SIST EN 12766-2:2001
(Main)Petroleum products and used oils - Determination of PCBs and related products - Part 2: Calculation of polychlorinated biphenyl (PCB) content
Petroleum products and used oils - Determination of PCBs and related products - Part 2: Calculation of polychlorinated biphenyl (PCB) content
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.
Mineralölerzeugnisse und Gebrauchtöle - Bestimmung von PCBs und verwandten Produkten - Teil 2: Berechnung des Gehaltes an polychlorierten Biphenylen (PCB)
Anwendungsbereich
Diese Norm legt zwei Berechnungsverfahren (?Verfahren A" und ?Verfahren B") für den PCB-Gehalt fest.
Die Basis für diese Gehaltsbestimmung ist den chromatographischen Ergebnissen aus EN 12766-1 entnommen. In EN 12766-1 sind alle notwendigen experimentellen Schritte für die spezifische Analyse von ungebrauchten, gebrauchten und behandelten (z. B. entchlorierten) Mineralölerzeugnissen, einschließlich synthetischer Schmieröle und Mischungen von Pflanzenölen, beschrieben.
Das Verfahren ist ebenfalls anwendbar auf Mineralölerzeugnisse und synthetische Schmierstoffe, die in geeigneter Weise aus anderen Materialien, z. B. aus Abfallstoffen, gewonnen werden.
Beide Berechnungsverfahren haben unterschiedliche Stärken und Schwächen, welche in den folgenden Abschnitten beschrieben sind, und die vor Anwendung in einem bestimmten Fall zu berücksichtigen sind. Die richtige Anwendung entweder des Verfahrens A oder des Verfahrens B muss sorgfältig ausgewählt werden, bevor man es in einer bestimmten Situation einsetzt.
Bei Anwendung des Verfahrens A muss besondere Aufmerksamkeit der Vermeidung von Störungen durch Nicht-PCB-Stoffe, die im Chromatogramm auftreten können, gewidmet werden.
Deshalb kann Verfahren A vorwiegend für die Analyse von gebrauchten und ungebrauchten Isolierölen eingesetzt werden. Es wird empfohlen, das Berechnungsverfahren ohne besondere Vorsichtsmaßnahmen nicht für andere als die oben erwähnten Produkte einzusetzen.
Die Berechnung nach Verfahren A kann zwei verschiedene Ergebnisse (?Alle Wahrscheinlichen" bzw. ?Alle Möglichen") ergeben. Deshalb muss bei der Ergebnisbeurteilung besondere Vorsicht aufgewendet werden, um die Ergebnisse richtig zu interpretieren.
Produits pétroliers et huiles usagées - Détermination des PCB et produits connexes - Partie 2: Calcul de la teneur en polychlorobiphényles (PCB)
La présente Norme prescrit deux procédures de calcul (« méthode A » et « méthode B ») pour la teneur en PCB. Les bases de cette quantification sont extraites des résultats chromatographiques de l'EN 12766-1:2000 dans laquelle toutes les procédures expérimentales nécessaires sont décrites pour l'analyse spécifique des produits pétroliers usagés, non usagés et traités (par exemple déchlorés), et comprenant les huiles lubrifiantes synthétiques et des mélanges d'huiles végétales. La méthode est également applicable aux produits pétroliers et aux huiles lubrifiantes synthétiques correctement récupérées a partir d'autres produits, par exemple des produits usagés. Chacune des deux méthodes possede ses propres points forts et points faibles. Ceux-ci sont exposés dans les paragraphes suivants et doivent etre pris en compte avant utilisation d'une des deux méthodes dans une application particuliere.
Lors de l'utilisation de la méthode A un soin particulier doit etre pris pour éviter les interférences occasionnées par des composés autres que des PCB, qui peuvent apparaître sur le chromatogramme. En conséquence la méthode A doit etre utilisée préférentiellement pour l'analyse d'huiles isolantes neuves ou usagées. Il est recommandé d'utiliser la méthode de calcul A avec des précautions particulieres pour des produits autres que ceux mentionnés ci-dessus. La méthode de calcul A est en mesure de donner deux séries de résultats, (« tous congéneres probables » et « tous congéneres possibles ») . Par conséquent des précautions doivent etre prises pour interpréter ces résultats d'une maniere correcte.
