1、BRITISH STANDARDBS EN 15192:2006Characterisation of waste and soil Determination of Chromium(VI) in solid material by alkaline digestion and ion chromatography with spectrophotometric detectionThe European Standard EN 15192:2006 has the status of a British StandardICS 13.030.10; 13.080.10g49g50g3g38
2、g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIBS EN 15192:2006This
3、 British Standard was published under the authority of the Standards Policy and Strategy Committee on 28 February 2007 BSI 2007ISBN 978 0 580 50299 6National forewordThis British Standard was published by BSI. It is the UK implementation of EN 15192:2006.The UK participation in its preparation was e
4、ntrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3, Characterization of waste.A list of organizations represented on B/508/3 can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are re
5、sponsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.Amendments issued since publicationAmd. No. Date CommentsLicensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEUROPEAN STANDARDNORME EUROPENNEE
6、UROPISCHE NORMEN 15192November 2006ICS 13.030.10; 13.080.10English VersionCharacterisation of waste and soil - Determination ofChromium(VI) in solid material by alkaline digestion and ionchromatography with spectrophotometric detectionCaractrisation des dchets et des sols - Dosage duchrome VI dans l
7、es matriaux solides par digestion alcalineet chromatographie ionique avec dtectionspectrophotomtriqueCharakterisierung von Abfllen und Boden - Bestimmungvon sechswertigem Chrom in Feststoffen durch alkalischenAufschluss und lonenchromatographie mit photometrischerDetektionThis European Standard was
8、approved by CEN on 6 October 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nation
9、alstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notifie
10、d to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands,
11、Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form
12、 and by any means reservedworldwide for CEN national Members.Ref. No. EN 15192:2006: ELicensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 2 Contents Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and Definitions .5 4
13、 Safety remarks .5 5 Principle6 6 Apparatus .7 7 Reagents.8 8 Sample pretreatment .10 9 Alkaline digestion procedure .10 10 Analytical procedure .11 11 Calculation14 12 Expression of results 14 13 Test report 14 Annex A (informative) Alternative methods for direct determination of Cr(VI) in the alka
14、line digestion solution16 Annex B Ion chromatographic system.17 Annex C (informative) Requirements for test portion preparation 18 Annex D (informative) Background on methods for the determination of Cr(VI) in solid samples19 D.1 Summary of literature methods for Cr (VI) determinations in solids 619
15、 D.2 Theoretical kinetic background for Cr(III)-Cr(VI) inter-conversions 6 .19 D.3 Special needs for Cr(VI) determination in soil extracts 720 D.4 Determination of Cr(VI) in glass .21 D.5 Determination of Cr(VI) in air particulate matter 21 Annex E (informative) Validation .22 Bibliography 26 Licens
16、ed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 3 Foreword This document (EN 15192:2006) 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 gi
17、ven the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2007, and conflicting national standards shall be withdrawn at the latest by May 2007. According to the CEN/CENELEC Internal Regulations, the national standards organizations of
18、the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slove
19、nia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 4 Introduction Under environmental conditions chromium in compounds exists in the trivalent, Cr(III), or the hexavalent, Cr(VI) state. Cr(I
20、II) is an essential trace element for mammals, including man, whereas it is presumed that Cr(VI) compounds are genotoxic and potentially carcinogenic in humans. Interconversion of trivalent and hexavalent chromium species can occur during sample preparation and analysis, but these processes are mini
