à décanter, de capacité 2 l.
5.6 Fioles coniques, de capacité 500 ml.
5.7 Évaporateur, Kuderna Danish (voir Figure 1).

D’autres évaporateurs, par exemple un évaporateur tournant, peuvent être utilisés s’ils s’avèrent tout aussi

appropriés.

5.8 Laine de quartz ou laine de verre silanisée, rincée à l’éther de pétrole ou à l’hexane.

AVERTISSEMENT La manipulation de laine de quartz est un risque pour la santé en raison du

dégagement de fines particules de quartz dont il convient d’empêcher l’inhalation en utilisant une hotte de

laboratoire et en portant un masque à poussière.

5.9 Perles facilitant l’ébullition, de verre ou de porcelaine, rincées à l’éther de pétrole ou à l’hexane.

5.10 Tubes à essais étalonnés, de capacité 15 ml et munis d’un bouchon en verre rodé.

5.11 Tubes de chromatographie (voir Figure 2).
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ISO 10382:2002(F)

5.12 Chromatographe en phase gazeuse, équipé d’un système d’injection non discriminant, d’une colonne

capillaire et d’un détecteur à capture d’électrons (ECD) basé sur Ni.

NOTE 1 L’utilisation d’une source radioactive scellée dans le détecteur ECD nécessite une licence d’autorisation en

conformité avec les réglementations nationales.

NOTE 2 Les chromatographes en phase gazeuse équipés de deux détecteurs et de dispositifs reliant les deux colonnes

capillaires au même système d’injection conviennent très bien pour cette analyse; avec ce type d’appareil, l’analyse de

confirmation peut être réalisée simultanément.

5.13 Colonne capillaire, en silice fondue d’une longueur de 50 m et d’un diamètre intérieur d’environ 0,25 mm,

recouverte d’une couche de polysiloxane réticulé.

D’autres colonnes peuvent être utilisées également bien que, dans certains cas, on obtienne une séparation non

satisfaisante. Une colonne revêtue d’une phase polaire modérée, par exemple CP-Sil 19, OV 1701 etc., doit être

utilisée pour confirmer le résultat obtenu.

NOTE Les temps de rétention pour les PCB et POC sur les colonnes capillaires revêtues de CP-Sil 8 et CP-Sil 19 sont

indiquées à l’annexe A.
© ISO 2002 – Tous droits réservés 5
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ISO 10382:2002(F)
Légende
1 Tube à essais gradué, capacité 15 ml ISO 383 29/32
2 Ballon à distiller ISO 383 14/23
3 Ballon récepteur
4 Condensateur à reflux
Tous les joints doivent être en conformité avec l’ISO 383.
Figure 1 — Exemple d'un évaporateur (Kuderna Danish)
6 © ISO 2002 – Tous droits réservés
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ISO 10382:2002(F)
Dimensions en millimètres
Figure 2 — Exemple de tube de chromatographie
6 Préparation des solutions étalons de PCB et de POC

Préparer des solutions étalons primaires concentrées de chaque composé individuel d’environ 0,4 mg/ml dans le

n-heptane en pesant approximativement 10 mg de chacun des étalons (4.9) à 0,1 mg près et en les dissolvant

dans 25 ml de n-heptane.

Vérifier la pureté des solutions étalons primaires par une analyse par chromatographie en phase gazeuse des

solutions concernées. Utiliser de préférence un détecteur relativement courant tel qu’un détecteur à ionisation de

flammes (FID) ou un détecteur de conductibilité thermique (TCD).

Ajouter de faibles quantités (2 ml à 10 ml) de ces solutions étalons primaires de chaque composé individuel à une

solution étalon mélangée de PCB et de POC comprenant les étalons internes (voir annexe B). Avec cette solution,

préparer les solutions étalons de travail par dilution, conformément à l’annexe B.

Il convient que les colonnes de chromatographie en phase gazeuse utilisées permettent de séparer complètement

les composants présents dans les solutions étalons mélangées.

Conserver les solutions étalons primaires et les solutions étalons diluées à l’abri de la lumière et à une température

inférieure à 4 °C.

NOTE Les solutions sont stables pendant au moins un an dans la mesure où l’évaporation de solvant est négligeable.

