1、BSI Standards Publication Soil quality Determination of some selected phenols and chlorophenols Gas chromatographic method with mass spectrometric detection PD ISO/TS 17182:2014National foreword This Published Document is the UK implementation of ISO/TS 17182:2014. The UK participation in its prepar
2、ation was entrusted to Technical Committee EH/4, Soil quality. 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 necessary provisions of a contract. Users are responsible for its correct application
3、. The British Standards Institution 2014. Published by BSI Standards Limited 2014 ISBN 978 0 580 76247 5 ICS 13.080.10 Compliance with a British Standard cannot confer immunity from legal obligations. This Published Document was published under the authority of the Standards Policy and Strategy Comm
4、ittee on 31 December 2014. Amendments issued since publication Date Text affected PUBLISHED DOCUMENT PD ISO/TS 17182:2014 ISO 2014 Soil quality Determination of some selected phenols and chlorophenols Gas chromatographic method with mass spectrometric detection Qualit du sol Dosage de quelques phnol
5、s et chlorophnols slectionns Mthode par chromatographie en phase gazeuse avec dtection par spectromtrie de masse TECHNICAL SPECIFICATION ISO/TS 17182 Reference number ISO/TS 17182:2014(E) First edition 2014-12-15 PD ISO/TS 17182:2014 ISO/TS 17182:2014(E)ii ISO 2014 All rights reserved COPYRIGHT PROT
6、ECTED DOCUMENT ISO 2014 All rights 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. Per
7、mission can be requested from either 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 PD ISO/TS 17182:2014
8、 ISO/TS 17182:2014(E)Contents Page Foreword iv 1 Scope . 1 2 Normative references 3 3 Principle 3 4 Interferences 3 4.1 Interference with sampling and extraction 3 4.2 Interference with GC-MS determination 4 5 Reagents 4 5.1 Products used in their commercially available form 4 5.2 Aqueous solutions
9、4 5.3 Standard solutions of phenols . 5 6 Apparatus and equipment 5 7 Sampling 6 8 Procedure. 6 8.1 Test portion 6 8.2 Dry matter content 6 8.3 Blank sample 6 8.4 Standard sample 6 8.5 Extraction 6 8.6 Acetylation 7 8.7 Gas chromatographic analysis . 7 8.8 Calibration 7 9 Calculation 8 9.1 Calculati
10、on of the content of substance i in the extract . 8 9.2 Calculation of the content of selected phenol soil sample per dry matter (mg/kg dry matter) . 9 10 Test report . 9 Annex A (informative) Typical concentrations of the standard solutions .10 Annex B (informative) Example of gas chromatographic c
11、onditions 11 Bibliography .15 ISO 2014 All rights reserved iii PD ISO/TS 17182:2014 ISO/TS 17182:2014(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is norm
12、ally 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 t
13、he 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
17、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 2014 All rights reserved PD ISO/TS 17182:2014
18、Soil quality Determination of some selected phenols and chlorophenols Gas chromatographic method with mass spectrometric detection WARNING Phenols and chlorophenols are both toxic and corrosive and should be handled with care. Methanol and acetonitrile are toxic and acetic acid is corrosive. Latex o
19、r nitrile gloves and eye protection should be worn at all times. Spills should immediately be wiped up with adsorbent tissue and placed in sealed containers used for the disposal of toxic chemicals. Samples should be treated as toxic and harmful. Extreme care shall be taken through all steps of the
20、extraction procedure, which shall be performed in a fume hood. All solvent wastes shall be collected and treated as hazardous waste. Thus, there is a contamination risk in the laboratory. 1 Scope This International Standard describes the gas chromatographic determination of phenols, methyl phenols,
21、di-methylphenols and tri-methylphenols (see Table 1) and selected chlorophenols (see Table 2) by using mass spectrometric detection in soil samples. This method can also be used for other solid samples, such as sediments and solid wastes. This International Standard describes an acidic liquid extrac
