1、BS EN 14582:2016Characterization of waste Halogen and sulfur content Oxygen combustion in closedsystems and determinationmethodsBSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 14582:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implement
2、ation of EN 14582:2016. It supersedes BS EN 14582:2007 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee B/508/3, Characterization of waste.A list of organizations represented on this committee can beobtained on request to its secretary.This publication d
3、oes not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 89310 0ICS 13.030.40Compliance with a British Standard cannot confer immunity fromlegal
4、 obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 August 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 14582:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14582 August 2016 ICS 13
5、.030.40 Supersedes EN 14582:2007English Version Characterization of waste - Halogen and sulfur content - Oxygen combustion in closed systems and determination methods Caractrisation des dchets - Teneur en halognes et en soufre - Combustion sous oxygne en systmes ferms et mthodes de dosage Charakteri
6、sierung von Abfllen - Halogen- und Schwefelgehalt - Sauerstoffverbrennung in geschlossenen Systemen und BestimmungsmethodenThis European Standard was approved by CEN on 17 June 2016. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving t
7、his 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 CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official
8、 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 CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Aus
9、tria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Swed
10、en, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CE
11、N national Members. Ref. No. EN 14582:2016 EBS EN 14582:2016EN 14582:2016 (E) 2 Contents Page European foreword . 4 Introduction 5 1 Scope 6 2 Normative references 6 3 Terms and definitions . 6 4 Principle . 6 5 Interferences 7 6 Hazards . 7 7 Reagents and control mixtures 7 7.1 Reagents . 7 7.2 Con
12、trol mixtures 7 8 Sample conservation and pretreatment of test portion . 8 9 Equipment . 9 10 Procedure. 9 10.1 General 9 10.2 Choice of the absorption solution 10 10.3 Preparation of the bomb . 11 10.4 Combustion 11 10.5 Collection of the halides and sulphate 12 10.6 Cleaning procedure . 12 11 Reco
13、mmended methods of determination . 13 12 Control measurements . 13 13 Evaluation . 13 14 Test report 14 Annex A (informative) Performance characteristics . 15 Annex B (informative) Oxygen flask combustion by Schoeniger . 18 B.1 General . 18 B.2 Principle 18 B.3 Interferences and hazards 18 B.4 Reage
14、nts and control mixtures . 18 B.5 Equipment 18 B.6 Safety precautions . 19 B.7 Procedure 19 B.7.1 General . 19 B.7.2 Choice of the absorption solution 19 BS EN 14582:2016EN 14582:2016 (E) 3 B.7.3 Sample preparation . 20 B.7.4 Combustion . 20 B.8 Determination methods; control measurements; data eval
15、uation and test report . 20 B.9 Performance characteristics 21 Annex C (informative) Recovery yields obtained for control mixtures with different absorption solutions and analytical techniques . 24 Annex D (informative) Examples of possible control substances 27 Annex E (informative) Additional resu
16、lts of inter-laboratory tests 29 Annex F (informative) Summary of general requirements and recommendations 31 Annex G (informative) Additional validation data 32 G.1 General . 32 G.2 Samples 32 G.3 Homogeneity and stability 33 BS EN 14582:2016EN 14582:2016 (E) 4 European foreword This document (EN 1
17、4582:2016) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, 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 February 2017,
18、and conflicting national standards shall be withdrawn at the latest by February 2017. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. This document s
19、upersedes EN 14582:2007. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic
20、of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 14582:2016EN 14582:2016 (E) 5 Introduction Sulfur and ha
21、logens (fluorine, chlorine, bromine and iodine) may be found in materials in various forms. During the combustion of these materials, corrosive and harmful compounds may be released. The determination of sulfur and halogens by oxygen combustion may be used to assess the suitability of waste for inci
22、neration. The determination of the resultant halides and sulphate can be achieved by many different techniques, e.g. using atomic emission spectrometry, titrimetry or ion chromatography. Validation data of these different techniques are given in Annex A (informative). Another method, oxygen flask co
23、mbustion by Schoeniger, did not pass the method validation due to lack of participants. This method is described in Annex B (informative). Anyone dealing with waste and sludge analysis should be aware of the typical risks of that kind of material irrespective of the parameter to be determined. Waste
24、 and sludge samples may contain hazardous (e.g. toxic, reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction. Consequently these samples should be handled with special care. Gases which may be produced by microbiological or chemical activity are pote
25、ntially flammable and will pressurize sealed containers. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations should be followed with respect to all hazards associated with this method. BS EN 14582:2016EN 14582:2016 (E) 6 1 Scope This standard specif
26、ies a combustion method for the determination of halogen and sulfur contents in materials by combustion in a closed system containing oxygen (calorimetric bomb), and the subsequent analysis of the combustion product using different analytical techniques. This method is applicable to solid, pasty and
27、 liquid samples containing more than 0,025 g/kg of halogen and/or 0,025 g/kg of sulfur content. The limit of detection depends on the element, the matrix and the determination technique used. Insoluble halides and sulphate present in the sample or produced during the combustion step are not complete
28、ly determined by these methods. 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 referenc
29、ed document (including any amendments) applies. EN 14346, Characterization of waste - Calculation of dry matter by determination of dry residue or water content EN 15002, Characterization of waste - Preparation of test portions from the laboratory sample EN ISO 3696, Water for analytical laboratory
