EN ISO 10301:1997

SLOVENSKI STANDARD
01-januar-1998
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Water quality - Determination of highly volatile halogenated hydrocarbons - Gas-
chromatographic methods (ISO 10301:1997)
Wasserbeschaffenheit - Bestimmung leichtflüchtiger halogenierter Kohlenwasserstoffe -
Gaschromatographische Verfahren (ISO 10301:1997)
Qualité de l'eau - Dosage des hydrocarbures halogénés hautement volatils - Méthodes
par chromatographie en phase gazeuse (ISO 10301:1997)
Ta slovenski standard je istoveten z: EN ISO 10301:1997
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

INTERNATIONAL IS0
STANDARD 10301
First edition
1997-04-I 5
Water quality -
Determination of highly
volatile halogenated hydrocarbons -
Gas-chromatographic methods
Qualit de I’eau - Dosage des hydrocarbures halog&& hautemen t vola tils -
Mkthodes par chromatographie en phase gazeuse
Reference number
IS0 10301:1997(E)
IS0 10301:1997(E)
Contents
SECTION 1: General
1 .I Scope
1.2 Normative references
1.3 Definition
SECTION 2: Liquid/liquid extraction and analysis by gas chromatography
2.1 Principle
2.2 Interferences
2.3 Reagents
2.4 Apparatus
2.5 Sampling and sample preparation
2.6 Procedure
2.7 Calibration
2.8 Identification and evaluation
2.9 Expression of results
2.10 Precision data
2.11 Test report
0 IS0 1997
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced
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microfilm, without permission in writing from the publisher.
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Printed in Switzerland
ii
IS0 10301:1997(E)
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SECT ‘ION 3: Static headspace method and ana lysis by gas chromatography 22
3.1 Principle
3.2 Interferences 22
3.3 Reagents 22
3.4 Apparatus
3.5 Sampling
3.6 Procedure
3.7 Calibration
3.8 Identification and evaluation 29
3.9 Expression of results 31
3.10 Precision data
3.11 Test report
Annex A (informative) Characteristics of highly volatile halogenated
hydrocarbons
Annex B (informative) Examples of gas chromatograms for highly volatile
halogenated hydrocarbons
Annex C (informative) Example of a microseparator 45
Annex D (informative) Sensitivity of electron-capture detector 46
Annex E (informative) Extraction recovery with pentane
Annex F (informative) Qualitative method for testing the quality of
“penicillin type” stoppers 48
Annex G (informative) Collection of samples
. . .
III
IS0 10301:1997(E)
Foreword
IS0 (the International Organization for Standardization) is a worldwide federation of
national standards bodies (IS0 member bodies). The work of preparing International
Standards is normally carried out through IS0 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.
IS0 collaborates closely with the International Electrotechnical Commission (IEC) on
all matters of electrotechnical standardization.
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.
International Standard IS0 10301 was prepared by Technical Committee lSO/TC 147,
Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods.
Annexes A to G of this International Standard are for information only.
IV
@ IS0 IS0 10301:1997(E)
Introduction
Highly volatile halogenated hydrocarbons are used in industrial, commercial and
domestic fields, and can enter a water body via waste water and may consequ ently
contaminate drinking water. Furthermore, they can originate from the use of chl orine
as an oxidizing agent in water and waste-water treatment. They also can be
introduced by inappropriate handling. In addition, they can be formed by
decomposition of higher molecular mass organohalogen derivatives.
In uncontaminated ground water and rain water, the concentrations of halogenated
hydrocarbons are generally below 0,l ug/l. In surface water they may be higher,
depending on the origin and quality of the water. In untreated waste water the
concentrations may reach saturation of the aqueous phase. In general, the solubility
of these compounds in organic solvents and in fatty material exceeds their solubility
in water.
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INTERNATIONAL STANDARD @ ~so IS0 10301:1997(E)
Water quality - Determination of highly volatile
halogenated hydrocarbons - Gas-chromatographic
methods
Section 1 : General
II . Scope
This International Standard specifies two methods for the determination of highly
volatile halogenated hydrocarbons using gas chromatography.
