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In terms of chemical interactions, ascorbic acid assays are rarely investigated. This study reports the synergisms and antagonisms of redox-active PM species with implications for the estimation of aerosol particle toxicity.

Agro-industrial areas are frequently affected by various sources of atmospheric pollutants that have a negative impact on public health and ecosystems. However, air quality in these areas is infrequently monitored because of their smaller population compared to large cities, especially in developing countries. The Cauca River valley (CRV) is an agro-industrial region in southwestern Colombia, where a large fraction of the area is devoted to sugarcane and livestock production. The CRV is also affected by road traffic and industrial emissions. This study aims to elucidate the chemical composition of particulate matter fine mode (PM2.5) and to identify the main pollutant sources before source attribution. A sampling campaign was carried out at a representative site in the CRV region, where daily averaged mass concentrations of PM2.5 and the concentrations of water-soluble ions, trace metals, organic and elemental carbon, and various fractions of organic compounds (carbohydrates, n alkanes, and polycyclic aromatic hydrocarbons – PAHs) were measured. The mean PM2.5 was 14.4±4.4 µg m−3, and the most abundant constituent was organic material (52.7 % ± 18.4 %), followed by sulfate (12.7 % ± 2.8 %), and elemental carbon (7.1 % ± 2.5 %), which indicates the presence of secondary aerosol formation and incomplete combustion. Levoglucosan was present in all samples, with a mean concentration of (113.8±147.2 ng m−3), revealing biomass burning as a persistent source. Mass closure using the elemental carbon (EC) tracer method explained 88.4 % on PM2.5, whereas the organic tracer method explained 70.9 % of PM2.5. We attribute this difference to the lack of information of specific organic tracers for some sources, both primary and secondary. Organic material and inorganic ions were the dominant groups of species (79 % of PM2.5). OMprim and OMsec contribute 24.2 % and 28.5 % to PM2.5. Inorganic ions as sulfate, nitrate, and ammonia constitute 19.0 %, EC 7.1 %, dust 3.5%, particle-bounded water (PBW) 5.3 %, and trace element oxides (TEOs), 0.9 % of PM2.5. The aerosol was acidic, with a pH of 2.5±0.4, mainly because of the abundance of organic and sulfur compounds. Diagnostic ratios and tracer concentrations indicate that most PM2.5 was emitted locally and had contributions of both pyrogenic and petrogenic sources, that biomass burning was ubiquitous during the sampling period and was the main source of PAHs, and that the relatively low PM2.5 concentrations and mutagenic potentials are consistent with low-intensity, year-long biomass burning (BB) and sugarcane pre-harvest burning in the CRV.

Climate extremes in tandem with biodiversity change affect emissions of biogenic volatile organic compounds (BVOCs) from plants and, as a result, the formation of biogenic secondary organic aerosols (BSOA). The resulting BSOA can have a wide variety of impacts, such as on Earth’s radiative balance and cloud formation. However, it is unclear to what extent changes in BVOC emissions and BSOA formation are related to biodiversity. Here we present a conceptual framework of the relationships between biodiversity and BVOC emissions based on our current mechanistic understanding and existing knowledge. We tested parts of this framework using a tree diversity experiment as a case-study. We find that the amount of BVOCs in most cases decreases with biodiversity, implying that tree mixtures produce less than expected BVOC compared to tree monocultures. However, some BSOA compounds increased and some decreased relative to what is expected from monocultures. Based on these mixed results, we recommend further field measurements on the patterns of BVOC emission and BSOA formation across biodiversity gradients to improve our understanding and accuracy of the amounts of the compounds emitted. Future studies need a multidisciplinary approach to open a new research nexus where the fields of climate science, biology and atmospheric chemistry interact.

Particulate nitrate ( pNO 3 − ) has long been considered a permanent sink for NO x (NO and NO 2 ), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of pNO 3 − can recycle HONO and NO x back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of pNO 3 − , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O 3 in both polluted and clean environments.

This study examines carbohydrates, amino acids, and lipids as important contributors to organic carbon (OC) in the tropical Atlantic Ocean at the Cape Verde Atmospheric Observatory (CVAO). The above compounds were measured in both surface seawater and in ambient sub-micron aerosol particles to investigate their sea-to-air transfer, including their enrichment in the sea surface microlayer (SML), potential atmospheric in situ formation or degradation, and their oceanic contribution to the ambient marine aerosol particles. In bulk seawater and the SML, similar distributions among species were found for the lipids and carbohydrates with moderate SML enrichments (enrichment factors EFSML = 1.3 ± 0.2 and 1.1 ± 0.5 respectively). In contrast, the amino acids exhibited a higher enrichment in the SML with an average EFSML of 2.3 ± 0.4, although they are less surface-active than lipids. The same compounds studied in the seawater were found on the ambient sub-micron aerosol particles, whereas the lipids' enrichment was more pronounced (EFaer.=1.6×105) compared to the amino acids and carbohydrates (EFaer.=1.5×103 and 1.3×103 respectively), likely due to their high surface activity and/or the lipophilic character. Detailed molecular analysis of the seawater and aerosol particles revealed changes in the relative abundance of the individual organic compounds. They were most pronounced for the amino acids and are likely related to an in situ atmospheric processing by biotic and/or abiotic reactions. On average, 49 % of the OC on the aerosol particles (=∧97 ng m−3) could be attributed to the specific components or component groups investigated in this study. The majority (43 %) was composed of lipids. Carbohydrates and amino acids made up less than 1 % of the OC. This shows that carbohydrates, at least when resolved via molecular measurements of single sugars, do not comprise a very large fraction of OC on marine aerosol particles, in contrast to other studies. However, carbohydrate-like compounds are also present in the high lipid fraction (e.g. as glycolipids), but their chemical composition could not be revealed by the measurements performed here. Previously determined OC components at the CVAO, specifically amines, oxalic acid, and carbonyls, comprised an OC fraction of around 6 %. Since the identified compounds constituted about 50 % of the OC and belong to the rather short-lived biogenic material probably originating from the surface ocean, a pronounced coupling between ocean and atmosphere was indicated for this oligotrophic region. The remaining, non-identified OC fraction might in part contain recalcitrant OC; however, this fraction does not constitute the vast majority of OC in the aerosol particles investigated here.

