1、BSI Standards PublicationBS ISO 13913:2014Soil quality Determinationof selected phthalates usingcapillary gas chromatographywith mass spectrometricdetection (GC/MS)BS ISO 13913:2014 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 13913:2014.The UK participation
2、 in its preparation was entrusted to TechnicalCommittee EH/4, Soil quality.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapp
3、lication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 72174 8ICS 13.080.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Commi
4、ttee on 30 September 2014.Amendments issued since publicationDate Text affectedBS ISO 13913:2014 ISO 2014Soil quality Determination of selected phthalates using capillary gas chromatography with mass spectrometric detection (GC/MS)Qualit du sol Dtermination de phthalates slectionns en utilisant la c
5、hromatographie gazeuse capillaire avec dtection par spectromtrie de masseINTERNATIONAL STANDARDISO13913First edition2014-02-01Reference numberISO 13913:2014(E)BS ISO 13913:2014ISO 13913:2014(E)ii ISO 2014 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2014All rights reserved. Unless otherwise s
6、pecified, 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 either ISO at the address below o
7、r ISOs member body in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS ISO 13913:2014ISO 13913:2014(E) ISO 2014 All rights reserved iiiContents PageForeword iv
8、Introduction v1 Scope . 12 Normative references 13 Principle 24 Interferences 24.1 General . 24.2 Interferences during sampling 24.3 Cross contamination 24.4 Interferences in gas chromatography . 25 Reagents 25.1 General . 26 Apparatus . 46.1 General . 47 Sampling and sample storage . 68 Procedure.
9、68.1 Preparation of glass apparatus . 68.2 Drying of the sample 68.3 Extraction 78.4 Clean-up 78.5 Gas chromatography 88.6 Blank monitoring 88.7 Identification of individual compounds 89 Calibration 99.1 General . 99.2 Calibration with internal standard 99.3 Verification of calibration . 1010 Calcul
10、ation .1111 Expression of results .1212 Precision 1213 Test report 12Annex A (informative) Repeatability and reproducibility data .13Annex B (informative) Example of a reference solution for multipoint calibration 16Annex C (informative) Examples for gas chromatographic conditions .18Annex D (inform
11、ative) Flow scheme of the determination of phthalates .20Bibliography .21BS ISO 13913:2014ISO 13913:2014(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is nor
12、mally 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 part in
13、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 particular th
14、e 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 this docu
15、ment 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 www.iso.or
16、g/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 to the WTO p
17、rinciples in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics.iv ISO 2014 All rights reservedBS ISO 13913:2014ISO 1391
18、3:2014(E)IntroductionThis International Standard is applicable and validated 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 validatedMatrix Materials used for validati
19、onSludge Municipal sludgeBiowaste Fresh compostSoil Sludge amended soil ISO 2014 All rights reserved vBS ISO 13913:2014BS ISO 13913:2014Soil quality Determination of selected phthalates using capillary gas chromatography with mass spectrometric detection (GC/MS)WARNING Persons using this Internation
20、al Standard should be familiar with usual laboratory practice. 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
21、any national regulatory conditions.IMPORTANT It is absolutely essential that tests conducted according to this International Standard be carried out by suitably trained staff.1 ScopeThis International Standard specifies a method for the determination of selected phthalates in sludge, treated biowast
22、e, and soil, after extraction and gas chromatographic analysis with mass spectrometric detection.The method is applicable for the determination of phthalates (see Table 2) at the lowest mass content of 0,1 mg/kg to 0,5 mg/kg (expressed as dry matter), depending on the individual substance.The applic