© ISO 2002 – Tous droits réservés 7
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ISO 10382:2002(F)
7 Échantillonnage et conservation des échantillons
7.1 Échantillonnage

Obtenir des échantillons de sol représentatifs conformément à l’ISO 10381-1 en utilisant des appareils

d’échantillonnage selon l’ISO 10381-2.
7.2 Conservation et prétraitement des échantillons

Les échantillons doivent subir un prétraitement le plus tôt possible. Conserver les échantillons à l’abri de la lumière

et à une température inférieure à 10 °C, si possible dans un réfrigérateur. Pour les POC, la durée de conservation

des échantillons de sol brut ne doit pas dépasser sept jours. Déterminer la teneur en matières sèches dans le sol

brut conformément à l’ISO 11465. Concasser les échantillons en l’absence d’homogénéité suffisante pour prélever

un échantillon d’essai représentatif. Il convient de procéder à un concassage par cryogénie après le séchage

chimique avec du sulfate de sodium anhydre (4.5) conformément à l’ISO 14507.

Pour les échantillons séchés, il est permis, s’ils restent hermétiquement fermés, de les conserver pendant une

période plus longue à température ambiante (environ un mois).
8 Mode opératoire
8.1 Essai à blanc

Avant de traiter les échantillons, procéder à un essai à blanc suivant 8.2 à 8.5 en utilisant la même quantité de

réactifs que pour l’extraction, la purification et l’analyse d’un échantillon. Pour les échantillons concassés par

cryogénie, procéder à l’essai à blanc en utilisant 8 g de sulfate de sodium (4.5) et 2 g de talc auxquels sont ajoutés

tous les réactifs nécessaires.

Si la valeur à blanc est excessivement élevée, c'est-à-dire si elle est supérieure à 10 % de la valeur d'intérêt la plus

basse, en trouver la cause en examinant l'ensemble de la procédure étape par étape.

Pour des mesures à la limite de quantification, même des réactifs appropriés pour l'analyse des résidus peuvent ne

pas répondre à ce critère. Dans ce cas, un nombre suffisant d’essais à blanc doit être incorporé dans chaque série

d'échantillons.

Il convient que les valeurs à blanc soient inférieures à la limite de détection des analytes considérés.

8.2 Extraction et concentration
8.2.1 Échantillons obtenu par concassage cryogénique

Prélever 20 g d’échantillon obtenu par concassage cryogénique et les placer dans une fiole conique (5.6). Ajouter

50 ml d’acétone (4.2) à l’échantillon d’essai et procéder à l’extraction en agitant vigoureusement pendant 15 min

avec un agitateur mécanique (5.3). Ajouter ensuite 50 ml d’éther de pétrole (4.1) et agiter de nouveau

soigneusement pendant 15 min. Procéder de nouveau à l’extraction avec 50 ml d’éther de pétrole (4.1). Récupérer

les extraits dans une ampoule à décanter d’une capacité de 2 l et retirer l’acétone en agitant deux fois avec 500 ml

d’eau. Sécher l’extrait sur du sulfate de sodium anhydre et passer l’extrait sec au concentrateur (5.7). Rincer le

sulfate de sodium trois fois avec 10 ml d’éther de pétrole et ajouter le solvant utilisé pour les rinçages à l’extrait.

8 © ISO 2002 – Tous droits réservés
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ISO 10382:2002(F)
8.2.2 Échantillons de sol brut

Prélever 20 g d’échantillon de sol brut et les placer dans une fiole conique (5.6). Ajouter 50 ml d’acétone (4.2) à

l’échantillon d’essai et procéder à l’extraction en agitant vigoureusement pendant 15 min avec un agitateur (5.3).

Ajouter ensuite 50 ml d’éther de pétrole (4.1) et agiter de nouveau soigneusement pendant 15 min. Procéder de

nouveau à l’extraction avec 50 ml d’éther de pétrole (4.1).

Si la teneur en eau de l’échantillon est supérieure à 25 %, il faut augmenter la quantité d’acétone. Il convient que le

rapport acétone:eau soit égal à 9:1 au moins. Le rapport acétone:éther de pétrole doit être maintenu constant à

1:2.

Récupérer les extraits dans une ampoule à décanter d’une capacité de 2 l et retirer l’acétone en agitant deux fois

avec 500 ml d’eau. Sécher l’extrait sur du sulfate de sodium anhydre et passer l’extrait sec au concentrateur (5.7).

Rincer le sulfate de sodium trois fois avec 10 ml d’éther de pétrole et ajouter le solvant utilisé pour les rinçages à

l’extrait.

D’autres techniques d’extraction, telles que l’extraction par ultrasons, par micro-ondes ou l’extraction par fluide

pressurisé, peuvent être appropriées. Cependant, si d’autres méthodes d’extraction sont utilisées, il faut prouver

que les performances sont comparables à celles de la méthode décrite dans la présente Norme internationale.

8.2.3 Concentration

Ajouter à l’extrait une perle facilitant l’ébullition (5.9) et concentrer l’extrait à environ 10 ml. Passer l’extrait

concentré dans un tube à essai étalonné (5.10) et concentrer à 1 ml à l’aide d’un léger courant d’azote à

température ambiante.

