Publications

Biomass burning organic aerosol (BBOA), containing brown carbon chromophores, plays a critical role in atmospheric chemistry and climate forcing. However, the effects of evaporation on BBOA volatility and viscosity under different environmental conditions remain poorly understood. This study focuses on the molecular characterization of laboratory-generated BBOA proxies from wood pyrolysis emissions. The initial mixture, \u201cpyrolysis oil (PO₁)\u201d, was progressively evaporated to produce more concentrated mixtures (PO_1.33, PO₂, and PO₃) with volume reduction factors of 1.33, 2, and 3, respectively. Chemical speciation and volatility were investigated using temperature-programmed desorption combined with direct analysis in real-time ionization and high-resolution mass spectrometry (TPD-DART-HRMS). This novel approach quantified saturation vapor pressures and enthalpies of individual species, enabling the construction of volatility basis set distributions and the quantification of gas-particle partitioning. Viscosity estimates, validated by poke-flow experiments, showed a significant increase with evaporation, slowing particle-phase diffusion and extending equilibration times. These findings suggest that highly viscous tar ball particles in aged biomass burning emissions form as semivolatile components evaporate. The study highlights the importance of evaporation processes in shaping BBOA properties, underscoring the need to incorporate these factors into atmospheric models for better predictions of BBOA aging and its environmental impact.

Poor air quality is increasingly linked to gastrointestinal diseases, suggesting a potential correlation with human intestine health. However, this relationship remains largely unexplored due to limited research. This study used a controlled mouse model exposed to cooking oil fumes (COFs) and metagenomics, transcriptomics, and metabolomics to elucidate interactions between intestine microbiota and host metabolism under environmental stress. Our findings reveal that short-term COF inhalation induces pulmonary inflammation within 3 days and leads to gastrointestinal disturbances, elucidating a pathway connecting respiratory exposure to intestinal dysfunction. The exposure intensity significantly correlates with changes in intestinal tissue integrity, microbial composition, and metabolic function. Extended exposure of 7 days disrupts intestine microbiota and alters tryptophan metabolism, with further changes observed after 14 days, highlighting an adaptive response. These results highlight the vulnerability of intestinal health to airborne pollutants and suggest a pathway through which inhaled pollutants may affect distant organ systems.

The light absorption enhancement (E_abs) of black carbon (BC) coated with non-BC materials is crucial in the assessment of radiative forcing, yet its evolution during photochemical aging of plumes from biomass burning, the globe's largest source of BC, remains poorly understood. In this study, plumes from open burning of corn straw were introduced into a smog chamber to explore the evolution of E_abs during photochemical aging. The light absorption of BC was measured with and without coating materials by using a thermodenuder, while the size distributions of aerosols and composition of BC coating materials were also monitored. E_abs was found to increase initially, and then decrease with an overall downward trend. The lensing effect dominated in E_abs at 520 nm, with an estimated contribution percentages of 47.5%94.5%, which is far greater than light absorption of coated brown carbon (BrC). The effects of thickening and chemical composition changes of the coating materials on E_abs were evaluated through comparing measured E_abs with that calculated by the Mie theory. After OH exposure of 1 × 10¹⁰ molecules cm⁻³ s, the thickening of coating materials led to an E_abs increase by 3.2% ± 1.6%, while the chemical composition changes or photobleaching induced an E_abs decrease by 4.7% ± 0.6%. Simple forcing estimates indicate that coated BC aerosols exhibit warming effects that were reduced after aging. The oxidation of light-absorbing C_xH_y compounds, such as polycyclic aromatic hydrocarbons (PAHs), to C_xH_yO and C_xH_yO_>1 compounds in coating materials may be responsible for the photobleaching of coated BrC.

