SIST EN ISO 23161:2019
(Main)Soil quality - Determination of selected organotin compounds - Gas-chromatographic method (ISO 23161:2018)
Soil quality - Determination of selected organotin compounds - Gas-chromatographic method (ISO 23161:2018)
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 (soil-like 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.
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.
Bodenbeschaffenheit - Bestimmung ausgewählter Organozinnverbindungen - Gaschromatographisches Verfahren (ISO 23161:2018)
Dieses Dokument legt ein Verfahren zur gaschromatographischen Identifizierung und Quantifizierung von Organozinnverbindungen (OZVs) in Böden, wie in Tabelle 1 angegeben, fest.
Dieses Dokument ist ebenfalls auf Proben von Sedimenten, Schlämmen und Abfällen (bodenähnliche Materialien) anwendbar.
Der Arbeitsbereich ist von dem angewendeten Nachweisverfahren und der für die Untersuchung genommenen Probemenge abhängig.
Die Bestimmungsgrenze der Einzelverbindungen ist etwa 10 µg/kg.
Qualité du sol - Dosage d'une sélection de composés organostanniques - Méthode par chromatographie en phase gazeuse (ISO 23161:2018)
Le présent document spécifie une méthode d'identification et de quantification des composés organostanniques (OTC) dans les sols comme spécifié dans le Tableau 1.
Le présent document est également applicable aux échantillons de sédiments, de boues et de déchets (matières semblables au sol).
La plage de travail dépend de la technique de détection utilisée et de la quantité d'échantillon prélevée pour l'analyse.
La limite de quantification applicable à chaque composé est d'environ 10 µg/kg.
Kakovost tal - Določevanje izbranih organokositrovih spojin - Metoda plinske kromatografije (ISO 23161:2018)
Ta dokument določa metodo plinske kromatografije za ugotavljanje in kvantifikacijo organokositrovih spojin (OTC) v prsteh iz preglednice 1.
Dokument se uporablja tudi za vzorce usedlin, blata in odpadkov (prsti podobnih materialov).
Delovni razpon je odvisen od uporabljene tehnike za detekcijo in količine odvzetega vzorca za analizo.
Meja kvantifikacije spojine znaša približno 10 μg/kg.
Organokositrove katione je mogoče določiti samo v skladu s tem dokumentom po derivatizaciji. Anionski del, ki je vezan na organokositrov kation, je odvisen predvsem od kemičnega okolja in se ne določa s to metodo. Peralkilirane organokositrove spojine se obnašajo povsem drugače od njihovih osnovnih spojin. Tetraalkilirane organokositrove spojine, ki so že peralkilirane, kot je tetrabutilkositer, določimo neposredno brez derivatizacije.
Lastnosti, kot so porazdelitev velikosti delcev, vsebnost vode in vsebnost organskih snovi v trdnih snoveh, ki se analizirajo s pomočjo tega dokumenta, se zelo razlikujejo. Priprava vzorca je ustrezno zasnovana in upošteva lastnosti organokositrovih spojin ter matrike za analizo.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 23161:2019
01-februar-2019
1DGRPHãþD
SIST EN ISO 23161:2012
.DNRYRVWWDO'RORþHYDQMHL]EUDQLKRUJDQRNRVLWURYLKVSRMLQ0HWRGDSOLQVNH
NURPDWRJUDILMH ,62
Soil quality - Determination of selected organotin compounds - Gas-chromatographic
method (ISO 23161:2018)
Bodenbeschaffenheit - Bestimmung ausgewählter Organozinnverbindungen -
Gaschromatographisches Verfahren (ISO 23161:2018)
Qualité du sol - Dosage d'une sélection de composés organostanniques - Méthode par
chromatographie en phase gazeuse (ISO 23161:2018)
Ta slovenski standard je istoveten z: EN ISO 23161:2018
ICS:
13.080.10 .HPLMVNH]QDþLOQRVWLWDO Chemical characteristics of
soils
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
SIST EN ISO 23161:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN ISO 23161:2019
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SIST EN ISO 23161:2019
EN ISO 23161
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2018
EUROPÄISCHE NORM
ICS 13.080.10 Supersedes EN ISO 23161:2011
English Version
Soil quality - Determination of selected organotin
compounds - Gas-chromatographic method (ISO
23161:2018)
Qualité du sol - Dosage d'une sélection de composés Bodenbeschaffenheit - Bestimmung ausgewählter
organostanniques - Méthode par chromatographie en Organozinnverbindungen - Gaschromatographisches
phase gazeuse (ISO 23161:2018) Verfahren (ISO 23161:2018)
This European Standard was approved by CEN on 31 August 2018.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2018 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 23161:2018 E
worldwide for CEN national Members.