Epidemiological studies have shown that desert dust exposure affects respiratory health. We aimed to investigate the NLRP3 inflammasome-caspase-1 pathway-dependent inflammatory properties of Saharan dust (SD) in a macrophage model and an air-liquid interface (ALI) co-culture model of the alveolar epithelium. Under submerged conditions wild-type (WT) and NLRP3-/- THP-1 cells were exposed to SD at 50 µg/cm². Using a Vitrocell® Cloud, A549/THP-1 WT ALI co-cultures were exposed to SD or DQ12 quartz at non-cytotoxic concentrations of 10, 20, and 30 µg/cm². Additionally, ALI co-cultures containing NLRP3-/- or CASPASE1/- THP-1 cells were exposed to SD. SD was found to contain endotoxin, and caused manifold higher interleukin (IL)-1β secretion in WT than in NLRP3/- THP-1 cells. Baked SD (220°C, overnight) induced IL-1β secretion to a ~4-fold lower extent. Co-exposure to baked SD and endotoxin synergistically restored the IL-1β secretion. In ALI co-cultures SD but not DQ12 upregulated the expression and secretion of IL-1β, IL-6, IL-8, and tumor necrosis factor α. The secretion of these cytokines was strongly decreased in co-cultures with CASPASE1/- or NLRP3/- THP-1 cells. The screening of multiple SD samples on WT THP-1 cells revealed that their inflammatory potencies strongly depended on the sampling day and location. The surprisingly strong SD-mediated activation of the NLRP3 inflammasome emphasizes its hazardousness and the need for risk mitigation strategies. Therefore, the connection between the toxicity of SD and its composition, especially its microbial components, needs to be further unraveled. Supported by the Leibniz Collaborative Excellence Programme project DUSTRISK.

Daily concentrations of inorganic and organic compounds associated with PM10, i.e., atmospheric particulate matter with aerodynamic diameter of less than 10 µm, was determined at the south Mediterranean coastal area located in Bou Ismail, 40 km west of the Algiers city area in Algeria. From September 2011 to January 2012, chemical characterization of aerosol particles comprising water-soluble ions (WSI), trace metals, carbonaceous aerosols, the anhydrosugars levoglucosan and arabitol, dicarboxylic acids, and semi-volatile organic compounds (SVOC), i.e., alkanes, PAHs, and hopanes, was carried out by using a variety of analytical techniques. Overall, the concentrations of selected ionic species were similar to those reported at other Mediterranean sites, ranging from 3.62 µg m–3 to 5.20 µg m–3 for the monthly total WSI. Sulfate was the most abundant ion. The total concentrations of semi-volatile organic compounds (SVOC) recorded in Bou Ismail ranged from 7.06 to 58.8 ng m–3 for n-alkanes, from 2.44 to 35.3 ng m–3 for polycyclic aromatic hydrocarbons (PAHs), from 0.14 to 1 ng m–3 for hopanes, and from 0.67 to 13.2 ng m–3 for n-alkan-2-one. In order to reconcile species concentrations and their emission sources, sampling days were grouped into two categories according to air mass origin. In the first group, the aerosol particles were mainly of a marine origin, while those of the second group originated in the dust sector. A source analysis of total contents organic compounds (PAHs, alkanes, hopanes, and alkanones) and individual inorganic compounds by spearman rank correlation illustrated that the principal sources consisted of sea salt, secondary aerosol, and biomass burning. Additionally, PM10 constituent diagnostic ratios and the carbon preference index (CPI) for n-alkanes indicated the importance of anthropogenic emissions.

Aerosol particles are important constituents of the atmosphere due to their role in controlling climate-related processes. In addition, their impacts on air quality and human health make it essential to study. However, the characterization and the identification of natural and anthropogenic atmospheric particles can be challenging due to the complex mixture occurring during atmospheric transport. Background locations such as high-altitude sites provide valuable infrastructure for obtaining representative data for understanding various pathways for aerosol interactions useful in assessing atmospheric composition. However, information about aerosol characteristics at high-altitude in the African regions and their relation to urban aerosol composition is still not well understood. In the present study, PM10 and PM2.5 particulate matter was characterized at two different sites in the North African region of Morocco. A background site located at the newly established AM5 research station in the Middle Atlas region at an altitude of 2100 m and an urban site situated in a polluted city, Fez. The goal was to determine chemical components, evaluate Saharan dust’s role on the PM10 concentrations between the sites, and assess the impact of urban pollution on background aerosol composition. The results indicate that the background aerosol composition is influenced by both regional and trans-regional transport. Despite the site's proximity to the Sahara Desert, the deserts influence on the atmospheric composition was observed for only 22% of the time and this was mainly seasonal. Marine air masses were more dominant with a mixture of sea salt and polluted aerosol from the coastal regions especially during wintertime. Furthermore, high concentrations of mineral dust were observed during the daytime due to the resuspension of road dust. At the same time, an increase of PAHs and anthropogenic metals such as Pb, Ni, and Cu were found during the nighttime because of the boundary layer variation. The Fez's urban site is characterized by a high contribution of elemental carbon (6%) and organic biomass tracers (3%) such as Levoglucosane and 4-nitrophenol.

Oxidative potential (OP) assays are feasible methods to comprehensively understand how exposure to atmospheric chemical components can influence the formation of reactive oxygen species (ROS) in the human body. The increase of ROS concentration can enhance the oxidation of numerous components, such as of the DNA, proteins, and lipids, which cause mutations and cell damage, leading to respiratory illness. According to available studies, the mechanisms of PM-related health effects are not totally understood. The aim of the present study is to assess which available assays are suitable for evaluating the OP of different Mineral dust (MD) samples and what limitations may apply to either method. Cell-free assays are assessed including methods based on the interaction of ascorbic acid (AA) and dithiothreitol (DTT) with soluble aerosol chemical components. Oxidative potential experiments were carried out on both commercially available standard solutions, ultrapure water (DTT) and buffer solution (AA), as well as on soluble extracts of one-quarter filter samples obtained using both shaking and ultrasound procedures. Most limitations were related to high concentrations of transition metals in the buffer solution composition, which was treated using Chelex 100 sodium resin. Transition metals were strongly correlated to both methods, such as Ti, Cr, V, and Mn for DTT assays, and Fe, and Sr for AA assay. The mineral dust OP values were lower than the OP of particulate matter samples from urban metropolitan centers. Such results could be related to the fewer metal and quinone concentrations in the MD samples in comparison to the urban sample. DTT assay has shown more sensibility to the MD content compared with AA chemical procedure. These assays contribute to building an impact-evaluation model for assessing the variation of MD OP based on its different chemical composition.

