EN 14902:2005
(Main)Ambient air quality - Standard method for the measurement of Pb, Cd, As and Ni in the PM10 fraction of suspended particulate matter
Ambient air quality - Standard method for the measurement of Pb, Cd, As and Ni in the PM10 fraction of suspended particulate matter
This European Standard specifies a method for the determination of particulate lead (Pb), cadmium (Cd), arsenic (As) and nickel (Ni) in ambient air that can be used in the framework of the European Council Directive on Ambient Air Quality Assessment and Management [1] and the 1st [2] and 4th [3] Daughter Directives. Performance requirements with which the method has to comply are specified in this European Standard. The performance characteristics of the method were determined in comparative field validation tests carried out at four European locations (see [4]).
This European Standard specifies a method for sampling of Pb, Cd, As and Ni as part of the PM10 aerosol, microwave digestion of the samples and analysis by graphite furnace atomic absorption spectrometry or by inductively coupled plasma (quadrupole) mass spectrometry.
This European Standard is applicable for the measurement of Pb, Cd, As and Ni as part of the PM10 aerosol fraction in the concentration ranges listed in Table 1.
Table 1 - Working ranges of the method in ng/m³
From To
Pb 1 4 000
Cd 0,1 50
As 0,5 350
Ni 2 100
The actual lower limits of the working ranges depend upon the variability of the laboratory filter blank (5.3.1). The lower limits of the working ranges given in Table 1 are expected values based upon performance achieved in the field validation tests. Similarly the upper limits of the working ranges have been set arbitrarily based upon the maximum daily values measured during the field validation tests. The method can be applied to higher concentrations provided the PM10 collection characteristics of the sampler are not compromised.
Außenluftbeschaffenheit - Standardisiertes Verfahren zur Bestimmung von Pb/Cd/As/Ni als Bestandteil der PM10-Fraktion des Schwebstaubes
Diese Europäische Norm legt ein Verfahren zur Bestimmung von partikelgebundenem Blei (Pb), Cadmium (Cd), Arsen (As) und Nickel (Ni) in der Außenluft fest, das im Rahmen der Europäischen Ratsrichtlinie über die Beurteilung und Kontrolle der Luftqualität [1] und der ersten [2] bzw. vierten [3] Tochterrichtlinie eingesetzt werden kann. Verfahrensanforderungen, denen dieses Verfahren genügen muss, sind in dieser Europäischen Norm spezifiziert. Die Verfahrenskenngrößen wurden in vergleichenden Feldvalidierungstests an vier europäischen Messorten bestimmt (siehe [4]).
Diese Europäische Norm legt ein Probenahmeverfahren für Pb, Cd, As und Ni als Bestandteil des PM10-Aerosols, einen Mikrowellenaufschluss der Probe und die Analyse mittels Graphitrohr-Atomabsorptionsspektrometrie oder mittels Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) fest.
Diese Europäische Norm gilt für die Messung von Pb, Cd, As und Ni als Bestandteil der PM10-Aerosolfraktion in den in Tabelle 1 aufgeführten Konzentrationsbereichen.
Tabelle 1 - Arbeitsbereiche des Verfahrens
von bis
Pb 1 4000
Cd 0,1 50
As 0,5 350
Ni 2 100
Die tatsächlichen unteren Grenzen der Arbeitsbereiche werden von der Variabilität der Laborfilterblindwerte (5.3.1) bestimmt. Die in Tabelle 1 angegebenen unteren Grenzen der Arbeitsbereiche sind Erwartungswerte, die auf den Ergebnissen der Feldvalidierungstests basieren. Entsprechend wurden die oberen Grenzen der Arbeitsbereiche orientierend an den maximalen Tageswerten während der Feldvalidierungstests festgelegt. Das Verfahren kann auch für höhere Konzentrationen eingesetzt werden sofern die PM10-Sammelcharakteristik des Probenahmegerätes nicht beeinträchtigt ist.
Qualité de l'air ambiant - Méthode normalisée de mesure du plomb, du cadmium, de l'arsenic et du nickel dans la fraction MP10 de matière particulaire en suspension
La présente Norme européenne spécifie une méthode pour le dosage du plomb (Pb), du cadmium (Cd), de l'arsenic (As) et du nickel (Ni) dans l'air ambiant, qui peut être utilisée dans le cadre de la directive du Conseil de l'Union Européenne 96/62/CE [1], relative à l'évaluation et à la gestion de la qualité de l'air, et des première [2] et quatrième [3] directives filles. Les exigences de performance auxquelles la méthode doit se conformer sont spécifiées dans la présente Norme européenne. Les caractéristiques de performance de la méthode ont été établies par des essais comparatifs de validation réalisés sur le terrain en quatre lieux distincts en Europe (voir [4]).
