|
oSIST prEN ISO 23161:2017
01-januar-2017
.DNRYRVWWDO'RORþHYDQMHL]EUDQLKRUJDQRNRVLWURYLKVSRMLQ0HWRGDSOLQVNH
NURPDWRJUDILMH ,62)',6
Soil quality - Determination of selected organotin compounds - Gas-chromatographic
method (ISO/FDIS 23161:2016)
Bodenbeschaffenheit - Bestimmung ausgewählter Organozinnverbindungen -
Gaschromatographisches Verfahren (ISO/FDIS 23161:2016)
Qualité du sol - Dosage d'une sélection de composés organostanniques - Méthode par
chromatographie en phase gazeuse (ISO/FDIS 23161:2016)
Ta slovenski standard je istoveten z: prEN ISO 23161
ICS:
13.080.10 .HPLMVNH]QDþLOQRVWLWDO Chemical characteristics of
soils
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
oSIST prEN ISO 23161:2017 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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oSIST prEN ISO 23161:2017
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oSIST prEN ISO 23161:2017
FINAL
INTERNATIONAL ISO/FDIS
DRAFT
STANDARD 23161
ISO/TC 190/SC 3
Soil quality — Determination of
Secretariat: DIN
selected organotin compounds — Gas-
Voting begins on:
201612-02 chromatographic method
Voting terminates on:
Qualité du sol — Dosage d’une sélection de composés
20170224
organostanniques — Méthode par chromatographie en phase gazeuse
ISO/CEN PARALLEL PROCESSING
RECIPIENTS OF THIS DRAFT ARE INVITED TO
SUBMIT, WITH THEIR COMMENTS, NOTIFICATION
OF ANY RELEVANT PATENT RIGHTS OF WHICH
THEY ARE AWARE AND TO PROVIDE SUPPOR TING
DOCUMENTATION.
IN ADDITION TO THEIR EVALUATION AS
Reference number
BEING ACCEPTABLE FOR INDUSTRIAL, TECHNO
ISO/FDIS 23161:2016(E)
LOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON
OCCASION HAVE TO BE CONSIDERED IN THE
LIGHT OF THEIR POTENTIAL TO BECOME STAN
DARDS TO WHICH REFERENCE MAY BE MADE IN
©
NATIONAL REGULATIONS. ISO 2016
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oSIST prEN ISO 23161:2017
ISO/FDIS 23161:2016(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2016, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
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www.iso.org
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oSIST prEN ISO 23161:2017
ISO/FDIS 23161:2016(E)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 2
3 Terms and definitions . 2
4 Principle . 2
5 Reagents . 4
5.1 General . 4
5.2 Chemicals . 4
5.3 Standards . 5
5.4 Preparation of reagents and solutions . 6
5.5 Cleanup . 7
6 Apparatus . 8
6.1 Requirements for glassware . 8
6.2 Sampling apparatus . 8
6.3 Additional apparatus . 8
7 Procedure. 9
7.1 Sampling and sample pretreatment . 9
7.2 Sample extraction . 9
7.2.1 General. 9
7.2.2 Acidic extraction and derivatization of an aliquot .10
7.2.3 Alkaline treatment and in situ derivatization .10
7.2.4 Separate determination of TTBT in the field-moist sample .10
7.3 Cleanup of the extract .11
7.3.1 General.11
7.3.2 Silica and aluminium oxide cleanup.11
7.4 Determination of dry mass .11
7.5 Measurement .11
7.5.1 Gas chromatographic separation .11
7.5.2 Detection and identification .12
8 Calibration .12
9 Recovery rates of the internal standard compounds .13
10 Quantification .14
11 Expression of results .15
12 Validation .15
13 Test report .15
Annex A (informative) Information about the procedure .16
Annex B (informative) Additional clean-up procedures .18
Annex C (informative) Information about typical instrumental conditions .20
Annex D (informative) Information about GC-MS identification.31
Annex E (informative) Validation data .33
Bibliography .37
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oSIST prEN ISO 23161:2017
ISO/FDIS 23161:2016(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 nongovernmental, 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.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment,
as well as information about ISO’s adherence to the World Trade Organization (WTO) principles in the
Technical Barriers to Trade (TBT) see the following URL: www.iso.org/iso/foreword.html.
The committee responsible for this document is ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical
methods and soil characteristics.
This second edition cancels and replaces the first edition (ISO 23161:2009), of which it constitutes a
minor revision.
The changes compared to the previous edition are as follows:
— the Note to Clause 1 and Table 2 have been moved to Clause 4;
— former Note 4 to Clause 4 has been changed to normal text and moved above Note 1;
— former second sentence in 5.5.5 has been changed to Note;
— in 7.2.2 and 7.2.3, a Note has been added;
— the presentation of tables in Annex E has been improved;
— the Bibliography has been updated.