Transparent exopolymer particles (TEP) exhibit the properties of gels and are ubiquitously found in the world oceans. Possibly, TEP may enter the atmosphere as part of sea spray aerosol. Here, we report number concentrations of TEP (diameter > 4.5 µm) in ambient aerosol and cloud water samples from the tropical Atlantic Ocean as well as in generated aerosol particles using a plunging waterfall tank that was filled with the ambient sea water. The ambient TEP concentrations ranged between 7 × 102 and 3 × 104 #TEP m−3 in supermicron aerosol particles and correlations to sodium (Na+) and calcium (Ca2+) (R2 = 0.5) suggested some contribution via bubble bursting. Cloud water TEP concentrations were between 4 × 106 and 9 × 106 #TEP L−1 corresponding to equivalent air concentrations of 2–4 × 103 #TEP m−3. The TEP concentrations in the tank-generated aerosol particles, produced from the same waters and sampled with an equivalent system, were significantly lower (4 × 102–2 × 103 #TEP m−3) compared to the ambient concentrations. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factor for TEP in the atmosphere was calculated. The tank-generated TEP were enriched by a factor of 50 compared to sea water and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEP specifically. TEP enrichment in the ambient atmosphere was on average 1 × 103 in cloud water and 9 × 103 in ambient aerosol particles and therefore about two orders of magnitude higher than the corresponding enrichment from the tank study. Such high enrichment of supermicron particulate organic constituents in the atmosphere is uncommon and we propose that atmospheric TEP concentrations resulted from a combination of enrichment during bubble bursting transfer from the ocean and TEP in-situ formation in atmospheric phases. Abiotic in-situ formation might have occurred from aqueous reactions of dissolved organic precursors that were present in particle and cloud water samples, while biotic formation involves bacteria, which were abundant in the cloud water samples. The ambient TEP number concentrations were two orders of magnitude higher than recently reported ice nucleating particle (INP) concentrations measured at the same location. As TEP likely possess good properties to act as INP, in future experiments it is worth studying if a certain part of TEP contributes a fraction of the biogenic INP population.

Agro-industrial areas are frequently affected by various sources of atmospheric pollutants that negatively impact public health and ecosystems. However, air quality in these areas is infrequently monitored because of their lower population density compared to large cities, especially in developing countries. The Cauca River Valley (CRV) is an agro-industrial region in Southwest Colombia, where a large fraction of the area is devoted to sugarcane and derivatives production. CRV is also affected by road traffic and industrial emissions. This study aims to elucidate the chemical composition of particulate matter fine mode (PM2.5) and to identify the main pollutant sources before source attribution. For this, a sampling campaign was carried out at a representative site of the CRV region, where daily-averaged mass concentrations of PM2.5 and the concentrations of water-soluble ions, trace metals, organic and elemental carbon, and various fractions of organic compounds (carbohydrates, n-alkanes, and polycyclic aromatic hydrocarbons – PAHs) were measured. Mean PM2.5 was 14.38 ± 4.35 ug m−3, and the most abundant constituent was organic material (52.99 % ± 17.79 %), followed by ammonium sulfate (16.12 % ± 3.98 %), and elemental carbon (6.95 % ± 2.52 %), which indicates secondary aerosol formation and incomplete combustion. Levoglucosan was present in all samples with a mean concentration of (113.8 ± 147.2 ng m−3) revealing biomass burning as a persistent source. The diagnostic ratios applied to organic compounds revealed the influence of petrogenic and pyrogenic sources. Principal component analysis identified the influence of traffic-generated road dust, secondary aerosol formation, gasoline and diesel combustion vehicle exhaust, vegetative detritus, and resuspended agriculture soil. However, no single component was dominant nor explained the CRV PM2.5 chemical species variance. Many components had equally important roles instead. Likewise, sugarcane pre-harvest burning, a frequent activity in CRV, was not identified as an independent component. This aerosol and trace gas source contributed to various components and was correlated to the formation of secondary aerosols.

Aliphatic amines are important constituents of the marine environment. However, their biogenic origins, formation processes and roles in atmospheric chemistry are still not well understood. Here we present measurements of monomethylamine (MMA), dimethylamine (DMA) and diethylamine (DEA) from two intensive sampling campaigns at the Cape Verde Atmospheric Observatory (CVAO), a remote marine station in the tropical Atlantic Ocean. The amines were measured in the sea surface microlayer (SML), in bulk seawater, in the gas and the submicron particulate aerosol phase. Additionally, a 24-month record of amine concentrations in aerosol particles, together with other particle constituents and biological and meteorological parameters, is presented. In the SML, mean amine concentrations were in the range 20–50 nmol L−1. The correlation of the amines to chlorophyll-a (R2 = 0.52) and the abundance of the diatom pigment fucoxanthin may indicate that amines were formed via algal production. Amine concentrations in the gas and particulate aerosol phases were dominated by DMA, with average concentrations of 4.5 ng m−3 and 5.6 ng m−3, respectively. Average MMA concentrations were 0.8 ng m−3 in the gas phase and 0.2 ng m−3 in the particle phase. DEA was present in the particle phase with an average concentration of 3.9 ng m−3, but was not detected in the gas phase. Sea to air fluxes for MMA and DMA were calculated from the seawater and gaseous amine concentrations; these varied from −8.7 E−14 to +4.0 E−13 mol m−2 s−1 and from −1.9 E−12 to +2.17 E−12 mol m−2 s−1, respectively. While the flux for MMA was mainly positive, suggesting an oceanic source for this analyte, the flux for DMA could be both positive and negative, indicating that 2-way transport may be occurring. Principal component analysis of the 24-month dataset of amines in aerosol particles revealed that the particulate amines were not directly linked to the identified sources. It seems that the transfer of amines was being determined by gas to particle conversion rather than via primary processes. The correlation of both seawater- and gas phase-amines with biological indicators suggests that they were partly linked and that the amine abundance in the atmosphere (gas phase) reflected biological processes in seawater. In contrast, particulate amine concentrations did not show such a direct response and might have other significant sources and environmental drivers.

