1、BRITISH STANDARD Characterization of waste - Microwave assisted digestion with hydrofluoric (HF), nitric (“O,), and hydrochloric (HCl) acid mixture for subsequent determination of elements The European Standard EN 13656:2002 has the status of a British Standard ICs 13.030.40 NO COPYING WITHOUT BSI P
2、ERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BS EN 13656:2002 3ritish Standards BS EN 13656:ZOOZ Amd. No. National foreword Date Comments This British Standard is the official English language version of EN 13656:2002. The UK participation in its preparation was entrusted by Technical Committee B/
3、508, Waste management, to Subcommittee B/508/3, Characterization of waste, which has the responsibility to: - - aid enquirers to understand the text; present to the responsible internationaliEuropean committee any enquiries on the interpretation, or proposals for change, and keep the UK interests in
4、formed; monitor related international and European developments and promulgate them in the UK. - A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referre
5、d to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisio
6、ns of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. This British Standard, having been prepared under the direction of the Building and Civil Engineering Sector Policy Su-ary of pages pages
7、 This document comprises a front cover, an inside front cover, the EN title page, to 25 and a back cover. and Strategy was The BSI copyright date displayed in this document indicates when the published under the authority of the Standards Policy and was last issued. Strategy Committee on 22 October
8、2002 Amendments issued since publication O BSI 22 October 2002 ISBN O 580 40625 3 i- EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13656 October 2002 ICs 13.030.40 English version Characterization of waste - Microwave assisted digestion with hydrofluoric (HF), nitric (“O3) and hydrochloric (H
9、CI) acid mixture for subsequent determination of elements Caractrisation des dchets - Digestion assiste par micro- ondes avec un mlange dacides fluorhydrique (HF). nitrique (“03) et chlorhydrique (HCI) pour la dtermination ultrieure dlments contenus dans les dchets Charakterisierung von Abfllen -Auf
10、schluss mittels Mikrowellengert mit einem Gemisch aus Fluorwasserstoffsure (HF), Salpetersure (“03) und Salzsure (HCI) fr die anschlieende Bestimmung der Elemente im Abfall This European Standard was approved by CEN on 19 August 2002. CEN members are bound to comply with the CENICENELEC Internal Reg
11、ulations which stipulate the conditions for giving this 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 Management Centre or to any CEN member. This Eu
12、ropean Standard exists in three official 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 Management Centre has the same status as the official versions. CEN members are the nati
13、onal standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland. Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMITE EUROPEEN DE NORMALISATION EURO
14、PISCHES KOMITEE FOR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels O 2002 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13656:2002 E EN 13656:2002 (E) Contents Page Foreword . 3 1 Scope 5 2 Normative references .
15、5 3 Terms and definitions . 5 4 Safety remarks 6 5 Sample 6 5.1 Sample pre-treatment . 6 6 Equipment 7 6.1 . 1 Microwave unit 7 5.2 Mass of test portion . 7 6.1 Closed vessel system 7 6.1.2 Digestion vessels . 7 6.2 Semi-open vessel system . 7 6.2.1 Microwave unit . . 7 6.2.2 Digestion vessels 8 6.3
16、 General equipment . 8 7 Reagents 8 8 Interferences and sources of error . 8 8.1 General informations 8 8.2 8.3 Semi-open vessel system . 9 9 Procedure . 9 9.1 Blank test 9 9.2 Procedure for closed vessels 9 9.2.1 Amount of samples and reagents . 10 9.2.2 Digestion . 10 9.2.3 9.3 Procedure for semi-
17、open vessels 11 9.3.1 9.3.2 Digestion and complexation of HF . 11 9.3.3 Preparation of the solution for analysis . 11 1 O Test report 12 Annex A (normative) Calibration of the power adjustment . 13 Annex B (informative) Validation 14 Bibliography 25 Closed vessel system . 9 Complexation of HF 10 9.2
18、.4 Preparation of the solution for analysis . 10 Amount of samples . 11 2 EN 13656:2002 (E) Foreword This document EN 13656:2002 has been prepared by Technical Committee CENTTC 292 “Characterization of waste“, the secretariat of which is held by NEN. This European Standard shall be given the status
