1、BS EN 15841:2009ICS 13.040.20NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDAmbient air quality Standard methodfor determination ofarsenic, cadmium,lead and nickel inatmospheric depositionThis British Standardwas published under theauthority of the StandardsPol
2、icy and StrategyCommittee on 31 December2009 BSI 2009ISBN 978 0 580 63153 5Amendments/corrigenda issued since publicationDate CommentsBS EN 15841:2009National forewordThis British Standard is the UK implementation of EN 15841:2009.The UK participation in its preparation was entrusted to TechnicalCom
3、mittee EH/2/3, Ambient atmospheres.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct application.Compliance with a British Stan
4、dard cannot confer immunityfrom legal obligations.BS EN 15841:2009EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15841 November 2009 ICS 13.040.20 English Version Ambient air quality - Standard method for determination of arsenic, cadmium, lead and nickel in atmospheric deposition Qualit de la
5、ir ambiant - Mthode normalise pour la dtermination des dpots darsenic, de cadmium, de nickel et de plomb Luftbeschaffenheit - Messverfahren zur Bestimmung von Arsen, Kadmium, Blei and Nickel in atmosphrischer Deposition This European Standard was approved by CEN on 17 October 2009. CEN members are b
6、ound to comply with the CEN/CENELEC Internal Regulations 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
7、 CEN Management Centre or to any CEN member. This European 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 CEN Management Centre has the same s
8、tatus as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Roma
9、nia, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reserved
10、worldwide for CEN national Members. Ref. No. EN 15841:2009: EBS EN 15841:2009EN 15841:2009 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Terms, definitions and abbreviations 54 Principle 75 Apparatus and reagents 86 Sampling 117 Sample preparation 128 Quality control . 149 Calcula
11、tion of results . 1410 Performance characteristics determined in lab and field tests . 1711 Reporting of results 20Annex A (informative) Standard operating procedures for sampling . 22Annex B (informative) Estimation of the measurement uncertainty of the method 26Annex C (informative) Uncertainty bu
12、dget 30Annex ZA (informative) Relationship between this European Standard and the essential requirements of EU Directives 31Bibliography . 32BS EN 15841:2009EN 15841:2009 (E) 3 Foreword This document (EN 15841:2009) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat o
13、f which is held by DIN. 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 May 2010, and conflicting national standards shall be withdrawn at the latest by May 2010. Attention is drawn to the possibi
14、lity that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Ass
15、ociation, and supports essential requirements of EU Directive(s). For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this document. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound
16、to implement this European Standard: Austria, Belgium, Bulgaria, 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, Swit
17、zerland and the United Kingdom. BS EN 15841:2009EN 15841:2009 (E) 4 1 Scope This European Standard specifies three methods for the determination of deposition of arsenic (As), cadmium (Cd) nickel (Ni) and lead (Pb), that can be used in the framework of the European Council Directive on Ambient Air Q
18、uality Assessment and Management 1 and the 4thAir Quality Daughter Directive 2. This European Standard specifies performance requirements with which the method has to comply in order to meet the data quality objectives given in the Directives. The performance characteristics of the method were deter
19、mined in comparative field validation tests carried out at four European locations 3. This European Standard specifies methods for sampling wet-only and bulk deposition of As, Cd, Ni and Pb, sample treatment and analysis by graphite furnace atomic absorption spectrometry (GF-AAS) or by inductively c
20、oupled plasma mass spectrometry (ICP-MS). The method is applicable for deposition measurements in a) rural and remote areas; b) industrial areas; c) urban areas. The standard is validated for the working ranges listed in Table 1. Table 1 Validated working ranges for the methods Lower limit(g/m day)
21、Upper limit(g/m day) As 0,05 2 Cd 0,01 1 Ni 0,05 25 Pb 0,1 65NOTE The ranges given are based upon the values measured in the field validation test. The upper and lower limits are the observed minimum and maximum values measured during the field validation tests. The actual lower limits of the workin