Trans-boundary PM10 transport into eastern Germany was quantified by comparing mean PM10 concentrations during western and eastern air mass inflow under similar meteorological conditions and calculating an “increment East” as a proxy for the trans-boundary PM10 fraction. Data of 10 measurement stations located in Berlin, Brandenburg, Mecklenburg-Western Pomerania and Saxony were used for winter 2016/17 and revealed trans-boundary PM10 increments of 0–30 μg m−3 on average, depending on meteorological conditions. On average over all days with positive increments, trans-boundary transport contributed 13 μg m−3 or 44% to the total PM10 concentration in the regional background. During pollution periods with elevated PM10 concentrations of >30 μg m−3 at rural background sites, this contribution lied between 44 and 62%, while it decreased to about 20% for moderate PM10 concentrations between 20 and 30 μg m−3 and was negligible for PM10 concentrations 80% of the trans-boundary PM10 fraction imported from eastern neighbouring countries can be explained by combustion emissions and formation of secondary particle mass, i.e. ammonium sulfate and organic matter, with the latter typically exceeding the contributions from combustion. Source contributions of these two PMF factors within the increment East were correlated, indicating combustion-related emissions of SO2 and volatile organic compounds leading to the observed secondary trans-boundary PM10 mass. Higher increment East values for cold than for warm days imply emissions from domestic heating in eastern European countries, presumably from the combustion of solid fuels such as wood and coal, as the dominant source for trans-boundary PM10 in eastern Germany. A case study for a traffic-impacted pollution hotspot in the city of Berlin showed an average contribution of about 30% from trans-boundary transport, while regional background, urban background and local traffic emissions explained about 40, 10, and 20% of PM10 mass concentrations during days with eastern air mass inflow where the increment East approach could be applied together with the incremental Lenschow approach. The results of this study reinforce the need of PM10 mitigation measures at different spatial scales, ranging from municipal to international levels.

Over the past few decades, the metal elements (MEs) in atmospheric particles have aroused great attention. Some well-established techniques have been used to measure particle-bound MEs. However, each method has its own advantages and disadvantages in terms of complexity, accuracy, and specific elements of interest. In this study, the performances of inductively coupled plasma-optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectroscopy (TXRF) were evaluated for quality control to analyze data accuracy and precision. The statistic methods (Deming regression and significance testing) were applied for intercomparison between ICP-OES and TXRF measurements for same low-loading PM

Mountain and high-altitude sites provide representative data for the lower free troposphere and various pathways for aerosol interactions, changing boundary layer heights useful in understanding atmospheric composition. However, few studies exist in African regions despite its diversity in both natural and anthropogenic emissions. For this reason, the ATLAS Mohamed V (AM5) observatory in the Middle Atlas region was established to provide the necessary infrastructure for detailed atmospheric studies in the North African high-altitude region. Here, results of a field study conducted to determine the aerosol chemical composition in this region, understand its variations, and importance in assessing global and regional changes in the atmospheric composition is reported. Particulate matter (PM10) filter samples (200) were collected using a high-volume (500l/min) collector in a 12h sampling interval from August to December 2017. The chemical composition of the samples was analyzed for trace metals, ions, elemental carbon, organic carbon, aliphatic hydrocarbons, and polycyclic aromatic hydrocarbon (PAHs) content. The results show that the high-altitude aerosol composition is influenced by regional and transregional transport of different pollutants. Local sources play an important role during periods when the wind speed is low, especially during autumn. Despite the proximity of the site to the Saharan Desert, its influence on the atmospheric composition was mainly seasonal and accounted for only 14% of the sampling duration. The chemical composition was dominated by inorganic elements, mainly suspended dust (47%) and ionic species (16%), and followed by organic matter (15%), water content (12%), and indeterminate mass (9%). Biogenic organics contributed up to 7% of the organic matter with high contributions from compounds such as Nonacosane, Heptacosane, and 2-Pentadecanone. Four main air masses characterized the inflow to the site, which often leads to different aerosol chemical compositions. Mineral dust influenced was seasonal and ranged between 20 and 70% of the PM mass with peaks observed during the summer and was accompanied by high concentrations of SO42- of up to 1.3 µg/m³. PM10 concentrations during winter were low (< 30 µg/m³), with a dominance of marine air masses (53%) carrying aerosols rich in sea salt and polluted anthropogenic aerosols from the coastal regions (Rabat and Casablanca). During the day-time, mineral dust contribution to PM increased by about 42% due to road dust resuspension. In contrast, during night-time, an increase in the concentrations of PAHs, ketones, and anthropogenic metals such as Pb, Ni, and Cu was found due to variations in the boundary layer height. The results provide first insights into typical North African high-altitude background aerosol chemical composition useful for long-term assessment of climate and regional influence of air pollution in North Africa.

Trace metals in ambient particulate matter and cloud are considered key elements of atmospheric processes as they affect air quality, environmental ecosystems, and cloud formation. However, they are often available at trace concentrations in these media such that their analysis requires high-precision and sensitive techniques. In this study, different analytical methods were applied to quantify trace metals in particulate matter (PM) samples collected on quartz and polycarbonate filters as well as cloud water, using the Total reflection X-Ray Fluorescence (TXRF) technique. These methods considered the measurement of filter samples directly without and with chemical pretreatment. Direct measurements involved the analysis of PM samples collected on polycarbonate filters and cloud water samples after they are brought onto TXRF carrier substrates. The chemical treatment method involved the assessment of different acid digestion procedures on PM sampled on quartz filters. The solutions applied were reverse aqua regia, nitric acid, and a combination of nitric acid and hydrogen peroxide. The effect of cold-plasma treatment of samples on polycarbonate filters before TXRF measurements was also investigated. Digestion with the reverse aqua regia solution provided lower blanks and higher recovery in comparison to other tested procedures. The detection limits of the elements ranged from 0.3 to 44 ng cm−2. Ca, K, Zn, and Fe showed the highest detection limits of 44, 35, 6, and 1 ng cm−2, while As and Se had the lowest of 0.3 and 0.8 ng cm−2, respectively. The method showed higher recovery for most trace metals when applied to commercially available reference materials and field samples. TXRF measurements showed good agreement with results obtained from ion chromatography measurements for elements such as Ca and K. Cold-plasma treatment did not significantly lead to an increase in the detected concentration, and the results were element specific. Baking of the quartz filters prior to sampling showed a reduction of more than 20 % of the filter blanks for elements such as V, Sr, Mn, Zn, and Sb. The methods were applied successfully on ambient particulate matter and cloud water samples collected from the Atlas Mohammed V station in Morocco and the Cape Verde Atmospheric Observatory. The obtained concentrations were within the range reported using different techniques from similar remote and background regions elsewhere, especially for elements of anthropogenic origins such as V, Pb, and Zn with concentrations of up to 10, 19, and 28 ng m−3, respectively. Enrichment factor analysis indicated that crustal matter dominated the abundance of most of the elements, while anthropogenic activities also contributed to the abundance of elements such as Sb, Se, and Pb. The results confirm that TXRF is a useful complementary sensitive technique for trace metal analysis of particulate matter in the microgram range as well as in cloud water droplets.