Naftni derivati in rabljena olja - Določevanje PCB in sorodnih proizvodov - 2. del: Izračun količine polikloriranega bifenila (PCB)
General Information
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Mineralölerzeugnisse und Gebrauchtöle - Bestimmung von PCBs und verwandten Produkten - Teil 2: Berechnung des Gehaltes an polychlorierten Biphenylen (PCB)Produits pétroliers et huiles usagées - Détermination des PCB et produits connexes - Partie 2: Calcul de la teneur en polychlorobiphényles (PCB)Petroleum products and used oils - Determination of PCBs and related products - Part 2: Calculation of polychlorinated biphenyl (PCB) content75.100MazivaLubricants, industrial oils and related products75.080Naftni proizvodi na splošnoPetroleum products in generalICS:Ta slovenski standard je istoveten z:EN 12766-2:2001SIST EN 12766-2:2001en01-december-2001SIST EN 12766-2:2001SLOVENSKI
STANDARD
SIST EN 12766-2:2001
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 12766-2July 2001ICS 75.080; 75.100English versionPetroleum products and used oils - Determination of PCBs andrelated products - Part 2: Calculation of polychlorinated biphenyl(PCB) contentProduits pétroliers et huiles usagées - Détermination desPCB et produits connexes - Partie 2: Calcul de la teneur enpolychlorobiphényles (PCB)Mineralölerzeugnisse und Gebrauchtöle - Bestimmung vonPCBs und verwandten Produkten - Teil 2: Berechnung desGehalts an polychlorierten Biphenylen (PCB)This European Standard was approved by CEN on 9 June 2001.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards 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 translationunder the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the officialversions.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 STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2001 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 12766-2:2001 ESIST EN 12766-2:2001
EN 12766-2:2001 (E)2ForewordThis 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 anidentical text or by endorsement, at the latest by January 2002, and conflicting national standards shall bewithdrawn 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.EN 12766, Petroleum products and used oils - Determination of PCBs1) and related productsPart 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using anelectron capture detector (ECD)Part 2: Calculation of polychlorinated biphenyl (PCB) contentPart 3: Determination and calculation of PCB related products2According to the CEN/CENELEC Internal Regulations, the national standards organizations of thefollowing 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 polychlorinatedterphenyls. The definition includes PCBs proper, PCTs and also PCBTs (polychlorinated benzyltoluenes), tradename“Ugilec”.2 Part 3 of EN 12766 is under developmentSIST EN 12766-2:2001
EN 12766-2:2001 (E)31
ScopeThis standard specifies two calculation procedures (“method A” and “method B”) for PCB content. Thebasis for this quantification is taken from the chromatographic results of EN 12766-1:2000 in which allnecessary 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 fromother materials, e.g. from waste materials. Both methods have different strengths and weaknesses whichare 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 aspecific application.Using method A, special care needs to be exercised to avoid interferences from non PCB substanceswhich may occur in the chromatogram. Therefore, method A can be used predominantly for the analysisof used and unused insulating oils. It is recommended not to use calculation method A without specialprecautions for other than above-mentioned products. Calculation method A can produce two alternativesets of results, (“All Probables” and “All Possibles”). Therefore, care needs to
be taken in order tointerpret these results in the correct manner.Method B uses as intermediate result the sum of six congeners, which belong to the most abundant inalmost all technical PCB materials, thereby minimizing potential interferences from other (coeluting) nonPCB substances. To obtain the PCB content, the intermediate sum from six congeners needs to bemultiplied by a multiplication factor. Calculation Method B can be used predominantly for the analysis ofliquids from used and waste materials of unknown origin and for samples with low PCB contents.2
Normative ReferencesThis European Standard incorporates, by dated and undated reference, provisions from otherpublications. These normative references are cited at the appropriate places in the text and thepublications are listed hereafter. For dated references, subsequent amendments to or revisions of any ofthese 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 anelectron capture detector (ECD)EN 61619, Insulating liquids - Contamination by polychlorinated biphenyls (PCBs) - Method ofdetermination by capillary column gas chromatography (IEC 61619:1997)EN ISO 4259, Petroleum products - Determination and application of precision data in relation to methodsof test (ISO 4259:1992/Cor 1:1993)SIST EN 12766-2:2001
EN 12766-2:2001 (E)43