30、use - Specification and test methods (ISO 3696) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. NOTE Be aware that the above definitions are valid for this empirical EN only and do not comply with scientific definitions of sulfur and halogen cont
31、ent. 3.1 sulfur content sum of sulfur contained as organic and inorganic compounds that can be converted to sulphate by combustion and then absorbed or dissolved in an aqueous solution 3.2 halogen content sum of halogens contained as organic and inorganic compounds that can be converted to halides (
32、fluoride, chloride, bromide, iodide) by combustion and then absorbed or dissolved in an aqueous solution 4 Principle The sample is oxidized by combustion in a closed system (a bomb containing oxygen under pressure). Halogenated and sulfur containing compounds are converted to fluoride, chloride, bro
33、mide, iodide and sulphate, which are absorbed and/or dissolved in an absorption solution. Several methods may be used for the determination of halides and sulphate concentrations in the absorption solution. The method may be used for samples that burn with difficulty, which involves the use of a com
34、bustion enhancer. BS EN 14582:2016EN 14582:2016 (E) 7 5 Interferences There are no interferences in the combustion step described in this standard but interferences may occur during the subsequent determination of sulphate and halides (see corresponding standards). Insoluble halides and sulphate pre
35、sent in the sample or produced during the combustion step are not completely determined by these methods. The choice of absorption solutions may introduce interferences depending on the analytical technique used. 6 Hazards Hydrogen peroxide is very caustic; potassium and sodium hydroxide are corrosi
36、ve and hydrazine hydrate is harmful, toxic and carcinogenic. Thus the operator shall wear goggles and gloves and shall work under a fume hood when handling this reagent. As this method uses a gas (oxygen) at a high temperature and a high pressure, precautions shall be taken by the operator. 7 Reagen
37、ts and control mixtures 7.1 Reagents 7.1.1 General All reagents shall be at least of analytical grade and suitable for their specific purposes. Particularly, they shall be free of sulfur and halogens. The reagents correspond to the chemical compounds used for the preparation of the absorption soluti
38、ons; they are not all necessary depending on the choice of the solutions made by the laboratory for the determination of halides and sulfur (see Annex C). 7.1.2 Water of grade 1 as specified in EN ISO 3696. 7.1.3 Sodium hydroxide (NaOH) or potassium hydroxide (KOH) pellets. 7.1.4 Sodium bicarbonate
39、NaHCO3and sodium carbonate Na2CO3. 7.1.5 Hydrogen peroxide (about 30 %) (H2O2). 7.1.6 Hydrazine hydrate (H2N-NH2H2O), reagent grade about 50 % 60 %. 7.1.7 Ascorbic acid (C6H8O6). 7.1.8 Oxygen, free of combustible material, available at a pressure of 3 MPa to 4 MPa (30 atm to 40 atm) (e.g. medical gr
40、ade). 7.1.9 Combustion enhancer (e.g. paraffin). 7.1.10 Aluminium oxide, Al2O3, neutral, particle size 200 m, pre-heated to 600 C. 7.1.11 Gelatine or aceto-butyrate capsules. 7.2 Control mixtures Select a certified reference material (CRM) or create an appropriate control mixture by choosing the con
41、trol substances in combination so all elements that shall be determined in the samples are BS EN 14582:2016EN 14582:2016 (E) 8 represented. The amount of halogen and sulfur contents shall be in the same range of the element contents of the samples and approximately in the middle of the working range
42、 of the determination techniques. If necessary, dilute with cellulose or aluminium oxide to get a suitable element content. The mixture of the control substances and the cellulose or aluminium oxide needs to be homogenized, e.g. using a pestle with mortar or ball mill. Table D.1 lists examples of co
43、ntrol substances that give complete (90 % to 110 %) recoveries of halogen and sulfur. NOTE Combined combustion of iodine and sulfur may interact to improve the reduction of iodine to iodide and the oxidation of sulfur to sulphate. If the actual samples only contain one of the elements, a combined co
44、ntrol mixture may give false assurance of the method capacity. Examples of composition for a control mixture to determine fluorine, chlorine and sulfur (control mixture 1) and another control mixture for bromine and iodine (control mixture 2) are detailed in Table 1. Table 1 Examples of control mixt
45、ure to test the recoveries of halogens and sulfur with a defined analytical method Control mixture 1 Control mixture 2 Amount of control substances 0,50 g of 4-fluoro-benzoic acid 2,0 g of 4-chloro-benzoic acid 2,0 g sulfanilic acid 55,0 g cellulose 0,25 g 4-bromo-benzoic acid 0,25g 4-iodo-benzoic a
46、cid 59,5 g cellulose Content of halogens and sulfur 1,130 g/kg fluorine 7,547 g/kg chlorine 6,170 g/kg sulfur 1,656 g/kg bromine 2,132 g/kg iodine 8 Sample conservation and pretreatment of test portion Biological active laboratory samples should be stored at 4 C and the analyses of halogen and sulfu
47、r should be carried out within seven days after sampling. If this is not possible, the samples should be further preserved by e.g. freezing, if possible, to minimize biodegradation and loss of volatile halogenated and sulfur compounds. The test sample is prepared according to EN 15002. For solid mat
48、erials, the particle size should be less than 200 m. During preparation of the test sample, the use of halogenated polymers, e.g. PVC gloves, should be avoided. Drying the laboratory sample may be carried out for homogenization purposes if the sample, according to the accuracy of the method, contain
49、s only negligible amounts of halogen and sulfur compounds volatile at the temperature intended for the drying process. Dry matter is determined according to EN 14346 on a separate sub sample (the result will be used for calculation). Heterogeneous moist or paste like samples may be mixed with aluminium oxide (7.1.10) until granular material is obtained and then reduced to a granular powder, preferably with a particle size less than 200 m. In this case, the ratio of aluminium oxide to sample should be incorporated into the calculation of the halogen and sulfur con