La présente Norme européenne spécifie une méthode de prélèvement du plomb, du cadmium, de l'arsenic et du nickel contenu dans la fraction MP10 de l'aérosol, de digestion par micro-ondes des échantillons et d'analyse par spectrométrie d'absorption atomique en four graphite ou par spectrométrie de masse (quadripolaire) couplée à un plasma induit.
La présente Norme européenne est applicable à la mesure du plomb, du cadmium, de l'arsenic et du nickel, dans la fraction MP10 de l'aérosol dans les plages de concentrations indiquées dans le Tableau 1.
Tableau 1 - Plages de concentrations de la méthode en ng/m3
De À
Pb 1 4 000
Cd 0,1 50
As 0,5 350
Ni 2 100
Les limites inférieures des plages de concentration dépendent de la variabilité du filtre vierge de laboratoire (5.3.1). Les limites inférieures indiquées dans le Tableau 1 sont les valeurs escomptées sur la base des performances obtenues lors des essais de validation de terrain. De même, les limites supérieures des plages de concentrations ont été fixées arbitrairement sur la base des valeurs journalières maximales mesurées lors des essais de validation de terrain. La méthode est applicable à des concentrations supérieures à condition que les caractéristiques de collecte des MP10 du préleveur ne soient pas compromises.
Kakovost zunanjega zraka – Standardna metoda za določevanje Pb, Cd, As in Ni v frakciji PM10 lebdečih delcev
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-december-2005
Kakovost zunanjega zraka – Standardna metoda za določevanje Pb, Cd, As in Ni v
frakciji PM10 lebdečih delcev
Ambient air quality - Standard method for the measurement of Pb, Cd, As and Ni in the
PM10 fraction of suspended particulate matter
Außenluftbeschaffenheit - Standardisiertes Verfahren zur Bestimmung von Pb/Cd/As/Ni
als Bestandteil der PM10-Fraktion des Schwebstaubes
Qualité de l'air ambiant - Méthode normalisée de mesure du plomb, du cadmium, de
l'arsenic et du nickel dans la fraction MP10 de matiere particulaire en suspension
Ta slovenski standard je istoveten z: EN 14902:2005
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
EUROPEAN STANDARD
EN 14902
NORME EUROPÉENNE
EUROPÄISCHE NORM
August 2005
ICS 13.040.20
English version
Ambient air quality - Standard method for the measurement of
Pb, Cd, As and Ni in the PM10 fraction of suspended particulate
matter
Qualité de l'air ambiant - Méthode normalisée pour la Außenluftbeschaffenheit - Standardisiertes Verfahren zur
mesure de Pb, Cd, As et Ni dans la fraction MP10 de la Bestimmung von Pb/Cd/As/Ni als Bestandteil der PM10
matière particulaire en suspension Fraktion des Schwebstaubes
This European Standard was approved by CEN on 27 June 2005.
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 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 translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.
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, Norway, Poland, Portugal, Slovakia,
Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels
© 2005 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 14902:2005: E
worldwide for CEN national Members.
Contents
.................................................................................................................................................. Page
Foreword .3
1 Scope .4
2 Normative references.5
3 Terms, definitions and abbreviations .5
4 Principle.8
5 Requirements .9
6 Reagents and gases.10
7 Apparatus .11
8 Sampling.12
9 Analysis .14
10 Quality control.22
11 Calculation of results.23
12 Estimation of the measurement uncertainty of the method.26
13 Performance characteristics determined in field tests .27
14 Reporting of results .32
Annex A (informative) Examples of closed vessel microwave digestion procedures .33
Annex B (informative) Typical laboratory filter blank values as determined in the field validation tests.35
Annex C (informative) Analytical interferences.36
Annex D (informative) Approach to uncertainty estimation used in the field validation tests .40
Annex E (normative) List of minimum QA / QC procedures.46
Annex F (informative) Procedure for the determination of the uncertainty of the method for an
individual laboratory .48
Annex ZA (informative) Relationship with EU Directives .53
Bibliography .54
Foreword
This European Standard (EN 14902:2005) has been prepared by Technical Committee CEN/TC 264 “Air quality”,
the secretariat of 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 February 2006, and conflicting national standards shall be withdrawn at the latest
by February 2006.
This European Standard has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association (see Annex ZA).
According to the CEN/CENELEC Internal Regulations, the national standards organizations of 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, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
1 Scope
This European Standard specifies a method for the determination of particulate lead (Pb), cadmium (Cd), arsenic
(As) and nickel (Ni) in ambient air that can be used in the framework of the European Council Directive on Ambient
st th
Air Quality Assessment and Management [1] and the 1 [2] and 4 [3] Daughter Directives. Performance
requirements with which the method has to comply are specified in this European Standard. The performance
characteristics of the method were determined in comparative field validation tests carried out at four European
locations (see [4]).
This European Standard specifies a method for sampling of Pb, Cd, As and Ni as part of the PM10 aerosol,
microwave digestion of the samples and analysis by graphite furnace atomic absorption spectrometry or by
inductively coupled plasma (quadrupole) mass spectrometry.
