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ABSTRACT: Thermal-optical analysis is a conventional method for determining the carbonaceous aerosol fraction and for classifying it into organic carbon, OC, and elemental carbon, EC. Unfortunately, the different thermal evolution protocols in use can result in a wide elemental carbon-to-total carbon variation by up to a factor of five. In Europe, there is currently no standard procedure for determining the carbonaceous aerosol fraction which implies that data from different laboratories at various sites are of unknown accuracy and cannot be considered comparable. In the framework of the EU-project EUSAAR (European Supersites for Atmospheric Aerosol Research), a comprehensive study has been carried out to identify the causes of differences in the EC measured using different thermal evolution protocols; thereby the major positive and negative biases affecting thermal-optical analysis have been isolated and minimised to define an optimised protocol suitable for European aerosols. Our approach to improve the accuracy of the discrimination between OC and EC was essentially based on four goals. Firstly, charring corrections rely on faulty assumptions – e.g. pyrolytic carbon is considered to evolve completely before native EC throughout the analysis –, thus we have reduced pyrolysis to a minimum by favoring volatilisation of OC. Secondly, we have minimised the potential negative bias in EC determination due to early evolution of light absorbing carbon species at higher temperatures in the He-mode, including both native EC and combinations of native EC and pyrolytic carbon potentially with different specific cross section values. Thirdly, we have minimised the potential positive bias in EC determination resulting from the incomplete evolution of OC during the He-mode which then evolves during the He/O2-mode, potentially after the split point. Finally, we have minimised the uncertainty due to the position of the OC/EC split point on the FID response profile by introducing multiple desorption steps in the He/O2-mode. Based on different types of carbonaceous PM encountered across Europe, we have defined an optimised thermal evolution protocol, the EUSAAR_2 protocol, as follows: step 1 in He, 200°C for 120 s; step 2 in He 300°C for 150 s; step 3 in He 450°C for 180 s; step 4 in He 650°C for 180 s. For steps 1–4 in He/O2, the conditions are 500°C for 120 s, 550°C for 120 s, 700°C for 70 s, and 850°C for 80 s, respectively.
Atmospheric Measurement Techniques Discussions. 01/2009;
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Rodríguez S,
R. Van Dingenen, Putaud J.-P,
Dell&apos,
Acqua A,
Pey J,
Querol X,
Alastuey A,
Chenery S,
Ho K.-F,
R M Harrison,
Tardivo R,
Scarnato B,
Gianelle V
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ABSTRACT: A physicochemical characterization of the urban fine aerosol (aerosol number size distribution, chemical composition and mass concentrations) in Milan, Barcelona and London is presented in this article. The objective is to obtain a comprehensive picture on the involvement of the microphysical processes of the aerosol dynamic in the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) link between "aerosol chemistry and mass concentrations" with the "number size distribution". The mass concentrations of the fine PM2.5 aerosol exhibit a high correlation with the number concentration of particles >100 nm (which only accounts for 80% of fine particles). Organic matter (OM) and black-carbon (BC) are the only aerosol components showing a significant correlation with ultrafine particles (attributed to vehicles emissions), whereas ammonium-nitrate, ammonium-sulphate and also OM and BC correlate with N>100(nm) (attributed to gas-to-particle transformation mechanisms and some primary emissions). Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM2.5 concentrations and number N>100(nm) concentrations, exhibit correlated day-to-day variations which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the fact that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM2.5 particles urban pollution events" tend to occur when condensation processes have made particles grow enough to produce significant concentrations of N>100(nm). In contrast, because the low contribution of ultrafine particles to the fine aerosol mass concentrations, high "ultrafine particles N100 nm and PM2.5").
Atmospheric Chemistry and Physics Discussions. 01/2007;
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Rodríguez S,
R. Van Dingenen, Putaud J.-P,
Dell&apos,
Acqua A,
Pey J,
Querol X,
Alastuey A,
Chenery S,
Ho K.-F,
Harrison R,
Tardivo R,
Scarnato B,
Gemelli V
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ABSTRACT: A physicochemical characterization, including aerosol number size distribution, chemical composition and mass concentrations, of the urban fine aerosol captured in MILAN, BARCELONA and LONDON is presented in this article. The objective is to obtain a comprehensive picture of the microphysical processes involved in aerosol dynamics during the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) the link between "aerosol chemistry and mass concentrations" with the "number size distribution".
