1、Foodstuffs - Guidelines for the calibration and quantitative determination of pesticide residues and organic contaminants using chromatographic methodsPD CEN/TS 17061:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE T
2、ECHNISCHE SPEZIFIKATION CEN/TS 17061 September 2017 ICS 67.050 English Version Foodstuffs - Guidelines for the calibration and quantitative determination of pesticide residues and organic contaminants using chromatographic methods Produits alimentaires - Lignes directrices pour ltalonnage et le dosa
3、ge des rsidus de pesticides et contaminants organiques par des mthodes chromatographiques Lebensmittel - Leitfaden fr die Kalibrierung und die Auswertung von Analysenergebnissen bei der Anwendung chromatographischer Methoden fr die quantitative Bestimmung von Pflanzenschutzmittelrckstnden und organi
4、schen Kontaminanten 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 ques
5、tion 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 standar
6、ds 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 Mac
7、edonia, 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 COMIT EUROPEN DE NORMALIS
8、ATION EUROPISCHES KOMITEE FR 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 worldwide for CEN national Members. Ref. No. CEN/TS 17061:2017 ENational forewordThis Published Document is the UK implement
9、ation of CEN/TS 17061:2017.The UK participation in its preparation was entrusted to Technical Committee AW/275, Food analysis - Horizontal methods.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the ne
10、cessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 94293 8ICS 67.050Compliance with a British Standard cannot confer immunity from legal obligations.This Published Document
11、was published under the authority of the Standards Policy and Strategy Committee on 31 October 2017.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/TS 17061:2017TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 17061 September 201
12、7 ICS 67.050 English Version Foodstuffs - Guidelines for the calibration and quantitative determination of pesticide residues and organic contaminants using chromatographic methods Produits alimentaires - Lignes directrices pour ltalonnage et le dosage des rsidus de pesticides et contaminants organi
13、ques par des mthodes chromatographiques Lebensmittel - Leitfaden fr die Kalibrierung und die Auswertung von Analysenergebnissen bei der Anwendung chromatographischer Methoden fr die quantitative Bestimmung von Pflanzenschutzmittelrckstnden und organischen Kontaminanten This Technical Specification (
14、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 Eu
15、ropean 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
16、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,
17、 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 COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC M
18、anagement Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TS 17061:2017 EPD CEN/TS 17061:2017CEN/TS 17061:2017 (E) 2 Contents Page European foreword . 4 1 Scope 5 2 Principle . 5 3 Ge
19、neral 5 4 Execution and calculation of calibrations 6 4.1 General/specifications 6 4.1.1 Working range 6 4.1.2 Number of calibration points 6 4.1.3 Permissible quantities for determination of response (peak areas or peak heights and peak ratio, respectively) 7 4.1.4 Stability of calibration function
20、s . 8 4.2 Calibration functions . 8 4.2.1 Selection of appropriate calibration function 8 4.2.2 Visual linearity test 8 4.2.3 Mathematical check of linearity 9 4.2.4 Calibration with interpolation functions 9 4.3 Test for matrix effects 10 4.4 Basic calibration and calibration by means of external s
21、tandard 10 4.4.1 Basic calibration . 10 4.4.2 Calculation by means of external standard in case of linear calibration function without significant ordinate intercept . 10 4.4.3 Calculation by means of external standard using linear calibration function. 11 4.4.4 Calculation by means of external stan
22、dard using quadratic calibration function . 11 4.4.5 Calculation by means of external standard using nonlinear calibration function or weighted regression 12 4.5 Calculation by means of internal standard . 12 4.5.1 General . 12 4.5.2 Calculation with internal correction standard 13 4.5.3 Calculation
23、 with stable-isotope labelled standard 14 4.6 Calibration using standard addition procedures . 16 4.6.1 General . 16 4.6.2 Standard addition to the final extract. 16 4.6.3 Standard addition to the sample before extraction . 17 4.7 Procedural calibration . 18 4.8 Calibration with chemical conversion
24、of the standard 18 5 Quality assurance . 18 5.1 Qualification of the chromatographic system 18 5.1.1 Equipment qualification 18 5.1.2 Drift of a calibration system . 19 5.1.3 Performance criteria for GC and HPLC measurements 19 5.2 Examination of integration results 19 5.3 Permissible blank values i
25、n relation to the lower limit of working range . 19 5.4 Frequency of calibrations . 20 5.5 Number of analytes to be calibrated for “multi-methods” 20 5.6 Handling of substances with multiple peaks . 20 PD CEN/TS 17061:2017CEN/TS 17061:2017 (E) 3 5.7 Quality control chart . 20 6 Expression of results
26、 (units, number of significant figures). 22 7 Examples 23 7.1 Example 1 Test for variance inhomogeneity . 23 7.2 Example 2 Selection of appropriate calibration function . 23 7.3 Example 3 Test for matrix effects 30 7.4 Example 4 Calibration with external standard 31 7.5 Example 5 Calibration with in
27、ternal standard . 33 7.6 Example 6 Calculation with stable-isotope labelled standard 34 7.7 Example 7 Standard addition to final extract . 35 Bibliography . 37 PD CEN/TS 17061:2017CEN/TS 17061:2017 (E) 4 European foreword This document (CEN/TS 17061:2017) has been prepared by Technical Committee CEN
28、/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. Annex A (infor
29、mative) contains a list of abbreviations. 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, For