This European Standard is applicable for the measurement of Pb, Cd, As and Ni as part of the PM10 aerosol
fraction in the concentration ranges listed in Table 1.
Table 1 — Working ranges of the method in ng/m³
From To
Pb 1 4 000
Cd
0,1 50
As 0,5 350
Ni 2 100
The actual lower limits of the working ranges depend upon the variability of the laboratory filter blank (5.3.1). The
lower limits of the working ranges given in Table 1 are expected values based upon performance achieved in the
field validation tests. Similarly the upper limits of the working ranges have been set arbitrarily based upon the
maximum daily values measured during the field validation tests. The method can be applied to higher
concentrations provided the PM10 collection characteristics of the sampler are not compromised.
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.
EN 12341:1998, Air quality – Determination of the PM10 fraction of suspended particulate matter – Reference
method and field test procedure to demonstrate reference equivalence of measurement methods.
ENV 13005:1999, Guide to the expression of uncertainty in measurement
3 Terms, definitions and abbreviations
3.1 Terms and definitions
For the purpose of this European Standard, 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
metalloid of interest present in the sample
3.1.2
blank solution
solution prepared from a laboratory filter blank or a field filter blank by the process of sample dissolution
NOTE A laboratory filter blank solution or a field filter blank solution might need to be subjected to further operations, e.g.
dilution and/or addition of an internal standard(s), if such operations are applied to the sample solutions in order to produce test
solutions that are ready for analysis.
3.1.3
calibration blank solution
calibration solution prepared without addition of stock standard solution or working standard solution, for which the
concentration of the analyte(s) of interest is considered to be zero
3.1.4
calibration solution
solution used for calibration of the analytical instrument, containing the analyte(s) of interest at (a) suitable
concentration(s), prepared by dilution of the stock standard solution(s) or the working standard solution(s)
NOTE The technique of matrix-matching is normally used when preparing calibration solutions.
3.1.5
certified reference material
reference material, in which one or more of property values are certified by a technically valid procedure,
accompanied by or traceable to a certificate or other documentation that is issued by a certifying body [5]
3.1.6
field filter blank
filter that is taken through the same procedure as a sample, except that no air is drawn through it. It is transported
to the sampling site, mounted in the sampling unit, dismounted, returned to the laboratory and worked up in the
same way as a sample
Equal to ISO Guide 30 (GUM) Geneva 1993.
3.1.7
internal standard solution
solution added to sample, blank and calibration solutions to correct for instrumental fluctuations during analysis,
containing (a) suitable element(s) at (a) suitable concentration(s)
3.1.8
instrumental detection limit
lowest amount of an analyte that is detectable using an instrument, as determined by repeated measurements of a
reagent blank
3.1.9
laboratory filter blank
unused filter that does not leave the laboratory and is taken through the same analytical procedure as a sample.
This filter is taken from the same batch as used for sampling
3.1.10
limit value
level fixed on the basis of scientific knowledge, with the aim of avoiding, preventing or reducing harmful effects on
human health and/or the environment as a whole, to be attained within a given period and not to be exceeded once
attained
3.1.11
matrix interference
non-spectral interference
matrix effect
interference of a non-spectral nature caused by a difference between the matrix of the calibration and test solutions
3.1.12
matrix-matching
technique, used to minimise the effect of matrix interferences on analytical results, that involves preparation of
calibration solutions in which the concentrations of acids and other major solutes are matched with those in the test
solutions
3.1.13
method detection limit
lowest amount of an analyte that is detectable using the method, as determined by analysis of laboratory filter
blanks
3.1.14
PM10
target specification for sampling the thoracic particles
[EN 12341:1998]
3.1.15
PM10 reference sampler
by convention, a sampling instrument that possesses the required performance characteristics, in order to assess
the PM 10 mass concentration
[EN 12341:1998]
3.1.16
PM10 sampler
sampling instrument whose performance has been demonstrated to be equivalent to a PM 10 reference sampler
3.1.17
quality control solution
solution that is analysed together with the sample solutions to provide information on the repeatability of the
analytical method, results for which are plotted on a quality control chart to verify that a method is performing
satisfactorily
3.1.18
quantification limit
lowest amount of an analyte that is quantifiable with a given confidence level using the method, as determined by
analysis of laboratory filter blanks
3.1.19
reagent blank solution
solution that contains all the reagents used during the analysis of the sample, but without the sample and filter
matrix
3.1.20
repeatability (of results of measurements)
closeness of the agreement between the results of successive measurements of the same measurand carried out
under the same conditions of measurement [6]
3.1.21
reproducibility (of results of measurements)
closeness of the agreement between the results of measurements of the same measurand carried out under
changed conditions of measurement [6]
3.1.22
sample solution
solution prepared from a sample by the process of sample dissolution
NOTE A sample solution might need to be subjected to further operations, e.g. dilution and/or addition of an internal
standard(s), in order to produce a test solution that is ready for analysis.
