SIST EN 15841:2010

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Luftbeschaffenheit - Messverfahren zur Bestimmung von Arsen, Cadmium, Blei und Nickel in atmosphärischer DepositionQualité de l'air ambiant - Méthode normalisée pour la détermination des dépôts d'arsenic, de cadmium, de nickel et de plombAmbient air quality - Standard method for determination of arsenic, cadmium, lead and nickel in atmospheric deposition13.040.20Kakovost okoljskega zrakaAmbient atmospheresICS:Ta slovenski standard je istoveten z:EN 15841:2009SIST EN 15841:2010en,fr,de01-februar-2010SIST EN 15841:2010SLOVENSKI
STANDARD
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE 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
Qualité de l'air ambiant - Méthode normalisée pour la détermination des dépots d'arsenic, de cadmium, de nickel et de plomb
Luftbeschaffenheit - Messverfahren zur Bestimmung von Arsen, Kadmium, Blei and Nickel in atmosphärischer Deposition This European Standard was approved by CEN on 17 October 2009.
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 without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the 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 status 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, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
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COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
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B-1000 Brussels © 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15841:2009: ESIST EN 15841:2010

Standard operating procedures for sampling . 22Annex B (informative)
Estimation of the measurement uncertainty of the method . 26Annex C (informative)
Uncertainty budget . 30Annex ZA (informative)
Relationship between this European Standard and the essential requirements of EU Directives . 31Bibliography . 32 SIST EN 15841:2010

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 Quality Assessment and Management [1] and the 4th Air 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 determined 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 coupled 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(µg/m² day) Upper limit(µg/m² day) As 0,05 2 Cd 0,01 1 Ni 0,05 25 Pb 0,1 65 NOTE 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 working 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 references, 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 measurement 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
[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 measurements 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 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. SIST EN 15841:2010

SOP written set of procedures that details the method of an operation, analysis, or action whose techniques and procedures are thoroughly prescribed and that is accepted as the method for performing certain routine or repetitive tasks SIST EN 15841:2010

3.1.22 wet-only collector collector open only during precipitation events, typically a funnel-bottle combination 3.2 Abbreviations 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/GAW 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 method.
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 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. wind 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 SIST EN 15841:2010

5.1.5 Hydrogen peroxide (H2O2), mass fraction about 30 % High purity grade (concentration stated by the manufacture or supplier < 0,005 mg/l for As, Cd, Ni and Pb (typical concentration are generally ten times lower)). 5.2 Sampling equipment 5.2.1 General Depending on site characteristics (6.1), three different types of collectors can be used to measure deposition of arsenic, cadmium, nickel and lead: wet-only (3.1.22), bulk (3.1.3) and Bergerhoff collector (3.1.2). The two SIST EN 15841:2010

See Annex A for examples of sampling standard operating procedures. 5.2.3 Wet-only collector A wet-only collector is used to sample precipitation only (3.1.12). The wet-only collectors shall be open during precipitation events and be closed during dry periods. An automated wet-only collector should have the following components: a precipitation sample container (funnel+bottle combination), a lid that opens and closes over the sample container orifice, a precipitation sensor, a motorized drive mechanism with associated electronic controls, and a support structure to house the components.
It is recommended that the sampler is temperature controlled to avoid freezing and evaporation of the rain water.
The collection efficiency for a wet-only collector is dependent on the sensitivity of the sensor. The sensor should be designed with a response, which will cause the lid to open when the precipitation intensity exceeds 0,05 mm/h [5].
Samplers shall be designed for sampling during all seasons and all relevant climatic conditions. Thus, a heating device could be included for melting snow and to prevent the formation of ice in the funnel or bottle during winter.
NOTE Depending on climatic conditions, it can be useful to cool the samples in locations where high rates of evaporation are expected during summer. 5.2.4 Bulk collector
A bulk collector consists of a bottle+funnel combination openly exposed at all times (3.1.3). In order to prevent insects, leaves, etc. from entering the collection bottle use a sieve made of e.g. polycarbonate. The sieve should be free and not tied up in the funnel neck. SIST EN 15841:2010

A Bergerhoff collector is a bucket installed on a top of a post. Optionally this can be equipped with a bird guard. NOTE The Bergerhoff collectors used in the field trial had a collecting volume of 1,5 l and an opening of about 100 mm in diameter. 5.3 Laboratory equipment 5.3.1 General Ordinary laboratory apparatus and the laboratory equipment given in 5.3.2 to 5.3.5 are required. 5.3.2 Microwave digestion system
A microwave digestion system including chemical resistant vessels as described in EN 14902 shall be used for digestion of Bergerhoff samples (see 7.3) and filters (see 7.2.2). The microwave cavity shall be corrosion resistant and well ventilated, with all electronics protected against corrosion to ensure safe operation. Ensure that the manufacturer’s safety recommendations are followed. NOTE A leakage detection or pressure control system is very useful, since it provides a safeguard against the possibility of sample loss due to excessive pressure build-up and partial venting of the sample vessels. 5.3.3 Drying device This is either a hot plate or a furnace to evaporate the Bergerhoff samples to dryness. 5.3.4 Graphite furnace-atomic absorption spectrometer (GF-AAS)
Equipped with hollow cathode lamps or electrodeless discharge lamps for the elements of interest, capable of carrying out simultaneous background correction at the measurement wavelengths using a continuum source such as a deuterium lamp to correct for non-specific attenuation or using a Zeeman background correction system. 5.3.5 Inductively coupled plasma - mass spectrometer (ICP-MS)
Mass spectrometer (e.g. quadrupole instrument) capable of scanning the mass range from 5 u (unified atomic mass unit) to 250 u with a minimum resolution capability of 1 u peak width at 5 % peak height, equipped with a data system that allows correction of isobaric interferences and the application of the internal standard technique. NOTE The use of alternative ICP-MS instrumental configurations, e.g. high resolution mass spectrometers, quadrupole mass spectrometers equipped with reaction or collision cells, cold plasma systems, etc., can reduce spectral interferences. SIST EN 15841:2010