Atmospheric traffic-related elements (TRE) generated from traffic-related emissions have been linked to a wide range of human diseases and also affect the ecosystem. This study focuses on data from the Nigerian air quality network along the segment of the National Highway Roads (NHR), inner-city Major Roads (MR) and Rural Roads (RR) in Ibadan. The aim of this near-road monitoring was to assess the levels of TRE, determine the particulate matter (PM10) concentrations and mineralogical composition of the PM10 particles.Sixty particulate matter (PM10) samples were collected from 5 traffic-related stations (2-NHR; 2-MR; 1-RR) (six samples from each station) in the study area using traffic-related high-volume air sampler with PM10 cut-off on cellulose filter. PM10 concentration was calculated from the difference in weight of the filter and flow rate of the sampler while the mineralogical composition of the PM10 was determined by single-particle analysis using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDXS) techniques, and the TRE were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES).The results of the PM10 concentration showed that NHR had the highest concentration of 1194.30 µg/m3, while the lowest concentration was observed in RR (36.33 µg/m3), these correspond to the level of traffic density in both stations, the former having 60,000 vehicle/day while the later had 10 concentrations in the NHR and the MR were classified as being unhealthy-hazardous to humans living very close to this environment on the basis of the air quality index (AQI). The most abundant mineral particles were clay (53%), quartz (9%) and rock-forming minerals (3) was observed in NHR, while those of Cu, Mo and Mn (5.45 µg/m3, 6.67 µg/m3 and 11.78 µg/m3 respectively) was observed in MR. Principal component analysis (PCA) revealed four factors (PC1 to PC4). In PC1 26.57% of the variability was observed and loaded with Ba (0.76), Pb (0.82), V (0.85) while PC 2 could explain 17.94% variability and had La (0.67), Mn (0.83) and Mo (0.68), PC 3 explained 15.91% variance loaded with Cd (0.84) and Zn (0.77), and PC 4 gave account of 13.83% of the variance and was loaded with Cu (0.86). PC1 and PC2 were products of both gasoline and diesel engine while PC3 and PC4 were generated from engine oil, brake and tyre wares. The calculated enrichment factor classified the TRE as being moderate to highly contaminated in both NHR and MR while RR was considered relatively uncontaminated. Keywords: Traffic-related elements; Air quality index; National highway roads; Major roads; Rural roads

The project MarParCloud (marine biological production, organic aerosol particles and marine clouds: a process chain) aims at achieving a better understanding of the biological production of organic matter (OM)in the oceans, its export into marine aerosol particles and finally its ability to act as ice and cloud condensation nuclei (INP and CCN). The core of MarParCloud comprised a field campaign at the Cape Verde Atmosphere Observatory (CVAO) in autumn 2017, where a variety of chemical, physical, biological and meteorological approaches were applied. The investigations included concerted measurements of the bulk water, the Sea Surface Microlayer (SML), ambient aerosol particles on the ground (30 m a.s.l.) and in mountain heights (744 m) as well as cloud water. Important aspects of the ocean atmosphere Interactions focusing on marine OM have been addressed through detailed observation and modeling approaches.Key variables comprised the chemical characterization of the atmospherically relevant OM components (e.g. lipids, proteins, sugars) in the ocean and the atmosphere as well as measurements of INP and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analysed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modelling studies supported the experimental analysis.Here we show the proof of concept of the connection between organic matter emission from the ocean to the atmosphere and up to the cloud level. A link between the ocean and the atmosphere was clearly observed as (i) the particles measured at the surface are well mixed within the marine boundary layer up to cloud level and (ii) ocean-derived compounds can be found in the aerosol particles at mountain height and in the cloud water. The organic measurements will be implemented in a new source function for the oceanic emission of OM. However, from a perspective of particle number concentrations, the marine contributions to both CCN and INP are rather limited.

Size-resolved trace metal concentrations at four sites in Leipzig (Germany) and its surrounding were assessed between the winter of 2013 and the summer of 2015. The measurements were performed in parallel at; traffic dominated (Leipzig – Mitte, LMI), traffic and residential dominated (Eisenbahnstrasse, EIB), urban background (TROPOS, TRO) and regional background (Melpitz, MEL) sites. In total, 19 trace metals, i.e. K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Ba, V, Pb, Ni, Cr, Sr, Sn, Sb, Co and Rb were analysed using total reflection x-ray fluorescence (TXRF). The major metals were Fe, K and Ca with concentrations ranging between; 31–440 ng/m3, 42–153 ng/m3 and 24–322 ng/m3, respectively, while the trace metals with the lowest concentrations were Co, Rb and Se with concentrations of; Traffic at LMI contributed to about 75% of Cr, Ba, Cu, Sb, Sn, Ca, Co, Mn, Fe and Ti concentrations while regional activities contributed to more than 70% of K, Rb, Pb, Se, As and V concentrations. Traffic dominated trace metals were often observed in the coarse mode while the regional background dominated trace metals were often observed in the fine mode. Trace metal sources were related to crustal matter and road dust re-suspension for metals such as Ca, Fe, Co, Sr, and Ti, brake and tire wear (Cu, Sb, Ba, Fe, Zn, Pb), biomass burning (K, Rb), oil and coal combustion (V, Zn, As, Pb). Crustal matter contributed 5–12% in winter and 8–19% in summer of the PM10 mass. Using Cu and Zn as markers for brake and tire wear, respectively, the estimated brake and tire wear contributions to the PM10 mass were 0.1–0.8% and 1.7–2.9%, respectively. The higher contributions were observed at the traffic sites while the lower contributions were observed at the regional background site. In total, non-exhaust emissions could account for about 10–22% of the PM10 mass in the summer and about 7–15% of the PM10 mass in the winter.

