Unknown BRITISH STANDARD BS EN 12766 2 2001 BS 2000 462 2 2001 Methods of test for petroleum and its products — Petroleum products and used oils — Determination of PCBs and related products — Part 2 C[.]
BRITISH STANDARD Methods of test for petroleum and its products — Petroleum products and used oils — Determination of PCBs and related products — Part 2: Calculation of polychlorinated biphenyl (PCB) content (Identical with IP 462.2:2001) The European Standard EN 12766-2:2001 has the status of a British Standard ICS 75.080; 75.100 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BS EN 12766-2:2001 BS 2000-462.2: 2001 BS EN 12766-2:2001 National foreword This British Standard is the official English language version of EN 12766-2:2001 The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the responsibility to: — aid enquirers to understand the text; — present to the responsible European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; — monitor related international and European developments and promulgate them in the UK A list of organizations represented on this committee can be obtained on request to its secretary Additional information This British Standard, having been prepared under the direction of the Sector Policy and Strategy Committee for Materials and Chemicals, was published under the authority of the Standards Policy and Strategy Committee on 22 August 2001 It is noted that this British Standard contains two methods for the estimation of PCB content Technical Committee PTI/13 has been advised that method B may allow samples that should be classified as PCB to escape this classification and thus place the public at risk Therefore, attention is drawn to the fact that the preferred method for use in the UK is method A The Institute of Petroleum publishes and sells all parts of BS 2000, and all BS EN petroleum test methods that would be part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 parts” and individually Further information is available from: The Institute of Petroleum, 61 New Cavendish Street, London W1M 8AR Tel: 020 7467 7100 Fax: 020 7255 1472 Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue A British Standard does not purport to include all the necessary provisions of a contract Users of British Standards are responsible for their correct application Compliance with a British Standard does not of itself confer immunity from legal obligations Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages to 18, an inside back cover and a back cover The BSI copyright date displayed in this document indicates when the document was last issued Amendments issued since publication © The Institute of Petroleum and BSI 22 August 2001 ISBN 580 38132 Amd No Date Comments EN 12766-2 EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM July 2001 ICS 75.080; 75.100 English version Petroleum products and used oils - Determination of PCBs and related products - Part 2: Calculation of polychlorinated biphenyl (PCB) content Produits pétroliers et huiles usagées - Détermination des PCB et produits connexes - Partie 2: Calcul de la teneur en polychlorobiphényles (PCB) Mineralölerzeugnisse und Gebrauchtöle - Bestimmung von PCBs und verwandten Produkten - Teil 2: Berechnung des Gehalts an polychlorierten Biphenylen (PCB) This European Standard was approved by CEN on June 2001 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 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 Management Centre has the same status as the official versions CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 © 2001 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members B-1050 Brussels Ref No EN 12766-2:2001 E EN 12766-2:2001 (E) Foreword This European Standard has been prepared by Technical Committee CEN/TC 19 "Petroleum