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Introduction
It is absolutely essential that tests conducted in accordance with this document be carried out by
suitably qualified staff.
It can be noted whether, and to what extent, particular problems will require the specification of
additional boundary conditions.
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oSIST prEN ISO 23161:2017
FINAL DRAFT INTERNATIONAL STANDARD ISO/FDIS 23161:2016(E)
Soil quality — Determination of selected organotin
compounds — Gas-chromatographic method
WARNING — Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address all of the safety problems, if any, associated with its
use. It is the responsibility of the user to establish appropriate safety and health practices and to
ensure compliance with any national regulatory conditions.
IMPORTANT — It is absolutely essential that tests, conducted in accordance with this document,
be carried out by suitably qualified staff.
1 Scope
This document specifies a gas-chromatographic method for the identification and quantification of
organotin compounds (OTCs) in soils as specified in Table 1.
This document is also applicable to samples from sediments, sludges and wastes (soillike materials).
The working range depends on the detection technique used and the amount of sample taken for
analysis.
The limit of quantification for each compound is about 10 µg/kg.
Table 1 — Organotin compounds, which can be determined in accordance with this document
(4−n)+
R Sn R n Name Acronym
n
a
Organotin cations
3+
BuSn Butyl 1 Monobutyltin cation MBT
2+
Bu Sn Butyl 2 Dibutyltin cation DBT
2
+
Bu Sn Butyl 3 Tributyltin cation TBT
3
3+
OcSn Octyl 1 Monooctyltin cation MOT
2+
Oc Sn Octyl 2 Dioctyltin cation DOT
2
+
Ph Sn Phenyl 3 Triphenyltin cation TPhT
3
+
Cy Sn Cyclohexyl 3 Tricyclohexyltin cation TCyT
3
Peralkylated organotin
Bu Sn Butyl 4 Tetrabutyltin TTBT
4
a
Organotin compounds are measured after derivatization.
Organotin cations can only be determined in accordance with this document after derivatization. The
anionic part bound to the organotin cation is mainly dependent on the chemical environment and is
not determined using this method. The peralkylated organotin compounds behave in a completely
different way from their parent compounds. Tetraalkylated organotin compounds which are already
peralkylated, such as tetrabutyltin, are determined directly without derivatization.
The properties such as particle size distribution, water content and organic matter content of the solids
to be analysed using this document vary widely. Sample pretreatment is designed adequately with
respect to both the properties of the organotin compounds and the matrix to be analysed.
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2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 11465, Soil quality — Determination of dry matter and water content on a mass basis —
Gravimetric method
ISO 16720, Soil quality — Pretreatment of samples by freeze-drying for subsequent analysis
ISO 22892, Soil quality — Guidelines for the identification of target compounds by gas chromatography and
mass spectrometry
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http://www.electropedia.org/
— ISO Online browsing platform: available at http://www.iso.org/obp
3.1
organotin compound
substance containing 1 to 4 SnC bonds
Note 1 to entry: The number of Sn-C bonds is a measure for the degree of substitution.
3.2
organotin cation
part of the organotin compound (3.1) that contains all Sn-C bonds and is formally charged
3.3
organotin cation derivatives
non-dissociated tetrasubstituted organotin compounds which are produced by derivatization
3.4
solid
soil, sediment, sludge and waste (soillike material)
4 Principle
For the ionic and the nonionic organotin compounds (see Table 1), a different sample pretreatment and
sample preparation are necessary. For the determination of organotin cations, laboratory samples are
pretreated by freeze drying and grinding. This procedure enables to achieve homogeneity of the sample
to be achieved. The determination of nonionic TTBT cannot be carried out with freezedried materials
due to evaporation losses; thus, it shall be determined in the field-moist sample. Organotin cations can
only be determined after derivatization, whereas TTBT is already peralkylated and can be determined
without derivatization (see the flowchart in Figure 1).
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Figure 1 — Flowchart for the pretreatment and analysis of selected organotin compounds
For the determination of organotin compounds, two alternative extraction methods are given, both
followed by in situ derivatization with a tetraethylborate compound and simultaneous extraction
with hexane:
a) treatment with acetic acid;
b) treatment with methanolic potassium hydroxide.
Treatment with potassium hydroxide provides some degree of digestion and is recommended especially
when the solid contains high amounts of organic and biological materials.
NOTE 1 If it is necessary to take a large amount of sample, extraction and derivatization can be done in two
steps. An aliquot of the extract can be taken for derivatization. This also applies for samples with high levels of
contamination by organotin compounds.
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NOTE 2 During in situ derivatization, the solid phase is still present. This supports the extraction by
continuous changing of the polar organotin cations to the nonpolar organotin cation derivates. In situ methods
can improve the extraction efficiency, particularly for monoalkylated organotin compounds.
NOTE 3 Other extraction techniques can be applied if a comparable extraction efficiency is achieved.