The most recent European regulation, the Euro 6d emission standard, require all gasoline direct injection (GDI) vehicles to use both a three-way catalyst (TWC) and a gasoline particle filter (GPF) as exhaust aftertreatment. These aftertreatment methods are aimed at reducing NOx and primary particle emissions. However, the formation of secondary organic aerosols (SOA) from the volatile organic compound (VOC) emissions of a Euro 6d compliant GDI vehicles, equipped with a GPF is yet not investigated. Therefore, to explore the SOA formation and effects of the GPF, the exhaust of a Euro 6d compliant GDI vehicle was characterized at 4 different steady state speeds, idling(0 km/h), 50, 80 and 100 km/h. The exhaust was oxidised in the Photochemical emissions aging flow tube reactor (PEAR) by reactions with OH radicals equivalent of 2.1 days of atmospheric day time oxidation. It was found that the GPF completely removes primary particles larger than 10 nm, at all investigated vehicle speeds. However, significant SOA was formed after oxidation, with the highest SOA formation potential pr kg fuel consumed at 50km/h. The main SOA precursors were determined to be Toulene, Xylene and Trimethyl-Benzene which were found to account for at least 50% of SOA formed at all driving speeds. Furthermore, high emissions of NH3 could be observed in the exhaust throughout all driving conditions which resulted in the subsequent formation of NH4NO3 after aging. The formation of NH4NO3 additionally facilitated the co-condensation of organic gas phase products after OH oxidation enhancing SOA mass even further.

Emissions from road traffic and residential heating contribute to urban air pollution. Advances in emission reduction technologies may alter the composition of emissions and affect their fate during atmospheric processing. Here, emissions of a gasoline car and a wood stove, both equipped with modern emission mitigation technology, were photochemically aged in an oxidation flow reactor to the equivalent of one to five days of photochemical aging. Fresh and aged exhausts were analyzed by ultrahigh resolution mass spectrometry. The gasoline car equipped with a three-way catalyst and a gasoline particle filter emitted minor primary fine particulate matter (PM2.5), but aging led to formation of particulate low-volatile, oxygenated and highly nitrogen-containing compounds, formed from volatile organic compounds (VOCs) and gases incl. NOx, SO2, and NH3. Reduction of the particle concentration was also observed for the application of an electrostatic precipitator with residential wood combustion but with no significant effect on the chemical composition of PM2.5. Comparing the effect of short and medium photochemical exposures on PM2.5 of both emission sources indicates a similar trend for formation of new organic compounds with increased carbon oxidation state and nitrogen content. The overall bulk compositions of the studied emission exhausts became more similar by aging, with many newly formed elemental compositions being shared. However, the presence of particulate matter in wood combustion results in differences in the molecular properties of secondary particles, as some compounds were preserved during aging.

This study investigates daily variations in redox potential of water- and organic-soluble PM2.5 during Delhis monsoon season, offering insights into its chemical composition, cytotoxicity, and oxidative threat to various lung conditions. PM2.5 samples, categorized by pollution levels, showed an average intrinsic oxidative potential (OPmDTT) of 27.5 pmol min1 μg1, OH generation of 51.1 pmol μg1, and antioxidant capacity (AOC) in both gallic acid and trolox equivalency of 62.5 and 35.3 pmol μg1, respectively. Water-soluble redox-active compounds (RACs) contributed to approximately 67% of the PM2.5 redox potential. The polar-phase distribution of RACs in PM2.5 can be modified by atmospheric photochemistry and precipitation. Biomass burning emerged as a pivotal pollution source, with polluted PM2.5 samples exhibiting higher cytotoxicity and oxidative stress in A549 cells. All PM2.5 compounds impaired cellular respiration, reducing the oxygen consumption rates in A549 cells. Intrinsic OPmDTT and OH generation of PM2.5 were influenced by lung fluid variants, such as exogenous nicotine and endogenous inflammatory protein. This study provides a comprehensive perspective on PM2.5 pollution and its toxicity in Delhi, India during distinct pollution periods and also points out the importance of considering population disparities and individual health status in assessing PM2.5 health impacts.

