Physical aerosol properties and their relation to air mass origin at Monte Cimone (Italy) during the first MINATROC campaign

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 the 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-&mu;m number size distributions, aerosol hygroscopicity near 90% RH, refractory size distribution at 270&deg;C and equivalent 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. <P style='line-height: 20px;'> 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-&mu;m modes are strongly affected by the air mass origin, with highest levels in NW-European air masses, versus very clean, free tropospheric air coming from the N-European sector. During a brief but distinct dust episode, the coarse mode is clearly enhanced. <P style='line-height: 20px;'> The observed hygroscopic behavior of the aerosol is consistent with the chemical composition described by Putaud et al.&nbsp;(2004), but no closure between known chemical composition and measured hygroscopicity could be made because the hygroscopic properties of the water-soluble organic matter (WSOM) are not known. The data suggest that WSOM is slightly-to-moderately hygroscopic (hygroscopic growth factor GF at 90% relative humidity between 1.05 and 1.51), and that this property may well depend on the air mass origin and history. <P style='line-height: 20px;'> External mixing of aerosol particles is observed in all air masses through the occurrence of two hygroscopicity modes (average GF of 1.22 and 1.37, respectively). However, the presence of 'less' hygroscopic particles has mostly such a low occurrence rate that the average growth factor distribution for each air mass sector actually 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. <P style='line-height: 20px;'> The presented physical measurements finally allow us to provide a partitioning of the sub-&mu;m aerosol in four non-overlapping fractions (soluble/volatile, non-soluble/volatile, refractory/non-black carbon, black carbon) which can be associated with separate groups of chemical compounds determined with chemical-analytical techniques (ions, non-water soluble organic matter, dust, elemental carbon). All air masses except the free-tropospheric N-European and Dust episodes show a similar composition within the uncertainty of the data (53%, 37%, 5% and 5% respectively for the four defined fractions). Compared to these sectors, the dust episode shows a clearly enhanced refractory-non-BC fraction (17%), attributed to dust in the accumulation mode, whereas for the very clean N-EUR sector, the total refractory fraction is 25%, of which 13% non-BC and 12% BC

Lidar and in situ observations of continental and Saharan aerosol: closure analysis of particles optical and physical properties

Single wavelength polarization lidar observations collected at Mt. Cimone (44.2º N, 10.7º E, 1870 m a.s.l.) during the June 2000 MINATROC campaign are analyzed to derive tropospheric profiles of aerosol extinction, depolarization, surface area and volume. Lidar retrievals for the 2170-2245 m level are compared to the same variables as computed from in situ measurements of particles size distributions, performed at the mountain top Station (2165 m a.s.l.) by a differential mobility analyzer (DMA) and an optical particle counter (OPC). A sensitivity analysis of this closure experiment shows that mean relative differences between the backscatter coefficients obtained by the two techniques undergo a sharp decrease when hygroscopic growth to ambient humidity is considered for the DMA dataset, otherwise representative of dry aerosols. Minimization of differences between lidar and size distribution-derived backscatter coefficients allowed to find values of the &quot;best&quot; refractive index, specific to each measurement. These results show the refractive index to increase for air masses proceeding from Africa and Western Europe. Lidar depolarization was observed to minimize mainly in airmasses proceeding from Western Europe, thus indicating a spherical, i.e. liquid nature for such aerosols. Conversely, African, Mediterranean and East Europe aerosol showed a larger depolarizing fraction, mainly due to coexisting refractory and soluble fractions. The analysis shows average relative differences between lidar and in-situ observations of 5% for backscatter, 36% for extinction 41% for surface area and 37% for volume. These values are well within the expected combined uncertainties of the lidar and in situ retrievals. Average differences further decrease during the Saharan dust transport event, when a lidar signal inversion model considering non-spherical scatterers is employed. The quality of the closure obtained between particle counter and lidar-derived aerosol surface area and volume observations constitutes a validation of the technique adopted to retrieve such aerosol properties on the basis of single-wavelength lidar observations

Chemical mass balance of size-segregated atmospheric aerosol in an urban area of the Po Valley, Italy

