1、BS EN 16175-2:2016Sludge, treated biowasteand soil Determination ofmercuryPart 2: Cold-vapour atomic fluorescencespectrometry (CV-AFS)BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 16175-2:2016 BRITISH STANDARDNational forewordThis British Standard is the UK i
2、mplementation of EN 16175-2:2016.BSI, as a member of CEN, is obliged to publish EN 16175-2 as a British Standard. However, attention is drawn to the fact that during the development of this European Standard, the UK committee voted against its approval as a European Standard.The UK committee is conc
3、erned that some of the conditions attached to the validation trials lack clarity.It is also the opinion of the UK committee that validation trials for horizontal methods should include conditions for the preparation and extraction of the original sample.The UK participation in its preparation was en
4、trusted to Technical Committee H/-/4, Environmental Testing Programmes.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 appl
5、ication. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 91015 9ICS 13.030.01; 13.080.10Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and St
6、rategy Committee on 31 October 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 16175-2:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16175-2 October 2016 ICS 13.030.01; 13.080.10 Supersedes CEN/TS 16175-2:2013English Version Sludge, treated biowaste an
7、d soil - Determination of mercury - Part 2: Cold-vapour atomic fluorescence spectrometry (CV-AFS) Boues, biodchets traits et sols - Dtermination du mercure - Partie 2: Spectromtrie de fluorescence atomique de vapeur froide (SFA-VP) Schlamm, behandelter Bioabfall und Boden - Bestimmung von Quecksilbe
8、r - Teil 2: Kaltdampf-Atomfluoreszenzspektrometrie (CV-AFS) This European Standard was approved by CEN on 19 March 2016. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard withou
9、t 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 versions (English, French, German). A version in any other la
10、nguage 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 Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denm
11、ark, 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, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE
12、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 CEN national Members. Ref. No. EN 16175-2:2016 EBS EN 16175-2:201
13、6EN 16175-2:2016 (E) 2 Contents Page European foreword . 3 Introduction 4 1 Scope 5 2 Normative references 5 3 Principle . 5 4 Interferences 5 5 Reagents . 6 6 Apparatus . 7 7 Procedure. 8 7.1 Test solution . 8 7.2 Test blank solution . 8 7.3 Preparation of the calibration solutions 8 7.4 Calibratio
14、n . 8 7.5 Measurement of test sample . 8 8 Calculation and expression of results 9 8.1 Calculation . 9 8.2 Expression of results 9 9 Performance data 9 10 Test report . 9 Annex A (informative) Repeatability and reproducibility data . 11 Bibliography . 12 BS EN 16175-2:2016EN 16175-2:2016 (E) 3 Europ
15、ean foreword This document (EN 16175-2:2016) has been prepared by Technical Committee CEN/TC 444 “Test methods for environmental characterization of solid matrices”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publicatio
16、n of an identical text or by endorsement, at the latest by April 2017, and conflicting national standards shall be withdrawn at the latest by April 2017. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not
17、 be held responsible for identifying any or all such patent rights. This document supersedes CEN/TS 16175-2:2013. The preparation of the previous edition of this analytical method by CEN is based on a mandate by the European Commission (Mandate M/330), which assigned the development of standards on
18、sampling and analytical methods for hygienic and biological parameters as well as inorganic and organic determinants, aiming to make these standards applicable to sludge, treated biowaste and soil as far as this is technically feasible. This document contains the following technical changes in compa
19、rison with the previous edition: repeatability and reproducibility data have been added from a European interlaboratory comparison organized by the German Federal Institute for Materials Research and Testing BAM in 2013 (see Annex A). EN 16175, Sludge, treated biowaste and soil Determination of merc
20、ury comprises the following parts: Part 1: Cold-vapour atomic absorption spectrometry (CV-AAS); Part 2: Cold-vapour atomic fluorescence spectrometry (CV-AFS). According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement thi
21、s European Standard: Austria, 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, Slovaki