23、ability of the method to other phthalates not specified in Table 2 is not excluded except the isomeric mixtures, e.g. DiNP (Di-isononylphthalate), but shall be verified in each case.Table 2 Phthalates that can be determined according to this International StandardNo Name Formula AbbreviationMolar ma
24、ssg/molCAS-RNa1 Dimethylphthalate C10H10O4DMP 194,2 00131-11-32 Diethylphthalate C12H14O4DEP 222,2 00084-66-23 Dipropylphthalate C14H18O4DPP 250,3 00131-16-84 Di-(2-methyl-propyl)phthalate C16H22O4DiBP 278,4 00084-69-55 Dibutylphthalate C16H22O4DBP 278,4 00084-74-26 Butylbenzylphthalate C19H20O4BBzP
25、 312,4 00085-68-77 Dicyclohexylphthalate C20H26O4DCHP 330,4 00084-61-78 Di-(2-ethylhexyl)phthalate C24H38O4DEHP 390,6 00117-81-79 Dioctylphthalate C24H38O4DOP 390,6 00117-84-010 Didecylphthalate C28H46O4DDcP 446,7 00084-77-511 Diundecylphthalate C30H50O4DUP 474,4 03648-20-2aChemical Abstracts Servic
26、e Registry Number.2 Normative referencesThe 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 (in
27、cluding any amendments) applies.ISO 5667-13, Water quality Sampling Part 13: Guidance on sampling of sludgesINTERNATIONAL STANDARD ISO 13913:2014(E) ISO 2014 All rights reserved 1BS ISO 13913:2014ISO 13913:2014(E)ISO 5667-15, Water quality Sampling Part 15: Guidance on the preservation and handling
28、of sludge and sediment samplesISO 10381-2, Soil quality Sampling Part 2: Guidance on sampling techniquesISO 11465, Soil quality Determination of dry matter and water content on a mass basis Gravimetric methodISO 14507, Soil quality Pretreatment of samples for determination of organic contaminantsISO
29、 22892, Soil quality Guidelines for the identification of target compounds by gas chromatography and mass spectrometry3 PrincipleThe dried sample, dried by freeze drying or with sodium sulfate, is extracted with ethyl acetate on the shaking device. An aliquot of the extract is cleaned with aluminium
30、 oxide (if necessary) followed by gas chromatographic separation using capillary columns and identification and quantification of the phthalates by mass spectrometry.4 Interferences4.1 GeneralDue to their use as plasticizer agents, phthalates are ubiquitous. The sources of phthalates are multiple an
31、d shall be checked and reduced by every laboratory, itself. Therefore, special attention shall be paid to avoid contaminations.4.2 Interferences during samplingIn order to avoid interferences and cross contaminations, do not use plastic materials (e.g. pipes, etc.).4.3 Cross contaminationChemicals a
32、nd analytical equipment can be of various qualities. Cross contamination is likely to occur with laboratory air. Therefore, remove, as far as possible, plastic materials from the laboratory. Cleaning agents often contain phthalates and can severely contaminate the laboratory air if in use regularly.
33、 Therefore, refrain from using these agents during application of this procedure.Using plastic gloves during pretreatment can increase the contamination.4.4 Interferences in gas chromatographyPhthalates can bleed from the septa of the injector into the gas chromatograph; therefore, use septa that ar
34、e not likely to contaminate the system.Fittings, e.g. of syringes, or equipment and septa of the sampling bottles (6.5) can also contain phthalates.5 Reagents5.1 GeneralAll reagents shall be of recognized analytical grade.Use only reagents with negligibly low concentration of phthalates and verify b
35、y blank determinations and, if necessary, apply additional cleaning steps.2 ISO 2014 All rights reservedBS ISO 13913:2014ISO 13913:2014(E)5.2 Nitrogen, N2, of high purity, at least a volume fraction of 99,9 % for drying and, if necessary, for concentration by evaporation.5.3 Helium, He, of high puri
36、ty, at least a volume fraction of 99,999 %.5.4 Ethyl acetate, C4H8O2, phthalate-free, high purity.5.5 Methanol, CH3OH.5.6 Isooctane, C8H18(2,2,4-trimethylpentane).5.7 Quartz wool, heated to 400 C for at least 4 h.5.8 Aluminium oxide, Al2O3, neutral, 50 m to 200 m particle size, heated to 400 C for a
