SIST EN ISO 11369:1998
(Main)Water quality - Determination of selected plant treatment agents - Method using high performance liquid chromatography with UV detection after solid-liquid extraction (ISO 11369:1997)
Water quality - Determination of selected plant treatment agents - Method using high performance liquid chromatography with UV detection after solid-liquid extraction (ISO 11369:1997)
Wasserbeschaffenheit - Bestimmung ausgewählter Pflanzenbehandlungsmittel - Verfahren mit der Hochauflösungs-Flüssigkeitschromatographie mit UV-Detektion nach Fest-Flüssig-Extraktion (ISO 11369:1997)
Das in dieser Norm beschriebene Verfahren ist anwendbar auf die Bestimmung ausgewählter Pflanzenbehandlungsmittel, einige ihrer Hauptabbauprodukte (Metaboliten) in Trinkwasser in Massenkonzentrationen > 0,05 micro g/l. Das Verfahren darf auch auf weitere, hier nicht genannte Substanzen und auf die Untersuchung von Oberflächenwasser ausgedehnt werden, vorausgesetzt, daß das Verfahren für jeden individuellen Fall abgesichert wird.
Qualité de l'eau - Dosage de certains agents de traitement des plantes - Méthode par chromatographie en phase liquide a haute performance (CLHP) avec détection UV apres extraction solide-liquide (ISO 11369:1997)
La présente Norme internationale décrit une méthode pour la détermination d'agents organiques de traitement des plantes dans les eaux potables et les eaux souterraines en utilisant la chromatographie en phase liquide à haute performance (CLHP) avec détection UV après extraction solide-liquide. La méthode décrite dans la présente Norme internationale est applicable à la détermination de certains agents de traitement des plantes et de certains de leurs principaux produits de dégradation (métabolites) dans l'eau destinée à la consommation humaine pour une concentration limite validée supérieure à environ 0,1 µg/l. Des valeurs supplémentaires limites indiquent que cette limite peut être étendue à 0,05 µg/l (voir des exemples au tableau 1). La méthode peut être étendue à d'autres types de substances et à l'eau souterraine, sous réserve que la méthode soit validée pour chaque cas particulier. Le choix des agents de traitement des plantes et des principaux produits de dégradation figurant au tableau 1 a été arrêté en fonction des connaissances acquises au moment de l'essai interlaboratoire (conduit en 1992). Des données relatives à d'autres substances sont données en annexe A.
Kakovost vode - Določanje izbranih sredstev za zaščito rastlin - Metoda z uporabo tekočinske kromatografije visoke ločljivosti (ISO 11369:1997)
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 11369:1998
01-januar-1998
.DNRYRVWYRGH'RORþDQMHL]EUDQLKVUHGVWHY]D]DãþLWRUDVWOLQ0HWRGD]XSRUDER
WHNRþLQVNHNURPDWRJUDILMHYLVRNHORþOMLYRVWL ,62
Water quality - Determination of selected plant treatment agents - Method using high
performance liquid chromatography with UV detection after solid-liquid extraction (ISO
11369:1997)
Wasserbeschaffenheit - Bestimmung ausgewählter Pflanzenbehandlungsmittel -
Verfahren mit der Hochauflösungs-Flüssigkeitschromatographie mit UV-Detektion nach
Fest-Flüssig-Extraktion (ISO 11369:1997)
Qualité de l'eau - Dosage de certains agents de traitement des plantes - Méthode par
chromatographie en phase liquide a haute performance (CLHP) avec détection UV apres
extraction solide-liquide (ISO 11369:1997)
Ta slovenski standard je istoveten z: EN ISO 11369:1997
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
SIST EN ISO 11369:1998 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN ISO 11369:1998
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SIST EN ISO 11369:1998
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SIST EN ISO 11369:1998
IS0
INTERNATIONAL
STANDARD 11369
First edition
1997-08-01
Water quality - Determination of selected
plant treatment agents - Method using
high performance liquid chromatography
with UV detection after solid-liquid
extraction
Qua/it6 de I’eau - Dosage de certains agents de traitement des p/antes -
Mkthode par chromatographie en phase liquide & haute performance (CLHP)
avec dgtection UV apr& extraction solide liquide
Reference number
IS0 11369: 1997(E)
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SIST EN ISO 11369:1998
IS0 11369:1997(E)
Page
Contents
1
0.0.~.~~.~.~.~.~.~.~.
1 Scope
2
2 llnterferences . . . . . . . . . . . . . . . . . . . . .~.~.