Ice nucleating particles (INPs) in the troposphere can form ice in clouds via heterogeneous ice nucleation. Yet, atmospheric number concentrations of INPs (NINP) are not well characterized and although there is some understanding of their sources, it is still unclear to what extend different sources contribute, nor if all sources are known. In this work, we examined properties of INPs at Cape Verde from different sources, the oceanic sea surface microlayer (SML) and underlying water (ULW), the atmosphere close to both sea and cloud level as well as cloud water. Both enrichment and depletion of NINP in SML compared to ULW were observed. The enrichment factor (EF) varied from roughly 0.4 to 11, and there was no clear trend in EF with temperature. NINP in PM10 sampled at Cape Verde Atmospheric Observatory (CVAO) at any particular temperature spanned around 1 order of magnitude below −15 °C, and about 2 orders of magnitude at warmer temperatures (>−12 °C). NINP in PM1 were generally lower than those in PM10 at CVAO. About 83 ± 22 %, 67 ± 18 % and 77 ± 14 % (median ± standard deviation) of INPs had a diameter > 1 µm at ice activation temperatures of −12, −15, and −18 °C, respectively. Among the 17 PM10 samples at CVAO, three PM10 filters showed elevated NINP at warm temperatures, e.g., above 0.01 std L−1 at −10 °C. However, for NINP in PM1 at CVAO, this is not the case. At these higher temperatures, often biological particles have been found to be ice active. Consequently, the difference in NINP between PM1 and PM10 at CVAO, suggests that biological ice active particles were present in the super-micron size range. NINP in PM10 at CVAO was found to be similar to that on Monte Verde (MV, at 744 m a.s.l.) during non-cloud events. During cloud events, most INPs on MV were activated to cloud droplets. When highly ice active particles were present in PM10 filters at CVAO, they were not observed in PM10 filters on MV, but in cloud water samples, instead. This is direct evidence that these INPs which are likely biological are activated to cloud droplets during cloud events. In general, Cape Verde was often affected by dust from the Saharan desert during our measurement. For the observed air masses, atmospheric NINP in air fit well to the concentrations observed in cloud water. When comparing concentrations of both sea salt and INPs in both seawater and PM10 filters, it can be concluded that sea spray aerosol (SSA) only contributed a minor fraction to the atmospheric NINP. Therefore it can be said that, unless there would be a significant enrichment of NINP during the formation of SSA particles, NINP was mainly dominated by mineral dust at cold temperatures with few contributions from possible biological particles at warmer temperatures.

In the framework of the MarParCloud (Marine biological production, organic aerosol particles and marine clouds: a Process Chain) project, measurements were carried out on the islands of Cape Verde, to investigate the abundance, properties, and sources of aerosol particles in general and cloud condensation nuclei (CCN) in particular, both close to sea and cloud level heights. A thorough comparison of particle number concentration (PNC), particle number size distribution (PNSD) and CCN number concentration (NCCN) at the Cape Verde Atmospheric Observatory (CVAO, sea level station) and Monte Verde (MV, cloud level station) reveals that during times without clouds the aerosol at CVAO and MV are similar and the boundary layer is generally well mixed. Therefore, data obtained at CVAO can be used to describe the aerosol particles at cloud level. Cloud events were observed at MV during roughly 58 % of the time and during these, a large fraction of particles were activated to cloud droplets. A trimodal parameterization method was deployed to characterize PNC at CVAO. Based on number concentrations in different aerosol modes, four well separable types of PNSDs were found, which were named the marine type, mixture type, dust type1 and dust type2. Aerosol particles differ depending on their origins. When the air masses came from the Atlantic Ocean, sea spray can be assumed to be one source for particles, besides for new particle formation. For these air masses, PNSDs featured the lowest number concentration in Aitken, accumulation and coarse mode. Particle number concentrations for the sea spray aerosol (SSA, i.e., the coarse mode for these air masses) accounted for about 3.7 % of NCCN,0.30 % (CCN number concentration at 0.30 % supersaturation) and about 1.1 % to 4.4 % of Ntotal (total particle number concentration). When the air masses came from the Saharan desert, we observed enhanced Aitken, accumulation and coarse mode particle number concentrations and overall increased NCCN. NCCN,0.30 % during the strongest observed dust periods is about 2.5 times higher than that during marine periods. However, the particle hygroscopicity parameter κ for these two most different periods shows no significant difference and is generally similar, independent of air mass. Overall, κ averaged 0.28, suggesting the presence of organic material in particles. This is consistent with previous model work and field measurement. There is a slight increase of κ with increasing particle size, indicating the addition of soluble, likely inorganic material during cloud processing.

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42−,NO3−, NH4+, Cl−, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L−1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L−1 for minor ions, 5.4 µmol L−1 for H2O2 (aq), 1.9 µmol L−1 for S(IV), and 3.9 mgC L−1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20–40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60–66 % for solute concentrations and 52–80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56–0.94, 0.79–0.99, 0.71–98, and 0.67–0.92 for SO42−, NO3−, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42−, NO3−, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and “U” shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5–10) in the smallest droplets for many solutes.

Mineral dust needs to be characterized comprehensively since it contributes to the climate change in Tajikistan / Central Asia. Lidar results from the measurements of mineral dust during CADEX are compared with results of sun photometer measurements, satellite-based measurements, and chemical analysis of ground samples. Although the dust is often advected from far-range sources, it impacts on the local conditions considerably.

Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2–111.6 and 1.1–32.1 ng m−3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L−1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L−1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol–cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

The export of organic matter from ocean to atmosphere represents a substantial carbon flux in the Earth system, yet the impact of environmental drivers on this transfer is not fully understood. This work presents dissolved and particulate organic carbon (DOC, POC) concentrations, their enrichment factors in the sea surface microlayer (SML), and equivalent measurements in marine aerosol particles across the Atlantic Ocean. DOC concentrations averaged 161 ± 139 µmol L–1 (n = 78) in bulk seawater and 225 ± 175 µmol L–1 (n = 79) in the SML; POC concentrations averaged 13 ± 11 µmol L–1 (n = 80) and 17 ± 10 µmol L–1 (n = 80), respectively. High DOC and POC enrichment factors were observed when samples had low concentrations, and lower enrichments when concentrations were high. The impacts of wind speed and chlorophyll-a levels on concentrations and enrichment of DOC and POC in seawater were insignificant. In ambient submicron marine aerosol particles the concentration of water-soluble organic carbon was approximately 0.2 µg m–3. Water-insoluble organic carbon concentrations varied between 0.01 and 0.9 µg m–3, with highest concentrations observed when chlorophyll-a concentrations were high. Concerted measurements of bulk seawater, the SML and aerosol particles enabled calculation of enrichment factors of organic carbon in submicron marine ambient aerosols, which ranged from 103 to 104 during periods of low chlorophyll-a concentrations and up to 105 when chlorophyll-a levels were high. The results suggest that elevated local biological activity enhances the enrichment of marine-sourced organic carbon on aerosol particles. However, implementation of the results in source functions based on wind speed and chlorophyll-a concentrations underestimated the organic fraction at low biological activity by about 30%. There may be additional atmospheric and oceanic parameters to consider for accurately predicting organic fractions on aerosol particles.

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 &pm; 55.5 μg m−2, while the mineral dust and sea salt means were 27.9 &pm; 48.7 and 11.1 &pm; 5.5 μg m−2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 &pm; 0.6 μg m−3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 &pm; 8.5% (62 &pm; 42%) in Saharan-dust-dominated air mass to 30 \\textpm 12% (87 &pm; 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

Aerosol chemical composition was characterized during the Central Asian Dust Experiment (CADEX) at Dushanbe (Tajikistan). Aerosol samples were collected during a period of 2 months from March to May 2015 using a high volume DIGITEL DHA-80 sampler on quartz fiber filters. The filters were analyzed for their ionic, trace metals as well as organic and elemental carbon (OC/EC) content. The aerosol mass showed strong variation with mass concentration ranging from 18 μg/m3 to 110 μg/m3. The mineral dust concentrations varied between 0.9 μg/m3 and 88 μg/m3. Days of high aerosol mass loadings were dominated by mineral dust, which made up to about 80% of the aerosol mass while organic matter and inorganic ions made up about 70% of the aerosol mass during days of low aerosol mass loadings. The mineral dust composition showed different trace metal signatures in comparison to Saharan dust with higher Ca content and Ca/Fe ratios twice as high as that observed in Saharan dust. Strong influence of anthropogenic activities was observed in the trace metal concentrations with Zn and Pb concentrations ranging from 7 to 197 ng/m3 and 2 to 20 ng/m3, respectively. Mineral dust and anthropogenic activities relating to traffic, combustion as well as metallurgical industrial emissions are identified as the sources of the aerosol during this period.

Global sulfate production plays a key role in aerosol radiative forcing; more than half of this production occurs in clouds. We found that sulfur dioxide oxidation catalyzed by natural transition metal ions is the dominant in-cloud oxidation pathway. The pathway was observed to occur primarily on coarse mineral dust, so the sulfate produced will have a short lifetime and little direct or indirect climatic effect. Taking this into account will lead to large changes in estimates of the magnitude and spatial distribution of aerosol forcing. Therefore, this oxidation pathway-which is currently included in only one of the 12 major global climate models-will have a significant impact on assessments of current and future climate.

Size-resolved trace metal concentrations of 15 elements in aerosol particles at the Cape Verde Atmospheric Observatory (CVAO) under remote background conditions were investigated through analysis of aerosol samples collected during intensive field studies from January 2007 to November 2011 using total reflection x-ray fluorescence (TXRF). The identification of the main air mass origin that influence remote marine aerosol in the northern tropical Atlantic has been investigated. In total, 317 samples were collected. The dataset was analyzed according to the main air mass inflow at the station. We found that remote conditions make up about 45% of the meteorological conditions in a year at CVAO and thus the northern tropical Atlantic. Surprisingly, air masses from North America are often responsible for higher trace metal concentrations in this region. Elements such as Zn, Pb, Cu, Cr, Ni, and V were mostly found in the submicron size fractions, while elements with dominant crustal or oceanic origin such as Fe, Ti, Mn, Sr, and Rb were found in the coarse fractions (>1 μm). The highest metal concentrations, especially for Zn (3.23 ng m−3), Cu (0.81 ng m−3), Sr (2.63 ng m−3), and Cr (0.53 ng m−3), were observed in air masses originating from North America and the concentrations were within the same concentration range to those reported previously in the literature for remote marine aerosols. Fe (12.26 ng m−3), Ti (0.91 ng m−3), and Mn (0.35 ng m−3) showed higher concentrations when air mass came from Europe and the Canary Islands. Pb concentration was low (−3) and did not vary significantly with air mass direction. The low Pb concentration is indicative of the complete phase-out of leaded gasoline even in African countries. Crustal enrichment factor values decreased from fine to coarse-mode particles with low values (20) for Zn, Cu, Ni, Cr, Pb, and Se. The observed enrichment of the elements was attributed to crustal, marine, anthropogenic, and biogenic sources, as well as long-range transport and resuspension. Zn, Cu and Pb were indicators of anthropogenic activities, while Ti and Sr were indicators of crustal and marine origin, respectively. Oceanic and biogenic emissions might have contributed to most of the Se observed. This work provides the first long-term size-resolved trace metals study for remote tropical northern Atlantic marine aerosols and the dataset could serve as good initiation of yearly flux estimates.

