an inclusive view of saharan dust advections to italy and the central mediterranean

Abstract We address observations of physical and chemical properties of Saharan dust advections (SDA) as observed in the Central Mediterranean basin, within the framework of the LIFE+10, DIAPASON project ( www.diapason-life.eu ). DIAPASON aimed at the definition of best practices and tools to detect and evaluate the contribution of Saharan dust to ground particulate matter (PM) loads. Polarization-sensitive, automated lidar-ceilometers (PLC) are one of the tools prototyped and used in the Rome area to reach this goal. The results presented in this study focus on: 1) the effectiveness of various observational tools at detecting and characterizing atmospheric dust plumes, and 2) processes and properties of Saharan dust advections reaching the central Mediterranean region. In this respect, the combination of numerical model forecasts and time-resolved (at least hourly) PLC or chemical observations was found to constitute an efficient way to predict and confirm the presence of Saharan dust. In the period 2011–2014, Saharan dust advections were observed to reach over Rome on about 32% of the days. In some 70% of these days the dust reached the ground in dry conditions, while 30% of advection days involved wet deposition. Dry (wet) deposition was found to maximize (minimize) in summer. The northern Sahara between Algeria and Tunisia (Grand Erg Oriental), was confirmed as the most frequent region of origin of the dust mobilized towards central Italy. Secondary source regions include northern Morocco and Libya. On a statistical basis, Saharan advections to Rome were preceded by increasing atmospheric pressure and stability. These conditions were found to favor the accumulation of aerosols related to local emission sources before the SDA reached the ground. Meteorology (precipitation and turbulence in primis) resulted to be an important modulator of PM concentrations during SDAs. Magnitude and timing of these factors should be well considered to correctly evaluate the dust share in PM loads or the related health effects. Saharan advections observed during DIAPASON affected particle concentrations down to diameters of about 0.6–1 μm, with number concentrations peaking at the 2.5 μm diameter range. These advections were associated with a significant increase in Si-rich particles containing a non-negligible fraction of water. Rainfall was observed to preferentially remove dust particles larger than 2 μm, causing a significant depletion in the Ca-rich fraction with respect to the Si-rich one. The increase in PLC depolarization ratios above 5%, as well as the hourly PIXE records of the Si/Ca ratio increasing above 1 were found to represent good markers for the actual presence of Saharan dust particulate matter, when Saharan advection conditions are occurring

A new methodology to assess the performance and uncertainty of source apportionment models II: The results of two European intercomparison exercises

The performance and the uncertainty of receptor models (RMs) were assessed in intercomparison exercises employing real-world and synthetic input datasets. To that end, the results obtained by different practitioners using ten different RMs were compared with a reference. In order to explain the differences in the performances and uncertainties of the different approaches, the apportioned mass, the number of sources, the chemical profiles, the contribution-to-species and the time trends of the sources were all evaluated using the methodology described in Belis et al. (2015). In this study, 87% of the 344 source contribution estimates (SCEs) reported by participants in 47 different source apportionment model results met the 50% standard uncertainty quality objective established for the performance test. In addition, 68% of the SCE uncertainties reported in the results were coherent with the analytical uncertainties in the input data. The most used models, EPA-PMF v.3, PMF2 and EPA-CMB 8.2, presented quite satisfactory performances in the estimation of SCEs while unconstrained models, that do not account for the uncertainty in the input data (e.g. APCS and FA-MLRA), showed below average performance. Sources with well-defined chemical profiles and seasonal time trends, that make appreciable contributions (>10%), were those better quantified by the models while those with contributions to the PM mass close to 1% represented a challenge. The results of the assessment indicate that RMs are capable of estimating the contribution of the major pollution source categories over a given time window with a level of accuracy that is in line with the needs of air quality management

Evaluation of receptor and chemical transport models for PM10 source apportionment