Samples of brown carbon (BrC) material were collected from smoke emissions originating from wood pyrolysis experiments, serving as a proxy for BrC representative of biomass burning emissions. The acquired samples, referred to as \u201cpyrolysis oil (PO₁),\u201d underwent subsequent processing by thermal evaporation of their volatile compounds, resulting in a set of three additional samples with volume reduction factors of 1.33, 2, and 3, denoted as PO_1.33, PO₂, and PO₃. The chemical compositions of these PO_x samples and their BrC chromophore features were analyzed using a high-performance liquid chromatography instrument coupled with a photodiode array detector and a high-resolution mass spectrometer. The investigation revealed a noteworthy twofold enhancement of BrC light absorption observed for the progression of PO₁ to PO₃ samples, assessed across the spectral range of 300-500 nm. Concurrently, a decrease in the absorption Ångstrom exponent (AAE) from 11 to 7 was observed, indicating a weaker spectral dependence. The relative enhancement of BrC absorption at longer wavelengths was more significant, as exemplified by the increased mass absorption coefficient (MAC) measured at 405 nm from 0.1 to 0.5 m²/g. Molecular characterization further supports this darkening trend, manifesting as a depletion of small oxygenated, less absorbing monoaromatic compounds and the retention of relatively large, less polar, more absorbing constituents. Noteworthy alterations of the PO₁ to PO₃ mixtures included a reduction in the saturation vapor pressure of their components and an increase in viscosity. These changes were quantified by the mean values shifting from approximately 1.8 × 10³ μg/m³ to 2.3 μg/m³ and from ∼10³ Pa·s to ∼10⁶ Pa·s, respectively. These results provide quantitative insights into the extent of BrC aerosol darkening during atmospheric aging through nonreactive evaporation. This new understanding will inform the refinement of atmospheric and chemical transport models.

Global ground-level measurements of elements in ambient particulate matter (PM) can provide valuable information to understand the distribution of dust and trace elements, assess health impacts, and investigate emission sources. We use X-ray fluorescence spectroscopy to characterize the elemental composition of PM samples collected from 27 globally distributed sites in the Surface PARTiculate mAtter Network (SPARTAN) over 20192023. Consistent protocols are applied to collect all samples and analyze them at one central laboratory, which facilitates comparison across different sites. Multiple quality assurance measures are performed, including applying reference materials that resemble typical PM samples, acceptance testing, and routine quality control. Method detection limits and uncertainties are estimated. Concentrations of dust and trace element oxides (TEO) are determined from the elemental dataset. In addition to sites in arid regions, a moderately high mean dust concentration (6 μg/m3) in PM2.5 is also found in Dhaka (Bangladesh) along with a high average TEO level (6 μg/m3). High carcinogenic risk (>1 cancer case per 100000 adults) from airborne arsenic is observed in Dhaka (Bangladesh), Kanpur (India), and Hanoi (Vietnam). Industries of informal lead-acid battery and e-waste recycling as well as coal-fired brick kilns likely contribute to the elevated trace element concentrations found in Dhaka.

Decades of research have established the toxicity of soot particles resulting from incomplete combustion. However, the unique chemical compounds responsible for adverse health effects have remained uncertain. This study utilized mass spectrometry to analyze the chemical composition of extracted soot organics at three oxidation states, aiming to establish quantitative relationships between potentially toxic chemicals and their impact on human alveolar basal epithelial cells (A549) through metabolomics-based evaluations. Targeted analysis using MS/MS indicated that particles with a medium oxidation state contained the highest total abundance of compounds, particularly oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) composed of fused benzene rings and unsaturated carbonyls, which may cause oxidative stress, characterized by the upregulation of three specific metabolites. Further investigation focused on three specific OPAH standards: 1,4-naphthoquinone, 9-fluorenone, and anthranone. Pathway analysis indicated that exposure to these compounds affected transcriptional functions, the tricarboxylic acid cycle, cell proliferation, and the oxidative stress response. Biodiesel combustion emissions had higher concentrations of PAHs, OPAHs, and nitrogen-containing PAHs (NPAHs) compared with other fuels. Quinones and 9,10-anthraquinone were identified as the dominant compounds within the OPAH category. This knowledge enhances our understanding of the compounds contributing to adverse health effects observed in epidemiological studies and highlights the role of aerosol composition in toxicity.

