From May 2011 to December 2012, samples of PM10 were collected in the Atmosphere, Biosphere, Climate – Integrated Station (ABC-IS) using different instruments in parallel. These samples were collected to perform the chemical characterization of PM10, especially those species that are not  analyzed routinely. These samples were used for a study on the levels of trace elements (Cavalli et al, 2012) and the comparability of two analytical methods to determine trace elements in PM10 (Yatkin et al., 2012). In addition, a thorough chemical characterization of the PM10 collected in this monitoring campaign is planned to be used as input for a receptor model exercise to identify the sources of PM in this site. The results of the quality tests were  positive  and the  comparability between the different gravimetric methods was good, especially for concentrations below 60 µg/m3.JRC.H.2 - Air and Climat

BELIS Claudio

BOROWIAK Annette

CANCELINHA Jose

PEDRONI Valerio

JRC Publications Repository

   Report EUR 25802 EN 2 0 1 2  Claudio A. Belis Valerio Pedroni Jose Cancelinha Annette Borowiak  Determination of Particulate Matter according to CEN and EMEP standards at the Atmosphere Biosphere and Climate-Integrated Station (ABC-IS), Ispra (IT)                      European Commission Joint Research Centre Institute for Environment and Sustainability  Contact information Claudio A. Belis Address: Joint Research Centre, Via Enrico Fermi 2749, TP 441, 21027 Ispra (VA), Italy E-mail: claudio.belis@jrc.ec.europa.eu Tel.: +39 0332 786644 Fax: +39 0332 785236  http://ies.jrc.ec.europa.eu/ http://www.jrc.ec.europa.eu/  This publication is a Technical Report by the Joint Research Centre of the European Commission.  Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication.  Europe Direct is a service to help you find answers to your questions about the European Union Freephone number (*): 00 800 6 7 8 9 10 11 (*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed.  A great deal of additional information on the European Union is available on the Internet. It can be accessed through the Europa server http://europa.eu/.  JRC79144  EUR 25802 EN  ISBN 978-92-79-28424-3 (pdf)  ISSN 1831-9424 (online)  doi: 10.2788/8320  Luxembourg: Publications Office of the European Union, 2013  © European Union, 2013  Reproduction is authorised provided the source is acknowledged.  Printed in Italy 3   Introduction  From May 2011 to December 2012, samples of PM10 were collected in the Atmosphere, Biosphere, Climate – Integrated Station (ABC-IS) using different instruments in parallel. These samples were collected to perform the chemical characterization of PM10, especially those species that are not  analyzed routinely. These samples were used for a study on the levels of trace elements (Cavalli et al, 2012) and the comparability of two analytical methods to determine trace elements in PM10 (Yatkin et al., 2012). In addition, a thorough chemical characterization of the PM10 collected in this monitoring campaign is planned to be used as input for a receptor model exercise to identify the sources of PM in this site. The objective of the present report is to describe the tests aiming at ensuring the quality of the measurements and the comparability between the different sampling methodologies .  Sampling equipment  In the ABC-IS PM10 samples are collected using Partisol samplers in conformity with the US-EPA reference method and are weighed after conditioning at 20% relative humidity (Table 1). Other samples were collected following the same scheme with samplers FAI Hydra and Leckel SEQ 47/50, which are compliant with the EN 12341 standard of the European Committee for Standardization (CEN) (Table 1). The SEQ 47/50 sampling system has been operated in Ispra building 44, approximately 450 m away from the ABC-IS sampling site. The FAI Hydra is a dual sampling line instrument. For this monitoring campaign these sampling lines were fitted with two different types of filters:  Quartz Pallflex tissuequartz 2500QAT and Teflon Pall Teflo ®, whereas the SEQ system was operated with quartz filters only. In order to balance the sampling and analytical effort with the time resolution and data coverage , 24 hour PM10 samples were collected from 8.00 UTM to 8.00 UTM every 6th day, matching the sampling scheme in place for the standard EMEP PM10 parameters. By selecting this setup it was expected to approximate annual average values and seasonal trends of PM10 concentration and chemical composition.        