21、mised, to the extent possible, by the sample preparation methods prescribed by this standard. Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 5 1 Scope This standard describes the determination of Cr(VI) in solid waste material and soil by
22、 alkaline digestion and ion chromatography with spectrophotometric detection. This method can be used to determine Cr(VI)-mass fractions in solids higher than 0,1 mg/kg. NOTE In case of reducing or oxidising waste matrix no valid Cr(VI) content can be reported. 2 Normative references The following r
23、eferenced documents are indispensable for the application of this European Standard. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 15002, Characterization of waste Preparation of test
24、 portions from the laboratory sample EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories (ISO/IEC 1705:2005) ISO 11464, Soil quality Pretreatment of samples f
25、or physico-chemical analysis 3 Terms and Definitions For the purposes of this European Standard, the following terms and definitions apply. 3.1 alkaline digestion process of obtaining a solution containing the analyte of interest from a sample under alkaline conditions. Alkaline digestion may or may
26、 not involve complete dissolution of the sample 3.2 speciation analysis activities of measuring the quantity of one or more individual chemical species in a sample, e.g. Cr(VI) in a particular sample or matrix 4 Safety remarks Anyone dealing with waste and soil analysis has to be aware of the typica
27、l risks of the material irrespective of the parameters determined. Waste and soil samples may contain hazardous (e.g. toxic, reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction. Consequently, it is recommended that these samples should be handled w
28、ith special care. The gases which may be produced by microbiological or chemical activity are potentially flammable and can pressurise sealed bottles. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations should be followed with respect to all hazards
29、 associated with this method. Avoid any contact with the skin, ingestion or inhalation of Cr(VI) compounds. Cr(VI) compounds are genotoxic and potentially carcinogenic to humans. Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 6 5 Principl
30、e 5.1 Digestion This standard describes an alkaline digestion procedure for extracting Cr(VI) from soluble, adsorbed and precipitated forms of chromium compounds in solid waste materials and soil. To quantify the content of Cr(VI) in a solid matrix, three criteria must be satisfied: 1) digestion sol
31、ution must solubilize all species of Cr(VI); 2) conditions of the digestion must not induce reduction of native Cr(VI) to Cr(III); 3) method must not cause oxidation of native Cr(III) contained in the sample to Cr(VI). The alkaline digestion described in this standard meets these criteria for a wide
32、 spectrum of solid matrices. Under the alkaline conditions of the digestion, neglectable reduction of Cr(VI) or oxidation of native Cr(III) is expected. The additon of Mg2+in a phosphate buffer to the alkaline solution prevents air oxidation of trivalent chromium 1, 6, 32. NOTE Background on methods
33、 for the determination of Cr(VI) in solid samples is given in Annex D and 4, 5, 6. 5.2 Determination Quantification of Cr(VI) in the alkaline digestion solution should be performed using a suitable technique with appropriate accuracy. For this purpose ion chromatography is used to separate Cr(VI) fr
34、om interferences. Following this ion chromatographic separation, Cr(VI) is measured spectrophotometrically either at 365 nm (direct UV detection) or after post-column derivatisation with 1,5-diphenylcarbazide in acid solution at 540 nm. Post-column derivatisation involves reaction of 1,5-diphenylcar
35、bazide with Cr(VI) to produce trivalent chromium and diphenylcarbazone. These then combine to form a trivalent chromium-diphenylcarbazone complex containing the characteristic magenta chromagen (max= 540 nm). NOTE 1 The choice of detection method is based upon the required sensitivity. Direct UV det
36、ection is less sensitive than detection after post-column derivatisation with 1,5-diphenylcarbazide. NOTE 2 Hyphenated methods with ion chromatographic separation and detection techniques, such as inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma atomic emission spe