Section 2 specifies a method for the determination by liquid/liquid extraction of highly
volatile halogenated hydrocarbons in drinking water, ground water, swimming pool
water, most rivers and lakes and many sewage and industrial effluents. Typical values
of “quantification limits” are given in table 1.
Table 1 - Typical values of “quantification limits“ for some highly volatile
halogenated hydrocarbons using liquid/liquid extraction
Compound p!ipxmq
1 Dichloromethane
150 ---1
1 Chloroform I 0,05 - 0,3 I
IO,01 - 0,l
1 Carbon tetrachloride
I
I l,l-Dichloroethane Il,O-5
I
I 1,2-Dichloroethane 15- 10
--I
1 l,l,l-Trichloroethane IO,02 - 0,l
I
I 1,1,2,2-Tetrachloroethane IO,05 - 0,l
I
IO,01 - 0,05
I Hexachloroethane
I
I cis-1,2-Dichloroethylene I5 - 50
~~~ ---I
1 trans-1,2-Dichloroethylene II -10 I
IO,05 - 0,l
I Trichloroethylene
I
I Tetrachloroethylene
IO1 I I
I Hexachlorobutadiene
I WI ---I
I Tribromomethane lo I 1 I
I 1,1,2-Trichlorotrifluoroethane , I
lo1
Section 3 specifies a method for the determination of highly volatile halogenated
hydrocarbons in drinking water, surface waters and ground water by a static head-
space method. Typical values of “quantification limits” are given in table 2.
In practise, the head-space method is applicable for industrial effluents as a screening
method, but in some cases it is necessary to confirm the result by the liquid-liquid
extraction method.
NOTE : When applying this International Standard, the guide on analytical
quality control for water analysis (see lSO/TR 13530) should be followed,
especially for the calibration steps.

IS0 10301:1997(E) 0 IS0
Table 2 - Typical values of “quantification limits” for some highly volatile
halogenated hydrocarbons using static head-space method
1.2 Normative references
The following standards contain provisions which, through reference in this text,
constitute provisions of this International Standard. At the time of publication, the
editions indicated were valid. All standards are subject to revision, and parties to
agreements based on this International Standard are encouraged to investigate the
possibility of applying the most recent editions of the standards indicated below.
Members of IEC and IS0 maintain registers of currently valid International Standards.
IS0 5667-1:1980, Water quality - Sampling - Part 1 : Guidance on the design of
sampling programmes
IS0 5667-2:1991, Water quality - Sampling - Part 2 : Guidance on sampling
techniques
Water quality -
Guide to analytical quality control for water
lSO/rR 13530:-l’
analysis
‘) In preparation.
IS0 10301:1997(E)
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1.3 Definition
For the purposes of this International Standard, the following definition applies :
1.3.1 highly volatile halogenated hydrocarbons: Fluorinated, chlorinated, brominated
and/or iodinated mainly nonaromatic hydrocarbons composed of one to six atoms of
carbon.
NOTE Their boiling points generally fall within the range of 20 “C to 220 “C at atmospheric pressure
(see annex A).
IS0 10301:1997(E)
Section 2 : Liquid/liquid extraction and analysis by gas
chromatography
2.1 Principle
The highly volatile halogenated hydrocarbons are extracted into an organic solvent.
The solution is then analysed by gas chromatography with an electron-capture
detector or any other suitable detector.
2.2 Interferences
Interferences can be due to the sampling procedure, vials and stoppers, solvents,
gases, organic compounds in the laboratory atmosphere and contamination from the
autosampler. Procedures for minimizing contamination are given in 2.5 and 2.6.
2.3 Reagents
All reagents shall be of sufficient purity so as to not give rise to significant interfering
peaks in the gas chromatogram of the solvent extract. The purity of reagents shall be
verified by a suitable procedure, for example, by blank determinations (see 2.6.4).