22、tion of soil, followed by acetylation and then liquid/liquid extraction. Determination takes place by gas chromatography and mass spectrometric detection. With this method, phenols and chlorophenols can be determined at the lowest of mass concentrations ranging from approximately 0,01 mg/kg to 0,1 m
23、g/kg depending on the component sensitivity and the quantity of sample used. In some cases, complete separation of isomers cannot be achieved. Then the sum is reported. NOTE With this method, other higher methylated phenols can also be analysed provided that the suitability and the validity of the m
24、ethod is proven. Table 1 Target phenolic compounds with relevant mass fractions of respective acetylated compounds for MS-detection Compound CAS-RN a Chemical formula Acetylated compounds Fragmentation b1 stmass Relative intensity % 2 ndmass Relative intensity % phenol 108-95-2 C 6 H 6 O 94 100 66 2
25、6 2-methylphenol (o-cresol) 95-48-7 C 7 H 8 O 108 100 107 68 3-methylphenol (m-cresol) 108-39-4 C 7 H 8 O 108 100 107 85 4-methylphenol (p-cresol) 106-44-5 C 7 H 8 O 108 100 107 92 2,3-dimethylphenol 596-75-0 C 8 H 10 O 122 90 107 100 2,4-dimethylphenol 105-67-9 C 8 H 10 O 122 100 107 85 2,5-dimethy
26、lphenol 95-87-4 C 8 H 10 O 122 100 107 90 2,6-dimethylphenol 576-261-1 C 8 H 10 O 122 100 107 92 aChemical abstract service registry number. bSpectral database for organic compounds (SDBS). TECHNICAL SPECIFICATION ISO/TS 17182:2014(E) ISO 2014 All rights reserved 1 PD ISO/TS 17182:2014 ISO/TS 17182:
27、2014(E) Compound CAS-RN a Chemical formula Acetylated compounds Fragmentation b1 stmass Relative intensity % 2 ndmass Relative intensity % 3,4-dimethylphenol 95-65-8 C 8 H 10 O 122 99 107 100 3,5-dimethylphenol 108-68-9 C 8 H 10 O 122 100 107 68 2,3,5-trimethylphenol 697-82-5 C 9 H 12 O 136 87 121 1
28、00 2,3,6-trimethylphenol 2416-94-6 C 9 H 12 O 136 90 121 100 2,4,6-trimethylphenol 527-60-6 C 9 H 12 O 136 10 121 85 3,4,5-trimethylphenol 527-54-8 C 9 H 12 O 136 70 121 100 2-ethylphenol 90-00-6 C 8 H 10 O 107 100 122 48 3-ethylphenol 620-17-7 C 8 H 10 O 122 48 107 100 4-ethylphenol 123-07-9 C 8 H
29、10 O 107 100 122 35 4-propylphenol 645-56-7 C 9 H 12 O 107 100 136 25 4-isopropylphenol 99-89-8 C 9 H 12 O 121 100 136 28 2-hydroxybiphenyl 90-43-7 C 12 H 10 O 170 100 141 23 Internal standards 2-fluorophenol 367-12-4 C 6 H 5 FO 112 100 64 58 4-fluorophenol 371-41-5 C 6 H 5 FO 112 100 64 18 3-fluoro
30、-2-methyl- phenol 452-72-2 C 7 H 7 FO 126 100 97 29 4-fluorocatechol 367-32-8 C 6 H 5 FO 2 128 100 75 28 aChemical abstract service registry number. bSpectral database for organic compounds (SDBS). Table 2 Target chlorophenolic compounds with relevant mass fractions of respective acetylated compound
31、s for MS-detection Compound CAS-RN a Chemical formula Acetylated compounds Fragmentation1 stmass Relative intensity % 2 nd mass Relative intensity % 2-chlorophenol 95-57-8 C 6 H 5 OCl 128 100 130 34 3-chlorophenol 108-43-0 C 6 H 5 OCl 128 100 130 29 4-chlorophenol 106-48-9 C 6 H 5 OCl 128 100 130 35
32、 2,6-dichlorophenol 87-65-0 C 6 H 4 OCl 2 162 100 164 67 2,4-dichlorophenol 120-83-2 C 6 H 4 OCl 2 162 100 164 66 2,5-dichlorophenol 583-78-8 C 6 H 4 OCl 2 162 164 3,5-dichlorophenol 591-35-5 C 6 H 4 OCl 2 162 100 164 66 2,3-dichlorophenol 576-24-9 C 6 H 4 OCl 2 162 100 164 66 3,4-dichlorophenol 95-
33、77-2 C 6 H 4 OCl 2 162 100 164 66 2,4,6-trichlorophenol 88-06-2 C 6 H 3 OCl 3 196 100 198 98 aChemical abstract service registry number.Table 1 (continued) 2 ISO 2014 All rights reserved PD ISO/TS 17182:2014 ISO/TS 17182:2014(E) Compound CAS-RN a Chemical formula Acetylated compounds Fragmentation1
34、stmass Relative intensity % 2 nd mass Relative intensity % 2,3,6-trichlorophenol 933-75-5 C 6 H 3 OCl 3 196 100 198 100 2,3,5-trichlorophenol 933-78-8 C 6 H 3 OCl 3 196 100 198 100 2,4,5-trichlorophenol 95-95-4 C 6 H 3 OCl 3 196 96,1 198 100 2,3,4-trichlorophenol 15950-66-0 C 6 H 3 OCl 3 196 100 198
35、 98 3,4,5-trichlorophenol 609-19-8 C 6 H 3 OCl 3 196 100 198 100 2,3,4,5-tetrachlorophenol 4901-51-3 C 6 H 2 OCl 4 230 232 2,3,5,6-tetrachlorophenol 935-95-5 C 6 H 2 OCl 4 230 79 232 100 2,3,4,6-tetrachlorophenol 58-90-2 C 6 H 2 OCl 4 230 78 232 100 pentachlorophenol 87-86-5 C 6 HOCl 5 264 66 266 10