International audienceA 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

Mass closure on the chemical species in size-segregated atmospheric aerosol collected in an urban area of the Po Valley, Italy

International audienceA 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

Size-segregated aerosol mass closure and chemical composition in Monte Cimone (I) during MINATROC

International audiencePhysical 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 (mGM), chemical analyses (mmCA), and by converting particle size distribution to aerosol mass concentrations (mmSD). Mean random uncertainties associated with the determination of mmGM, mmCA, and mmSD 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

A comparison of aerosol chemical and optical properties from the 1st and 2nd Aerosol Characterization Experiments

Shipboard measurements of aerosol chemical composition and optical properties were made during both ACE-1 and ACE-2. ACE-1 focused on remote marine aerosol minimally perturbed by continental sources. ACE-2 studied the outflow of European aerosol into the NE Atlantic atmosphere. A variety of air masses were sampled during ACE-2 including Atlantic, polar, Iberian Peninsula, Mediterranean, and Western European. Reported here are mass size distributions of non-sea salt (nss) sulfate, sea salt, and methanesulfonate and submicron and supermicron concentrations of black and organic carbon. Optical parameters include submicron and supermicron aerosol scattering and backscattering coefficients at 550 nm, the absorption coefficient at 550±20 nm, the Ångström exponent for the 550 and 700 nm wavelength pair, and single scattering albedo at 550 nm. All data are reported at the measurement relative humidity of 55%. Measured concentrations of nss sulfate aerosol indicate that, relative to ACE-1, ACE-2 aerosol during both marine and continental flow was impacted by continental sources. Thus, while sea salt controlled the aerosol chemical composition and optical properties of both the submicron and supermicron aerosol during ACE-1, it played a relatively smaller role in ACE-2. This is confirmed by the larger average Ångström exponent for ACE-2 continental aerosol of 1.2±0.26 compared to the ACE-1 average of -0.03±0.38. The depletion of chloride from sea salt aerosol in ACE-2 continental air masses averaged 55±25% over all particle sizes. This compares to the ACE-2 marine average of 4.8±18% and indicates the enhanced interaction of anthropogenic acids with sea salt as continental air masses are transported into the marine atmosphere. Single scattering albedos averaged 0.95±0.03 for ACE-2 continental air masses. Averages for ACE-2 and ACE-1 marine air masses were 0.98±0.01 and 0.99±0.01, respectively

Clues for a standardised thermal-optical protocol for the assessment of organic and elemental carbon within ambient air particulate matter

Along with some research networking programmes, the European Directive 2008/50/CE requires chemical speciation of fine aerosol (PM_2.5), including elemental (EC) and organic carbon (OC), at a few rural sites in European countries. Meanwhile, the thermal-optical technique is considered by the European and US networking agencies and normalisation bodies as a reference method to quantify EC–OC collected on filters. Although commonly used for many years, this technique still suffers from a lack of information on the comparability of the different analytical protocols (temperature protocols, type of optical correction) currently applied in the laboratories. To better evaluate the EC–OC data set quality and related uncertainties, the French National Reference Laboratory for Ambient Air Quality Monitoring (LCSQA) organised an EC–OC comparison exercise for French laboratories using different thermal-optical methods (five laboratories only). While there is good agreement on total carbon (TC) measurements among all participants, some differences can be observed on the EC / TC ratio, even among laboratories using the same thermal protocol. These results led to further tests on the influence of the optical correction: results obtained from different European laboratories confirmed that there were higher differences between OC_TOT and OC_TOR measured with NIOSH 5040 in comparison to EUSAAR-2. Also, striking differences between EC_TOT / EC_TOR ratios can be observed when comparing results obtained for rural and urban samples, with EC_TOT being 50% lower than EC_TOR at rural sites whereas it is only 20% lower at urban sites. The PM chemical composition could explain these differences but the way it influences the EC–OC measurement is not clear and needs further investigation. Meanwhile, some additional tests seem to indicate an influence of oven soiling on the EC–OC measurement data quality. This highlights the necessity to follow the laser signal decrease with time and its impact on measurements. Nevertheless, this should be confirmed by further experiments, involving more samples and various instruments, to enable statistical processing. All these results provide insights to determine the quality of EC–OC analytical methods and may contribute to the work toward establishing method standardisation

