CEN/TS 17062:2017
(Main)Foods of plant origin - Multimethod for the determination of pesticide residues in vegetable oils by LC-MS/MS
Foods of plant origin - Multimethod for the determination of pesticide residues in vegetable oils by LC-MS/MS
This European Technical Specification describes a method for the analysis of pesticide residues in plant oils (fat content > 90 %, water content < 5 %). It has been validated in an interlaboratory test with olive oil. However, laboratory experiences are available also for other kind of oils such as sunflower seed oil, sesame oil, flax seed oil, rape seed oil, grape seed oil, thistle oil and pumpkin seed oil.
Pflanzliche Lebensmittel - Multiverfahren zur Bestimmung von Pestizidrückständen in pflanzlichen Ölen mit LC-MS/MS
Diese europäische Technische Spezifikation beschreibt ein Verfahren zur Bestimmung von Pflanzenschutzmittel-Rückständen in pflanzlichen Ölen (Fettgehalt > 90 %, Wassergehalt < 5 %). Das Verfahren wurde in einem Ringversuch mit Olivenöl validiert. Laborerfahrungen sind jedoch auch bei anderen Ölsorten wie Sonnenblumenöl, Sesamöl, Leinöl, Rapsöl, Traubenkernöl, Distelöl und Kürbiskernöl vorhanden.
Aliments d’origine végétale - Multiméthode de détermination de la teneur en résidus de pesticides dans les huiles végétales par CL-SM/SM
La présente Spécification technique européenne décrit une méthode d’analyse des résidus de pesticides dans les huiles végétales (teneur en matière grasse > 90 %, teneur en eau < 5 %). Elle a été validée lors d’un essai interlaboratoire avec de l’huile d’olive. Toutefois, les expériences menées en laboratoire sont également disponibles pour d’autres types d’huiles telles que l’huile de tournesol, l’huile de sésame, l’huile de lin, l’huile de colza, l’huile de pépins de raisin, l’huile de chardon et l’huile de pépins de courge.
Hrana rastlinskega izvora - Večelementna metoda za določanje ostankov pesticidov v rastlinskih oljih z LC-MS/MS
Ta evropska tehnična specifikacija določa metodo za analizo ostankov pesticidov v rastlinskih oljih (vsebnost maščob > 90 %, vsebnost vode < 5 %). Potrjena je bila v okviru medlaboratorijskega preskusa z olivnim oljem. Rezultati laboratorijskih preskusov pa so na voljo tudi za druga olja, kot so olje iz sončničnih semen, sezamovo olje, olje iz lanenih semen, olje iz oljne repice, olje grozdnih pečk, olje iz semen žafranike in bučno olje.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-november-2017
+UDQDUDVWOLQVNHJDL]YRUD9HþHOHPHQWQDPHWRGD]DGRORþDQMHRVWDQNRY
SHVWLFLGRYYUDVWOLQVNLKROMLK]/&0606
Foods of plant origin - Multimethod for the determination of pesticide residues in
vegetable oils by LC-MS/MS
Pflanzliche Lebensmittel - Multiverfahren zur Bestimmung von Pestizidrückständen in
pflanzlichen Ölen mit LC-MS/MS
Aliments d'origine végétale - Multiméthode de détermination des résidus de pesticides
dans les huiles végétales par CL-SM/SM
Ta slovenski standard je istoveten z: CEN/TS 17062:2017
ICS:
67.050 Splošne preskusne in General methods of tests and
analizne metode za živilske analysis for food products
proizvode
67.200.10 5DVWOLQVNHLQåLYDOVNH Animal and vegetable fats
PDãþREHLQROMD and oils
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
CEN/TS 17062
TECHNICAL SPECIFICATION
SPÉCIFICATION TECHNIQUE
September 2017
TECHNISCHE SPEZIFIKATION
ICS 67.050
English Version
Foods of plant origin - Multimethod for the determination
of pesticide residues in vegetable oils by LC-MS/MS
Aliments d'origine végétale - Multiméthode de Pflanzliche Lebensmittel - Multiverfahren zur
détermination de la teneur en résidus de pesticides Bestimmung von Pestizidrückständen in pflanzlichen
dans les huiles végétales par CL-SM/SM Ölen mit LC-MS/MS
This Technical Specification (CEN/TS) was approved by CEN on 11 May 2017 for provisional application.