4    Table 1. Technical characteristics of the equipment used for PM10 sample collection              FAI Hydra Sequential Gravimetric Dual Sampler. PM10 inlet according to CEN EN12341  Dual channel sequential sampling Sampling flow-rate 38.3 l/min Two filters contemporaneously (1 quartz filter and 1 teflon filter) every sixth day              2 LECKEL SEQ 47/50  equipped with PM10 inlet according to CEN EN 12341, one of which with scrubber  Sampling flow-rate 38.3 l/min 1 quartz filter every sixth day            PARTISOL PLUS 2025  U.S. EPA PM-2.5 and PM-10 reference method designation Sequential sampling with a 16-filter capacity  Sampling flow-rate 16.7 l/min 1 quartz filter every sixth day  5  Weighing facilities and methods   The gravimetric determinations were carried out in two different facilities. One of them, located in Ispra building 44, operates in conformity with the cited EN standard 12341 while the other facility, located in building 29, is operated according to a protocol that has been developed within the framework of the EMEP programme. The used methods are described more in detail in the section below.  CEN WEIGHING METHOD  Filters are pre-conditioned for 48 hours in an air-controlled room with a temperature of 20 ± 1 ºC and a relative humidity of 50 ± 3 %. Weighing is performed with an analytical balance (METTLER TOLEDO AX26) connected to a PC that stores automatically the measurements (Figure 1).  This balance is calibrated according to the Italian national calibration system (SIT) standards in order to assure the traceability of the measurements to a primary standard and estimate the weighing uncertainty.              Figure 1. CEN weighing facility  EMEP WEIGHING METHOD  Filters are pre-conditioned for 24 hours in a glove controlled box at a temperature of 20 ± 2 ºC and a relative humidity of 20 ± 5 %. The relative humidity is controlled by an automated system that controls a dry air input valve (Figure 2). Weighing is performed with an analytical balance (Satorius MC5).  6            Figure 2. EMEP weighing facility  Quality checks  In order to assure the quality of the measurements the following quality controls were performed:  Flow rate check: monthly. Field blanks in every sampler: monthly.  Comparison between balances Mettler AX26 and Sartorius MC5 using same weights: annually.  Comparison between CEN vs EMEP gravimetric methods, intensive campaign: 03/12/2011 ÷ 15/12/2011. Comparison between CEN-sampling EMEP weighing vs. CEN, intensive campaign: 10/10/2012 ÷ 19/10/2012 .  Balance intercomparison  A comparison of the performance of the two balances used in each weighing facility was carried out. For that purpose the mass of the same reference weights was determined 10 times in each facility. The observed masses obtained with the two balances were comparable and standard deviations of both weighing systems were well below 1 µg (Table 2).        7  Table 2    Balance intercomparison 10 replicates Mettler AX26 Sartorius MC5 weight mg 100 100 standard deviation 0,000843 0,000675 weight mg 50 50 standard deviation 0,000632 0,000789  Flow rate checks  As specified in the EN standard 12341, deviations in the actual flow rate from the nominal flow rate were kept under control. The instruments in conformity with CEN have warning systems for these parameters and register day and time of irregular values. In order to check possible drifts in the instrument flow-meters a flow rate check is performed every month on the instrumentation using a certified flow-meter. The results of these tests, reported in table 3, confirm that sampling flow was stable and within the EN12341 requirements.  Table 3.  Flow rate check    Fai Q  Fai  T   Leckel 66  Leckel 68 units  l/min  l/min  l/min  l/min April 38,2 38,3 38,2 38,3 May 38,2 38,2 38,2 38,2 June 38,2 38,2 38,2 38,2 July 38,2 38,2 38,3 38,2 August-September 38,1 38,1 38,2 38,3 October 38,2 38,3 38,2 38,4 November 38,4 38,2 38,2 38,2   Field blanks  Field blanks are filters that undergo the same process as sampled filters with the only exception that they are not exposed to ambient air flow. These filters are useful to assess the influence of filter storage and transportation before, during and after sampling. However, only partial information on sampling artifacts can be obtained with this method. This test was introduced from the beginning of the monitoring campaign for FAI samplers and subsequently was applied to the Leckel instruments. Field blank masses in the Leckel samplers were on average higher than those observed in FAI 8  samplers (table 4). In the FAI sampler field blanks were almost always below the threshold of 60 µg (including both quartz and Teflon filters) while those in the Leckel samplers were almost always above that value. The cause of this difference is under investigation.  