products, lubricants and related products", 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 January 2002, and conflicting national standards shall be withdrawn at the latest by January 2002 In this standard Annex A and B are normative This standard includes a Bibliography This European standard is one of a series of standards as listed below 1) EN 12766, Petroleum products and used oils - Determination of PCBs and related products Part 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using an electron capture detector (ECD) Part 2: Calculation of polychlorinated biphenyl (PCB) content Part 3: Determination and calculation of PCB related products 2 According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom 1) PCBs as defined in: Council directive 96/59/EC of 1996-09-16 on the disposal of polychlorinated biphenyls and polychlorinated terphenyls The definition includes PCBs proper, PCTs and also PCBTs (polychlorinated benzyltoluenes), tradename “Ugilec” 2 Part of EN 12766 is under development EN 12766-2:2001 (E) Scope This standard specifies two calculation procedures (“method A” and “method B”) for PCB content The basis for this quantification is taken from the chromatographic results of EN 12766-1:2000 in which all necessary experimental procedures are described for the specific analysis of unused, used and treated (e.g dechlorinated) petroleum products including synthetic lubricating oils and mixtures of vegetable oils The method is also applicable to petroleum products and synthetic lubricating oils suitably recovered from other materials, e.g from waste materials Both methods have different strengths and weaknesses which are described in the next paragraphs and which must be considered before use in a specific application Proper application of either method A or method B needs to be carefully considered before use in a specific application Using method A, special care needs to be exercised to avoid interferences from non PCB substances which may occur in the chromatogram Therefore, method A can be used predominantly for the analysis of used and unused insulating oils It is recommended not to use calculation method A without special precautions for other than above-mentioned products Calculation method A can produce two alternative sets of results, (“All Probables” and “All Possibles”) Therefore, care needs to be taken in order to interpret these results in the correct manner Method B uses as intermediate result the sum of six congeners, which belong to the most abundant in almost all technical PCB materials, thereby minimizing potential interferences from other (coeluting) non PCB substances To obtain the PCB content, the intermediate sum from six congeners needs to be multiplied by a multiplication factor Calculation Method B can be used predominantly for the analysis of liquids from used and waste materials of unknown origin and for samples with low PCB contents Normative References This European Standard incorporates, by dated and undated reference, provisions from other publications These normative references are cited at the appropriate places in the text and the publications are listed hereafter For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision For undated references the latest edition of the publication referred to applies (including amendments) EN 12766-1:2000, Petroleum products and used oils - Determination of PCBs and related products Part 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using an electron capture detector (ECD) EN 61619, Insulating liquids - Contamination by polychlorinated biphenyls (PCBs) - Method of determination by capillary column gas chromatography (IEC 61619:1997) EN ISO 4259, Petroleum products - Determination and application of precision data in relation to methods of test (ISO 