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3 Normatives references
2
Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4
2
5 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6 Apparatus
4
7 Sampling and samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
a Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
9 Calibration
13
Evaluation .0.*.
10
14
. . . . . . . . . . . . . . . . . . . . . . . . . . . .*.
11 Expression of results
14
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12 Test report
14
13 Precision data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.............................................. 15
Annex A (informative) Recovery rates
........................ 17
Annex B (informative) Results of interlaboratory trial
0 IS0 1997
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 the publisher.
International Organization for Standardization
Case postale 56 l Cl-l-121 1 Geneve 20 l Switzerland
lnternet: central @ iso.ch
X.400: c=ch; a=400net; p=iso; o=isocs; sxentral
Printed in Switzerland
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SIST EN ISO 11369:1998
@ IS0 IS0 11369: 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 11369 was prepared by Technical Committee
ISOmC 147, Water quality, Subcommittee SC 2, physical, chemical and
biochemical methods.
Annexes A and B of this International Standard are for information only.
. . .
III
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SIST EN ISO 11369:1998
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IS0 11369: 1997(E)
INTERNATIONAL STANDARD @ IS0
Wuter quality - Determination of selected plant treatment agents - Method using
high performance liquid chromatography with UV detection after solid-liquid extraction
1 Scope
This International Standard describes a method for the determination of organic plant treatment agents in
drinking and ground water using high performance liquid chromatography (HPLC) with UV detection after
solid-liquid extraction.
The method described in this International Standard is applicable to the determination of selected plant
treatment agents and some of their main degradation products (metabolites) in drinking water with a validated
reporting limit of about 0,l pg/I. Limited additional data indicate that it can be extended to 0,05 pg/I (see table 1
for examples). The method may be extended to include additional substances and ground water, provided the
method is validated for each individual case.
The selection of the plant treatment agents and main degradation products in table 1 has been made according
to the knowledge at the time of the interlaboratory trial (1992). Data for some other substances are given in
annex A.
Plant treatment agents to which this International Standard applies
Table 1 -
Name Molecular Molar mass CAS No.” Substance
formula family2’
I
Atrazine w4w
215,7 001912-24-9
T
Chlorotoluron w,,w~
212,7 0 15545-48-9
H
240,7 021725-46-z
Cyanazine** T
w3wi
Desethylatrazine * C,H,CIN, 186,6
006190-65-4 T
Diuron 233,l 000330-54-1 H
wocI*w
Hexazinone**
w ,,w, 252,3 051235-04-2
T
lsoproturon
C,*H,*w 206,3 034123-59-6
H
Linuron wow 20,
249,l 000330-55-2
H
277,8 067129-08-Z
Metazachlor A
w&w03
Methabenzthiazuron c,,H,,wS
221,3 018691-97-9 H
Metobromuron** 259,l 003060-89-7 H
W,WO2
Metolachlor
w,,cw 283,8 051218-45-2
A
Metoxuron** w,,wO*
228,7 19937-59-8
H
Monolinuron W,WO2
214,6 1746-81-2 H
Sebutylazine** W,CIN5 228,7
00728-69-3 T
enylurea herbicide; A: substituted anilide
*: Main degradation product of atrazine
Not included in the performance data
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SIST EN ISO 11369:1998
IS0 11369:1997(E)
2 Interferences
2.1 Interferences with the enrichment
The commercially available RP (reversed phase)-Cl8 materials are often of varying quality. Considerable
batch-to-batch differences regarding quality and selectivity of this material even from one manufacturer are
possible. The recovery may vary with the concentration. Co-extractants eluted from the sorbent material can
affect the blank and the recovery. Therefore the calibration and analysis are performed on exactly the same
batch of sorbent. Also any UV-absorbing material occurring in the water which passes through the procedure
and has a retention time similar to the standard will interfere. Suspended matter in the water sample may clog
the packing. In this case the water sample is filtered through a glass fibre filter prior to the enrichment.
2.2 Interferences with the HPLC measurement
Substances which absorb at the wavelengths of detection and have retention times similar to those of the
compounds to be investigated will interfere with the determination. This shall especially be taken into account
when examining samples other than ground- and drinking water.
3 Normative references
The following standards contain provisions which, through reference to 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
possiblity 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-l : 1980, Water quality - Sampling - Part 7: Guidance on the design of sampling programmes
IS0 5667-2 : 199 1, Water quality - Sampling - Part 2: Guidance on sampling techniques
IS0 5667-3: 1994, Water quality - Sampling - Part 3: Guidance on the preservation and handling of samples
IS0 8466-l: 1990, Water quality - Calibration and evaluation of analytical methods and estimation of
performance characteristics - Part 7: Statistical evaluation of the linear calibration function.