The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to
submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard.
CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS
available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in
parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached.
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: Avenue Marnix 17, B-1000 Brussels
© 2017 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 17062:2017 E
worldwide for CEN national Members.
Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Principle . 4
4 Reagents . 4
5 Apparatus . 7
6 Procedure. 7
7 Evaluation of results . 9
8 Precision . 10
9 Test report . 11
Annex A (informative) Examples of experimental conditions . 12
A.1 HPLC-System 1. 12
A.2 HPLC-System 2. 12
A.3 HPLC-System 3. 13
A.4 HPLC system 4 . 13
Annex B (informative) Precision data and recovery . 15
Annex C (informative) Scheme of procedure (for 2 g of sample) . 24
Annex D (informative) Complementary information - Recovery studies . 25
Bibliography . 26
European foreword
This document (CEN/TS 17062:2017) has been prepared by Technical Committee CEN/TC 275 “Food
analysis - Horizontal methods”, the secretariat of which is held by DIN.
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.
WARNING — The application of this Technical Specification may involve hazardous materials,
operations and equipment. This Technical Specification does not claim to address all the safety
problems associated with its use. It is the responsibility of the user of this Technical
Specification to establish appropriate safety and health practices and to determine the
applicability of regulatory limitations prior to use.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to announce this Technical Specification: 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.
1 Scope
This Technical Specification describes a method for the analysis of pesticide residues in plant oils (fat
content > 90 %, water content < 5 %). It has been validated in an interlaboratory test with olive oil.
However, laboratory experiences are available also for other kind of oils such as sunflower seed oil,
sesame oil, flax seed oil, rape seed oil, grape seed oil, thistle oil and pumpkin seed oil.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
CEN/TS 17061:2017, Foodstuffs — Guideline for the calibration and quantitative determination of
chromatographic methods for the determination of pesticide residues and organic contaminants
3 Principle
The homogeneous sample is extracted with acetonitrile. After centrifugation, an aliquot of the organic
phase is cleaned-up by dispersive solid phase extraction (D-SPE; sorbents PSA and C18). To separate
co-extracted fat a freeze-out step of the acetonitrile phase can be applied. After clean up an additional
centrifugation step is performed. The extracts are acidified by adding a small amount of formic acid, to
improve the storage stability of certain base-sensitive pesticides. The final extract can be directly used
for LC-MS/MS analysis. A scheme of the procedure is given in Annex C.
NOTE In contrast to the method described in EN 15662 [1], this procedure does not include any addition of
water.
4 Reagents
Unless otherwise specified, use reagents of recognized analytical grade. Take every precaution to avoid
possible contamination of water, solvents, sorbents, inorganic salts, etc.
4.1 Water, HPLC quality.
4.2 Acetonitrile, HPLC quality.
4.3 Methanol, HPLC quality.
4.4 Acetic acid.
4.5 Ammonium formate.
4.6 Formic acid solution in acetonitrile, volume concentration σ = 5 ml formic acid/100 ml :
Dilute 5 ml of formic acid (mass fraction w ≥ 95 %) to 100 ml with acetonitrile (4.2).
1) ®
4.7 Primary secondary amin sorbent (PSA), e.g. Bondesil-PSA 40 µm Agilent No. 12213023 .
Other amino sorbents may be used, but investigations may be necessary to prove equivalency especially
regarding analyte losses and pH value of the end extracts.
4.8 C-18-sorbent (Octadecyl-silyl-modified silica gel), Bulk material 50 µm.
4.9 Internal standard and quality control standard solutions in acetonitrile, mass concentration
ρ = 10 µg/ml to 100 µg/ml.