30、mer 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. PD CEN/TS 17061:2017CEN/TS 17061
31、:2017 (E) 5 1 Scope This Technical Specification describes the execution of calibration and quantitative evaluation of chromatographic procedures for the determination of pesticides and organic contaminants in residue analysis. In addition, the essential requirements for calibration are outlined. Th
32、e calibration of analytical procedures and the evaluation of analytical results need to be conducted according to uniform principles in order to allow for a comparison of analytical results (even from different analytical procedures). They constitute the basis of any method validation and of the qua
33、lity assurance within laboratories 1, 2, 3. This Technical Specification does not consider issues of identification/qualification and extraction efficiency. 2 Principle This document describes the approach for the calibration of chromatographic procedures. The following types of calibration are disc
34、ussed in more detail: external calibration with linear calibration function; external calibration with quadratic calibration function; calibration with internal standard and linear calibration function; calibration with internal standard and quadratic calibration function; calibration with standards
35、 labelled with stable isotopes (isotopic dilution analysis); standard addition to final extract; standard addition to sample. For this purpose, the calibration function and the selection criteria are illustrated on the basis of examples. The calculation formulae refer to the final extract ready for
36、analysis (“test solution”). The description is rounded off by essential items of quality assurance, e.g. the qualification of chromatographic systems or the quality control chart. 3 General Calibration of a system is understood as the determination of a functional relationship between a measurable q
37、uantity and a concentration to be determined. The chosen type of calibration depends on the various analytical problems/tasks. It is performed in connection with the respective series of measurements. Basic calibration is regarded as the determination of the functional relationship when an analyte i
38、s to be determined for the first time by means of a particular measurement system. Depending on the problem and on the type of reference solution used, it is distinguished between: calibration with external standard; calibration with internal standard; calibration with standard addition; calibration
39、 of the entire procedure. PD CEN/TS 17061:2017CEN/TS 17061:2017 (E) 6 In case of the calibration with external standard, the calibration solutions can be prepared either with a pure solvent (standards in solvent) or with sample extracts which evidently do not contain significant amounts of the analy
40、te(s) (matrix-matched standards). The application of a simple linear-regression calculation requires a linear relationship between the content of substance and the measured value. The linearity test can be performed visually and/or mathematically. A mathematical check is performed, e.g. by means of
41、the goodness-of-fit test according to Mandel or by means of residual analysis. The residuals are the deviations of the measurement values from the values predicted by the regression line (see Example 1 in 7.1). 4 Execution and calculation of calibrations 4.1 General/specifications 4.1.1 Working rang
42、e The range of measurement represented by the lowest and the highest calibration point constitutes the range of concentrations for which the determined calibration function applies (working range). Only within this range, the measured values are reliable and, therefore, can be used for the calculati
43、on of analyte contents. At the upper and lower end, the prediction interval becomes wider i.e. the measurement error increases progressively. The highest precision is found in the middle of the working range 4. The detector response from the analytes in the sample extract has to lie within the worki
44、ng range. Extracts containing residues above the calibrated range shall be diluted. If the calibration solutions are matrix-matched the matrix concentration in the calibration standards should also be diluted, see 5. The calibration range shall be adjusted to the respective residue concentrations in
45、 the test solution (real-sample concentrations which often occur in practice) and should cover a maximum of two orders of magnitudes. Where appropriate, several calibration functions shall be established by means of calibration solutions. The lower limit of the practical working range usually repres
46、ents the lowest calibration level, see 5. It shall be equal to or lower than the Reporting Limit (RL). The RL may not be lower than the Limit of Quantification (LOQ). 4.1.2 Number of calibration points 4.1.2.1 General For the working range of calibration functions, calibration solutions with differe
47、nt concentrations of pesticides or contaminants are prepared (depending on the requirement, three to five calibration points), the concentrations of which are as equidistantly distributed over the working range as possible. The concentrations shall start at the lower limit of the practical working r
48、ange. If the working range has to cover one order of magnitude, three calibration points are necessary, while five calibration points are necessary for two orders of magnitude (depending on the covered concentration range, e.g. 1, 3, 10, 30 and 100 times the lowest calibrated concentration). PD CEN/
49、TS 17061:2017CEN/TS 17061:2017 (E) 7 4.1.2.2 Acceptability of single-point calibrations A single-point calibration is sufficient if the linearity of the calibration function has been checked over a longer period of time and has been evaluated as stable and if the blank values as well as the intercept are negligibly small. The concentration level should be in the upper fraction of the working range. The analyte concentrations in the calibration and test solutions should be within the range proposed DG-SANTE, if the