19、of a national standard, either by publication of an identical text or by endorsement, at the latest by April 2003, and conflicting national standards shall be withdrawn at the latest by April 2003. In this European Standard the annex A is normative and the annexe B is informative. According to the C
20、ENKENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain
21、, Sweden, Switzerland and the United Kingdom. 3 EN 13656:2002 (E) Introduction The purpose of the method is to bring the elements to be determined in many types of waste into solution to provide a rapid digestion for analysis. Elements extractable by this procedure can in many instances be described
22、 as ,total“. On another hand they cannot be regarded as available for leaching, as the extraction procedure is too vigorous to represent natural processes. 4 EN 13656:2002 (E) I Scope This European Standard specifies methods of microwave assisted digestion with hydrofluoric (HF), nitric (“03) and hy
23、drochloric (HCI) acid mixture. Solutions produced by the methods are suitable for analysis e.g. by atomic absorption spectrometry (FLAAS, HGAAS, CVAAS, GFAAS), inductively coupled plasma emission spectrometry (ICP-OES) and inductive coupled plasma mass spectrometry (ICP-MS). The method is applicable
24、 to the microwave assisted acid digestion of waste for example for the following elements: Al, Sb, As, B, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe, Pb, Mg, Mn, Hg, Mo, Ni, P, K, Se, Ag, S, Na, Sr, Sn, Te, Ti, TI, V, Zn. 2 Normative references This European Standard incorporates by dated or undated reference,
25、provisions from other publications. These normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated i
26、n it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). EN IS0 3696: 1995, Water for analytical laboratory use - Specification and test methods (IS0 3696: 1987). 3 Terms and definitions For the purposes of this European
27、Standard, the following terms and definitions apply. 3.1 digestion mineralization of the organic matter of a sample and dissolution of its mineral part, more or less completely, when reacted with a reagent mixture 3.2 sample portion of material selected from a larger quantity of material ENV 12506:2
28、001 3.3 laboratory sample sample or sub-sample(s) sent to or received by the laboratory ENV 12506:2001 3.4 test sample; analytical sample sample, prepared from the laboratory sample, from which test portions are removed for testing or analysis ENV 12506:2001 3.5 test portion; analytical portion quan
29、tity of material of proper size for measurement of the concentration or other properties of interest, removed from the test sample ENV 12506:2001 NOTE 1 The test portion may be taken from the laboratory sample directly if no preparation of sample is required (e.g. with liquids), but usually it is ta
30、ken from the prepared test sample. 5 EN 13656:2002 (E) NOTE 2 A unit or increment of proper homogeneity, size and fineness, needing no further preparation, may be a test portion. 3.6 dry residue dry matter expressed as a percentage by mass after drying at 105 “C f 5 “C to the constancy of weight 3.7
31、 digestion vessel special flask where the test portion and the acid mixture are filled in and the digestion is performed 3.8 microwave unit whole microwave digestion system (oven and associated equipment) 3.9 microwave unit cavity inner part of the microwave unit in which the digestion vessel is loc
32、ated and the microwave digestion is performed 3.1 O focused microwave unit microwave unit in which a precise control of the electric field is made by using a wave guide NOTE Microwaves are focused at the bottom part of the digestion vessel. 4 Safety remarks All this work has to be performed by skill
33、ed persons. The reagents used within this European Standard are strongly corrosive and partly very toxic. Safety precautions are absolutely necessary due to strong corrosive reagents, high temperature and high pressure. All procedures have to be performed in a hood or in closed force-ventilated equi
34、pment. By the use of strong oxidising reagents the formation of explosive organic intermediates is possible especially when dealing with samples with a high organic content. Do not open pressurised vessels before they have cooled down. Avoid contact with the chemicals and the gaseous reaction produc
35、ts. Samples and solutions have to be disposed of according to regulations. People performing the test shall be informed on the specific risk of HF. 5 Sample 5.1 Sample pre-treatment The test portion should be transferred into the vessel as it is without any pre-treatment if possible.This is applicab
