1、 ISO 2013 Soil quality Determination of polychlorinated biphenyls (PCB) by gas chromatography with mass selective detection (GC-MS) and gas chromatography with electron- capture detection (GC-ECD) Qualit du sol Dtermination des polychlorobiphnyles (PCB) par chromatographie en phase gazeuse avec dtec
2、tion slective de masse (GC-MS) et chromatographie en phase gazeuse avec dtection par capture dlectrons (GC-ECD) INTERNATIONAL STANDARD ISO 13876 First edition 2013-11-15 Reference number ISO 13876:2013(E) ISO 13876:2013(E)ii ISO 2013 All rights reserved COPYRIGHT PROTECTED DOCUMENT ISO 2013 All righ
3、ts reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from ei
4、ther ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ISO 13876:2013(E) ISO 2013 All rights reserved iii C
5、ontents Page Foreword iv Introduction v 1 Scope . 1 2 Normative references 1 3 T erms and definitions . 2 4 Principle 2 5 Interferences 3 5.1 Interference with sampling and extraction 3 5.2 Interference with GC 3 6 Safety remarks 3 7 Reagents 4 7.1 General . 4 7.2 Reagents for extraction 4 7.3 Reage
6、nts for clean-up 4 7.4 Gas chromatographic analysis . 7 7.5 Standards . 7 7.6 Preparation of standard solutions . 9 8 Apparatus 10 9 Sample storage and preservation 11 9.1 Sample storage .11 9.2 Sample pretreatment 11 10 Procedure12 10.1 Blank test 12 10.2 Extraction .12 10.3 Concentration14 10.4 Cl
7、ean-up of the extract 14 10.5 Addition of the injection standard 17 10.6 Gas chromatographic analysis (GC) .18 10.7 Mass spectrometry (MS) .18 10.8 Electron capture detection (ECD) 23 11 Performance characteristics .25 12 Precision 25 13 Test report 25 Annex A (informative) Repeatability and reprodu
8、cibility data .26 Annex B (informative) Examples for retention times of PCBs 28 Bibliography .29 ISO 13876:2013(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standar
9、ds is normally carried out through ISO 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
10、 part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In par
11、ticular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives). Attention is drawn to the possibility that some of the elements of
12、 this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see
13、www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement. For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence t
14、o the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information The committee responsible for this document is ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics.iv ISO 2013 All rights reserved ISO 13876:20
15、13(E) Introduction Polychlorinated biphenyls (PCB) have been widely used as additives in industrial applications where chemical stability has been required. This stability, on the other hand, creates environmental problems when PCBs are eventually released into the environment. Since some of these P
16、CB compounds are highly toxic, their presence in the environment (air, water, soil, sediment, and waste) is regularly monitored and controlled. At present, determination of PCB is carried out in these matrices in most of the routine laboratories following the preceding steps for sampling, pretreatme
17、nt, extraction, and clean-up by measurement of specific PCB by means of gas chromatography in combination with mass spectrometric detection (GC-MS) or gas chromatography with electron capture detector (GC-ECD). The European Standard EN 16167:2012 on which this International Standard is based, was de
18、veloped in the European project HORIZONTAL. It is the result of a desk study “3-12 PCB” and aims at evaluation of the latest developments in assessing PCBs in sludge, soil, treated biowaste, and neighbouring fields. Taken into account the different matrices and possible interfering compounds, this E
19、uropean Standard does not contain one possible way of working. Several choices are possible, in particular, relating to clean-up. Detection with both MS-detection and ECD-detection is possible. Two different extraction procedures and 11 clean-up procedures are described. The use of internal and inje
20、ction standards is described in order to have an internal check on choice of the extraction and clean-up procedure. The method is, as far as possible, in agreement with the method described for PAHs (see ISO 13859). It has been tested for ruggedness. This International Standard is applicable and val
21、idated for several types of matrices as indicated in Table 1 (see also Annex A for the results of the validation). Table 1 Matrices for which this International Standard is applicable and validated Matrix Materials used for validation Sludge Municipal sewage sludge Biowaste Compost ISO 2013 All righ
22、ts reserved v Soil quality Determination of polychlorinated biphenyls (PCB) by gas chromatography with mass selective detection (GC-MS) and gas chromatography with electron- capture detection (GC-ECD) WARNING Persons using this International Standard should be familiar with usual laboratory practice
23、. This International Standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutel
24、y essential that tests conducted according to this International Standard be carried out by suitably trained staff. 1 Scope This International Standard specifies a method for quantitative determination of seven selected polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB
25、180) in sludge, treated biowaste, and soil using GC-MS and GC-ECD (see Table 2). Table 2 Target analytes of this International Standard Target analyte CAS-RN a PCB28 2,4,4-trichlorobiphenyl 7012-37-5 PCB52 2,2,5,5-tetrachlorobiphenyl 35693-99-3 PCB101 2,2,4,5,5-pentachlorobiphenyl 37680-37-2 PCB118
26、2,3,4,4,5-pentachlorobiphenyl 31508-00-6 PCB138 2,2,3,4,4,5-hexachlorobiphenyl 35056-28-2 PCB153 2,2,4,4,5,5-hexachlorobiphenyl 35065-27-1 PCB180 2,2,3,4,4,5,5-heptachlorobiphenyl 35065-29-3 aChemical Abstracts Service Registry Number. The limit of detection depends on the determinants, the equipmen
27、t used, the quality of chemicals used for the extraction of the sample, and the clean-up of the extract. Under the conditions specified in this International Standard, a limit of application of 1 g/kg (expressed as dry matter) can be achieved. Sludge and treated biowaste can differ in properties and