3.1.23
sampling method
all steps of the measuring procedure that describe the process of collecting an air sample
3.1.24
sample preparation
all operations carried out on a sample, after transportation and storage, to prepare it for analysis, including
transformation of the sample into a measurable state, where necessary
3.1.25
sample digestion
sample dissolution
process of obtaining a solution containing the analytes of interest from a sample. This can involve complete
dissolution of the sample
3.1.26
stock standard solution
solution used for preparation of calibration solutions, containing one or more of the analyte(s) of interest at (a)
concentration(s) traceable to national or International Standards
3.1.27
sub-sample (of a filter)
part of a large filter, cut out for analytical reasons, that is representative of the whole
3.1.28
suspended particulate matter
notion of all particles surrounded by air in a given, undisturbed volume of air
[EN 12341:1998]
3.1.29
target value
concentration in the ambient air fixed with the aim of avoiding, preventing or reducing harmful effects on human
health and the environment as a whole, to be attained where possible over a given period [3]
3.1.30
test solution
blank solution or sample solution that has been subjected to all operations required to bring it into a state in which it
is ready for analysis, e.g. dilution and/or addition of an Internal Standard(s)
NOTE If subject to no further operations before analysis, then the blank test solution is identical to the blank solution. The
same is true for the sample test solution and sample solutions.
3.1.31
uncertainty (of a measurement)
parameter associated with the result of a measurement that characterises the dispersion of the values that could
reasonably be attributed to the measurand
[ENV 13005:1999]
3.1.32
working standard solution
solution prepared by dilution of the stock standard solution(s), that contains the analyte(s) of interest at (a)
concentration(s) better suited to preparation of calibration solutions
3.2 Abbreviations
AAS atomic absorption spectrometry;
amu atomic mass unit;
CRM certified reference material;
GFAAS graphite furnace atomic absorption spectrometry;
HDPE high density polyethylene;
HVS high volume sampler, as described in EN 12341:1998, Annex B.2;
ICP-MS inductively coupled plasma – mass spectrometry;
LDPE low density polyethylene;
LVS low volume sampler, as described in EN 12341:1998, Annex B.1;
PFA perfluoroalkoxy polymer;
PP polypropylene;
PTFE polytetrafluoroethylene;
SPM suspended particulate matter;
TFM tetrafluoromethoxil polymer.
4 Principle
The method is divided into two main parts: first the sampling in the field and second the analysis in the laboratory.
During sampling, particles containing Pb, Cd, As and Ni are collected by drawing a measured volume of air through
a filter mounted in a sampler designed to collect the PM10 fraction of suspended particulate matter. The sample
filter is transported to the laboratory and Pb, Cd, As and Ni are taken into solution by closed vessel microwave
digestion using nitric acid and hydrogen peroxide. The resultant solution is analysed by GFAAS or ICP-MS.
5 Requirements
5.1 Siting requirements
st th
The requirements for siting samplers given in the 1 Daughter Directive [2] (for Pb) and the 4 Daughter Directive
[3] (for Cd, As and Ni) shall be followed.
5.2 Sampling requirements
Sampling shall be performed using a PM10 sampler complying with the requirements of EN 12341. In general the
sampling time should be 24 h. However, low concentrations could require longer sampling times, whereas high
concentrations could require shorter ones.
NOTE In order to meet the requirements of this European Standard, particularly with respect to detection limits, it might be
necessary to increase the sampling time for samplers that have low flow rates.
5.3 Analytical requirements
5.3.1 Method detection limit
The method detection limits, based on laboratory filter blanks, shall be less than or equal to 10 % of the limit value
st th
for Pb and less than or equal to 10 % of the target values for Cd, As and Ni, as specified in the 1 and 4 Daughter
Directives [2], [3]. The method for calculating method detection limits is described in 11.5.
NOTE If it is necessary to perform measurements at lower concentrations within the working ranges of the method given in
Table 1, lower method detection limits will be necessary (see Table 7).
5.3.2 Recovery rate
The average recovery rates for the method, when determined in accordance with the procedure described in 10.3,
shall meet the requirements for recovery rates given in Table 2.
Table 2 — Minimum requirements for average recovery rates
Range of average
recovery rates
[%]
Pb 90 to 110
Cd 90 to 110
As 85 to 115
Ni 85 to 115
5.3.3 Homogeneity requirement for sub-samples
The relative standard deviation of the lead content of sub-samples, when determined in accordance with the
procedure described in 9.6, shall not exceed 5 %.
6 Reagents and gases
6.1 Water, ultrapure, distilled or deionised.
NOTE It is recommended that the water used be obtained from a water purification system that delivers ultrapure water
having a resistivity of 0,18 MΩ ·m or greater at 25 °C.
