EN 15192-2006 en Characterisation of waste and soil - Determination of Chromium(VI) in solid material by alkaline digestion and ion chromatography with spectrophotometric detection.pdf

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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、g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 15192:2006This British Standard was published under the authority of the Standards Policy and Strategy Co

3、mmittee 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 entrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3, Character

4、ization 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 responsible for its correct application.Compliance with a British Standard cannot confer immu

5、nity from legal obligations.Amendments issued since publicationAmd. No. Date CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15192November 2006ICS 13.030.10; 13.080.10English VersionCharacterisation of waste and soil - Determination ofChromium(VI) in solid material by alkaline digestion an

6、d ionchromatography with spectrophotometric detectionCaractrisation des dchets et des sols - Dosage duchrome VI dans les matriaux solides par digestion alcalineet chromatographie ionique avec dtectionspectrophotomtriqueCharakterisierung von Abfllen und Boden - Bestimmungvon sechswertigem Chrom in Fe

7、ststoffen durch alkalischenAufschluss und lonenchromatographie mit photometrischerDetektionThis European Standard was 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

8、 of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards 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 versi

9、on in any other language made by translationunder the responsibility of a CEN member into its own language and notified 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,

10、Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KO

11、MITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15192:2006: EEN 15192:2006 (E) 2 Contents Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3

12、 Terms and Definitions .5 4 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 determin

13、ation of Cr(VI) in the alkaline 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) d

14、eterminations in solids 619 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

15、 .22 Bibliography 26 EN 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 given the status of a national standard, either by publication of

16、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 the following countries are bound to implement this European Sta

17、ndard: 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, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 15192:200

18、6 (E) 4 Introduction Under environmental conditions chromium in compounds exists in the trivalent, Cr(III), or the hexavalent, Cr(VI) state. Cr(III) is an essential trace element for mammals, including man, whereas it is presumed that Cr(VI) compounds are genotoxic and potentially carcinogenic in hu

19、mans. Interconversion of trivalent and hexavalent chromium species can occur during sample preparation and analysis, but these processes are minimised, to the extent possible, by the sample preparation methods prescribed by this standard. EN 15192:2006 (E) 5 1 Scope This standard describes the deter

20、mination of Cr(VI) in solid waste material and soil by 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 c

21、an be reported. 2 Normative references The following referenced 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. E

22、N 15002, Characterization of waste Preparation of test 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 1705:2

23、005) ISO 11464, Soil quality Pretreatment of samples for 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 un

24、der alkaline conditions. Alkaline digestion may or may 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

25、 waste and soil analysis has to be aware of the typical 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

26、 is recommended that these samples should be handled with 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 regu

27、lations should be followed with respect to all hazards 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. EN 15192:2006 (E) 6 5 Principle 5.1 Digestion This standard describ

28、es 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 solution must solubilize all species of

29、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 spectrum of solid matrices. Under th

30、e 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 for the determination of Cr(VI) in s

31、olid 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) from interferences. Following this ion

32、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-diphenylcarbazide with Cr(VI) to produce trivale

33、nt 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 detection is less sensitive than detecti

34、on 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 spectroscopy (ICP-AES), may be used once

35、 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 also Annex D.3). For waste materials or

36、 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 also Annex D.2). Cr(VI) can be reduc

37、ed 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 alkaline solutions. This problem is

38、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) 43. EN 15192:2006 (E) 7 6 Apparatus

39、 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 magnetic stirrer, thermostatically controlled with a digestion vessel of 250 ml covered with a watch glass NOTE Other thermosta

40、tically 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 filters. 6.3 Membrane filters, 0,45 m pore size, chemically inert. 6.4 Ion chromatographic system, all components which come int

41、o 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 chromatographic column, suitable for chromate separation with a sufficient ion exchange capacity. 6.6 Detection system UV-VIS spe

42、ctrophotometer at 365 nm; or VIS spectrophotometer at 540 nm after post column derivatisation. EN 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 g

43、rade 2 water (electrical conductivity less than 0,1 mS m-1equivalent to resistivity 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 manufacturer

44、s of water purification systems as 18 M cm). 7.2 Sulphuric acid (H2SO4), concentrated, (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 d

45、ichromate (K2Cr2O7), w(K2Cr2O7) 99,9 % Dry to constant weight at 110 C, cool and 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 dihydrogen

46、phosphate (KH2PO4), w(KH2PO4) 99 % 7.12 Lead chromate (PbCrO4), w(PbCrO4) 99 % 7.13 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

47、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. The reagen

48、t solution is stable for 5 days. 7.14 Eluent solution Use an eluent solution appropriate to separate chromate over the ion chromatographic column (6.5). 7.15 Alkaline digestion solution, 0,5 mol/l sodium hydroxide (NaOH) / 0,28 mol/l sodium carbonate (Na2CO3) Dissolve 20,0 g of sodium hydroxide (7.8

49、) in approximately 500 ml of water (7.1). Add 30,0 g of sodium carbonate (7.3) and swirl to mix. Quantitatively transfer the solution into a 1 l volumetric flask. Dilute to the EN 15192:2006 (E) 9 mark with water. The pH of the digestion solution must be checked before use. The pH must be 11,5 or higher. Store in a polyethylene bottle at room temperature and prepare fresh monthly. 7.16 Calibration solutions of Cr(VI) 7.16.1 Cr(VI) standard stock solution, 1 000 mg/l Cr(VI) Dissolve 0,282 9 g of potassium