ISO/TR 13530:-“, Water quality - General guidance to analytical quality control for water analysis
4 Principle
The plant treatment substances in the water sample are extracted by solid-liquid extraction on RP-Cl8 material
(RP = reversed phase), eluted with a solvent and then separated, identified and quantified by high performance
liquid chromatography (HPLC) using UV detection.
5 Reagents
5.1 General requirements
Water, solvents and reagents shall be of sufficient purity (e.g. residue grade or HPLC grade) as far as available
and shall not contain any measurable UV absorbing substances interfering with the compounds of interest.
5.2 Nitrogen, high purity, for drying solvents and, if need be, for concentration by evaporation of the eluates.
5.3 Helium, high purity , for degassing HPLC solvents (see also 6.13)
1) To be published.
2
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SIST EN ISO 11369:1998
@ IS0 IS0 11369:1997(E)
5.4 Mineral acid, e. g. phosphoric acid, c(H,PO,) = 1 mol/l.
5.5 Sodium hydroxide solution c(NaOH) = 1 mol/l.
5.6 RP-Cl8 sorbent, for the solid-phase extraction. For quality and selectivity of the material see 2.1.
and if it has
NOTE: Other solid-phase adsorbents may be used, if the performance is corn parable to this material
been proved suitable according to 2.1
5.7 Solvents, e. g. methanol (CH,OH), acetonitrile (CH,CN), acetone (C,H,O).
WARNING These solvents, especially acetonitrile, are toxic agents. Caution shall be exercised when handling.
5.8 Reference standards (see table I), of high purity or certified material.
5.9 Solutions of the individual standards
Place 50 mg (for example) of the reference standards (see 5.8) into a 100 ml volumetric flask, dissolve it in
methanol or another solvent (see 5.7) and make up to volume with the solvent.
NOTE: Simazine is only poorly soluble in acetonitrile.
Store the solutions at about 4 “C, protected from light. They are stable for at least one month depending on the
compound of interest. For longer use, check regularly by comparison with an independent, preferably certified,
standard solution.
5.W Stock solution
volumetric
As an I example, pipette 1 ml. each of the solution of the individual substances (see 5.9) into a 100 m.t
and make up to volume with methanol or another solvent (5.7).
flask,
protected from light. They are stable for at least one month depending on the
Store the solutions at about 4 OC,
compound of interest.
5.11 Reference solutions for multipoint calibration
Prepare the solutions by an adequate dilution of the stock solution (5.10) or several stock solutions to have at
least 5 multicomponent reference solutions, e.g. Pi = 20 to 200 ng/ml. As solvent, use the initial HPLC eluant
mixture.
Store the reference solutions at about 4 OC, protected from light. They are stable for at least one week.
5.12 Buffer solutions for gradient elution
As an example, aqueous solution of ammonium acetate (CH,COONH,), or sodium acetate CH,COONa, concen-
tration 5 20 mmol/l. (See also the figures).
Filter the solution through a membrane filter, pore size 0,45 pm, before use.
NOTE: Due to microbiological activity, the shelf-life of the buffer may be limited. Therefore it should be replaced
every second day.
6 Apparatus
6.1 General requirements
Equipment or parts of it which may come into contact with the sample or its extract shall be free from residues
that could cause unacceptable interference in blanks. It is recommended to use glass, stainless steel or
polytetrafluoroethene (PTFE), and, for cartridges, also polypropene.
3
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SIST EN ISO 11369:1998
@ IS0
IS0 11369:1997(E)
6.2 Cartridges from polypropene or glass, filled with RP-Cl8, of e.g. internal diameter 9 mm, length 8 cm, or
commercially available prefilled cartridges.
6.3 Flat-bottom flasks or bottles for sampling, preferably brown glass, 1000 ml and 2000 ml, stoppered with
ground glass stoppers or with PTFE-lined screw caps.
6.4 Graduated cylinders, 10 ml and 1000 ml.
6.5 Glass vessels for the collection and evaporation of the eluates, such as centrifuge tubes, 12 ml, with
ground glass stoppers.
6.6 Equipment for evaporation of &J&es, e. g. rotary evaporator with vacuum stabilizer and
temperature-controlled water bath, or equipment for evaporation of solvent with nitrogen.