22、g ranges depend on the variability of the laboratory blank and the precipitation amount range in bulk and wet-only. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated refe
23、rences, the latest edition of the referenced document (including any amendments) applies. EN 14902:2005, Ambient air quality Standard method for the measurement of Pb, Cd, As and Ni in the PM10 fraction of suspended particulate matter EN ISO 20988:2007, Air quality Guidelines for estimating measurem
24、ent uncertainty (ISO 20988:2007) ISO 5725-2, Accuracy (trueness and precision) of measurement method and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method BS EN 15841:2009EN 15841:2009 (E) 5 3 Terms, definitions and abbreviations
25、 3.1 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1.1 analysis all operations carried out after sample preparation to determine the amount or concentration of the metals or metalloids of interest present in the sample 3.1.2 Bergerhoff collecto
26、r wide mouthed bucket mounted on a post, openly exposed at all time 3.1.3 bulk collector funnel-bottle combination openly exposed at all time NOTE In this standard two methods for the bulk collector are described: the “bulk bottle method” (only the liquid collected in the bottle is analysed) and the
27、 “bulk bottle+funnel method” (the liquid collected in the bottle plus the solid collected on the funnel are analysed). 3.1.4 bulk deposition sum of the deposition of sedimenting wet and dry particles NOTE Both bulk and Bergerhoff collectors sample bulk deposition. 3.1.5 coverage factor numerical fac
28、tor used as multiplier of the combined standard uncertainty in order to obtain an expanded uncertainty EN ISO 20988:2007, 3.3; ISO/IEC Guide 98:2008, 2.3.6 3.1.6 detection limit (DL), instrumental lowest amount of an analyte that is detectable using an instrument as determined by repeated measuremen
29、ts of a reagent blank 3.1.7 detection limit (DL), method lowest amount of an analyte detectable after the whole measurement process as determined by repeated measurements of different field blanks 3.1.8 dry deposition sum of the deposition of sedimenting dry particles, non sedimenting particles and
30、gases NOTE Dry deposition includes the following processes: atmospheric turbulent diffusion, adsorption, absorption, impaction and gravitational settling. The dry deposition process is affected by the type of underlying surface and surface conditions. BS EN 15841:2009EN 15841:2009 (E) 6 3.1.9 expand
31、ed uncertainty expanded measurement uncertainty quantity defining an interval )();( yUyyUypp+ about the result of a measurement that can be expected to encompass a large fraction p of the distribution of values that could reasonably be attributed to the measurand EN ISO 20988:2007, 3.4; ISO/IEC Guid
32、e 98:2008, 2.3.5 3.1.10 field blank artificial sample (e.g. de-ionised water) transported to the sampling site, mounted in the sampling unit, but not exposed to ambient air, returned to the laboratory and worked up in the same way as the deposition sample 3.1.11 laboratory blank artificial sample (e
33、.g. de-ionised water) worked up in the same way as the deposition sample in the laboratory 3.1.12 precipitation rain, snow, sleet, graupel and hail 3.1.13 reagent blank artificial sample (e.g. de-ionised water) that contains all the reagents used during analysis of the sample, but without the sample
34、 matrix 3.1.14 repeatability closeness of the agreement between the results of successive measurements of the same measurand carried out under the same conditions of measurements ISO/IEC Guide 98:2008, B.2.15 3.1.15 reproducibility closeness of the agreement between the results of measurements of th
35、e same measurand carried out under changed conditions of measurements ISO/IEC Guide 98:2008, B.2.15 3.1.16 sample digestion sample dissolution process to obtain a solution containing the analyte of interest 3.1.17 sample preparation all operations carried out on a sample, after transportation and st
36、orage, to prepare it for analysis, including transformation of the sample into a measurable state, where necessary 3.1.18 standard operating procedure SOP written set of procedures that details the method of an operation, analysis, or action whose techniques and procedures are thoroughly prescribed
37、and that is accepted as the method for performing certain routine or repetitive tasks BS EN 15841:2009EN 15841:2009 (E) 7 3.1.19 standard uncertainty standard measurement uncertainty measurements uncertainty expressed as a standard deviation EN ISO 20988:2007, 3.18; ISO/IEC Guide 98:2008, 2.3.1 3.1.