4259:1992/Cor 1:1993) EN 12766-2:2001 (E) Terms and definitions , As defined in several regulations and legislation e.g Directive 96/59/EC, the term "PCB" includes "PCT" and also "PCBT" For the purposes of this European Standard, however, "PCB" is defined on a molecular, chemical basis and its measurement and quantification is described in EN 12766-1:2000 and EN 12766-2 Also, the terms "PCT" and "PCBT" are defined in chemical terms, and prEN 12766-3 describes their measurement and quantification For analytical results to comply with the mentioned legislation, the total of PCB from EN 12766-2 and PCT plus PCBT from prEN 12766-3 shall be added For the purposes of this part of the standard, the following terms and definitions apply 3.1 polychlorinated biphenyl (PCB) a biphenyl substituted with one to 10 chlorine atoms NOTE For legal purposes, congeners with one, two or ten chlorine atoms may be excluded from this definition 3.2 congener any chlorine derivative of biphenyl, irrespective of the number of chlorine atoms NOTE There are 209 possible congeners These are listed in Annex C of EN 12766-1:2000 The congener numbers (IUPAC) are for easy identification; they not represent the order of chromatographic elution 3.3 DCB abbreviation for PCB congener 209, decachlorobiphenyl, used as reference and as an internal standard Calculation methods The results from method A and method B shall not be confused 4.1 Method A This calculation procedure is based on EN 61619 The gas chromatography used for method A is identical to EN 61619 and to EN 12766-1:2000 The calibration standards and test mixtures are also the same Method A uses the sum of the contribution of all congeners to produce a measurement for PCB content Lack of chromatographic resolution means that it is not possible to resolve the peaks for all congeners, so that some overlapping can occur For the calculation of PCB content, the EN 61619 method uses two tables of response factors produced from the literature values (see Bibliography) by taking into account the relative proportions of coeluting congeners in each peak Not all congeners are calibrated Nine congeners are taken across the range of elution times providing nine calibration windows Within each window, the calibration factor is extrapolated to adjust, for each congener, the response factor from the literature EN 12766-2:2001 (E) 4.1.1 Data-processing system The data system shall be set up according to the manufacturer's instructions Most systems require designation of a minimum of two reference points including the internal standard decachlorobiphenyl (DCB) 4.1.2 Data files The method requires data files containing experimental data (ERRT) and data originating from the literature For each peak of single or coeluting congeners the following data are filed in order of increasing ERRT (see Table A.1): Experimental Relative Retention Time (ERRT), Congener Number, Relative Response Factor (RRF) Two sets of RRF, based on data originating from [1], are provided in Table A.1 A weighted average response factor was calculated for each peak containing coeluting congeners using the relative proportions of the congeners found in commercial mixtures using data from [2], [3] and [4] "All probable" Some congeners have never been observed in commercial PCB mixtures So, in those cases where more than one congener coelutes under one chromatogram peak, the RRF of the group of congeners is weighted by exclusion of congeners not found in commercial mixtures Use this data set with unknowns and mixtures of commercial products "All possible" This class includes all 209 PCB congeners This data set is included for use with dechlorinated materials Table A.1 shows that where there is no co-elution (for example peak no 48) the RRF of each set has the same value