Table 1 shows a list of potential internal standards (ISTDs) and quality control (QC) standards that may
be used in this method.
Table 1 — Potential internal standards (ISTDs) or quality control (QC) standards
Compound Log P Suggested MS/MS MS/MS
(octanol-water concentration ESI (+) ESI (-)
partition C
ISTD
coefficient) [µg/ml]
Tris-(1,3-dichlorisopropyl)- 3,65 10 +++ +
phosphate
Linuron-D6 3,00 10 ++
Carbofuran-D3 1,80 10 ++
Chlorpyrifos-D10 4,70 10 +++
Bis-nitrophenyl urea 3,76 10 - +++
(nicarbazin)
4.10 Primary pesticide standards:
Use standards of known purity, only.
4.11 Pesticide stock solutions:
Prepare individual stock solutions of analytical standards at concentrations that are sufficient to allow
the preparation of complex pesticide working solutions that are used for the preparation of standard
solutions.
Usually, store stock solutions at ≤ −18 °C. Check the stability of stock solutions during storage regularly
[2]. In some cases the addition of acids or bases can be helpful to enhance stability and extend the
acceptable storage period. Before withdrawing any aliquot from this solution redissolve any
precipitation that may have occurred.
4.12 Pesticide working solutions:
Because of the broad applicability of this method and due to the partly divergent pH-stability of
pesticides, more than one working solution each containing one or more pesticides can be needed to
cover the entire pesticide spectrum of interest. These are prepared by mixing together defined volumes
of the required pesticide stock solutions (4.11) and appropriately diluting them with acetonitrile. The
1) ®
Bondesil-PSA is a product supplied by Agilent. This information is given for the convenience of users of this
European Technical Specification and does not constitute an endorsement by CEN of the product named.
Equivalent products may be used if they can be shown to lead to the same results.
pesticide concentrations in these mixtures should be sufficient to allow the preparation of the required
matrix matched standards (4.13.2) with moderate dilution of the blank sample extract (e.g. less than
20 %).
Usually, pesticide working solutions should be stored at low temperature in the dark. Check the stability
of pesticides contained in these mixtures during storage regularly [2] and adapt the storing conditions
accordingly. In some cases the addition of acids or bases can be helpful to enhance stability and extend
acceptable storage times.
4.13 Standard solutions (calibration mixtures):
4.13.1 Solvent-based standards:
Prepare solvent-based standards by mixing known volumes of the pesticide working solutions (4.12)
and make up to volume with acetonitrile. The preparation of solvent based calibration mixtures with
cal cal
different analyte concentrations (ρ ) and identical internal standard concentrations (ρ ) is
A ISTD
necessary to create a calibration graph.
cal
The concentration of the internal standards in the calibration mixtures (ρ ) shall be equivalent to
ISTD
the concentration of the internal standard in the sample extracts, as the internal standards are added
after extraction.
cal cal
The quotient V /V from the volume used (V ) shall be equivalent to the solution of the internal
ISTD Std ISTD
standard (4.9) and the final volume of the calibration standards (V ) shall be equivalent to the
Std
quotient V /V (see 6.1). If 60 µl ISTD solution (4.9) are added to 6 ml of aliquot of the
ISTD Aliquot
centrifugate, 6 ml of standard solution shall be spiked with 60 µl of ISTD solution. If other volumes of
calibration standards are used, the addition of ISTD solution shall be adjusted.
NOTE A pesticide concentration of 1 µg/ml correlates to a residue level of 5 mg/kg when a 2 g test portion is
employed.
4.13.2 Matrix-matched standards:
Prepare matrix-matched standards in the same way as solvent-based standards, however, instead of
pure acetonitrile use extracts of blank samples (samples, where no pesticides have been found with this
method). The extract is prepared as described in Clause 5 (but without ISTD addition). To minimize
errors caused by matrix induced effects during chromatography, it is best to choose similar
commodities (e.g. olive o
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.