The mass concentrations of the fine PM<sub>2.5</sub> aerosol exhibit a high correlation with the number concentration of >100 nm particles N>100 (nm) ("accumulation mode particles") which only account for 80% of fine particles number concentration. Organic matter and black-carbon are the only aerosol components showing a significant correlation with the ultrafine particles, attributed to vehicles exhausts emissions; whereas ammonium-nitrate, ammonium-sulphate and also organic matter and black-carbon correlate with N>100 (nm) and attributed to condensation mechanisms, other particle growth processes and some primary emissions. Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM<sub>2.5</sub> concentrations and number N>100 (nm) concentrations exhibit correlated day-to-day variations, which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the observation that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM<sub>2.5</sub> particles urban pollution events" tend to occur when condensation processes have made particles grow large enough to produce significant number concentrations of N>100 (nm) ("accumulation mode particles"). In contrast, because the low contribution of ultrafine particles to the fine aerosol mass concentrations, high "ultrafine particles N<100(nm) events" frequently occurs under low PM<sub>2.5</sub> conditions. The results of this study demonstrate that vehicles exhausts emissions are strongly involved in this ultrafine particles aerosol pollution.
Atmospheric Chemistry and Physics. 01/2007;
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Dentener F,
Kinne S,
Bond T,
Boucher O,
Cofala J,
Generoso S,
Ginoux P,
Gong S,
J. J. Hoelzemann,
Ito A,
Marelli L,
J. E. Penner, Putaud J.-P,
Textor C,
Schulz M,
G. R. van der Werf,
Wilson J
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ABSTRACT: Inventories for global aerosol and aerosol precursor emissions have been collected (based on published inventories and published simulations), assessed and prepared for the year 2000 (present-day conditions) and for the year 1750 (pre-industrial conditions). These global datasets establish a comprehensive source for emission input to global modeling, when simulating the aerosol impact on climate with state-of-the-art aerosol component modules. As these modules stratify aerosol into dust, sea-salt, sulfate, organic matter and soot, for all these aerosol types global fields on emission strength and recommendations for injection altitude and particulate size are provided. Temporal resolution varies between daily (dust and sea-salt), monthly (wild-land fires) and annual (all other emissions). These datasets benchmark aerosol emissions according to the knowledge in the year 2004. They are intended to serve as systematic constraints in sensitivity studies of the AeroCom initiative, which seeks to quantify (actual) uncertainties in aerosol global modeling.
Atmospheric Chemistry and Physics. 01/2006;
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ABSTRACT: Aerosol physical properties were measured at the Monte Cimone Observatory (Italy) from 1 June till 6 July 2000. The measurement site is located in the transition zone between continental boundary layer and the free troposphere (FT), at the border between the Mediterranean area and Central Europe, and is exposed to a variety of air masses. Sub-micrometer number size distributions, aerosol hygroscopicity at 90% RH, refractory size distribution at 270°C and black carbon mass were continuously measured. Number size distributions and hygroscopic properties indicate that the site is exposed to aged continental air masses, however during daytime it is also affected by upslope winds. The mixing of this transported polluted boundary layer air masses with relatively clean FT air leads to frequent nucleation events around local noon. Night-time size distributions including fine and coarse fractions for each air mass episode have been parameterized by a 3-modal lognormal distribution. Number and volume concentrations in the sub-micrometer modes are strongly affected by the air mass origin, with highest levels in NW-European air masses, versus very clean air in the ''Arctic'' episode. During the dust episode, the coarse mode is clearly enhanced. The observed hygroscopic behavior of the aerosol is consistent with the chemical composition described by Putaud et al. (2004a), but no closure could be made because the hygroscopic properties of the water-soluble organic matter is not known. The data suggest that WSOM is slightly-to-moderately hygroscopic, and that this property may well depend on the air mass origin and history. Although externally mixing is observed in all air masses, the occurrence of ''less'' hygroscopic particles has mostly such a low occurrence rate that the average growth factor distribution mostly appears as a single mode. This is not the case for the dust episode, where the external mixing between less hygroscopic and more hygroscopic particles is very prominent, and indicating clearly the occurrence of a dust accumulation mode, extending down to 50 nm particles, along with an anthropogenic pollution mode. The presented physical measurements finally allow us to provide a partitioning of the sub-µm aerosol in four non-overlapping fractions (soluble + volatile, non-soluble + volatile, refractory + non-BC, BC) which can be roughly associated with separate groups of chemical compounds (ions, organic matter, dust, BC). For what concerns the relative contributions of the fractions, all air masses except the free-tropospheric (FT) and Dust Episodes show a similar composition within the uncertainty of the data. The latter two have a significantly higher refractory fraction, which in the FT air mass is attributed to carbonaceous particles, and in the dust episode to a sub-µm accumulation mode of dust.