and where there is co-elution (for example peak no 49) there are different values for the different sets RRFs in Table A.1 are corrected for the instrument being used by the procedure in 4.1.5 4.1.3 Coeluting congeners More than one congener may coelute Peaks that fall within the window of ± 0,001 from the RRT shall be grouped together NOTE Table A.2 gives individual congener RRTs and the elution order 4.1.4 Determination of experimental relative retention times (ERRTs) 4.1.4.1 Run the test mixture (5.4.6 of EN 12766-1:2000), prepared according to 7.4 of EN 12766-1:2000, using the same GC conditions that are used for sample analysis Identify all the peaks by comparison with the example in Figure A.1 and calculate the ERRT for each peak as follows: ERRT x t x t 30 t 209 t 30 EN 12766-2:2001 (E) where: tx is the retention time of a chosen peak x; t30 is the retention time of congener 30 (reference); t209 is the retention time of congener 209 (reference and internal standard) Tabulate the results as shown in Table and enter the results in the data files (4.1.2) ERRTs shall be determined and entered into the data files for each individual GC system The system shall be recalibrated if there are any changes in GC conditions (e.g temperature program, etc.) Congeners 30 and 209 are chosen as reference peaks for the determination of ERRT as they are at each end of the chromatogram (test mixture) isolated from congeners occurring in commercial mixtures and allow accurate repeatable values of ERRTs to be obtained 4.1.4.2 Use the ERRT values of the congeners listed in Table below (determined in 4.1.4.1) to designate the reference peaks in the data-processing system Table - Reference Peaks/Congeners Peak numbers Reference peak congener numbers 30 ERRT (examples) 0,000 33 44 0,225 46 56/60 0,342 57 77/110 0,427 74 138/160/163 0,574 90 180 0,703 105 209 1,000 NOTE With the exception of congeners 30 and 209 the reference peaks were chosen because they are major components of commercial mixtures They will not occur in all samples, the number of reference peaks found will depend on the PCB mixture 4.1.5 Calculation of corrected relative response factors (CRRF) NOTE The experimental relative response factors (ERRFs) of the congeners may vary from instrument to instrument depending on the injection mode and the conditions of the electron capture detector They may also differ from those originating from [1] 4.1.5.1 The chromatogram is divided into nine segments (see Figure A.1 in annex A) each represented by one of the congeners listed in Table These congeners are normally present in commercial mixtures as major components (see Table A.1) 4.1.5.2 Using optimised chromatographic conditions as in clause of EN 12766-1:2000, inject a suitable aliquot of the cleaned-up congener mix calibration solution (9.5 of EN 12766-1:2000) Determine the experimental relative response factors (to DCB) for the congeners listed in Table using the following equation: ERRF i Ai m209 A209 mi EN 12766-2:2001 (E) where: A209 is the peak area/height for internal standard (DCB); Ai is the peak area/height for congener i; m209 is the concentration (µg/ml) of internal standard (DCB); mi is the concentration (µg/ml) of congener i NOTE CAUTION - some software packages may produce the inverse of this ERRF Take the average ERRF for a minimum of three determinations Table - Congeners for ERRF calibration Peak number Segment number Congener number (IUPAC) ERRT (examples) RRF (table A.2) 12 18 0,028 0,275 22 31 0,114 0,493 33 44 0,225 0,460 49 101 0,356 0,587 63 118 0,477 0,764 74 138 0,574 0,726 90 180 0,703 1,137 95 170 0,759 0,659 102 194 0,877 1,640 4.1.5.3 From the determined ERRF and the theoretical RRF value given in Table calculate the correction factor Ki for each congener: Ki ERRF i RRF i