Quantifying the Light-Absorption Properties and Molecular Composition of Brown Carbon Aerosol from Sub-Saharan African Biomass Combustion.

Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and emission factors. Our analysis revealed a linear relationship between the combined BrC species contribution to chamber-measured BB aerosol mass (0.4-14%) and the mass-absorption cross-section at 370 nm (0.2-2.2 m2 g-1). Hierarchical clustering resolved key molecular-level components from the BrC matrix, with photochemically aged emissions from leaf and cow-dung burning showing BrC fingerprints similar to those found in Botswana aerosols. These quantitative findings could potentially help refine climate model predictions, aid in source apportionment, and inform effective air quality management policies for human health and the global climate.

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

Molecular Understanding of the Enhancement in Organic Aerosol Mass at High Relative Humidity.

The mechanistic pathway by which high relative humidity (RH) affects gas-particle partitioning remains poorly understood, although many studies report increased secondary organic aerosol (SOA) yields at high RH. Here, we use real-time, molecular measurements of both the gas and particle phase to provide a mechanistic understanding of the effect of RH on the partitioning of biogenic oxidized organic molecules (from α-pinene and isoprene) at low temperatures (243 and 263 K) at the CLOUD chamber at CERN. We observe increases in SOA mass of 45 and 85% with increasing RH from 10-20 to 60-80% at 243 and 263 K, respectively, and attribute it to the increased partitioning of semi-volatile compounds. At 263 K, we measure an increase of a factor 2-4 in the concentration of C10H16O2-3, while the particle-phase concentrations of low-volatility species, such as C10H16O6-8, remain almost constant. This results in a substantial shift in the chemical composition and volatility distribution toward less oxygenated and more volatile species at higher RH (e.g., at 263 K, O/C ratio = 0.55 and 0.40, at RH = 10 and 80%, respectively). By modeling particle growth using an aerosol growth model, which accounts for kinetic limitations, we can explain the enhancement in the semi-volatile fraction through the complementary effect of decreased compound activity and increased bulk-phase diffusivity. Our results highlight the importance of particle water content as a diluting agent and a plasticizer for organic aerosol growth.

Exhaust and non-exhaust contributions from road transport to PM10 at a Southern European traffic site.

It is a well - established fact that road traffic is one of the main contributors to ambient levels of airborne particulate matter (APM). This study was carried out at a traffic site in which the PM10 levels are monitored all year round. A trend analysis of these levels revealed that over a decade there was no discernible trend, with the PM10 concentrations normally hovering around the EU limit values. In 2018, one of these limit values was exceeded. The contribution of traffic at the site was therefore investigated through a chemical speciation of 209 PM10 samples collected throughout this year. The speciation data were used in a source apportionment exercise in which the output of the PMF model was further refined using the lesser-known, constraint weighted non - negative matrix factorization (CW - NMF) model. This technique enabled the isolation of two factors clearly related to traffic, which were labelled as "exhaust contribution" (responsible for 3.4% of the PM10), "tire/brake wear contribution" (contributing 17% of the PM10). Additionally, a factor including both traffic resuspended dust and crustal material was also isolated and labelled "road dust/crustal" factor. The two contributors to the factor jointly contribute 18% to the PM10 and the contribution of the traffic resuspended dust was estimated at 7.3%. The traffic resuspended component of this factor together with the "tire/brake wear contribution" jointly make up the non-exhaust contribution of traffic - derived dust. Consonant with what has been known for quite some time, the exhaust fraction is the minor component of traffic PM10. It is therefore, clear that policies aimed at controlling traffic derived PM10 pollution at the receptor will have a minimal effect unless the non - exhaust emissions are adequately controlled.

High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures.

Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements.

Synergistic HNO3-H2SO4-NH3 upper tropospheric particle formation.

New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)1-4. However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region5,6. Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles-comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO3-H2SO4-NH3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.

Estimation of the contributions of the sources driving PM2.5 levels in a Central Mediterranean coastal town.

Receptor modelling techniques are widely used in order to identify the main natural and anthropogenic processes driving aerosol levels at a receptor. In this work, Positive Matrix Factorization (PMF) was used to apportion PM2.5 levels at a traffic site (Msida) located in a coastal town. 180 filters collected throughout a yearly sampling campaign conducted in 2016, were chemically characterized by light absorbance analysis, x-ray fluorescence and ion chromatography in order to determine the concentrations of black carbon, 17 elements and 5 ions, respectively. The resulting chemical data base was used in conjunction with PMF in order to identify the 7 components affecting the PM2.5 levels at the receptor site. Six of these sources are considered to be typical of the atmospheric composition of coastal traffic sites: traffic (27.3%), ammonium sulfate (23.6%), Saharan dust (15%), aged sea salt (12.7%), shipping (5%) and fresh sea salt (4.6%). This is the first time that such a study was carried out in Malta and helps in understanding the aerosol pollution climate of the Central Mediterranean, which is still relatively understudied when compared to the Eastern and Western Mediterranean. Furthermore, we have isolated a factor exclusive to Malta: the fireworks component, which is responsible for 2.9% of the PM2.5 and which has health implications due to its chemical composition. The results of this work should also serve to guide the policy makers in achieving the necessary emission reductions in order to achieve the WHO guideline for PM2.5 by 2020.

Author Correction: Cryoconite as a temporary sink for anthropogenic species stored in glaciers.

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Cryoconite as a temporary sink for anthropogenic species stored in glaciers.

Cryoconite, the typical sediment found on the surface of glaciers, is mainly known in relation to its role in glacial microbiology and in altering the glacier albedo. But if these aspects are relatively well addressed, the same cannot be said about the geochemical properties of cryoconite and the possible interactions with glacial and peri-glacial environment. Current glacier retreat is responsible for the secondary emission of species deposited in high-altitude regions in the last decades. The role played by cryoconite in relation to such novel geochemical fluxes is largely unknown. Few and scarce observations suggest that it could interact with these processes, accumulating specific substances, but why, how and to what extent remain open questions. Through a multi-disciplinary approach we tried to shed lights. Results reveal that the peculiar composition of cryoconite is responsible for an extreme accumulation capability of this sediment, in particular for some, specific, anthropogenic substances.

Results of an interlaboratory comparison of analytical methods for quantification of anhydrosugars and biosugars in atmospheric aerosol.

An interlaboratory comparison was performed to evaluate the analytical methods for quantification of anhydrosugars - levoglucosan, mannosan, galactosan - and biosugars - arabitol, glucose and mannitol - in atmospheric aerosol. The performance of 10 laboratories in Italy currently involved in such analyses was investigated on twenty-six PM (particulate matter) ambient filters, three synthetic PM filters and three aqueous standard solutions. An acceptable interlaboratory variability was found, determined as the mean relative standard deviation (RSD%) of the results from the participating laboratories, with the mean RSD% values ranging from 25% to 46% and decreasing with increasing sugar concentration. The investigated methods show good accuracy, evaluated as the percentage error (ε%) related to mean values, since method biases ranged within ±20% for most of the analytes measured in the different laboratories. The detailed investigation (ANOVA analysis at p < 0.05) of the contribution of each laboratory to the total variability and the measurement accuracy shows that comparable results are generated by the different methods, despite the great diversity in terms of extraction conditions, chromatographic separation - more recent LC (liquid chromatography) and EC (exchange chromatography) methods compared to more widespread GC (gas chromatography) - and detection systems, namely PAD (pulsed amperometric detection) or mass spectrometry.