Table 4.  Field blank mass   Leckel 66 Leckel 68 FAI Q FAI T units µg µg µg µg July 2011     43,5 0,5 August 2011     16 10 September 2011     49 56 October 2011     23,5   November 2011     23 58,5 December 2011     10,5 42,3 January 2012       49,5 February 2012   85,5 12 16 March 2012   5   33 April 2012 85,5 57 15 10,5 May 2012 128 67,5 35 43 June 2012 103,5 92 66,5 48 July 2012 95,5 131,5 98,5   August 2012 110 98 43 14,5 September 2012 142,5 140,5 65 10  Time trend of PM10   PM10 sampling started on 25/5/2012 with one 24 hour sample collected from 8.00 UTM to 8.00 UTM every 6th day to match the sampling scheme in place for the standard EMEP PM10 parameters. In order to obtain specific information concerning comparison of different systems or periods of particular interest three intensive campaigns with everyday sampling were carried out in the following time windows:  Intensive campaign 1: 03/12/2011 ÷ 15/12/2011 Intensive campaign 2 : 10/10/2012 ÷ 19/10/2012  Intensive campaign 3 : 30/11/2012 ÷ 21/12/2012 9   In figure 3 is reported the average trend of PM10 recorded from May 2011 to November 2012. The lowest levels are those observed during the warm season (from April to August) while the highest levels are those observed in the cold season, especially in early and late winter. This temporal pattern fits the main pollution episodes observed in PM2.5 which is sampled daily in this site.                Figure 3. Average trend of PM10 from 25/5/2011 to 9/11/2012 (µg/m³)  Comparisons between sampling and weighing protocols  The PM10 concentrations measured with the two lines of the FAI Hydra using different types of filters are quite comparable (r2= 0.99). Differences are within 2% and the intercept is close to 1 µg/m3 (Figure 3). Similar results are observed when comparing the two Leckel samplers (with and without scrubber).          10  Fai Q  vs Fai T (µg/m³) Leckel 68 vs Leckel 66 (µg/m³)                   Figure 3. Comparison of replicate measurements in the same type of instrument using orthogonal regression and the coefficient of determination.  Differences are more evident when comparing concentrations obtained with different sampling and weighing methods. The PM10 concentrations obtained with the FAI Hydra (CEN protocol) are 4% higher than those obtained with the Partisol (EMEP protocol). However at concentrations below 60 µg/m3, the values of FAI Hydra tend to be lower than those of the Partisol (figure 4). Same pattern is observed between Leckel and Partisol with differences in this case arriving at 10% and the intercept being quite negative.  Fai Q vs Partisol (µg/m³) Leckel vs Partisol (µg/m³)                   Figure 4. Comparison of measurements obtained with different gravimetric protocols instrument using orthogonal regression and the coefficient of determination.  Comparing instruments with different operating principles is even more critical. The scatter plots representing the comparison between gravimetric determinations (FAI) and concentrations obtained with TEOM FDMS, an automated measurement system, are shown in figure 5. The dispersion of the data around the regression line is higher and the coefficient of determination is ca. 0.89.   y=1.04x -3.07 R2=0.98 y=1.10x – 6.05 R2=0.97 y=1.03x -1.64 R2=0.99 y=0.98x –0.85 R2=0.99 11  Fai Q  vs  Teom (µg/m³)TEOM Fai T  vs  Teom (µg/m³)                  Figure 5. Comparison of PM10 concentrations obtained with different operating principles instrument using orthogonal regression and the coefficient of determination.  The values of the automated method are ca. 3-5 % lower than those of the gravimetric method with an intercept of ca. 2 µg/m3. However, it must be taken into account that the detection limit for TEOM FDMS is 5 µg/m3.  Similar regression parameters are observed for gravimetric measurements obtained with other instrument and other gravimetric protocol (Partisol). Almost 10% systematic underestimation of the Teom compared with the gravimetric Leckel is observed, which is compensated at low concentrations by a relatively high slope (ca. 3 µg/m3) (Figure 6).  