28、 also in the expected contamination levels of PCBs and presence of interfering substances. These differences make it impossible to describe one general procedure. This International Standard contains decision tables based on the properties of the sample and the extraction and clean-up procedure to b
29、e used. 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 a
30、ny amendments) applies. ISO 5667-15, Water quality Sampling Part 15: Guidance on the preservation and handling of sludge and sediment samples INTERNATIONAL ST ANDARD ISO 13876:2013(E) ISO 2013 All rights reserved 1 ISO 13876:2013(E) ISO 8466-1, Water quality Calibration and evaluation of analytical
31、methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration function ISO 114 65, Soil quality Determination of dry matter and water content on a mass basis Gravimetric method ISO 14507, Soil quality Pretreatment of samples for determination of organ
32、ic contaminants ISO 16720, Soil quality Pretreatment of samples by freeze-drying for subsequent analysis ISO 18512, Soil quality Guidance on long and short term storage of soil samples ISO 22892, Soil quality Guidelines for the identification of target compounds by gas chromatography and mass spectr
33、ometry 3 T erms a nd definiti ons For the purposes of this document, the following terms and definitions apply. 3.1 polychlorinated biphenyl PCB biphenyl substituted by one to ten chlorine atoms SOURCE: EN 15308:2008, 3.1 3.2 congener member of the same kind, class, or group of chemicals, e.g. anyon
34、e of the 209 individual PCBs SOURCE: EN 15308:2008, 3.2 Note 1 to entry: The IUPAC congener numbers are for easy identification; they do not represent the order of chromatographic elution. 3.3 critical pair pair of congeners that is separated to a predefined degree (e.g. R = 0,5) to ensure chromatog
35、raphic separation meets minimum quality criteria SOURCE: EN 15308:2008, 3.6 4 Principle Due to the horizontal character of this International Standard, different procedures for different steps (modules) are allowed. Which modules should be used depends on the sample. A recommendation is given in thi
36、s International Standard. Performance criteria are described and it is the responsibility of the laboratories applying this International Standard to show that these criteria are met. Use of spiking standards (internal standards) allows an overall check on the efficiency of a specific combination of
37、 modules for a specific sample. However, it does not necessarily give the information upon the extensive extraction efficiency of the native PCB bonded to the matrix. After pretreatment, according to the methods referred to in 9.2, the test sample is extracted with a suitable solvent. The extract is
38、 concentrated by evaporation. If necessary, interfering compounds are removed by a clean- up method suitable for the specific matrix. The eluate is concentrated by evaporation. The extract is analysed by gas chromatography. The various compounds are separated using a capillary column with a stationa
39、ry phase of low polarity. Detection occurs with mass spectrometry (MS) or an electron capture detector (ECD) (8.2.1).2 ISO 2013 All rights reserved ISO 13876:2013(E) PCBs are identified and quantified by comparison of relative retention times and relative peak heights (or peak areas) with respect to
40、 internal standards added. The efficiency of the procedure depends on the composition of the matrix that is investigated. 5 Interferences 5.1 Interference with sampling and extraction Use sampling containers of materials (preferably of steel, aluminium, or glass) that do not change the sample during
41、 the contact time. Avoid plastics and other organic materials during sampling, sample storage, or extraction. Keep the samples from direct sunlight and prolonged exposure to light. During storage of the samples, losses of PCBs can occur due to adsorption on the walls of the containers. The extent of
42、 the losses depends on the storage time. 5.2 Interference with GC Substances that co-elute with the target PCB can interfere with the determination. These interferences can lead to incompletely resolved signals and, depending on their magnitude, can affect accuracy and precision of the analytical re
43、sults. Peak overlap does not allow an interpretation of the result. Asymmetric peaks and peaks being broader than the corresponding peaks of the reference substance suggest interferences. Chromatographic separation between the following pairs can be critical. The critical pair PCB28 and PCB31 is use
44、d for selection of the capillary column (8.2.1). If molecular mass differences are present, quantification can be made by mass selective detection. If not or using ECD, the specific PCB is reported as the sum of all PCBs present in the peak. Typically, the concentrations of the co-eluting congeners
45、compared to those of the target congeners are low. When incomplete resolution is encountered, peak integration shall be checked and, when necessary, corrected. PCB28 PCB31 PCB52 PCB73 PCB101 PCB89/PCB90 PCB118 PCB106 PCB138 PCB164/PCB163 Presence of considerable amounts of mineral oil in the sample
46、can interfere with the quantification of PCB in GC-MS. In presence of mineral oil, GC-ECD can be preferred or mineral oil can be removed using clean-up procedure G (see 10.4.8) using DMF/n-hexane. Presence of tetrachlorobenzyltoluene (TCBT)-mixtures can disturb the determination of the PCB with GC-E
47、CD. 6 Safety remarks PCBs are highly toxic and shall be handled with extreme care. Avoid contact with solid materials, solvent extracts, and solutions of standard PCB. It is strongly advised that standard solutions are prepared centrally in suitably equipped laboratories or are purchased from suppli
48、ers specialized in their preparation. Solvent solutions containing PCB shall be disposed of in a manner approved for disposal of toxic wastes. For the handling of hexane, precautions shall be taken because of its neurotoxic properties. National regulations shall be followed with respect to all hazar
49、ds associated with this method. ISO 2013 All rights reserved 3 ISO 13876:2013(E) 7 Reagents 7.1 General All reagents shall be of recognized analytical grade. The purity of the reagents used shall be checked by running a blank test as described in 10.1. The blank shall be less than 50 % of the lowest reporting limit. 7.2 Reagents for extraction 7.2.1 Acetone (2-propanone), (CH 3 ) 2CO. 7.2.2 n-heptane, C 7 H 16 . 7.2.3 Petroleum ether, boiling range 40 C to 60 C. Hexane-like