36、le only if the test portion is representative for the laboratory sample and the effectiveness of the digestion is proven. If these conditions are not met a pre-treatment of the laboratory sample is necessary. This procedure shall not change the concentration of the elements of interest. NOTE Pre-tre
37、atment may include drying or grain size reduction below a particle size of 250 pm for solid waste or homogenizing by use of a high speed mixer or sonification for liquid samples. The mass of laboratory samples shall be sufficient for the multiple digestion procedures and determination of the dry res
38、idue. 6 EN 13656:2002 (E) 5.2 Mass of test portion The mass of test portion for a single digestion has to be selected in a way, that: - it is representative for the laboratory sample; - it complies with the specifications of manufacturer of the digestion unit. NOTE smaller quantities and digested se
39、perately. The individual digests should be combined prior to analysis. For representativity reason mass above 200 mg is to be preferred. Unless recommended by the manufacturer the amount of organic carbon shall not exceed 100 mg because of safety reasons in the case of closed digestion vessel. If th
40、e representative test portion exceeds the manufacturers specifications the test portion should be devided into 6 Equipment 6.1 Closed vessel system 6.1.1 Microwave unit The microwave unit shall provide programmable power which can be programmed to within f 10 W of the required power. Typical units p
41、rovide a nominal 600 W to 1 200 W of power. If necessary (referring to manufactures specifications) calibration of the microwave unit has to be performed (see annex A). The microwave unit has to comply to European and national regulations relevant to microwave radiation. The microwave unit cavity ha
42、s to be well ventilated. it has to have an exhaust air tube which is connected to a corrosion resistant laboratory air outlet system or the instrument is provided for use in a laboratory hood. All electronics are sufficiently protected against corrosion for safe operation. All parts which can have c
43、ontact with acids or their vapours have to be corrosion resistant. The microwave unit shall be designed in a way that guarantees homogeneous heating of the samples. The microwave unit cavity has to be built in a way that even in case of leakage or explosion of the vessels the safety of the operators
44、 can be guaranteed. Household instruments are not suitable for laboratory use. NOTE The microwave unit should include a temperature and/or pressure control system. 6.1.2 Digestion vessels The vessels used in the microwave unit shall be equiped with a pressure relieve valve or another technical equip
45、ment which avoids the bursting of the vessels at suddenly occuring excess pressure. The material of the vessels has to be inert to the acids used for digestion. The digestion vessel shall withstand the pressure of at least 8 bar. if the amount of organic carbon exceeds 100 mg it has to be ensured th
46、at the digestion vessel is capable of withstanding higher pressures. 6.2 Semi-open vessel system 6.2.1 Microwave unit The microwave unit shall be equiped with power control. Typical unit provides a nominal 200 W or 300 W of released power. If necessary, calibration of the microwave unit has to be pe
47、rformed by the manufacturer. The microwave unit shall comply with European and national regulations relevant to microwave radiation. 7 EN 13656:2002 (E) The microwave unit shall be designed for use in a laboratory hood. Fume extraction equipment, used to extract acid vapours from the reaction vessel
48、s during the digestion programme, shall have sufficient flow rate to prevent the release of dangerous vapours into the laboratory. All electronics shall be sufficiently protected against corrosion for safe operation. All parts which can be in contact with acids or their vapours shall be corrosion re
49、sistant. 6.2.2 Digestion vessels The vessel is working at atmospheric pressure and has to be connected with a reflux system to avoid losses of analytes. The vessel shall comply with the manufactures specifications and should have a minimum volume of 50 ml. The material of the vessels has to be inert to the reagents used for digestion. NOTE polytetrafluorethylen (PTFE) digestion vessels can be used. Quartz or borosilicated glass digestion vessels are not useable when hydrofluoric acid is used. For example 6.3 General equipment The following equipment is used