Atmospheric Chemistry and Physics Discussions. 01/2005;
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ABSTRACT: Physical and chemical characterizations of the atmospheric aerosol were carried out at Mt. Cimone (Italy) during the 4 June-4 July 2000 period. Particle size distributions in the size range 6nm-10µm were measured with a differential mobility analyzer (DMA) and an optical particle counter (OPC). Size-segregated aerosol was sampled using a 6-stage low pressure impactor. Aerosol samples were submitted to gravimetric and chemical analyses. Ionic, carbonaceous and refractory components of the aerosol were quantified. We compared the sub- and superµm aerosol mass concentrations determined by gravimetric measurements (m <sub>GM</sub> ), chemical analyses (mm <sub>CA</sub> ), and by converting particle size distribution to aerosol mass concentrations (mm <sub>SD</sub> ). Mean random uncertainties associated with the determination of mm <sub>GM</sub> , mm <sub>CA</sub> , and mm <sub>SD</sub> were assessed. The three estimates of the sub-µm aerosol mass concentration agreed, which shows that within experimental uncertainty, the sub-µm aerosol was composed of the quantified components. The three estimates of the super-µm aerosol mass concentration did not agree, which indicates that random uncertainties and/or possible systematic errors in aerosol sampling, sizing or analyses were not adequately accounted for. Aerosol chemical composition in air masses from different origins showed differences, which were significant in regard to experimental uncertainties. During the Saharan dust advection period, coarse dust and fine anthropogenic particles were externally mixed. No anthropogenic sulfate could be found in the super-µm dust particles. In contrast, nitrate was shifted towards the aerosol super-µm fraction in presence of desert dust.
Atmospheric Chemistry and Physics. 01/2004;
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ABSTRACT: A complete size segregated chemical characterisation was carried out for aerosol samples collected in the urban area of Bologna over a period of one year, using five-stage low pressure Berner impactors. An original dual-substrate technique was adopted to obtain samples suitable for a complete chemical characterisation. Total mass, inorganic, and organic components were analysed as a function of size, and a detailed characterisation of the water soluble organic compounds was also performed by means of a previously developed methodology, based on HPLC separation of organic compounds according to their acid character and functional group analysis by Proton Nuclear Magnetic Resonance. Chemical mass closure of the collected samples was reached to within a few percent on average in the submicron aerosol range, while a higher unknown fraction in the coarse aerosol range was attributed to soil-derived species not analysed in this experiment. Comparison of the functional group analysis results with model results simulating water soluble organic compound production by gas-to-particle conversion of anthropogenic VOCs showed that this pathway provides a minor contribution to the organic composition of the aerosol samples in the urban area of Bologna.
Atmospheric Chemistry and Physics. 01/2003;
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ABSTRACT: Physical and chemical characterizations of the atmospheric aerosol was carried out at Mt. Cimone (Italy) during the 4 June–4 July 2000 period. Particle size distributions in the size range 6 nm–10 μm were measured with a differential mobility analyzer (DMA) and a optical particle counter (OPC). Size-segregated aerosol was sampled using a 6-stage low pressure impactor. Aerosol samples were submitted to gravimetric and chemical analyses. Ionic, carbonaceous and refractory components of the aerosol were quantified. We compared the sub- and super-μm aerosol mass concentrations determined by gravimetric measurements (mGM), chemical analyses (mCA), and by converting particle size distribution to aerosol mass concentrations (mSC). Mean random uncertainties associated with the determination of mGM, mCA, and mSD were assessed. The three estimates of the sub-μm aerosol mass concentration agreed, which shows that within experimental uncertainty, the sub-μm aerosol was composed of the quantified components. The three estimates of the super-mm aerosol mass concentration did not agree, which indicates that random uncertainties and/or possible systematic errors in aerosol sampling, sizing or analyses were not adequately accounted for. Aerosol chemical composition in air masses from different origins showed differences, which were significant in regard to experimental uncertainties. During the Saharan dust advection period, coarse dust and fine anthropogenic particles were externally mixed. No anthropogenic sulfate could be found in the super-μm dust particles. In contrast, nitrate was shifted towards the aerosol super-μm fraction in presence of desert dust.
Atmospheric Chemistry and Physics Discussions. 01/2003;
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[show abstract]
[hide abstract]
ABSTRACT: A complete size segregated chemical characterisation was carried out for aerosol samples collected in the urban area of Bologna over a period of one year, using five-stage low pressure Berner impactors. An original dual-substrate technique was adopted to obtain samples suitable for a complete chemical characterisation. Total mass, inorganic, and organic components were analysed as a function of size, and a detailed characterisation of the water soluble organic compounds was also performed by means of a previously developed methodology, based on HPLC separation of organic compounds according to their acid character and functional group analysis by Proton Nuclear Magnetic Resonance. Chemical mass closure of the collected samples was reached to within a few percent on average in the submicron aerosol range, while a higher unknown fraction in the coarse aerosol range was attributed to soil-derived species not analysed in this experiment. Comparison of the functional group analysis results with model results simulating water soluble organic compound production by gas-to-particle conversion of anthropogenic VOCs showed that this pathway provides a minor contribution to the organic composition of the aerosol samples in the urban area of Bologna.
Atmospheric Chemistry and Physics Discussions. 01/2002;