37、t least 4 h.Store heat-treated aluminium oxide in covered flask or desiccator. Use within five days after heat-treatment.NOTE Alternative materials, like Florisil1)or silica can be used, provided their properties and capacity to separate are similar to aluminium oxide and their properties are checke
38、d according to 8.6.5.9 Internal standards.For example: deuterated di-n-butylphthalate, “D4-ring-DBP”; deuterated D4-C16H22O4; deuterated di-(2-ethylhexyl) phthalate “D4-ring-DEHP”; deuterated D4-C24H38O4; di-n-octylphthalate, “D4-ring-DOP”; D4- C24H38O4; 13C-labelled standards can also be used, if a
39、vailable.5.10 Reference substances.Table 2 gives a list of phthalates with defined mass concentrations for the preparation of reference solutions for the gas chromatographic procedure.5.11 Solutions of the single substances.In a 10-ml volumetric flask (6.13), transfer e.g. 10 mg of each of the refer
40、ence substances (5.10) in ethyl acetate (5.4) and bring to volume with ethyl acetate (5.4) (concentration: 1 g/l).Store the solutions in glass bottles at 18 C, protected from light, and check the concentration at least every three months.5.12 Stock solution.In a 10-ml volumetric flask (6.13), dissol
41、ve between 100 l and 500 l of the single substance solutions (5.11) and bring to volume with ethyl acetate (5.4) (concentration: 10 mg/l to 50 mg/l).1) This information is given for the convenience of users of this document and does not constitute an endorsement by ISO TC 190/SC 3 of the product nam
42、ed. Equivalent products may be used if they can be shown to lead to the same results. ISO 2014 All rights reserved 3BS ISO 13913:2014ISO 13913:2014(E)Store the solution in a glass bottle at 18 C, protected from light, and check the concentration at least every three months.5.13 Reference solutions f
43、or multipoint calibration (see Annex B).Prepare solutions by adequate dilution of the stock solution (5.12) and internal standards (5.9) with ethyl acetate (5.4).Store the solutions in glass bottles at 18 C, protected from light, and check the concentration at least every three weeks.5.14 Solution o
44、f the internal standards (see Annex B).5.14.1 Internal standard solution of D4-phthalates.Weigh e.g. 0,1 g of an internal standard phthalate (D4) (5.9) in a 10-ml volumetric flask (6.13) filled with about 5 ml of ethyl acetate (5.4) and bring to volume with ethyl acetate (5.4). Store the solution in
45、 a glass bottle at 18 C.5.14.2 Solution I internal standard mix.Combine the solutions of the single internal standard phthalates (5.9) e.g. by dilution 1:100 as follows: Transfer with a syringe 0,1 ml (6.15) of each solution into a 10-ml volumetric flask (6.13) filled with about 5 ml of ethyl acetat
46、e (5.4). Bring to volume with ethyl acetate. The final concentration of di-n-octylphthalate (D4), di-n-butylphthalate (D4), and di-(2-ethylhexylphthalate) is 100 mg/l in ethyl acetate (5.4).5.14.3 Solution II internal standard mix.Take from this 1:100 dilution (5.14.2) e.g. 250 l, transfer into a 25
47、0-ml volumetric flask (6.13), filled with 250 ml of ethyl acetate (5.4).The final concentration of di-n-octylphthalate (D4), di-n-butylphthalate (D4), and di-(2-ethylhexylphthalate) is 0,1 mg/l in ethyl acetate (5.4).5.14.4 Solution III internal standard mix.Dilute the solution I internal standard (
48、5.14.2.) 1:10. Pipette 1 ml of the solution (5.14.2.) in a 10-ml volumetric flask (6.13) filled with about 5 ml of ethyl acetate (5.4). Bring to volume with ethyl acetate. The final concentration of di-n-octylphthalate (D4), di-n-butylphthalate (D4), and di-(2-ethylhexylphthalate) is 10 mg/l in ethy
49、l acetate.5.15 Sodium sulfate, Na2SO4, heated to 400 C for at least 4 h.6 Apparatus6.1 GeneralEquipment or parts of it which are likely to come into contact with the sample or its extract shall be free from phthalates. This can be achieved by thorough cleaning of all glass apparatus and checked by the blank determination.6.2 Wide-neck flat bottomed flasks with glass stoppers, preferably brown glass, volumes 500 ml and 1 000 ml.6.3 Drying oven, capable of maintaining at a temperature of (105 5) C