EXAMPLE for congener 180, where determined ERRF180 = 1,030 literature RRF180 = 1,137 (Table 2, peak number 90) K180 1,030 0,906 1137 , 4.1.5.4 Multiply the RRFs of all peaks in each segment of the chromatogram (Table A.1) by the correction factor calculated for the corresponding selected congener e.g for congener 180 (the reference for segment 7); multiply each RRF in segment by 0,906 The resulting table of the corrected relative response factors (CRRFs) for “All possibles” and “All probables” will be the one to use for data files (4.1.2) 4.1.6 Examination of the chromatograms Chromatograms shall be examined visually for any spurious peaks or chromatographic problems and for interferences EN 12766-2:2001 (E) NOTE PCT and commercial mixtures of tetrachlorobenzyl toluene (Ugilec) may occur and can be mistaken for PCB They can be identified by their distinctive patterns, and prEN 12766-3 may be used for their quantification 4.1.7 Calculation of PCB content 4.1.7.1 Qualitative analysis Compare the chromatogram from the sample with standard chromatograms prepared according to EN 12766-1:2000, 5.4.6, to identify commercial mixtures such as Aroclor 1242, 1254 and 1260 4.1.7.2 Quantitative analysis 4.1.7.2.1 Calculation procedure The computer programme/software shall produce a list containing peak number with corresponding PCB congener numbers and the mass of PCB (mg) for each peak in the test portion, calculated from the mass of internal standard decachlorobiphenyl (DCB) in the test portion 4.1.7.2.2 Mass of PCB in each peak The mass of each congener or coeluting congeners (for each peak i) is calculated by the internal standard method using the corrected relative response factors derived from the "All probables" set, where there is no evidence of dechlorination, or the "All possibles" values for dechlorinated samples mi = Where: m209 Ai RRF 209 A209 CRRF i mi m209 is mass of peak i (mg) in the test portion; is mass of internal standard (mg) in the test portion (nominally 0,002 or 0,000 5); Ai is area/height of peak i; A209 is area/height of internal standard peak; RRF209 is relative response factor of internal standard (= 1,000); CRRFi is corrected relative response factor of peak i 4.1.7.2.3 Total quantity of PCB The masses of all individual peaks are summed to give the total amount of PCBs in mg in the solution prepared from the test sample according to 7.4 of EN 12766-1:2000 The total PCB content of the sample (mg/kg) is calculated using the initial weight of sample (g) in the test portion The result shall be presented after rounding to the nearest 0,1 mg/kg Content of PCBs in the sample = m 000 i weight of sample EN 12766-2:2001 (E) 4.2 Method B The gas chromatography used for Method B is identical to EN 61619 and to EN 12766-1:2000 The calibration standards and test mixtures are also the same Method B uses six congeners listed in the following paragraph for the calculation of an intermediate sum, which is then multiplied by a multiplication factor to yield the PCB content 4.2.1 Calculation of PCB content The following six congeners are determined according to EN 12766-1:2000 Congener No 28 52 101 153 138 180 Mass fraction per single congener [mg/kg] w1 w2 w3 w4 w5 w6 The sum of mass fractions obtained for each listed congener is then multiplied by a multiplication factor of five and rounded to the nearest 0,1 mg/kg to obtain the PCB content i6 w( PCB ) wi i 1 NOTE The multiplication factor five constitutes an averaged factor, representing an averaged content of the six selected congeners in a multitude of technical waste materials, experienced in many European countries during the last 15 years More information about the derivation of this factor and its ranges in extreme cases can be found in the literature (see Bibliography [5] –[11]) Calculation