37、ctroscopy (ICP-AES), may be used once validation of the chosen analytical method has been performed. 5.3 Interferences and sources of error Use of ion chromatography is necessary for the separation of Cr(VI) from possible interferences in the alkaline digestion solution from solid material 7 (see al
38、so Annex D.3). For waste materials or soils, where the Cr(III)/Cr(VI) ratio is expected to be high, Cr(VI) results may be biased due to method induced oxidation. This can be particularly expected in soils high in Mn content and amended with soluble Cr(III) salts or freshly precipitated Cr(OH)34 (see
39、 also Annex D.2). Cr(VI) can be reduced to Cr(III) during digestion from the sample due to reaction with reducing agents such as e.g. divalent iron. This problem is minimised in the described procedure using alkaline digestion solution 6 (see also Annex D.2). Cr(III) can be oxidised to Cr(VI) in hot
40、 alkaline solutions. This problem is minimised in the described procedure by adding magnesium to the alkaline digestion solution 3, 4, 6, 32 (see also Annex D.2). Overloading the analytical column capacity with high concentrations of anionic species (e.g. chloride) may cause underestimation of Cr(VI
41、) 43. Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15192:2006 (E) 7 6 Apparatus 6.1 Digestion equipment hotplate with a magnetic stirrer, thermostatically controlled with a digestion vessel of 250 ml covered with a watch glass; or heating block with a
42、 magnetic stirrer, thermostatically controlled with a digestion vessel of 250 ml covered with a watch glass NOTE Other thermostatically controlled digestion equipment with a magnetic stirrer can be used once validation has been performed. 6.2 Filtration equipment, suitable for using 0,45-m membrane
43、filters. 6.3 Membrane filters, 0,45 m pore size, chemically inert. 6.4 Ion chromatographic system, all components which come into contact with the sample or eluent stream shall be comprised of inert materials, e.g. polyetherether ketone (PEEK), as shall all connecting tubing (see Annex B). 6.5 Ion c
44、hromatographic column, suitable for chromate separation with a sufficient ion exchange capacity. 6.6 Detection system UV-VIS spectrophotometer at 365 nm; or VIS spectrophotometer at 540 nm after post column derivatisation. Licensed Copy: Wang Bin, na, Wed Apr 18 06:33:33 GMT+00:00 2007, Uncontrolled
45、 Copy, (c) BSIEN 15192:2006 (E) 8 7 Reagents During the analysis, only use reagents of recognised analytical grade, and water as specified in clause 7.1. 7.1 Water Water complying with the requirements for EN ISO 3696 grade 2 water (electrical conductivity less than 0,1 mS m-1equivalent to resistivi
46、ty greater than 0,01 M m at 25 C). It is recommended that the water used is obtained from a purification system that delivers ultrapure water having a resistivity greater than 0,18 M m (usually expressed by manufacturers of water purification systems as 18 M cm). 7.2 Sulphuric acid (H2SO4), concentr
47、ated, (H2SO4) 1,84 g/ml, w(H2SO4) 98 % 7.3 Sodium carbonate (Na2CO3), anhydrous, w(Na2CO3) 99,9 % 7.4 1,5-Diphenylcarbazide (C6H5.NH.NH)2CO), w(C6H5.NH.NH)2CO) 98% 7.5 Acetone (C3H6O) 7.6 Methanol (CH4O) 7.7 Potassium dichromate (K2Cr2O7), w(K2Cr2O7) 99,9 % Dry to constant weight at 110 C, cool and
48、store in a dessiccator. 7.8 Sodium hydroxide (NaOH), w(NaOH) 99 % 7.9 Magnesium chloride hexahydrate (MgCl2.6H2O), w(MgCl2.6H2O) 99 % 7.10 Dipotassium hydrogenphosphate (K2HPO4), w(K2HPO4) 99 % 7.11 Potassium dihydrogenphosphate (KH2PO4), w(KH2PO4) 99 % 7.12 Lead chromate (PbCrO4), w(PbCrO4) 99 % 7.
49、13 Diphenylcarbazide reagent solution Dissolve 0,125 g of 1,5-diphenylcarbazide (7.4) in 25 ml of acetone (7.5) or methanol (7.6) in a 250 ml volumetric flask. Fill 125 ml of water into a separate container, slowly add 7 ml of concentrated sulphuric acid (7.2), swirl to mix and allow to cool. Degass with e.g. helium or argon for 5 min to 10 min prior to adding to the 1,5-diphenylcarbazide solution. After combining the solutions, fill up to the mark with water and degass additionally for 5 min to 10 min.