When applying this method to the determination of other organotin compounds not specified in
the scope, its suitability has to be proven by proper in-house validation experiments, e.g. methyltin
compounds (see Table 2). Methyltin cations are unlikely to evaporate from aqueous solvents, but
peralkylated methyltin compounds are volatile and subject to losses (see C.3). Therefore, additional
precautions are established.
Table 2 — Methyltin compounds
(4−n)+
R Sn R n Name Acronym
n
3+
MeSn Methyl 1 Monomethyltin cation MMT
2+
Me Sn Methyl 2 Dimethyltin cation DMT
2
+
Me Sn Methyl 3 Trimethyltin cation TMT
3
The internal standard mix comprises four compounds representing four alkylation states in order to
mimic the behaviour of the target compounds. After alkylation, they cover a wide range of volatility.
A recovery of at least 80 % for derivatization/extraction and again 80 % for each clean-up step of the
internal standard compounds should be achieved. (For more information, see A.3.) Tetraalkylborate
is very reactive and will also alkylate other compounds in the matrix. Those compounds (and also
boroxines) may interfere with the target compounds during gas chromatographic determination and
influence detection. In order to protect the column and to reduce the interference in chromatography,
it will be necessary to apply a pre-cleaning step to most samples. Clean-up with silica or aluminium
oxide is the minimum; further cleanup steps (e.g. aluminium oxide/silver nitrate, silica/silver nitrate,
pyrogenic copper; see Annex B) may be applied if necessary.
The determination of the tetrasubstituted organotin compounds is carried out after cleanup and
concentration steps by separation with capillary gas chromatography and detected with a suitable
system [mass spectrometer (MS), (MS/MS), flame photometric detector (FPD), atomic absorption
spectrometer (AAS), atomic emission detector (AED), inductively coupled plasma/mass spectrometer
ICP/MS]. The concentrations are determined by calibration over the total procedure using aqueous
multicomponent calibration standard solutions in accordance with 5.4.3.
5 Reagents
5.1 General
Use reagents of highest purity, typically of pesticide grade or better. The reagents may contain
impurities of organotin compounds. It is absolutely essential to verify the blanks.
The water shall be free of interferences. Use water in accordance with Grade 3 of ISO 3696.
5.2 Chemicals
5.2.1 Acetic acid, CH COOH, glacial.
3
5.2.2 Sodium hydroxide solution, NaOH, 40 % (m/V).
5.2.3 Sodium acetate, CH COONa.
3
5.2.4 Sodium sulfate, Na SO , anhydrous.
2 4
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5.2.5 Potassium hydroxide, KOH.
5.2.6 Silica gel, grain size 0,085 mm to 0,28 mm (63 mesh to 200 mesh).
5.2.7 Aluminium oxide, Al O , alkaline.
2 3
5.2.8 Tetrahydrofurane, C H O, free of peroxides, free of water.
4 8
5.2.9 Acetone, (CH ) CO.
3 2
5.2.10 Hexane, C H .
6 14
NOTE Both n-hexane and 2-methylpentane (ihexane) have been found to be suitable.
5.2.11 Tetraethylborate compound, e.g sodium tetraethylborate, NaB(C H ) .
2 5 4
NOTE The active species during derivatization is the tetraethylborate anion. The choice of the cation
is arbitrary. Sodium tetraethylborate was chosen since it is commercially available. In principle, any other
tetraethylborate compound can be used for analysis, including complexes formed with tetrahydrofuran (THF). A
simple and rapid synthesis of a suitable derivatization agent is described in A.1.
WARNING — Sodium tetraethylborate may contain traces of triethylboron, which may cause
instantaneous combustion.
5.2.12 Methanol, CH OH.
3
5.2.13 Dichloromethane, CH Cl .
2 2
5.3 Standards
WARNING — Organotin compounds vary largely regarding toxicological properties towards
mammals with respect to the alkylation stage and type of alkyl group. Cautious handling of
reagents is mandatory at any time.
Table 3 lists the standards used for calibration of the target compounds (solution A), internal standards
(solution B) and injection standard (solution C). Additional information is provided concerning weighing
factors for calculation to organotin cations (for 100 % purity of the substances).
Table 3 — Standards and internal standards for calibration of target compounds
a b c
No. Standard Abbreviation Formula CAS-RN WF Solution
5.3.1 Monobutyltin trichloride MBTCl C H SnCl 1118463 0,623 A
4 9 3
5.3.2 Dibutyltin dichloride DBTCl (C H ) SnCl 683181 0,767 A
4 9 2 2
5.3.3 Tributyltin chloride TBTCl (C H ) SnCl 1461229 0,891 A
4 9 3
5.3.4 Tetrabutyltin TTBT (C H ) Sn 1461252 1,000 A
4 9 4
5.3.5 Monooctyltin trichloride MOTCl C H SnCl 3091256 0,686 A
8 17 3
5.3.6 Dioctyltin dichloride DOTCl (C H ) SnCl 3542367 0,830 A
8 17 2 2
5.3.7 Triphenyltin chloride TPhTCl (C H ) SnCl 639587 0,908 A
6 5 3
a
Chemical Abstracts Registration Number.
b
WF= Weighing factor = Molar mass of organotin cation/molar mass of organotin compound.
c
A for the multicomponentstandard solution in methanol.