Organic aerosol and global climate modelling: a review

The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies

In situ aerosol-size distributions and clear-column radiative closure during ACE-2

As part of the second Aerosol Characterization Experiment (ACE-2) during June and July of 1997, aerosol-size distributions were measured on board the CIRPAS Pelican aircraft through the use of a DMA and 2 OPCs. During the campaign, the boundary-layer aerosol typically possessed characteristics representative of a background marine aerosol or a continentally influenced aerosol, while the free-tropospheric aerosol was characterized by the presence or absence of a Saharan dust layer. A range of radiative closure comparisons were made using the data obtained during vertical profiles flown on 4 missions. Of particular interest here are the comparisons made between the optical properties as determined through the use of measured aerosol-size distributions and those measured directly by an airborne 14-wavelength sunphotometer and 3 nephelometers. Variations in the relative humidity associated with each of the direct measurements required consideration of the hygroscopic properties of the aerosol for size-distribution-based calculations. Simultaneous comparison with such a wide range of directly-measured optical parameters not only offers evidence of the validity of the physicochemical description of the aerosol when closure is achieved, but also provides insight into potential sources of error when some or all of the comparisons result in disagreement. Agreement between the derived and directly-measured optical properties varied for different measurements and for different cases. Averaged over the 4 case studies, the derived extinction coefficient at 525 nm exceeded that measured by the sunphotometer by 2.5% in the clean boundary layer, but underestimated measurements by 13% during pollution events. For measurements within the free troposphere, the mean derived extinction coefficient was 3.3% and 17% less than that measured by the sunphotometer during dusty and non-dusty conditions, respectively. Likewise, averaged discrepancies between the derived and measured scattering coefficient were −9.6%, +4.7%, +17%, and −41% for measurements within the clean boundary layer, polluted boundary layer, free troposphere with a dust layer, and free troposphere without a dust layer, respectively. Each of these quantities, as well as the majority of the >100 individual comparisons from which they were averaged, were within estimated uncertainties

Thermal-optical analysis for the measurement of elemental carbon (EC) and organic carbon (OC) in ambient air a literature review

Thermal-optical analysis is currently under consideration by the European standardization body (CEN) as the reference method to quantitatively determine organic carbon (OC) and elemental carbon (EC) in ambient air. This paper presents an overview of the critical parameters related to the thermal-optical analysis including thermal protocols, critical factors and interferences of the methods examined, method inter-comparisons, inter-laboratory exercises, biases and artifacts, and reference materials. The most commonly used thermal protocols include NIOSH-like, IMPROVE_A and EUSAAR_2 protocols either with light transmittance or reflectance correction for charring. All thermal evolution protocols are comparable for total carbon (TC) concentrations but the results vary significantly concerning OC and especially EC concentrations. Thermal protocols with a rather low peak temperature in the inert mode like IMPROVE_A and EUSAAR_2 tend to classify more carbon as EC compared to NIOSH-like protocols, while charring correction based on transmittance usually leads to smaller EC values compared to reflectance. The difference between reflectance and transmittance correction tends to be larger than the difference between different thermal protocols. Nevertheless, thermal protocols seem to correlate better when reflectance is used as charring correction method. The difference between EC values as determined by the different protocols is not only dependent on the optical pyrolysis correction method, but also on the chemical properties of the samples due to different contributions from various sources. The overall conclusion from this literature review is that it is not possible to identify the "best" thermal-optical protocol based on literature data only, although differences attributed to the methods have been quantified when possible.This work was undertaken under Mandate M/503 “Standardisation mandate to CEN, CENELEC and ETSI in support of the implementation of the Ambient Air Quality Legislation”, ENX “Ambient air – Measurement of airborne lemental carbon (EC) and organic carbon (OC) in PM 2.5 deposited on filters”.EUR 1,920 APC fee funded by the EC FP7 Post-Grant Open Access PilotPeer reviewe