6.2 Nitric acid (HNO ), concentrated, ρ 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 10 times lower)], sub-boiled before use if necessary.
WARNING Concentrated 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. Use suitable personal protective equipment (including suitable gloves, face
shield or safety spectacles, etc) when working with the concentrated or dilute nitric acid.
6.3 Nitric acid for cleaning purposes, add approximately 800 ml of ultrapure water (6.1) to a 1 litre one-mark
volumetric flask. Carefully add 100 ml of concentrated nitric acid (6.2) to the flask and swirl to mix. Allow to cool,
dilute to 1 l with water and mix thoroughly.
6.4 Hydrogen peroxide (H O ), mass fraction about 30 %, high purity grade [concentration stated by the
2 2
manufacturer or supplier < 0,005 mg/l for As, Cd, Ni and Pb (typical concentrations are generally 10 times lower)].
WARNING Hydrogen peroxide is corrosive and oxidising. Avoid exposure by contact with the skin or eyes. Use suitable
personal protective equipment (including suitable gloves, face shield or safety spectacles, etc) when working with hydrogen
peroxide.
6.5 Stock standard solutions, single element or multi-element. Use commercial standard solutions with certified
concentrations traceable to national or International Standards. Observe the manufacturer's expiration date or
recommended shelf life.
6.6 Working standard solution, prepare a working standard solution containing the analyte(s) of interest at a
concentration(s) that is better suited to preparation of the calibration solutions, if desired, by appropriate dilution of
the stock standard solutions (see 6.5).
e.g. NH H PO , Mg(NO ) or Pd(NO ) , or a combination of these, if required, for GFAAS
6.7 Matrix modifier,
4 2 4 3 2 3 2
analysis.
6.8 Argon, liquid or cylinder of a purity suitable for use in GFAAS or ICP-MS analysis.
6.9 Certified Reference Material (CRM), with a sample matrix that is as representative as possible of ambient air
PM10 particulate matter ).
) “NIST 1648 “Urban Particulate Matter” from National Institute of Standards & Technology, USA, is an example of a suitable
product available commercially. This information is given for the convenience of users of this European Standard and does not
constitute an endorsement by CEN of this product. NIST 1648 was used as reference material during the validation of the
method and is named in the text as CRM 1.”
7 Apparatus
7.1 Sampling equipment
7.1.1 PM10 samplers, equivalent to EN 12341. HVS or LVS may be used and the samplers may be single-filter
devices or sequential samplers.
NOTE To minimise contamination of the sample, all components of the filter holder in contact with the filter should be made
of a suitable material with as low a metal content as possible, such as PTFE, glass, quartz etc.
7.1.2 Greasing agent, if required, suitable for greasing the sampler impaction plate.
7.1.3 Filters, of a diameter suitable for use with the samplers (7.1.1), with a separation efficiency of at least
99,5 % at an aerodynamic diameter of 0,3 µm. Each new batch of filters shall be tested to confirm that the filter
blank variability is sufficiently low so that the method detection requirements of 5.3.1 are met.
NOTE 1 It is recommended that filters used should be sourced from a manufacturer who has determined the separation
efficiency of the filter material according to standard methods such as [8] or [9].
NOTE 2 The metal content of the filter should be as low as possible because it is usually the case that higher filter blank
values lead to higher variability of the blank values.
NOTE 3 Quartz fibre filters, cellulose nitrate and cellulose acetate membrane filters have been found suitable in the field
validation tests (see Annex B). Further information can be found in [10].
NOTE 4 In choosing a filter, the user should consider the initial pressure drop across the filter and the increase in this that
occurs due to the collection of the dust and ensure that there is no possibility of an excessive pressure drop developing during
sampling. This depends on the type of filter (i.e. membranes), unusual high concentrations of PM10, the use of longer sampling
time than 24 h and the capability of the sampling device to handle the resulting pressure drop. Quartz fibre filters are proven to
be efficient in most cases although they have weak mechanical properties.
7.1.4 Flowmeter, with a measurement uncertainty that is sufficient to enable the volumetric flow rate of the
samplers (7.1.1) to be measured to within ± 5 %. The calibration of the flowmeter shall be traceable to
(inter)national standards.
NOTE It is recommended that the flowmeter used should be capable of measuring the volumetric flow rate to within ± 2 %
or better.
7.2 Laboratory apparatus
Ordinary laboratory apparatus, and 7.2.1- 7.2.7.
7.2.1 Microwave digestion system, designed for closed vessel sample digestion in the laboratory, with power
output regulation, fitted with a temperature control system capable of sensing the temperature and automatically
adjusting the microwave power output. The microwave cavity shall be corrosion resistant and well ventilated, with
all electronics protected against corrosion to ensure safe operation.
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.
WARNING Ensure that the manufacturer’s safety recommendations are followed.