B for the solution of the internal standards in methanol.
C for the solution of the injection standards in hexane.
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Table 3 (continued)
a b c
No. Standard Abbreviation Formula CAS-RN WF Solution
5.3.8 Tricyclohexyltin chloride TCyTCl (C H ) SnCl 3091325 0,912 A
6 11 3
Internal standards
5.3.9 Monoheptyltin trichloride MHTCl C H SnCl 59344477 0,672 B
7 15 3
5.3.10 Diheptyltin dichloride DHTCl (C H ) SnCl 74340128 0,817 B
7 15 2 2
5.3.11 Tripropyltin chloride TPTCl (C H ) SnCl 2279767 0,875 B
3 7 3
5.3.12 Tetrapropyltin TTPT (C H ) Sn 2176989 1,000 B
3 7 4
5.3.13 Tetrapentyltin TTPeT (C H ) Sn 3765659 1,000 C
5 11 4
a
Chemical Abstracts Registration Number.
b
WF= Weighing factor = Molar mass of organotin cation/molar mass of organotin compound.
c
A for the multicomponentstandard solution in methanol.
B for the solution of the internal standards in methanol.
C for the solution of the injection standards in hexane.
5.4 Preparation of reagents and solutions
5.4.1 General requirements
Prepare the following (see also Table 3):
— multicomponent standard stock solution A in methanol (e.g. 1 mg/ml);
— multicomponent standard spiking solutions for calibration, by diluting solution A with methanol;
— stock solution B of internal standards in methanol (e.g. 1 mg/ml);
— spiking solution of the internal standards, by diluting solution B with methanol (e.g. 100 ng/ml);
— stock solution C of the injection standard in methanol (e.g. 2 mg/ml);
— injection standard solution, by diluting solution C (e.g. 2 µg/ml).
5.4.2 Blank solution
Add 20 ml of water (5.1) to an Erlenmeyer flask with a ground joint or a screw-capped
[polytetrafluoroethylene (PTFE) lined] vial.
5.4.3 Aqueous calibration solutions (multicomponent solution of organotin compounds in water)
For each working range, prepare at least six calibration solutions with appropriate concentration levels.
Add 20 ml of water (5.1) to an Erlenmeyer flask with a ground joint or a screw-capped (PTFE-lined) vial.
While stirring vigorously, pipette an appropriate volume of the respective spiking solution underneath
the surface and ensure that the spiking solution is well distributed in the water. Stir for additional 20 min.
5.4.4 Methanolic potassium hydroxide solution
Prepare a solution of 25 % (m/V) potassium hydroxide (5.2.5) in methanol (5.2.12). This is the
methanolic potassium hydroxide solution.
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5.4.5 Acetate buffer solution
Dissolve about 1 mol of sodium acetate (equal to 82 g of anhydrous sodium acetate) (5.2.3) in 500 ml
of water (5.1) in a 1 l volumetric flask. Add sufficient glacial acetic acid (5.2.1) to adjust to a pH of 4,5.
Dilute to volume with water (5.1) and mix well.
5.4.6 Solvent mixture
Prepare a solvent mixture of acetic acid, methanol and water with a volume ratio of 1:1:1.
5.4.7 Derivatization agent
Prepare an approximately 10 % (m/V) solution of tetraethylborate compound (5.2.11) in
tetrahydrofurane (5.2.8).
NOTE This solution is stable for about three months if stored under an inertgas blanket.
5.5 Clean-up
5.5.1 General requirements
A silica or aluminium oxide cleanup is the minimum requirement. Further cleanup steps (aluminium
oxide/silver nitrate, silica/silver nitrate, pyrogenic copper) may be applied if necessary (see Annex B).
A recovery of >80 % of the internal standards and target compounds shall be achieved for each clean-
up step.
5.5.2 Silica gel for the clean-up column
Heat silica gel (5.2.6) for at least 12 h at (500 ± 20) °C on a quartz plate in a muffle furnace. Ensure that
the temperature does not exceed 520 °C.
Allow the plate to cool in an oven to about 200 °C, transfer the silica to a widenecked glass bottle and
allow cooling to room temperature in a desiccator.
Add water to the cooled silica until a mass fraction of 3 % is reached. Close the bottle and homogenize
the contents for 2 h on a shaker.
5.5.3 Aluminium oxide for the clean-up column
Activate a
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