22、a, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16175-2:2016EN 16175-2:2016 (E) 4 Introduction This European Standard is applicable and validated for several types of matrices as indicated in Table 1 (see Annex A for the results of validation). Table 1 Matrices for whic
23、h this European Standard is applicable and validated Matrix Materials used for validation Sludge Municipal sludge Biowaste Compost Soil Soil WARNING Persons using this European Standard should be familiar with usual laboratory practice. This European Standard does not purport to address all of the s
24、afety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this European Standard b
25、e carried out by suitably trained staff. BS EN 16175-2:2016EN 16175-2:2016 (E) 5 1 Scope This European Standard specifies a method for the determination of mercury in aqua regia or nitric acid digests of sludge, treated biowaste and soil, obtained according to EN 16173 or EN 16174 using cold-vapour
26、atomic fluorescence spectrometry (CV-AFS). The lower working range limit is 0,003 mg/kg (dry matter basis). 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 editi
27、on cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 15934, Sludge, treated biowaste, soil and waste Calculation of dry matter fraction after determination of dry residue or water content EN 16173, Sludge, treated biowaste and
28、 soil Digestion of nitric acid soluble fractions of elements EN 16174, Sludge, treated biowaste and soil Digestion of aqua regia soluble fractions of elements EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) 3 Principle Mono- and divalent mercury is reduced
29、to the elemental form by tin(II) chloride solution or sodium borohydride in acid medium. Elemental mercury is stripped off from the solution in a closed system, by means of a stream of argon or nitrogen. The mercury vapour is injected into the cell of an atomic fluorescence spectrometer where the me
30、rcury atoms are excited by radiation of a specific wavelength, usually about 254 nm. The intensity of the fluorescence radiation is a function of mercury concentration. The concentrations are calculated using a calibration curve. NOTE The matrix of the solution analysed is dominated by the acids use
31、d in the digestion step. Tin(II) chloride as a reduction substance is recommended in this European Standard, because sodium borohydride reduces many elements commonly found in soil, sludge and waste extract solutions, to the elemental state, which may cause matrix problems under particular circumsta
32、nces. However, it is still possible to use sodium borohydride as reduction agent. The concentration range 0,1 g/l to 10 g/l in the test solution, corresponding to 0,003 mg/kg to 0,3 mg/kg of mercury, when a 3,0 g sample has been digested, can be determined directly. Higher concentrations can be dete
33、rmined if the test solution is diluted. Sensitivity can be increased by the amalgamation technique. 4 Interferences The presence of water vapour or aerosol in the fluorescence cell may cause suppression due to quenching. Water vapour should be removed from the carrier gas stream using a hygroscopic
34、membrane before entering the detector. The noble metals, such as gold and silver, amalgamate with mercury and, therefore, may cause suppression. Also anions, for instance sulfide, iodide and bromide, which complex strongly with mercury, can cause suppression. Fewer interferences arise from heavy met
35、als when tin(II) chloride is used rather than sodium borohydride. When flow systems are used, interference effects due to heavy metals may be less than indicated in Table 2. BS EN 16175-2:2016EN 16175-2:2016 (E) 6 Table 2 Tolerable concentrations of some matrix elements Element Acceptable concentrat
36、ion in the test solution mg/l Cu(II) 500 Ni(II) 500 Ag(I) 1 5 Reagents For the determination of mercury at trace and ultra-trace level, the reagents shall be of adequate purity. The concentration of mercury or interfering substances in the reagents and the water should be negligible compared to the
37、lowest concentration of mercury to be determined. 5.1 Water quality 2 according to EN ISO 3696 for all sample preparations and dilutions. 5.2 Hydrochloric acid, HCl, (HCl) = 1,18 g/ml, c(HCl) = 12 mol/l, w(HCl) = 370 g/kg. The same batch of hydrochloric acid shall be used throughout the procedure. 5
38、.3 Nitric acid, HNO3, (HNO3) = 1,4 g/ml, c(HNO3) = 15 mol/l w(HNO3) = 650 g/kg. The same batch of nitric acid shall be used throughout the procedure. 5.4 Nitric acid, diluted solution. Add 10 ml nitric acid (5.3) to 500 ml of water in a 1 000 ml volumetric flask, mix and fill to the mark with water.