NOTE 1 In southern Europe or other dry climatic regions the dry deposition can be of more importance than was tested in the field validation trial. Under these conditions, the wet-only and the bulk collector (bulk bottle method) can give misleading results. When establishing a new sampling site tests should be made before deciding on the sampling procedure. For bulk collector the deposition on the funnel walls should be analyzed (6.4) to estimate the contribution of deposition on the funnel. In addition, one should carry out filtration tests (7.2.2) to estimate the importance of non-dissolved metals in precipitation samples. NOTE 2 At high deposition levels both GF-AAS and ICP-MS may be used (see Table 2 to Table 4). For low concentration samples that often can be below the instrumental detection limit of GF-AAS, only ICP-MS is proven to work well. NOTE 3 At sites with much rainwater and/or snowfall the Bergerhoff collector may be inappropriate due to overflow of the sample collector. For sites with much snow and low temperature the addition of antifreezing and heavy metal free chemicals (e.g. ethylen glycol) can minimize overflow and/or prevent blasting of the collectors. 6.2 Sampling location The siting requirements should follow the guidelines in Annex III of the 4th Daughter Directive [2], which for deposition measurements in rural areas are harmonized with the guidelines from EMEP [4] and WMO/GAW [5]. The site chosen for sampling and measurements shall be representative of a larger area. The size of this area is determined by site characteristic (urban, industrial or rural) and the variability of the air and precipitation quality. The collector should as far as possible not be exposed in areas where unrepresentative strong winds occur like shores, cliffs and top of hills, but it should also not be sheltered by tall trees or buildings. The flow around the collector should be unrestricted, without any obstructions affecting the airflow in the vicinity of the sampler. The criteria depend on the site characteristic: a) Rural sites: There should be no obstacles, such as trees, above 30° from the rim of the precipitation collector, and buildings, hedges, or topographical features which may give rise to updraughts or downdraughts. See EMEP manual [4] for details; b) Urban and industry sites: One should seek to meet the same requirements but should be at least some metres away from buildings, trees and other obstacles. 6.3 Sampling requirements Sample devices, measuring equipment, etc. should always be handled with care to prevent contamination. Clean disposable plastic gloves should be used when collecting the samples. The inside of the funnel or the SIST EN 15841:2010

Extra precautions are needed when sampling heavy metals due to the sensitivity for contamination. The concentrations of heavy metals in precipitation are typically only a few nanograms per millilitre and it is important that the SOP is followed carefully. Immediately after disconnection of the sample bottle or bucket, close it with a screw cap. In order to prevent contamination, the precipitation bottle or bucket should be sent to the laboratory without transferring any precipitation into smaller transport bottles. It is important to avoid leaking during transport. NOTE 1 In some special cases it can be advisable to transport the collector in a cooling device to avoid algae growth. Acidification of the sample prevents algae growth, but this is usually not done before arrival at the laboratory (7.2.1). Further additives to prevent algae growth or freezing should in general be avoided due to the danger of contamination. The sample amount in the bulk and wet-only collectors shall be measured by weight. The sample mass is needed to calculate the sample volume (9.1). The precipitation shall be conserved in nitric acid, which is added either before or after the sampling (7.2.1). NOTE 2
If other measurements like nitrate are carried out at the site, it is recommended to avoid acidification of the sampler before sampling to prevent contamination of these measurements. Field blanks (3.1.10) shall be taken regularly, e.g. four times a year. These shall be used to check the procedure and not to correct the data. If the field blank is high, i.e. more than 20 % of the average deposition level of the corresponding site, necessary steps shall be taken to find the contamination sources and correct the procedure accordingly. Examples on how the SOP can be defined for the different collectors are described in Annex A. 6.4 Adsorption and deposition on the funnel walls (bottle+funnel method) At the start of a sampling program using wet-only or bulk collectors the funnel walls should be rinsed and the rinsing solution analysed to evaluate the importance of adsorption and deposition of As, Cd, Ni, and Pb on the funnel wall. If it turns out to have a significant influence, meaning more than 20 % of the measured deposition, the funnel rinsing needs to be included in the regular sampling procedure. The funnel should be washed with a known volume (e.g. 200 ml) of diluted nitric acid (e.g. 1 % HNO3 (5.1.4)), which is collected in a separate collection bottle and sent to the laboratory for analysis, 9.2. The funnel should regularly be sent to the laboratory for thorough cleaning with nitric acid (5.1.3). The time interval depends on the pollution level. NOTE 1 During the field test the funnel was cleaned in the laboratory every month. NOTE 2 If the deposition on the funnel is added to the bulk deposition, the sum is comparable to deposition measured by the Bergerhoff collector.
NOTE 3 The validation programme showed that this rinsing was efficient and more than 90 % of the deposition on the funnel was rinsed off after only one washing procedure. 7 Sample preparation
7.1 Sample storage The samples shall be stored in a dark and cool environment.
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