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SIST EN ISO 23161:2019
EN ISO 23161:2018 (E)
Contents Page
European foreword . 3
2
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SIST EN ISO 23161:2019
EN ISO 23161:2018 (E)
European foreword
This document (EN ISO 23161:2018) has been prepared by Technical Committee ISO/TC 190 "Soil
quality" in collaboration with Technical Committee CEN/TC 444 “Test methods for environmental
characterization of solid matrices” the secretariat of which is held by NEN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by May 2019, and conflicting national standards shall be
withdrawn at the latest by May 2019.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN ISO 23161:2011.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Endorsement notice
The text of ISO 23161:2018 has been approved by CEN as EN ISO 23161:2018 without any modification.
3
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SIST EN ISO 23161:2019
INTERNATIONAL ISO
STANDARD 23161
Second edition
2018-10
Soil quality — Determination of
selected organotin compounds — Gas-
chromatographic method
Qualité du sol — Dosage d'une sélection de composés
organostanniques — Méthode par chromatographie en phase gazeuse
Reference number
ISO 23161:2018(E)
©
ISO 2018
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SIST EN ISO 23161:2019
ISO 23161:2018(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2018
All rights reserved. Unless otherwise specified, or required in the context of its implementation, 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 written permission. Permission can be requested 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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CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2018 – All rights reserved
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SIST EN ISO 23161:2019
ISO 23161:2018(E)
Contents Page
Foreword .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
5.4.1 General requirements . 6
5.4.2 Blank solution . 6
5.4.3 Aqueous calibration solutions (multicomponent solution of organotin
compounds in water) . 6
5.4.4 Methanolic potassium hydroxide solution . 7
5.4.5 Acetate buffer solution . 7
5.4.6 Solvent mixture . 7
5.4.7 Derivatization agent . 7
5.5 Clean-up . 7
5.5.1 General requirements . 7
5.5.2 Silica gel for the clean-up column . 7
5.5.3 Aluminium oxide for the clean-up column . 7
5.5.4 Clean-up column . 7
5.5.5 Eluent for extract cleaning with silica gel . 8
5.5.6 Eluent for extract cleaning with aluminium oxide . 8
6 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 Clean-up of the extract .11
7.3.1 General.11
7.3.2 Silica and aluminium oxide clean-up.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 .14
12 Validation .15
13 Test report .15
Annex A (informative) Information about the procedure .16
Annex B (informative) Additional clean-up procedures .18
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Annex C (informative) Information about typical instrumental conditions .20
Annex D (informative) Information about GC-MS identification.31
Annex E (informative) Performance data .33
Bibliography .36
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SIST EN ISO 23161:2019
ISO 23161:2018(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.
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 voluntary nature of standards, 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.
This document was prepared by Technical Committee 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), which has been technically
revised.
The main changes compared to the previous edition are as follows:
— note in Clause 1 (converted to normal text) and Table 2 have been moved to Clause 4;
— former Note 4 in Clause 4 has been changed to normal text and moved above Note 1;
— other pretreatment procedures allowed in Clause 4 and in 7.1;
— former second sentence in 5.5.5 has been changed to Note;
— storage conditions has been changed to be consistent with ISO 5667-15;
— the Bibliography has been updated.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www .iso .org/members .html.
© ISO 2018 – All rights reserved v
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SIST EN ISO 23161:2019
INTERNATIONAL STANDARD ISO 23161:2018(E)
Soil quality — Determination of selected organotin
compounds — Gas-chromatographic method
WARNING — Persons using this document should be familiar with usual 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.
IMPORTANT — 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.
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 (soil-like 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
(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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ISO 23161:2018(E)
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:
— ISO Online browsing platform: available at https: //www .iso .org/obp
— IEC Electropedia: available at http: //www .electropedia .org/
3.1
organotin compound
substance containing 1 to 4 Sn-C 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 (soil-like material)
4 Principle
For the ionic and the non-ionic 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. The determination of non-ionic TTBT cannot be carried out with freeze-dried 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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SIST EN ISO 23161:2019
ISO 23161:2018(E)
Figure 1 — Flowchart for the pretreatment and analysis of selected organotin compounds
Beside freeze drying, other pretreatment procedures can be carried out, if the suitability has been proven.
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.
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 non-polar organotin cation derivatives. In situ methods
can improve the extraction efficiency, particularly for monoalkylated organotin compounds.
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ISO 23161:2018(E)
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. Clean-up with silica or aluminium oxide is the minimum;
further clean-up 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 clean-up 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
multi-component 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 and the glassware
can contain impurities of organotin compounds. It is absolutely essential to verify the blanks.
5.1.1 Water, in accordance with grade 3 of ISO 3696, the water shall be free of interferences.
5.2 Chemicals
5.2.1 Acetic acid, CH COOH, glacial.
3
5.2.2 Sodium hydroxide solution, NaOH, approximately 400 g/l (aqueous solution).
5.2.3 Sodium acetate, CH COONa.
3
5.2.4 Sodium sulfate, Na SO , anhydrous.
2 4
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).
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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 (i-hexane) 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
...
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