In this study, the performance of two types of source apportionment models was evaluated by assessing the results provided by 40 different groups in the framework of an intercomparison organised by FAIRMODE WG3 (Forum for air quality modelling in Europe, Working Group 3). The evaluation was based on two performance indicators: z-scores and the root mean square error weighted by the reference uncertainty (RMSEu), with pre-established acceptability criteria. By involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), the intercomparison provided a unique opportunity for their cross-validation. In addition, comparing the CTM chemical profiles with those measured directly at the source contributed to corroborate the consistency of the tested model results. The most commonly used RM was the US EPA- PMF version 5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) while more difficulties were observed with the source contribution time series (72% of RMSEu accepted). Industrial activities proved to be the most difficult sources to be quantified by RMs, with high variability in the estimated contributions. In the CTMs, the sum of computed source contributions was lower than the measured gravimetric PM10 mass concentrations. The performance tests pointed out the differences between the two CTM approaches used for source apportionment in this study: brute force (or emission reduction impact) and tagged species methods. The sources meeting the z-score and RMSEu acceptability criteria tests were 50% and 86%, respectively. The CTM source contributions to PM10 were in the majority of cases lower than the RM averages for the corresponding source. The CTMs and RMs source contributions for the overall dataset were more comparable (83% of the z-scores accepted) than their time series (successful RMSEu in the range 25% - 34%). The comparability between CTMs and RMs varied depending on the source: traffic/exhaust and industry were the source categories with the best results in the RMSEu tests while the most critical ones were soil dust and road dust. The differences between RMs and CTMs source reconstructions confirmed the importance of cross validating the results of these two families of models

Mass distributions and morphological and chemical characterization of urban aerosols in the continental Balkan area (Belgrade)

This work presents characteristics of atmospheric aerosols of urban central Balkans area, using a size-segregated aerosol sampling method, calculation of mass distributions, SEM/EDX characterization, and ICP/MS analysis. Three types of mass distributions were observed: distribution with a pronounced domination of coarse mode, bimodal distribution, and distribution with minimum at 1 μm describing the urban aerosol. SEM/EDX analyses have shown morphological difference and variation in the content of elements in samples. EDX spectra demonstrate that particles generally contain the following elements: Al, Ca, K, Fe, Mg, Ni, K, Si, S. Additionally, the presence of As, Br, Sn, and Zn found in air masses from southeast segment points out the anthropogenic activities most probably from mining activities in southeastern part of Serbia. The ratio Al/Si equivalent to the ratio of desert dust was associated with air masses coming from southeastern and southwestern segments, pointing to influences from North Africa and Middle East desert areas whereas the Al/Si ratio in other samples is significantly lower. In several samples, we found high values of aluminum in the nucleation mode. Samples with low share of crustal elements in the coarse mode are collected when Mediterranean air masses prevailed, while high share in the coarse mode was associated with continental air masses that could be one of the approaches for identification of the aerosol origin. Graphical abstract ᅟ.This work presents characteristics of atmospheric aerosols of urban central Balkans area, using a size-segregated aerosol sampling method, calculation of mass distributions, SEM/EDX characterization, and ICP/MS analysis. Three types of mass distributions were observed: distribution with a pronounced domination of coarse mode, bimodal distribution, and distribution with minimum at 1 mu m describing the urban aerosol. SEM/EDX analyses have shown morphological difference and variation in the content of elements in samples. EDX spectra demonstrate that particles generally contain the following elements: Al, Ca, K, Fe, Mg, Ni, K, Si, S. Additionally, the presence of As, Br, Sn, and Zn found in air masses from southeast segment points out the anthropogenic activities most probably from mining activities in southeastern part of Serbia. The ratio Al/Si equivalent to the ratio of desert dust was associated with air masses coming from southeastern and southwestern segments, pointing to influences from North Africa and Middle East desert areas whereas the Al/Si ratio in other samples is significantly lower. In several samples, we found high values of aluminum in the nucleation mode. Samples with low share of crustal elements in the coarse mode are collected when Mediterranean air masses prevailed, while high share in the coarse mode was associated with continental air masses that could be one of the approaches for identification of the aerosol origin