NOTE Des températures trop élevées et un débit trop important d’azote peuvent entraîner une perte des PCB et POC les

plus volatils.
8.3 Purification de l’extrait

Préparer une colonne d’adsorption en plaçant un petit bouchon en laine de quartz (5.8) dans le tube de

chromatographie (5.11) et en le garnissant avec 2,0 g ± 0,1 g d’oxyde d’aluminium maintenu au sec (4.7).

Avant emploi, il convient de vérifier le modèle d’élution de chaque série de colonnes d’oxyde d’aluminium et le

volume d’élution nécessaire à l’aide d’une solution étalon de PCB et de POC.

Avec une pipette, transférer l’extrait dans la colonne d’adsorption garnie et asséchée; rincer deux fois le tube à

essai avec 1 ml d’éther de pétrole et, dès que le niveau du liquide atteint la couche supérieure de la garniture

d’étanchéité de la colonne, transférer le solvant utilisé pour les rinçages dans la colonne avec la même pipette.

Éluer avec environ 20 ml d’éther de pétrole.

Séparer l’éluat en deux parties égales et conserver une partie pour une éventuelle analyse de l’extrait dilué.

Concentrer l’autre partie de l’éluat avec un léger courant d’azote sans chauffage supplémentaire jusqu’à obtenir un

volume final d’environ 1 ml.

NOTE 1 Des colonnes à utilisation unique disponibles dans le commerce peuvent être utilisées en alternative si elles

s’avèrent tout aussi appropriées.

La présence de soufre dans l’extrait de PCB et de POC non polaires peut perturber le signal chromatographique.

En cas de risque de présence de soufre élémentaire (entre autres, dans les sols anaérobies), l’éliminer comme

suit.

Ajouter 2 ml de réactif de sulfite-TBA (4.10) à 1 ml d’extrait concentré et agiter pendant 1 min. Ajouter 10 ml d’eau

et agiter de nouveau pendant 1 min. Séparer la phase organique de l’eau avec une pipette Pasteur et ajouter

quelques cristaux de sulfate de sodium anhydre pour éliminer les traces d’eau restantes.

NOTE 2 D’autres méthodes peuvent être utilisées en alternative pour éliminer le soufre, par exemple l’utilisation de cuivre

réduit (voir annexe D) si elles s’avèrent tout aussi appropriées.
© ISO 2002 – Tous droits réservés 9
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ISO 10382:2002(F)

S’il n’est pas nécessaire d’effectuer d’autres purifications, ajouter à l’extrait final 10 µl de la solution d’étalons

internes, contenant en étalons internes (4.9.3), par millilitre, 100 fois la concentration contenue dans un millilitre de

solution étalon de travail (voir annexe B).

8.4 Séparation par chromatographie en colonnes entre PCB et POC non polaires d’une part et

plusieurs POC polaires d’autre part

En cas d’échantillons très complexes, l’analyse par chromatographie en phase gazeuse peut donner une

séparation insuffisante. Dans ce cas, une séparation supplémentaire par chromatographie d’adsorption utilisant

l’ensemble de l’extrait concentré peut résoudre ce problème.

L’ensemble de l’extrait concentré est séparé par chromatographie en colonnes sur du gel de silice (4.8) en deux

fractions. La première fraction contient les PCB et les POC non polaires (HCB, p,p'-DDE, heptachlore, aldrine et

p,p'-DDT). La seconde fraction contient les POC un peu plus polaires (α-HCH, β-HCH, γ-HCH, dieldrine, endrine,

o,p'-DDD et α-endosulfan). Vérifier le modèle d'élution à l'aide d’une solution étalon de PCB et de POC. Si

nécessaire, régler l'activité du gel de silice en ajoutant plus d'eau si les composés mentionnés ci-dessus, issus de

la première fraction, apparaissent dans la seconde fraction ou si la première fraction ne contient pas les composés

mentionnés ci-dessus. Ajouter moins d'eau au gel de silice si les composés mentionnés ci-dessus, issus de la

seconde fraction, apparaissent dans la première fraction.

Séparer l'extrait comme suit. Placer un petit bouchon en laine de quartz dans le tube de chromatographie, le

remplir avec (1,5 ± 0,1) g de gel de silice (4.8) maintenu au sec et le recouvrir d'1 cm de sulfate de sodium. Avec

une pipette, transférer l’extrait concentré dans la colonne garnie et asséchée. Rincer deux fois le tube à essai avec

1 ml d'hexane. Dès que le niveau du liquide vient juste d'atteindre
...

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