This study investigated the redox potential and toxicological changes of wood smoldering emitted HULIS due to reactions in the atmosphere and in neutral lung fluids. Fresh HULIS aerosols exhibited substantial oxidative potential (OP) and antioxidant capacity (AOC). Nighttime oxidation via heterogeneous O₃ or NO₃˙ reactions impacted HULIS OP and AOC differently, with high humidity enhancing O₃ uptake and HULIS oxidation, causing a significant reduction in their redox potentials. The effective rate constants for HULIS redox-active components (RACs) by O₃ reaction increased with RH (

Dust events can be hazardous to society and human health and can cost hundreds of millions of dollars each. Inhalable suspended particulate matter with a diameter of under 10 μm (PM10) is of particular concern since it can cause an array of adverse health effects following short- and long-term exposure. Understanding recurring episodes of dust events will enable accurate and timely forecasts, helping mitigate their impacts and allow for better societal protection. Previous expert-based studies highlighted several dust sources and transport pathways into the Eastern Mediterranean region and further identified several weather systems that sustain these transport routes. But since supervised methods, i.e., manual classifications, may have disadvantages, it is often preferred to use unsupervised methods, or systematic classifications. Here, a novel climatological understanding of the link between weather systems and dust transport is achieved by systematically classifying dust events. Using ground PM10 measurements in Israel to objectively identify a climatological set of extreme dust events between 2003 and 2020, we combine atmospheric data from ERA5 and CAMS reanalysis data sets and apply a new, unsupervised, and unbiased method to classify dust events in the Eastern Mediterranean. Six coherent types emerge, corresponding to events governed by shallow and deep Mediterranean cyclones, Mediterranean dipoles, Sharav thermal lows, Arabian anticyclones, and local factors, respectively. Having different seasonality, these classes are insightful in mapping the meteorological conditions and weather systems governing dust emission and transport towards the Eastern Mediterranean. In this context, slantwise-descending dry intrusions are shown to be a key precursor dynamical feature common to the buildup of elevated dust concentrations in three of the clusters of the highest PM10 concentrations.

Soot particles (SP) are ubiquitous components of atmospheric particulate matter and have been shown to cause various adverse health effects. In the atmosphere, freshly emitted SP can be coated by condensed low-volatility secondary organic and inorganic species. In addition, gas-phase oxidants may react with the surface of SP. Due to the chemical and physical resemblance of SP carbon backbone with polyaromatic hydrocarbon species and their potent oxidation products, we investigated the biological responses of BEAS-2B lung epithelial cells following exposure to fresh- and photochemically aged-SP at the air-liquid interface. A comprehensive physical and chemical aerosol characterization was performed to depict the atmospheric transformations of SP, showing that photochemical aging increased the organic carbon fraction and the oxidation state of the SP. RNA-sequencing and qPCR analysis showed varying gene expression profiles for fresh- and aged-SP. Exposure to aged-SP increased DNA damage, oxidative damage, and upregulation of NRF2-mediated oxidative stress response genes compared to fresh-SP. Furthermore, aged-SP augmented inflammatory cytokine secretion and activated AhR-response, as evidenced by increased expression of AhR-responsive genes. These results indicate that oxidative stress, inflammation, and DNA damage play a key role in the cytotoxicity of SP in BEAS-2B cells, where aging leads to higher toxic responses. Collectively, our results suggest that photochemical aging may increase SP toxicity through surface modifications that lead to an increased toxic response by activating different molecular pathways.