Leckel  vs  Teom (µg/m³) Partisol  vs  Teom  (µg/m³)                   Figure 6. Comparison of PM10 concentrations obtained with different operating principles instrument using orthogonal regression and the coefficient of determination.    y=0.97x + 0.34 R2=0.88 y=0.95x + 1.35 R2=0.89 y=0.91x + 2.92 R2=0.86 y=0.99x - 2.48 R2=0.87 12  Concluding remarks  The monitoring campaign 2011-2012 at the ABC-IS monitoring network provided sound information about the levels of PM10 in the area. The results of the balance and flow rate quality check were satisfactory. The uncertainty between replicate samples collected with the same instrument fell within 2%. Higher differences were observed between samples collected with different gravimetric methods, especially at concentrations above 60 µg/m3. The greatest differences were those observed between measurements obtained with the gravimetric methods and the automated method based on oscillating microbalance (TEOM FDMS). This automated method presented values lower than those obtained with the gravimetric methods, with the exception of low concentrations where the uncertainty of the automated method is higher. The positive results of the quality tests and the good comparability between the different gravimetric methods, especially for concentrations below 60 µg/m3 suggest that the samples are fit for subsequent chemical characterization and their use for receptor modelling purposes.   References  Cavalli F. R. Passarella and V. Pedroni. 2012. Observations of trace elements in particulate matter in Ispra: 2011-2012 data. JRC technical report. EN 12341, 1998. Determination of the PM10 fraction of suspended particulate matter - Reference method and field test procedure to demonstrate reference equivalence of measurement methods. S. Yatkin, C. A. Belis, J. Cancelhina, F. Cavalli, R. Passarella, V. Pedroni, and M. Gerboles.2012. Assessment of comparability of heavy metal determined by EDXRF and ICPMS at the JRC EMEP station. JRC technical report.                                    European Commission EUR 25802 --- Joint Research Centre --- Institute for Environment and Sustainability  Title: Determination of PM according to CEN and EMEP standards at the Atmosphere Biosphere and Climate-Integrated Station (ABC-IS), Ispra (IT)  Author(s): Claudio A. Belis, Valerio Pedroni, Jose Cancelinha, Annette Borowiak  Luxembourg: Publications Office of the European Union  2013 -- 12 pp. -- 21.0 x 29.7 cm  EUR -- Scientific and Technical Research series -- ISSN 1831-9424 (online)  ISBN 978-92-79-28424-3 (pdf)   doi: 10.2788/8320  Abstract  From May 2011 to December 2012, samples of PM10 were collected in the Atmosphere, Biosphere, Climate -- Integrated Station (ABC-IS) using different instruments in parallel. The samples were collected to be used for chemical characterization of the PM10.  The objective of the present report is to describe the tests aiming at ensuring the quality of the measurements and the comparability between the different sampling methodologies. The positive results of the quality tests and the good comparability between the different gravimetric methods, especially for concentrations below 60 µg/m3 suggest that the samples are fit for subsequent chemical characterization and their use for modelling purposes.     As the Commission’s in-house science service, the Joint Research Centre’s mission is to provide EU policies with independent, evidence-based scientific and technical support throughout the whole policy cycle.  Working in close cooperation with policy Directorates-General, the JRC addresses key societal challenges while stimulating innovation through developing new standards, methods and tools, and sharing and transferring its know-how to the Member States and international community.  Key policy areas include: environment and climate change; energy and transport; agriculture and food security; health and consumer protection; information society and digital agenda; safety and security including nuclear; all supported through a cross-cutting and multi-disciplinary approach. LB-NA-25802-EN-N 

Determination of Particulate Matter according to CEN and EMEP standards at the Atmosphere Biosphere and Climate-Integrated Station (ABC-IS), Ispra (IT)

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Determination of Particulate Matter according to CEN and EMEP standards at the Atmosphere Biosphere and Climate-Integrated Station (ABC-IS), Ispra (IT)

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