A detailed source apportionment of size-resolved aerosol particles in the area of Leipzig, Germany, was performed. Sampling took place at four sites (traffic, traffic/residential, urban background, regional background) in parallel during summer 2013 and the winters 2013/14/15. Twenty-one samples were taken per season with a 5-stage Berner impactor and analysed for particulate mass, inorganic ions, organic and elemental carbon, water-soluble organic carbon, trace metals, and a wide range of organic species. The compositional data were used to estimate source contributions to particulate matter (PM) in quasi-ultrafine (up to 140 nm), accumulation mode, and coarse size ranges using Positive Matrix Factorisation (PMF) receptor modelling. Traffic (exhaust and general traffic emissions), coal combustion, biomass combustion, photochemistry, general secondary formation, cooking, fungal spores, urban dust, fresh sea/road salt, and aged sea salt were all found to contribute to different extents to observed PM concentrations. PMF derived estimates agreed reasonably with estimates from established macrotracer approaches. Quasi-ultrafine PM originated mainly from traffic (20–50%) and photochemistry (30–50%) in summer, while it was dominated by solid fuel (mainly biomass) combustion in winter (50–70%). Tentatively identified cooking aerosol contributed up to 36% on average at the residential site. For accumulation mode particles, two secondary sources typically contributed 40–90% to particle mass. In winter, biomass and coal combustion contributions were up to ca. 25% and 45%, respectively. Main sources of coarse particles were diverse and included nearly all PMF-resolved ones depending on season and air mass origin. For PM10, traffic (typically 20–40% at kerbside sites), secondary formation (30–60%), biomass combustion (10–15% in winter), and coal combustion (30–40% in winter with eastern air mass inflow) were the main quantified sources. At the residential site, contributions from biomass combustion derived up to 60% from local emissions. Coal combustion as a significant source was only present during eastern air mass inflow and showed very similar concentrations at all sites, indicating the importance of trans-boundary air pollution transport in the study area. Overall, nearly half of the PM10 mass was attributed to urban sources by a simple subtractive approach with highest reduction potentials of up to 80% for local (urban) mitigation measures in ultrafine and coarse particles. Local increments of elemental carbon have decreased by about 50% as compared to the year 2000, corroborating results from a former study on the positive effects of a low emission zone, implemented in Leipzig in 2011.

We report about first aerosol lidar measurements that were performed in Dushanbe, Tajikistan (Central Asia) during our Central Asian Dust EXperiment (CADEX) project. The determined intensive property depolarization ratio allows an aerosol characterization and often shows mineral dust at lofted layers during spring time and optically and geometrically thick layers that touch the surface during summer time. The intensive property lidar ratio shows lower values for Asian dust than the lidar ratios measured from Saharan dust during our former campaigns in Morocco and Cape Verde. We show one measurement example from CADEX, allocate the possible dust source area for this measurement and discuss the measured differences between Asian and Saharan dust.

Using a novel NMR option, magic angle spinning pulsed field gradient (MAS PFG) NMR, the mobility of aliphatic domains in humic substances in the presence of toluene (about 4.5 wt. %) has been monitored. Results show a strong correlation between the diffusivities of the mobile aliphatic chains and those of the adsorbed toluene molecules in the matrix as a function of temperature. Particularly, a strong influence of structural relaxation of the humic matrix on the diffusivity of toluene is observed. Our findings confirm that the aliphatic domains in humic substances play an important role in the mobility of sorbed contaminants within this matrix. These findings further confirm the potential of MAS PFG NMR method in monitoring diffusion processes in particulate humic substances.

A new NMR option for monitoring the mobility of organic contaminants in SOM in the solid state has been successfully applied for the first time. This recently available noninvasive technique, magic angle spinning pulsed-field gradient (MAS PFG) NMR, combines both NMR spectroscopy and diffusometry to selectively monitor the diffusion of compounds sorbed in porous media or polymer matrices. Using this technique, the diffusion of toluene in humic acid particles has been studied. Measurements were performed under varying temperatures from 25 to 80 degrees C. The obtained diffusion coefficients were found to be in good agreement with those obtained from computer simulations reported elsewhere. Our results show a strong influence of the interaction of toluene with humic acid on its diffusion in the matrix even at elevated temperatures of up to 80 degrees C. The Arrhenius plot of the diffusivities shows a decrease in the activation energy of diffusion above 50 degrees C by a factor of 3. This change of activation energy is attributed to a structural change in the humic acid matrix that influences the mobility of toluene.

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa with the later often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5 yr PM10 mean was 47.1 ± 55.5 μg m−3 while the mineral dust and sea salt means were 27.9 ± 48.7 μg m−3 and 11.1 ± 5.5 μg m−3, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 μg m−3, the aerosol mass, OC and EC, showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods where air mass inflow was predominantly of marine origin indicating that marine biogenic emissions were a significant source. Ammonium showed distinct maximum in spring and good correlation with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan dust dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in pure marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. PMF analysis identified three major aerosol sources including sea salt, aged sea salt and long range transport. The ionic budget was dominated by the first two of these factors while the long range transport factor could only account for about 14% of the total observed ionic mass.

Mass deposition fluxes of mineral dust to the tropical northeast Atlantic Ocean were determined within this study. In the framework of SOPRAN (Surface Ocean Processes in the Anthropocene), the interaction between the atmosphere and the ocean in terms of material exchange were investigated at the Cape Verde atmospheric observatory (CVAO) on the island Sao Vicente for January 2009. Five different methods were applied to estimate the deposition flux, using different meteorological and physical measurements, remote sensing, and regional dust transport simulations. The set of observations comprises micrometeorological measurements with an ultra-sonic anemometer and profile measurements using 2-D anemometers at two different heights, and microphysical measurements of the size-resolved mass concentrations of mineral dust. In addition, the total mass concentration of mineral dust was derived from absorption photometer observations and passive sampling. The regional dust model COSMO-MUSCAT was used for simulations of dust emission and transport, including dry and wet deposition processes. This model was used as it describes the AOD's and mass concentrations realistic compared to the measurements and because it was run for the time period of the measurements. The four observation-based methods yield a monthly average deposition flux of mineral dust of 12–29 ng m−2 s−1. The simulation results come close to the upper range of the measurements with an average value of 47 ng m−2 s−1. It is shown that the mass deposition flux of mineral dust obtained by the combination of micrometeorological (ultra-sonic anemometer) and microphysical measurements (particle mass size distribution of mineral dust) is difficult to compare to modeled mass deposition fluxes when the mineral dust is inhomogeneously distributed over the investigated area.