38、20 uncertainty (of a measurement) measurement uncertainty parameter associated with the result of a measurement that characterises the dispersion of the values that could reasonably be attributed to the measurement EN ISO 20988:2007, 3.18; ISO/IEC Guide 98:2008, B.2.18; 3.1.21 wet deposition sum of
39、depositions of sedimenting wet particles and droplets NOTE Wet particles and droplets in the atmosphere undergo the process of scavenging of any gases and/or particles. 3.1.22 wet-only collector collector open only during precipitation events, typically a funnel-bottle combination 3.2 Abbreviations
40、EMEP Co-operative programme for monitoring and evaluation of the long-range transmission of air pollutants in Europe GF-AAS Graphite Furnace - Atomic Absorption Spectrometry ICP-MS Inductively Coupled Plasma - Mass Spectrometry SOP Standard Operating Procedure CRM Certified Reference Material WMO/GA
41、W World Meteorological Organization/Global Atmosphere Watch 4 Principle Total atmospheric deposition of metals, which is defined as the sum of the deposition of sedimenting particles, non-sedimenting particles and gases, or sum of wet and dry deposition, cannot be determined by a single simple metho
42、d. The determination of the dry deposition requires micrometeorological measurements taking into account the turbulent atmospheric transport processes. Wet deposition and bulk deposition, however, can be estimated using suitable collectors. This standard describes methods to determine wet deposition
43、 and bulk deposition using wet-only and bulk collectors. The wet-only collector is designed to collect only sedimenting wet particles, while the bulk collector is designed to collect all sedimenting wet and dry particles. However, since the deposition process is affected by various factors, e.g. win
44、d speed, temperature, vegetation and surface type, the wet-only collector will not catch all sedimenting wet particles while some sedimenting dry particles, non-sedimenting particles and gases BS EN 15841:2009EN 15841:2009 (E) 8 will be collected. Also, the bulk collector will not catch all sediment
45、ing particles while some non-sedimenting particles and gases will be collected. The sample is transferred to the laboratory in the sampling bottle (wet only and bulk collector) or bucket (Bergerhoff collector). Arsenic, cadmium, nickel and lead are taken into solution by digestion techniques and ana
46、lysed by appropriate analytical instruments (i.e. ICP-MS and GF-AAS) depending on deposition level to be measured. Close to industrial sources bulk deposition of metals comprises approximately their atmospheric deposition. At background sites with high precipitation the measurement of bulk and wet d
47、eposition is shown to be equivalent. 5 Apparatus and reagents 5.1 Reagents 5.1.1 Ultrapure water distilled or deionised It is recommended that the water used should be obtained from a water purification system that delivers ultrapure water having a resistivity of 18,2 Mcm or greater at 25 C. 5.1.2 N
48、itric acid (HNO3), concentrated Density about 1,42 g/ml, mass fraction about 70 %, high purity grade (concentration stated by the manufacturer or supplier 0,005 mg/l for As, Cd, Ni and Pb (typical concentrations are generally ten times lower), sub-boiled before use if necessary. WARNING Concentrated
49、 nitric acid is corrosive and oxidising, and nitric acid fumes are irritants. Avoid exposure by contact with the skin or eyes, or by inhalation of fumes. Carry out the work in a fume cupboard. Use suitable personal protective equipment (including suitable gloves, face shield or safety glasses, etc.) when working with the concentrated or dilute nitric acid. 5.1.3 Nitric acid for cleaning purposes (2 % by volume) Add approximately 800 ml of ultrapure water to a 1 l acid cleaned vo