36、0 aChemical abstract service registry number. 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 o
37、f the referenced document (including any amendments) applies. ISO 3696, Water for analytical laboratory use Specification and test methods ISO 10381-1, Soil quality Sampling Part 1: Guidance on the design of sampling programmes ISO 11465, Soil quality Determination of dry matter and water content on
38、 a mass basis Gravimetric method ISO 14507, Soil quality Pretreatment of samples for determination of organic contaminants 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 chromatograp
39、hy and mass spectrometry 3 Principle The method described here is based on two steps. The first step includes a solid/liquid extraction: the phenols are extracted from field moist soil with methanol at low pH. The second step is the derivatization of phenols obtained in an aliquot of methanol in aqu
40、eous carbonate solution with acetic anhydride; the derivatives formed are extracted from this sample with cyclohexane. The cyclohexane fraction is analyzed by gas chromatography with mass spectrometric detection. 4 Interferences 4.1 Interference with sampling and extraction Standard laboratory glass
41、ware, appropriately cleaned and free of interfering compounds. Do not use any kind of plastic containers, since phenols can be adsorbed to these. Plastic materials can also contribute their impurities to the sample material. Surfactants, present in the sample, might disturb the proper extraction of
42、phenols.Table 2 (continued) ISO 2014 All rights reserved 3 PD ISO/TS 17182:2014 ISO/TS 17182:2014(E) 4.2 Interference with GC-MS determination Substances which have the same or nearly the same retention time of the target analytes and which give the same mass fragments (i.e. isomeric phenols other t
43、han stated in the table) might interfere with the determination. 5 Reagents During the analysis, unless otherwise stated, use only reagents of recognized analytical grade and water of at least grade 1 as defined in ISO 3696. Only commercially available certified standards of high purity shall be use
44、d. 5.1 Products used in their commercially available form 5.1.1 Gas chromatography gases, of a purity as recommended by the gas chromatography manufacturer. 5.1.2 Methanol, CH 3 OH, with a mass fraction of 99,5 %. 5.1.3 Cyclohexane, C 6 H 12or other hydrocarbon solvent like heptane. 5.1.4 Hydrochlor
45、ic acid, HCl, concentrated, with a mass fraction of 37 %. 5.1.5 Sodium hydroxide, NaOH. 5.1.6 Potassium carbonate, K 2 CO 3 . 5.1.7 Acetic anhydride, (CH 3 CO) 2 O, anhydrous. 5.1.8 Sodium sulfate, Na 2 SO 4 , anhydrous. Weigh portions of 2 g of sodium sulfate into test tubes with polytetrafluoroeth
46、ylene (PTFE) lined caps. Dry the test tubes at (550 20) C for 4 h 30 min without caps. Take them to a desiccator and let them cool. When cooled, put on the caps and store the tubes at room temperature. Sodium sulfate can also be dried in bigger portions and stored in a desiccator after cooling. Weig
47、h portions of 2 g into tubes when needed. 5.1.9 Selected phenol and chlorophenol standards, listed in Table 1 and Table 2. 5.1.10 S elect ed fluor ophenol standar ds, listed in Table 1 as internal standard. NOTE Other compounds such as isotopic and deuterated phenols which might not interfere with t
48、he GC-MS measurement can also be used as internal standards. 5.2 Aqueous solutions 5.2.1 Sodium hydroxide solution, NaOH, c(NaOH) = 0,1 mol/l. 5.2.2 Sodium hydroxide solution, NaOH, c(NaOH) = 0,5 mol/l. 5.2.3 Potassium carbonate solution, K 2 CO 3 , c(K 2 CO 3 ) = 0,1 mol/l. 5.2.4 Potassium carbonat
49、e solution, K 2 CO 3 , c(K 2 CO 3 ) = 5,2 mol/l.4 ISO 2014 All rights reserved PD ISO/TS 17182:2014 ISO/TS 17182:2014(E) 5.3 Standard solutions of phenols 5.3.1 Internal standard solution 5.3.1.1 General Fluorophenols can be used as suitable internal standard. 5.3.1.2 Stock solution Prepare the stock solution by weighing fluorophenols (5.1.10) and dissolving it in methanol (5.1.2). A suitable concentration is 1 mg/ml. Divide the stock solution into 5 ml bottles with tight caps, 1,5 ml to each, and