39、 5.5 Nitric acid, c(HNO3) = 2 mol/l, rinsing solution for glassware. Add 150 ml of nitric acid (5.3) to about 500 ml of water, and dilute with water to 1 000 ml. 5.6 Aqua regia, diluted solution. Add 21 ml hydrochloric acid (5.2) and 7 ml nitric acid (5.3) to 500 ml of water in a 1 000 ml volumetric
40、 flask, mix and fill to the mark with water. 5.7 Tin(II) chloride solution, (SnCl2 2 H2O) = 100 g/l. Dissolve 10 g of SnCl2 2 H2O in 30 ml of hydrochloric acid (5.2), transfer to a 100 ml volumetric flask and fill to the mark with water. The blank concentration of mercury can be reduced by bubbling
41、a stream of nitrogen through the solution for 30 min, if necessary. Prepare this solution on the day of use. A solution of lower concentration, e. g. 0,5 g in 100 ml, may be used with flow systems. Prepare this latter solution freshly on the day of use from the more concentrated solution by diluting
42、 with water. 5.8 Sodium borohydride solution, NaBH4, (NaBH4) = 30 g/l. 1 g sodium hydroxide, NaOH, is weighed into a 100 ml volumetric flask and dissolved in water. 3 g sodium borohydride, NaBH4, are weighed into a 100 ml volumetric flask, dissolved and diluted to the mark with the sodium hydroxide
43、solution. 5.9 Mercury standard stock solution, 1 000 mg/l BS EN 16175-2:2016EN 16175-2:2016 (E) 7 Use a commercially available quantitative stock solution with a mercury concentration of (1 000 2) mg/l. This solution is considered to be stable for at least one year, but in reference to guaranteed st
44、ability, see the recommendations of the manufacturer. 5.10 Mercury, standard solution I, 100 mg/l. Pipette 10 ml of the mercury standard stock solution (5.9) into a 100 ml volumetric flask, add 10 ml nitric acid (5.3), mix and fill to the mark with water. This solution is stable for one month. 5.11
45、Mercury, standard solution II, 1 mg/l. Pipette 1 ml of the mercury standard solution I (5.10) into a 100 ml volumetric flask, add 10 ml nitric acid (5.3), mix and fill to the mark with water. This solution is stable for 7 days. 5.12 Mercury, standard solution III, 100 g/l Pipette 10 ml of the mercur
46、y standard solution II (5.11) into a 100 ml volumetric flask, add 10 ml nitric acid (5.3), mix and fill to the mark with water. This solution shall be freshly prepared on the day of use. 5.13 Carrier gas, argon or nitrogen, with a purity of 99,99 %. 6 Apparatus 6.1 Usual laboratory apparatus All gla
47、ssware shall be carefully cleaned for low trace element determinations, e. g. by immersion in nitric acid rinsing solution (5.5) for a minimum of 6 h, followed by rinsing with water before use. The nitric acid shall be replaced each week. 6.2 Atomic fluorescence spectrometer (AFS) Equipped with a sp
48、ecific Hg lamp, a fixed 254 nm filter, a photomultiplier tube for the detection of fluorescence radiation and a suitable software for processing the output signal. Operate at a current recommended by the lamp or the instrument manufacturer. The gas supply (argon or nitrogen) should be equipped with
49、a two stage regulator. The use of a gas purifier consisting of activated carbon is recommended. The use of nitrogen instead of argon will cause a reduced sensitivity of the measurement. 6.3 Automated sample introduction system Automated mercury flow systems (flow injection systems or continuous flow systems) are very common for atomic fluorescence spectrometry. They allow a measurement of mercury in a concentration range which is about one order of magnitude lower. Manually operated systems or semi-automated batch systems are adequate as