of Precision Values These shall be calculated according to EN ISO 4259 Precision data for both Method A and Method B are given in annex B Test Report The test report shall include at least the following information: a) a reference to this European Standard and the calculation method used , i.e “Method A – All Probables” or “Method A – All Possibles” or “Method B”; b) the type and identification of sample under test; c) the sampling procedure used; EN 12766-2:2001 (E) d) the clean-up procedure used; e) the calculated PCB content; f) any deviation from the procedure described and any unusual features noted during the determinations; g) the date of the test 10 EN 12766-2:2001 (E) ANNEX A (normative) Test mixture Figure A.1 - Chromatogram for test mixture of Aroclors 1242/1254/1260 11 EN 12766-2:2001 (E) Figure A.1 - Chromatogram for a test mixture of Aroclors 1242/1254/1260 (continued) 12 EN 12766-2:2001 (E) Table A.1 - List of congeners, retention times and relative response factors Calibration Peak number 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Segment 1 2 3 4 4 5 ERRT (example) (-0,223) (-0,127) -0,124 -0,082 -0,062 -0,052 (-0,032) -0,014 0,000 (0,006) (0,013) 0,028 0,032 0,048 0,064 (0,072) 0,082 0,089 0,099 0,102 (0,110) 0,114 0,117 0,136 0,151 0,159 0,165 0,177 0,185 0,193 0,199 0,216 0,225 0,232 0,241 0,249 0,255 0,266 0,283 0,287 0,294 0,302 0,310 (0,322) 0,323 0,342 0,346 0,353 0,356 0,366 0,378 0,388 0,398 0,408 0,416 0,422 0,427 (0,448) 0,451 0,460 Congener numbers All probables All possibles (IUPAC (IUPAC numbers) numbers) 2,3 2,3 4,10 4,10 7,9 7,9 6 5,8 5,8 14 19 19 30 11 12,13 18 18 15,17 15,17 24,27 24,27 16,32 16,32 23 34 34,54 29 29 26 26 25 25 50 31 31 28 28 20,33,53 20,21,33,53 22,51 22,51 45 45 36 46 46 52,69 39,52,69,73 49 38,43,49 47,48,75 47,48,62,65,75 35 35,104 44 44 37,42,59 37,42,59 71,72 71,72 41,64 41,64 96 68,96 40 40,57,103 67,100 67,100 63 58,63 74 61,74,94 70 70,76,98 66,95 66,80,88,93,95,102 121 91 55,91 56,60 56,60,155 92 92 84 84 90,101 89,90,101 99 79,99,113 119 112,119,150 83 78,83,109 97 86,97,152 87,115 81,87,111,115,116, 117,125,145 85 85 136 120,136,148 77,110 77,110 154 151,82 151,82 135 124,135,144 RRFs (to DCB) All All probables possibles 0,035 0,026 0,026 0,217 0,131 0,453 0,473 0,334 0,334 0,105 0,143 0,268 0,267 0,267 0,720 0,039 0,166 0,275 0,275 0,182 0,182 0,541 0,565 0,346 0,318 0,439 0,535 0,427 0,557 0,557 0,529 0,529 0,439 0,439 0,599 0,493 0,493 0,750 0,750 0,405 0,569 0,936 0,960 0,474 0,474 0,459 0,411 0,411 0,389 0,473 0,569 0,474 0,621 0,709 0,329 0,365 0,460 0,460 0,613 0,577 0,448 0,507 0,510 0,508 0,634 0,565 0,524 0,521 0,639 0,587 0,589 0,686 0,578 0,545 0,417 0,531 0,672 0,501 0,615 0,801 0,712 0,472 0,472 0,339 0,339 0,581 0,538 0,528 0,614 0,723 0,650 0,557 0,665 0,554 0,571 0,903 0,774 0,649 0,398 0,559 0,681 0,617 0,649 0,510 0,453 0,500 0,681 0,710 13 EN 12766-2:2001 (E) 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 6 7 0,468 0,474 0,477 0,495 0,499 0,503 0,510 0,521 0,528 0,546 0,550 0,559 0,564 0,574 0,579 0,590 0,601 0,607 0,616 0,627 0,636 (0,641) 0,652 0,662 0,670 0,671 0,683 0,691 0,696 0,703 0,708 0,716 0,727 0,736 0,759 0,769 0,775 0,785 0,812 0,838 0,852 0,877 0,885 0,945 1,000 * Numbered according to IUPAC rules Ballschmitter & Zell numbering as follows: 107 123,149 118 134 114 122,131 146 132,153 105 141 179 130 137,176 138,160,163 158 126,129,178 175 187 183 128 167 185 174 177 202 156,171 201*,157,173 172 197 180 193 191 200* 169 170,190 198 199* 196,203 189 195,208 207 194 205 206 209 (internal standard) 107,108,147 106,123,149 118,139,140 134,143 114 122,131,133,142 146,161,165,188 132,153,184 105,127,168 141 179 130 137,176 138,160,163,164 158,186 126,129,178 166,175 159,182,187 162,183 128 167 185 174,181 177 202 156,171 201*,157,173 