Reagents can become contaminated by contact with air and other materials,
particularly plastics, or by degradation caused by the action of light. Store all reagents
in the dark in tightly sealed all-glass containers or other suitable vessels.
2.3.1 Water for the preparation of calibration solutions and blank
The quality of the water used shall be determined. For example, use the following
procedure as a suitable preparation method :
Place water in a bottle with a conical shoulder, nominal capacity 2 litres, fitted with a
ground-glass stopper, pretreated according to 2.4.2.
Determine the content of the highly volatile halogenated hydrocarbons in this water.
If the water is contaminated, purify as follows :
- position a glass delivery tube with a sintered glass distributor a few millimetres
above the bottom of the bottle ;
- heat the water to approximately 60 OC ;
- pass a stream of clean nitrogen (approximately 150-200 mI/min) through the
water for 1 h via the bubbler. Let the water cool to room temperature and
stopper the bottle ;
- store the water in a glass bottle in the dark.
@ IS0 IS0 10301:1997(E)
Subsequently verify again the absence of highly volatile halogenated hydrocarbons. If
contamination is found, use a purge gas of another source and repeat the procedure.
2.3.2 Gases for gas chromatography
Nitrogen, ultrapure, volume concentration minimum 99,996 %, or argon-methane
mixture, ultrapure. Other gases for gas chromatography shall be in accordance with
the instrument manufacturer’s instructions.
2.3.3 Extraction solvent (pentane) free from highly volatile chlorinated hydrocarbons
Analyse a sample of the extraction solvent by electron-capture gas chromatography to
ensure that it does not contain material giving rise to interfering peaks in the
chromatogram. If the compound of interest elutes in the same range as the extraction
solvent, then use other solvents such as hexane, petroleum ether, heptane or xylene
(for waste waters), providing that the validity of the result is maintained.
2.3.4 Sodium sulfate, anhydrous
Heat a portion of about 250 g to 300 g of Na,SO, at 500 OC k 20 “C for 4 h it 30 min ;
cool to about 200 “C in a muffle furnace and then to ambient temperature in a
desiccator containing magnesium perchlorate (2.3.6) or equivalent alternative.
2.3.5 Sodium thiosulfate
Prepare a sodium thiosulfate solution (30 g/l) by dissolving 46 g k 0,2 g of sodium
thiosulfate pentahydrate (Na,S,0,m5H,0) in 1 000 ml 2 5 ml water (see 2.3.1).
NOTE : Alternatively, solid sodium thiosulfate may be used.
2.3.6 Magnesium perchlorate
2.3.7 Water-miscible solvent
NOTE : Methanol, acetoneor dimethylformamide may be used.
2.3.8 Reference substances
Pure examples of the highly halogenated hydrocarbons to be determined are
required.
Store these reference substances in areas separate from sample extracts and the
solvent used for the extraction.
ambient temperature, it is recommended to use
which are gaseous at
NOTE : For reference substances
solutions.
commercially available
0 IS0
IS0 10301:1997(E)
2.3.9 Standard stock solutions
Prepare standard stock solutions by adding with a microlitre syringe defined
quantities of each reference substance (see 2.3.8) under the surface of a suitable
solvent.
NOTE Suitable solvents for the preparati on of standard stock solutions are acetone, pentane, hexane,
dimethylbenzen e or is0 Ioctane.
The containers containing the solutions shall be marked or weighed so that any
evaporation losses of the solvent may be recognized. The solutions shall be stored in
volumetric flasks with ground glass stoppers at a temperature of 4 “C in the dark.
Prior to use, they shall be brought to ambient temperature and the level of solvent
shall be adjusted, if necessary.
NOTE 1: A convenient concentration of standard stock solution is obtained by weighing 50 mg of the
reference substance and dissolving it in 100 ml of the solvent. The solution is stable for about
1 year.
NOTE 2: For practical reasons, it is recommended to use mixed standard stock solutions.
2.3.10 Intermediate standard solutions
Prepare intermediate standard solutions by a suitable dilution of the stock
solut
...