Terms and definitionsAs 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 andEN 12766-2. Also, the terms "PCT" and "PCBT" are defined in chemical terms, and prEN 12766-3describes their measurement and quantification.For analytical results to comply with the mentioned legislation, the total of PCB fromEN 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.3.1polychlorinated biphenyl (PCB)a biphenyl substituted with one to 10 chlorine atomsNOTE
For legal purposes, congeners with one, two or ten chlorine atoms maybe excluded from this definition.3.2congenerany chlorine derivative of biphenyl, irrespective of the number of chlorine atomsNOTE
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 do not represent the orderof chromatographic elution.3.3DCBabbreviation for PCB congener 209, decachlorobiphenyl, used as reference and as an internal standard4
Calculation methodsThe results from method A and method B shall not be confused.4.1
Method AThis 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. Thecalibration 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, sothat some overlapping can occur.For the calculation of PCB content, the EN 61619 method uses two tables of response factors producedfrom the literature values (see Bibliography) by taking into account the relative proportions of coelutingcongeners in each peak.Not all congeners are calibrated. Nine congeners are taken across the range of elution times providingnine calibration windows. Within each window, the calibration factor is extrapolated to adjust, for eachcongener, the response factor from the literature.SIST EN 12766-2:2001
EN 12766-2:2001 (E)54.1.1
Data-processing systemThe data system shall be set up according to the manufacturer's instructions. Most systems requiredesignation of a minimum of two reference points including the internal standard decachlorobiphenyl(DCB).4.1.2
Data filesThe method requires data files containing experimental data (ERRT) and data originating from theliterature. For each peak of single or coeluting congeners the following data are filed in order of increasingERRT (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 averageresponse factor was calculated for each peak containing coeluting congeners using the relativeproportions 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 morethan one congener coelutes under one chromatogram peak, the RRF of the group of congeners isweighted by exclusion of congeners not found in commercial mixtures. Use this data set with unknownsand 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 thesame value and where there is co-elution (for example peak no. 49) there are different values for thedifferent sets.RRFs in Table A.1 are corrected for the instrument being used by the procedure in 4.1.5.4.1.3
Coeluting congenersMore than one congener may coelute.
Peaks that fall within the window of ± 0,001 5 from the RRT shallbe 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 comparisonwith the example in Figure A.1 and calculate the ERRT for each peak as follows:ttttERRT3020930xxSIST EN 12766-2:2001
EN 12766-2:2001 (E)6where: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 1 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 systemshall 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 eachend of the chromatogram (test mixture) isolated from congeners occurring in commercial mixtures andallow accurate repeatable values of ERRTs to be obtained.4.1.4.2Use the ERRT values of the congeners listed in Table 1 below (determined in 4.1.4.1) to designate thereference peaks in the data-processing system.Table 1 - Reference Peaks/CongenersPeaknumbersReference peakcongener numbersERRT(examples)9300,00033440,2254656/600,3425777/1100,42774138/160/1630,574901800,7031052091,000NOTE
With the exception of congeners 30 and 209 the reference peaks werechosen because they are major components of commercial mixtures. Theywill not occur in all samples, the number of reference peaks found will dependon 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 frominstrument to instrument depending on the injection mode and the conditions of the electroncapture 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 representedby one of the congeners listed in Table 2. These congeners are normally present in commercial mixturesas major components (see Table A.1).4.1.5.2
Using optimised chromatographic conditions as in clause 8 of EN 12766-1:2000, inject a suitablealiquot 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 2 usingthe following equation:mAmAERRFi209209iiSIST EN 12766-2:2001
EN 12766-2:2001 (E)7where: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 2 - Congeners for ERRF calibrationPeaknumberSegmentnumberCongenernumberERRT(examples)RRF(table A.2)(IUPAC)121180,0280,275222310,1140,493333440,2250,4604941010,3560,5876351180,4770,7647461380,5740,7269071800,7031,1379581700,7590,65910291940,8771,6404.1.5.3
From the determined ERRF and the theoretical RRF value given in Table 2 calculate thecorrection factor Ki for each congener:iiiKERRFRRFEXAMPLEfor congener 180, wheredeterminedERRF180= 1,030lite
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