172,204 192,197 180 193 191 200* 169 170,190 198 199* 196,203 189 195,208 207 194 205 206 209 (internal standard) 0,718 0,511 0,764 0,644 0,901 0,662 0,639 0,615 0,825 1,187 0,723 0,836 0,939 0,771 0,994 0,670 0,335 0,985 0,857 1,043 0,936 1,262 0,708 0,886 1,023 1,124 0,662 1,029 1,009 1,137 1,244 1,294 1,010 0,734 0,782 0,939 0,705 0,287 1,325 0,593 1,164 1,640 1,234 1,469 1,000 0,727 0,656 0,663 0,633 0,901 0,862 0,770 0,709 0,690 1,187 0,723 0,836 0,953 0,878 1,034 0,919 0,625 0,949 0,882 1,043 0,936 1,262 1,058 0,886 1,023 1,124 0,662 0,867 1,090 1,137 1,244 1,294 1,010 0,734 0,904 0,939 0,705 1,265 1,325 0,593 1,164 1,640 1,234 1,469 1,000 199 (IUPAC) = 201 (Ballschmiter) 200 (IUPAC) = 199 (Ballschmiter) 201 (IUPAC) = 200 (Ballschmiter) NOTE The ERRT values in the table are examples determined from the chromatogram in Figure A.1 and should not be used in the method ERRT values shall be determined for the individual GC system being used NOTE Values appearing in parentheses are calculated values for peaks (congeners) that not appear in the test mixture, e.g ERRT (peak 44 = 0,322) NOTE References were used to aid the identification of congeners represented by each peak in the test mixture, listed in this table and shown on the chromatogram in Figure A.1 14 EN 12766-2:2001 (E) Table A.2 - Elution order of PCB Congener number (IUPAC) 10 14 19 30 11 12 13 18 15 17 24 27 16 32 23 34 54 29 26 25 50 31 28 21 33 20 53 51 22 45 36 46 39 69 73 52 43 38 49 47 75 48 65 62 35 104 44 37 59 42 72 71 41 64 Relative retention time to DCB 0,147 0,185 0,188 0,214 0,214 0,245 0,245 0,258 0,265 0,265 0,283 0,290 0,302 0,309 0,314 0,316 0,322 0,323 0,324 0,334 0,336 0,345 0,346 0,359 0,360 0,362 0,364 0,373 0,375 0,382 0,383 0,384 0,394 0,397 0,397 0,399 0,404 0,406 0,413 0,417 0,424 0,428 0,430 0,434 0,434 0,437 0,438 0,439 0,442 0,442 0,443 0,445 0,446 0,451 0,453 0,460 0,463 0,463 0,464 0,475 0,475 0,475 0,476 Relative factor response 0,035 0,035 0,017 0,230 0,033 0,606 0,341 0,334 0,181 0,105 0,268 0,267 0,720 0,394 0,157 0,176 0,275 0,094 0,362 0,696 0,435 0,392 0,244 0,439 0,535 0,320 0,556 0,529 0,439 0,599 0,493 0,750 0,931 0,392 0,636 0,317 0,527 0,960 0,474 0,259 0,411 0,305 0,705 0,510 0,367 0,442 0,413 0,569 0,745 0,567 0,488 0,738 1,008 0,329 0,400 0,460 0,509 0,527 0,695 0,484 0,411 0,480 0,539 Congener number (IUPAC) 68 96 40 103 57 100 67 58 63 61 94 74 70 76 98 102 93 66 80 95 88 121 91 55 155 56 60 92 84 89 90 101 113 99 79 119 150 112 109 78 83 152 97 86 116 125 81 145 117 115 87 111 85 148 120 136 77 110 154 82 151 135 144 Relative retention time to DCB 0,480 0,482 0,486 0,490 0,491 0,497 0,497 0,502 0,504 0,508 0,508 0,509 0,515 0,515 0,516 0,517 0,518 0,519 0,521 0,521 0,523 0,526 0,529 0,530 0,540 0,541 0,541 0,547 0,547 0,551 0,554 0,554 0,559 0,560 0,562 0,569 0,569 0,570 0,573 0,574 0,574 0,578 0,581 0,582 0,584 0,585 0,586 0,586 0,586 0,588 0,588 0,589 0,593 0,595 0,596 0,596 0,600 0,602 0,605 0,615 0,619 0,625 0,629 Relative factor response 0,637 0,378 0,634 0,533 0,527 0,515 0,527 0,535 0,639 1,074 0,396 0,589 0,578 0,509 0,548 0,400 0,586 0,567 0,639 0,389 0,605 0,672 0,501 0,728 0,515 0,728 0,892 0,472 0,339 0,493 0,536 0,587 0,530 0,538 0,774 0,723 0,498 0,728 0,845 0,979 0,557 0,460 0,554 0,700 1,228 0,488 0,529 0,596 0,781 0,995 0,896 0,580 0,649 0,486 0,654 0,390 0,335 0,571 0,500 0,679 0,689 0,617 0,769 15 EN 12766-2:2001 (E) Congener number (IUPAC) 124 147 108 107 123 149 106 118 139 140 143 134 114 142 131 122 133 165 188 146 161 184 132 153 105 168 127 141 179 130 176 137 160 163 164 138 186 158 129 126 178 166 175 Relative retention time to DCB 0,627 0,630 0,631 0,632 0,634 0,636 0,636 0,638 0,639 0,639 0,647 0,648 0,651 0,652 0,653 0,655 0,655 0,659 0,659 0,663 0,664 0,668 0,670 0,670 0,672 0,673 0,674 0,686 0,686 