7.2.2 Sample vessels, designed for high pressure microwave digestion, having a system for controlled
pressure relief, capable of withstanding an operating temperature of 220 °C and a pressure of at least 50 bar, and
having an internal volume of at least 50 ml, e.g. vessels having an inner liner and cover made of a microwave
transparent and chemically resistant material (usually a fluorocarbon polymer such as TFM or PFA).
7.2.3 One-mark volumetric flasks, made of borosilicate glass, quartz, polyethylene or fluorocarbon polymer.
NOTE Solutions with ultra-trace level analytes are commonly stored in thoroughly cleaned vessels made of polyethylene
(LDPE, HDPE) or fluorocarbon polymer (e.g. PFA, PTFE).
7.2.4 Punching tool, if required, suitable for taking sub-samples of large filters without contamination.
7.2.5 Transport containers, suitable for transport of filters from the sampling site back to the laboratory, made
of inert low metal background materials such as HDPE, PP, polycarbonate, PTFE, glass or quartz.
Either
7.2.6 Graphite furnace atomic absorption spectrometer, 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 (see 5.1.5 of [11]) or using a Zeeman background correction system.
Or
7.2.7 Inductively coupled plasma - mass spectrometer, quadrupole instrument capable of scanning the
mass range from 5 amu to 250 amu with a minimum resolution capability of 1 amu 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.
8 Sampling
8.1 Preparation of the sampling equipment
8.1.1 Consult the manufacturer’s instruction manual to determine the minimum voltage and power requirements
of the sampler (7.1.1) and ensure that an adequate power supply is available at the sampling site.
8.1.2 Clean the sampler inlet, suction pipe, filter change mechanism, filter cassettes and all other parts of the
sampler that can come in contact with the filter before use according to the manufacturer’s specifications. Similarly,
inspect greased parts like impaction plates before use, clean them if necessary and grease them again.
8.2 Handling of filters
Handle small filters using non-metallic and non-serrated blunt tweezers, so as to avoid contamination and damage.
For large filters this procedure might not be practicable, in which case handle them carefully using gloves made of
an appropriate material (e.g. non-powdered vinyl gloves), touching only the outside edges of the filters.
8.3 Preparation of filters
8.3.1 Reject filters that could have been contaminated, e.g. during packing and/or transport.
8.3.2 Inspect each filter before use for pin holes and other imperfections, such as chaffing, loose material,
discoloration and non-uniformity. For example, use a magnifying lens with a light or check in front of an area light.
Reject any filter if its integrity is suspect.
8.3.3 Assign each filter a unique identifier and place it in a labelled, sealed container (7.2.5) for storage and
transportation to the field. If the filter has to be marked for identification purposes, do not mark it in an area of the
filter that will be analysed.
8.3.4 Establish a filter log (i.e. a chain of custody book/record) in which to document the use of each filter.
Record the lot number of the filters used in the filter log. If the sampler to be used is a sequential sampler that
operates continuously for a programmed period, load the required number of filters into a labelled filter cartridge
and seal it ready for transportation to the field. Record details of which filter was loaded into which position in the
cartridge.
8.3.5 Take laboratory filter blanks (see 3.1.9) periodically during preparation of a batch of filters, so that the
number of laboratory filter blanks is at least 5 % of the number of filters that will be used for sampling in the field.
8.4 Sample collection
8.4.1 Set up the sampler (7.1.1) in the field according to the manufacturer’s instructions, ensuring that the siting
requirements in 5.1 are met.
8.4.2 Carry out a leak test and check the flow rate of the sampler using the calibrated flowmeter (7.1.4) before
use and at least every three months, following the manufacturer’s instructions. If the flow rate deviates by more
than 5 % from its nominal value, calibrate the sampler by adjusting the flow rate as necessary.
NOTE It is recommended that a leak test and a flow rate calibration are carried out in the laboratory in order to identify
problems with the sampler at an early stage.
8.4.3 Take field filter blanks (see 3.1.6) periodically at each site (at least once for every 20 filters used for
sampling).
8.4.4 Load either an unexposed filter (for single filter devices) or a cartridge of unexposed filters (for sequential
samplers) into the sampler at the start of the sampling period. Program the sampler following the manufacturer's
instructions, start the timer and record details of the start time, flow rate and filter code(s) in the filter log.
8.4.5 Collect the filter from the sampler at the end of the sampling period, replace it in its uniquely marked
transport container and seal it for transportation to the laboratory (for single filter devices). For sequential samplers,
collect the cartridge of used filters and prepare it for transportation to the laboratory.
NOTE If filters are folded for storage (for easier transportation), then it will be necessary to analyse the whole filter as
folding can affect the distribution of particles on the filter surface.
8.4.6 Record full details of each sample in the filter log, including the stop time, the flow rate, the air sample
volume, in m³; any mechanical or electrical failures, the meteorological conditions during the sampling period and
any other data that could be important for later evaluation of the sampling.