Results of the first European Source Apportionment intercomparison for Receptor and Chemical Transport Models

In this study, the performance of the source apportionment model applications were evaluated by comparing the model results provided by 44 participants adopting a methodology based on performance indicators: z-scores and RMSEu, with pre-established acceptability criteria. Involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), provided a unique opportunity to cross-validate them. In addition, comparing the modelled source chemical profiles, with those measured directly at the source contributed to corroborate the chemical profile of the tested model results. The most used RM was EPA- PMF5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) and more difficulties are observed with SCE time series (72% of RMSEu accepted). Industry resulted the most problematic source for RMs due to the high variability among participants. Also the results obtained with CTMs were quite comparable to their ensemble reference using all models for the overall average (>92% of successful z-scores) while the comparability of the time series is more problematic (between 58% and 77% of the candidates’ RMSEu are accepted). In the CTM models a gap was observed between the sum of source contributions and the gravimetric PM10 mass likely due to PM underestimation in the base case. Interestingly, when only the tagged species CTM results were used in the reference, the differences between the two CTM approaches (brute force and tagged species) were evident. In this case the percentage of candidates passing the z-score and RMSEu tests were only 50% and 86%, respectively. CTMs showed good comparability with RMs for the overall dataset (83% of the z-scores accepted), more differences were observed when dealing with the time series of the single source categories. In this case the share of successful RMSEu was in the range 25% - 34%.JRC.C.5-Air and Climat

Trace elements in size-segregated urban aerosol in relation to the anthropogenic emission sources and the resuspension

Size segregated particulate samples of atmospheric aerosols in urban site of continental part of Balkans were collected during 6 months in 2008. Six stages impactor in the size ranges: Dp ≤ 0.49 μm, 0.49 < Dp ≤ 0.95 μm, 0.95 < Dp ≤ 1.5 μm, 1.5 < Dp ≤ 3.0 μm, 3.0 < Dp ≤ 7.2 μm, and 7.2 < Dp ≤ 10.0 μm was applied for sampling. ICP-MS was used to quantify elements: Al, As, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Na, Ni, Mg, Mn, Pb, Sb, V, and Zn. Two main groups of elements were investigated: (1) K, V, Ni, Zn, Pb, As, and Cd with high domination in nuclei mode indicating the combustion processes as a dominant sources and (2) Al, Fe, Ca, Mg, Na, Cr, Ga, Co, and Li in coarse mode indicating mechanical processes as their main origin. The strictly crustal origin is for Mg, Fe, Ca, and Co while for As, Cd, K, V, Ni, Cu, Pb, and Zn dominates the anthropogenic influence. The PCA analysis has shown that main contribution is of resuspension (PC1, σ2 ≈ 30 %) followed by traffic (PC2, σ2 ≈ 20 %) that are together contributing around 50 % of elements in the investigated urban aerosol. The EF model shows that major origin of Cd, K, V, Ni, Cu, Pb, Zn, and As in the fine mode is from the anthropogenic sources while increase of their contents in the coarse particles indicates their deposition from the atmosphere and soil contamination. This approach is useful for the assessment of the local resuspension influence on element’s contents in the aerosol and also for the evaluation of the historical pollution of soil caused by deposition of metals from the atmosphere

Characterization of trace metals in airborne carbonaceous aerosols by single-particle EDX – Scanning Electron Microscopy