0,694 0,696 0,698 0,705 0,705 0,705 0,705 0,707 0,708 0,715 0,716 0,718 0,721 0,725 Relative factor response 0,745 0,527 0,935 0,718 0,583 0,502 0,882 0,764 0,634 0,591 0,622 0,644 0,901 1,069 0,746 0,636 1,008 0,946 0,644 0,639 0,849 0,882 0,641 0,604 0,825 0,735 0,512 1,187 0,723 0,836 0,9230 0,976 1,046 0,876 0,865 0,726 1,074 0,994 0,875 0,418 0,545 0,915 0,335 Congener number (IUPAC) 182 187 159 183 162 128 167 185 174 181 177 171 202 156 173 157 201 204 192 172 197 180 193 191 200 169 170 190 198 199 196 203 189 208 195 207 194 205 206 209 Relative retention time to DCB 0,729 0,729 0,729 0,736 0,737 0,739 0,745 0,748 0,759 0,759 0,765 0,771 0,771 0,772 0,777 0,780 0,781 0,783 0,788 0,789 0,790 0,797 0,800 0,805 0,809 0,822 0,833 0,833 0,843 0,846 0,852 0,852 0,871 0,888 0,888 0,898 0,917 0,922 0,963 1,000 Relative factor response 0,990 0,985 0,872 0,857 0,906 1,043 0,936 1,262 0,708 1,409 0,886 1,028 1,023 0,220 1,795 1,051 0,324 0,705 1,404 1,029 0,836 1,137 1,247 1,294 1,010 0,734 0,659 1,150 0,939 0,705 1,082 0,430 1,325 1,032 0,364 1,164 1,640 1,234 1,469 1,000 NOTE Results obtained with a high frequency column: crosslinked % phenyl-methyl silicone gum phase 50 m x 0,2 mm internal diameter x 0,11 µm film thickness NOTE The RRT’s and RRF’s in this table were calculated from the values in [4] to make them relative to DCB 16 EN 12766-2:2001 (E) Annex B (normative) Precision values B.1 Method A From measurements of commercial Aroclor mixtures in insulating oil the following precision data have been established This data is for a technical mixture in an ideal situation Repeatability The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following value only in one case in twenty: Repeatability (r) = + 0,1x (where x is the average of the two results in question) Reproducibility The difference between two single and independent results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following value only in one case in twenty: Reproducibility (R) = + 0,25x (where x is the average of the two results in question) In waste oil, where the congener patterns may change, measurements on single congeners have established that the repeatability (r) is given by 0,12(x+0,2) and the reproducibility (R) by 0,51(x+0,05) These two cases represent the extremes and the true precision data will be between the two B.2 Method B Repeatability The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values given in Table B.1 only in one case in twenty Reproducibility The difference between two single and independent results, obtained by different operators working in different laboratories on identical test material would in the long run, in the normal and correct operation of the test method, exceed the values given in Table B.1 only in one case in twenty, Table B.1 - Repeatability and reproducibility PCB content (mg/kg) Repeatability Reproducibility 0,5 2,0 20 2,0 8,5 50 4,0 22,5 17 EN 12766-2:2001 (E) Bibliography [1] M D Mullin, C M Pochini, S McCrindle, M Romkes, S H Safe and L M Safe, Environ Sci Technol., 18, (1984), 468 [2] Albro P.W., Corbett J.T and Schroeder J.L Journal of Chromatography, 205, (1981), 103 [3] Ballschmiter K and Zell M Fresenius' Zeitschrift für Analytische Chemie, 302, (1980), 20 [4] Schulz D.E., Petrick G and Duinker J.C Environ Sci Technol 23, (1989), 852-859 [5] Sauvain, J.J et al, Fresenius J Anal Chem 350 (1994), 555-562 [6] Brenk, F.-R et al, Erdöl und Kohle – Erdgas Petrochemie 38 (1985), 469-470 [7] Van den Berg, M et al, Environmental Health Perspective, 106(12), 775-792, 1988 [8] Frame, G et al, J High Resol Chromatogr 1996, 19, 657-668 [9] Schulz, D et al, J Environ Sci Technol 1989, 23, 852-859 [10] Frame, G et al, Chemosphere 1996, 33, 603-623 [11] Capel, P et al, 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