8.4.7 Clean and grease the inlet impaction plate, if applicable, at least once every 15 d of sampling. Perform
intensive cleaning of the PM10 sampling head according to the manufacturer’s instructions at least once every six
months.
9 Analysis
9.1 Cleaning of laboratory apparatus
9.1.1 Cleaning of microwave digestion vessels
Clean microwave digestion vessels before use by taking them through the same procedure used for sample
digestion (see 9.2), but adding just nitric acid (6.3) and hydrogen peroxide (6.4) to the vessels. Afterwards rinse the
vessels three times with ultrapure water (6.1). Shorter cleaning times or alternative cleaning procedures may be
used if it can be demonstrated that they are effective and that the method detection limit requirements (5.3.1) are
fulfilled.
If there are tide mark residues from the previous digestion, try to remove them by following the manufacturer’s
cleaning instructions or for example by using an ultrasonic bath.
NOTE It is advisable to retain a set of digestion vessels dedicated for the analysis of samples specified in this European
Standard.
9.1.2 Cleaning of labware
Clean all labware (volumetric flasks, autosampler tubes, etc) thoroughly before use according to the following
procedure:
• soak labware in nitric acid (6.3), at least overnight; and preferably for several days;
• rinse three times with nitric acid (6.3);
• rinse three times with ultrapure water (6.1);
• dry (at below 50 °C) and store in a dust protected area.
Alternative cleaning procedures may be used if it can be demonstrated that they are effective and the method
detection limit requirements (5.3.1) are fulfilled.
NOTE It is advisable to retain a set of labware dedicated for the analysis of samples specified in this European Standard.
9.2 Sample digestion
9.2.1 If the whole filter is to be analysed, transfer it into a labelled microwave sample vessel. If it is necessary to
ensure complete submersion of filter in the digestion acid, first fold the filter or cut it into small pieces using ceramic
scissors (made of aluminium oxide) or an alternative cutting implement that will not contaminate the sample.
Alternatively if only part of the filter is analysed, take a sub-sample from the filter using the punching tool (7.2.4) or
by cutting a strip from the filter.
NOTE The cutting off from a filter is described in 6.2.1 of [10].
Take care not to contaminate the sub-sample with wear from the punching tools or support plate under the punch.
Transfer the sub-sample into the digestion vessel.
NOTE It might be necessary to analyse a sub-sample of the filter because of the limited amount of material that can be
digested in the microwave digestion vessels used.
9.2.2 Carefully add suitable volumes of nitric acid (6.2) and hydrogen peroxide (6.4) to each vessel (e.g. 8 ml
nitric acid and 2 ml hydrogen peroxide for a 50 ml vessel size and a 50 mm diameter filter) and cover with the lid.
Place the sample vessels, evenly distributed, on the turntable of the microwave digestion apparatus, sealing them
according to the manufacturers' instructions. Alternative digestion mixtures which have been demonstrated to meet
the recovery rate requirements in 5.3.2 may also be used.
NOTE 1 Incomplete submersion of filters in the digestion acid causes a particular problem when filters are not fully dissolved
in the digestion procedure. In such circumstances it might be necessary to increase the digestion volume and the duration of the
microwave digestion programme, respecting the manufacturer’s recommendations regarding the maximum volume of acids.
NOTE 2 Sample digestion using hydrofluoric acid and nitric acid, as an alternative to nitric acid and hydrogen peroxide, has
also been evaluated in laboratory tests [7] and found to be applicable.
9.2.3 Program the apparatus to reach approximately 180 °C within 20 min, to increase slowly the temperature
up to approximately 220 °C and then to hold the temperature for about 20 min. The ramp and hold times are
dependent on the used apparatus and vessels and may be adjusted, for examples see Annex A. Alternative
procedures or heating techniques which have been demonstrated to meet the recovery rate requirements in 5.3.2
may also be used.
9.2.4 After the digestion procedure allow the vessels to return to room temperature. Carefully open the cooled
vessels in a fume cupboard and transfer the sample solutions into labelled volumetric flasks (7.2.3) of suitable
capacity (e.g. 50 ml) containing ultrapure water (6.1). Wash down the lid and the sides of each digestion vessel,
and the filter if it remains undigested, three times with ultrapure water and transfer the washings into the volumetric
flask. Dilute to the mark and shake well. Filter or centrifuge the solution to separate undissolved filter material or
sample, if necessary.
WARNING Pressurised vessels can be dangerous. Handle the vessels following the manufacturer’s instructions.
9.2.5 For digestion of the laboratory filter blanks (see 8.3.5) and the field filter blanks (see 8.4.3), follow the
procedure described in 9.2.1 to 9.2.4. Also prepare reagent blanks solutions by taking vessels without filters
through the procedure described in 9.2.2 to 9.2.4.
NOTE It is recommended to test the blank values of the reagents before use.