The presence of fine and ultrafine metal particles has been evidenced in size segregated airborne carbonaceous aerosols collected at one industrial and two background (urban and rural) sites during an extended field campaign in Central Italy. Analysis of the backscattered electrons (BSE) by SEM – EDX demonstrated an effective potential in evidencing main structural features of the metal content in identified carbon aerosols. Many observed ultrafine metal particles appear embedded in the skeleton of carbonaceous individual particles and aggregates in the coarse fraction, while the same is not evident in the case of mixed carbon-sulphates aerosol that has been detected in the submicron size. These carbon-sulphates formations include indeed nano-sized metal particles that appear physically combined but not embedded. Also, larger metal particles (ranging around 1 μm physical size) were observed close to carbon materials, but not included in their structure. Main compositional differences of metal particles with size segregation could be evidenced by energy – dispersive X ray spectrometry (EDX). Larger particles are mainly rich in Fe, frequently in presence of Mn, Cu, Cr and Zn in variable proportions; either oxidized or elemental metals were detected. On the other hand, ultrafine particles associated with carbon–sulphates aerosol are enriched in Pb and Zn, although the presence of other trace elements not detectable by SEM – EDX technique cannot be excluded. Moreover, Ce-enriched ultrafine particles were clearly determined in cenospheres. Conversely, inclusion of fine and ultrafine metal particles was rarely or not observed in soot aggregates

Characterization of trace metals in airborne carbonaceous aerosols by single-particle EDX – Scanning Electron Microscopy

The presence of fine and ultrafine metal particles has been evidenced in size segregated airborne carbonaceous aerosols collected at one industrial and two background (urban and rural) sites during an extended field campaign in Central Italy. Analysis of the backscattered electrons (BSE) by SEM – EDX demonstrated an effective potential in evidencing main structural features of the metal content in identified carbon aerosols. Many observed ultrafine metal particles appear embedded in the skeleton of carbonaceous individual particles and aggregates in the coarse fraction, while the same is not evident in the case of mixed carbon-sulphates aerosol that has been detected in the submicron size. These carbon-sulphates formations include indeed nano-sized metal particles that appear physically combined but not embedded. Also, larger metal particles (ranging around 1 μm physical size) were observed close to carbon materials, but not included in their structure. Main compositional differences of metal particles with size segregation could be evidenced by energy – dispersive X ray spectrometry (EDX). Larger particles are mainly rich in Fe, frequently in presence of Mn, Cu, Cr and Zn in variable proportions; either oxidized or elemental metals were detected. On the other hand, ultrafine particles associated with carbon–sulphates aerosol are enriched in Pb and Zn, although the presence of other trace elements not detectable by SEM – EDX technique cannot be excluded. Moreover, Ce-enriched ultrafine particles were clearly determined in cenospheres. Conversely, inclusion of fine and ultrafine metal particles was rarely or not observed in soot aggregates

Complex formation equilibria of some aromatic b-amino-alcohols

Complex formation equilibria of some aromatic β-amino-alcohols with zinc(II), cadmium(II) and silver(I) have been investigated. The structure of the considered ligands (2-amino-1-phenyl-1-propanol, 2-amino-3-phenyl-1-propanol and 2-amino-1,3-propanediol) are similar to some hormones and alcaloids, like adrenaline, noradrenaline and ephedrine, and differ each other for the number and the relative position of alcoholic and phenyl groups. Equilibria constants at 25 °C and μ = 0.5 M (KNO3) have been determined by potentiometric titrations. The comparison of the obtained values with those previously determined for some aliphatic β-aminoalcohols with the same polar heads has allowed to evidence the influence of aromatic ring on the coordinating properties of ligands, which is different depending on the considered metal ion. In particular, two contrasting effects have been evidenced. The electron withdrawing effect of the aromatic ring causes a decrease of amine basicity, more relevant when phenyl and hydroxylic groups are in 1-3 position, which reflects in a reduction of metal-NH2 coordination bond. This effect is predominant in the case of zinc(II) complexes and causes a reduction of complex stability which results directly proportional to the amine group basicity. On the other hand, in the case of silver(I) and cadmium(II) complexes, phenyl group seems to contribute directly to the coordination of the metal ion causing a stabilization of complexes