6.7 Glass vials with inert stopper, such as PTFE-coated septum, for storage of extracts.
6.8 Volumetric flasks, 1 ml, 10 ml, and 100 ml.
6.9 Microlitre syringes, 25 ~1, 50 ~1, 100 ~1, 250 ~1 and 1000 ~1, for manual injection into the HPLC system, for
preparation of the reference solutions and for adding the solvent to redissolve the residue of evaporated
eluates.
6.10 Borosilicate glass fibre filter diameter, O,75 to I,5 pm, with inorganic binding material.
6.11 Membrane filter for clear filtration of the extracts, such as a polyamide or cellulose membrane, pore
size 0,2 pm to 0,45 pm.
6.12 Vacuum or overpressure assembly, for sample enrichment and extract concentration.
6.13 Degassing system for the HPLC instrument.
6.14 Analytical column
Typical analytical column, length up to 300 mm, internal diameter 2 mm to 4,6 mm, packed with RP-Cl8
material, particle size 3 pm to 5 pm. The column shall be capable of a baseline resolution of the compounds
listed in table 1 (see also the figures).
6.15 High performance liquid chromatograph, consisting of
a) solvent gradient elution system with manual or automatic sampling application, designed for the desired
analytical working range;
b) degassing assembly, if necessary;
c) column thermostat, able to guarantee a constant temperature with less than k 1 OC deviation;
rray detector, for the on-line ret ording of absorption spectra in th
d) UV detector, preferably diode-a e range
200 nm to 350 nm, or alternatively, a detector capable of monitoring at least two different wavelengths.
e) data processing or integration system.
7 Sampling and samples
Use for sampling carefully cleaned, preferably brown, flat-bottom glass flasks (see 6.3). Rinse the flasks with
the water to be sampled; treat the ground glass stoppers or the lined caps in the same way.
Fill the bottles to the brim with the water to be examined.
4
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SIST EN ISO 11369:1998
@ IS0 ISO11369:1997( E)
Extract plant treatment substances from the water samples as soon as possible after sample collection.
To avoid interferences, collect samples as stated below and according to the approriate part of IS0 5667.
If storage is unavoidable, keep the water sample at 4 OC in the dark.
NOTE: Water samples may be stored at 4 “C and for not longer than 1 week.
8 Procedure
8.1 General requirements
It is absolutely essential that tests conducted according to this International Standard are carried out by
suitably qualified staff.
The same conditions (e.g. amount of adsorbent, type of cartridge, conditioning, sample volume and flow,
eluting steps and volumes) shall be used for all samples within one batch, including the procedure recovery
samples.
It should be investigated whether, and to what extent, particular problems will require the specification of
additional marginal conditions.
NOTE: Low recovery rates can result from using an insufficient amount of Cl8 sorbent or an insufficient volume of
methanol for the conditioning or elution step. Before analysing, these conditions should be checked and optimized
in each laboratory. For common recovery rates, see annex A.
8.2 Conditioning of the RP-Cl8 material
For a water volume of 1000 ml, place I,0 g to 2,0 g of RP-Cl8 material (see 5.6) into a cartridge or a glass
column ,or use an adequate commercial device.
NOTE: For more polar substances, e.g. metabolites, poor recoveries result when using 1 g/l for a one-litre sample.
Rinse the RP-Cl8 material in the cartridge or glass columns with five times its bed volume of eluting solvent
(see 5.7).
ng five times its volume) and use the moist carrier
Rewash with water (see 5.1) (usi materia I for the enrichment.
The sorbent shall remain moist.
8.3 Enrichment
by filtration through a glass fibre filter and record this in the final
If necessary, remove suspended matter
report.
If filtration is carried out, use spiked samples in order to verify that the recovery is not influenced
by this
additional ste
Measure the water sample to be examined, e. g. 1 000 ml, adjust the pH to 6 to 8 with either mineral acid (see
5.4) or sodium hydroxide solution (see 5.5).
Pass the water sample through 1 g of adsorbent at a flow rate of between 3 ml/min to 15 mI/min. If 2 g of
adsorben not exceed 25 ml/mi
t are used, the flowrate should n.
Regulate the flowrate by adjusting the vacuum or the overpressure, respectively.
Dry the sorbent, for example in a stream of nitrogen or air (at least 45 min of approx y 200 ml/min of
nitrogen or air, room temperature).
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SIST EN ISO 11369:1998
IS0 11369:1997(E)
8.4 Elution
Elute in the following way with at least 1 ml of solvent (see 5.7) per 500 mg of RP-Cl8 material (see 5.6).
Place half of the appropriate quantity of eluan
...
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