9.3 Selection of analytical technique
Follow either the procedure described in 9.4 GFAAS analysis or in 9.5 ICP-MS analysis.
9.4 GFAAS analysis
9.4.1 Method development
9.4.1.1 General
Develop and validate a method that is suitable for analysis of the sample solutions prepared in 9.2 using the
available GFAAS instrumentation. Use the default conditions given by the instrument manufacturer as a starting
point in the method development process. Refer to guidance on GFAAS method development available in standard
texts, in manuals provided by instrument manufacturers and in relevant International, European or national
Standards.
NOTE 1 For general guidelines on GFAAS see [12].
NOTE 2 Information on the methods used by laboratories participating in the field validation tests is given in the field
validation test report [7].
NOTE 3 The use of very concentrated acid solutions can damage the device and lead to problems of contamination mainly
for the measurement of Ni.
NOTE 4 Alternatively hydride generation atomic absorption spectrometry can be used for Arsenic analysis if it has been
demonstrated to meet the requirements in 5.3.1 and 5.3.2.
Test the developed method by digesting and analysing certified reference material. Calculate the analytical
recovery using the procedure described in 10.3 and verify that it meets the requirements specified in 5.3.2. It is also
very important to take account of any interferences (see C.1).
9.4.1.2 Analytical wavelengths
Suitable wavelengths for determination of Pb, Cd, As and Ni are given in the following table:
Table 3 — Suitable wavelengths for determination of Pb, Cd, As and Ni
Pb 283,2 nm or 217,0 nm
Cd 228,8 nm
As 193,7 nm
Ni 232,0 nm
9.4.1.3 Matrix modifiers
If necessary, use matrix modifiers (see 6.7) in order to minimise interference from the matrix on the analyte signal,
taking into account the recommendations of the manufacturer of the instrument used.
9.4.1.4 Furnace programme
Optimise the furnace programme for analysis of the sample solutions, using the instrument manufacturer’s default
conditions as a starting point.
9.4.1.5 Matrix-matching of calibration solutions
Decide to what extent it is necessary to match the matrix of the calibration solutions with that of the sample
solutions. If the sample solutions contain residue from the filter matrix it could be necessary to prepare the
calibration solutions by spiking laboratory filter blank solutions. If it is decided to match only the acid content of the
calibration and sample solutions ensure that no filter matrix effects exist. Alternatively, use the method of standard
additions.
NOTE In the laboratory tests [7] it has been shown that no significant filter matrix effect normally exists.
9.4.1.6 Calibration range
Select a range of concentrations over which to prepare the calibration solutions. Take into consideration the
maximum air concentration of each analyte that might need to be measured, the air sample volume and the sample
solution volume. Table 4 gives an indication of typical calibration ranges.
Table 4 — Typical calibration ranges
Typical range
µg/l
Pb 0 to 20
Cd 0 to 2
As
0 to 20
Ni 0 to 20
9.4.2 Preparation of calibration solutions
Prepare a calibration blank solution and at least three calibration solutions from the stock standard solutions (6.5)
or the working standard solution(s) (see 6.6), covering the range of concentrations selected in 9.4.1.6, matrix
matching if appropriate (see 9.4.1.5). Use freshly prepared calibration solutions unless it has been demonstrated
that calibration solutions are stable for a prolonged period.
9.4.3 Preparation for analysis
9.4.3.1 Visual inspection
Perform a visual check to ensure that the instrument and ancillaries are in good order before commencing work.
Follow the instrument manufacturer's recommendations.
9.4.3.2 Setting up the instrument
Set up instrumentation (spectrometer, lamps, cooling water supply, gas supply) according to the manufacturer´s
instructions. Condition the graphite tube before use, if necessary. Wait until the lamp energy is stable before
starting the first measurement.
9.4.3.3 Performance checks and fault diagnostics
Carry out suitable performance checks on a routine basis. Record the results of the tests, preferably using control
charts. Use more rigorous fault diagnostics if it is suspected that the instrument is not functioning properly. Follow
the instrument manufacturer's recommendations.
9.4.4 Analysis
9.4.4.1 Calibration
Measure the calibration solutions in order of increasing concentration and use the instrument's computer to
generate calibration functions for the metals of interest. Repeat the calibration if the determination coefficient for
any of the metals of interest, R , is less than 0,995.
9.4.4.2 Measurement of sample solutions
Make at least three replicate measurements of the reagent blank solutions, laboratory filter blank solutions, field
filter blank solutions and sample solutions and determine the concentrations of the metals of interest using the
appropriate calibration function. If the measured concentration of a sample solution is above three times the
method detection limit the relative standard deviation of the three replicate measurements shall be less than 10 %.
If this is not the case repeat the analysis and if the problem still exists check the instrumental set-up.
If the concentration of any of the metals of interest in a sample solution is found to be above the upper limit of the
calibration range, dilute the solution by a suitable factor and repeat the analysis. Record the diluti
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