Polar nitrated aromatic compounds (pNACs) are key ambient brown carbon chromophores; however, their formation mechanisms, especially in the aqueous phase, remain unclear. We developed an advanced technique for pNACs and measured 1764 compounds in atmospheric fine particulate matter sampled in urban Beijing, China. Molecular formulas were derived for 433 compounds, of which 17 were confirmed using reference standards. Potential novel species with up to four aromatic rings and a maximum of five functional groups were found. Higher concentrations were detected in the heating season, with a median of 82.6 ng m3 for Σ17pNACs. Non-negative matrix factorization analysis indicated that primary emissions particularly coal combustion were dominant in the heating season. While in the non-heating season, aqueous-phase nitration could generate abundant pNACs with the carboxyl group, which was confirmed by their significant association with the aerosol liquid water content. Aqueous-phase formation of 3- and 5-nitrosalicylic acids instead of their isomer of 4-hydroxy-3-nitrobenzoic acid suggests the existence of an intermediate where the intramolecular hydrogen bond favors kinetics-controlled NO2 nitration. This study provides not only a promising technique for the pNAC measurement but also evidence for their atmospheric aqueous-phase formation, facilitating further evaluation of pNACs climatic effects.

Processes influencing the transport of airborne bacterial communities in the atmosphere are poorly understood. Here, we report comprehensive and quantitative evidence of the key factors influencing the transport of airborne bacterial communities by dust plumes in the Eastern Mediterranean. We extracted DNA and RNA from size-resolved aerosols sampled from air masses of different origins, followed by qPCR and high-throughput amplicon sequencing of 16S ribosomal RNA gene and transcripts. We find that airborne bacterial community composition varied with air mass origin and particle size. Bacterial abundance, alpha diversity and species richness were higher in terrestrially influenced air masses than in marine-influenced air masses and higher in the coarse particle fraction (3.0 to 10.0µm) than in the fine fraction (0.49 to 1.5µm). This suggests that airborne bacteria mainly were associated with dust particles or transported as cell aggregates. High abundances of rRNA from human, animal and plant pathogen taxa indicate potential ecological impacts of atmospheric bacterial transport.

Human health is linked to climatic factors in complex ways, and climate change can have profound direct and indirect impacts on the health status of any given region. Susceptibility to climate change is modulated by biological, ecological and socio-political factors such as age, gender, geographic location, socio-economic status, occupation, health status and housing conditions, among other. In the Eastern Mediterranean and Middle East (EMME), climatic factors known to affect human health include extreme heat, water shortages and air pollution. Furthermore, the epidemiology of vector-borne diseases (VBDs) and the health consequences of population displacement are also influenced by climate change in this region. To inform future policies for adaptation and mitigation measures, and based on an extensive review of the available knowledge, we recommend several research priorities for the region. These include the generation of more empirical evidence on exposure-response functions involving climate change and specific health outcomes, the development of appropriate methodologies to evaluate the physical and psychological effects of climate change on vulnerable populations, determining how climate change alters the ecological determinants of human health, improving our understanding of the effects of long-term exposure to heat stress and air pollution, and evaluating the interactions between adaptation and mitigation strategies. Because national boundaries do not limit most climate-related factors expected to impact human health, we propose that adaptation/mitigation policies must have a regional scope, and therefore require collaborative efforts among EMME nations. Policy suggestions include a decisive region-wide decarbonisation, the integration of environmentally driven morbidity and mortality data throughout the region, advancing the development and widespread use of affordable technologies for the production and management of drinking water by non-traditional means, the development of comprehensive strategies to improve the health status of displaced populations, and fostering regional networks for monitoring and controlling the spread of infectious diseases and disease vectors.

Bacterial ice nucleation proteins (INPs) can cause frost damage to plants by nucleating ice formation at high sub-zero temperatures. Modeling of Pseudomonas borealis INP by AlphaFold suggests that the central domain of 65 tandem sixteen-residue repeats forms a beta-solenoid with arrays of outward-pointing threonines and tyrosines, which may organize water molecules into an ice-like pattern. Here we report that mutating some of these residues in a central segment of P. borealis INP, expressed in Escherichia coli, decreases ice nucleation activity more than the sections deletion. Insertion of a bulky domain has the same effect, indicating that the continuity of the water-organizing repeats is critical for optimal activity. The ~10 C-terminal coils differ from the other 55 coils in being more basic and lacking water-organizing motifs; deletion of this region eliminates INP activity. We show through sequence modifications how arrays of conserved motifs form the large ice-nucleating surface required for potency.

The microbiome of atmospheric dust events has raised increasing interest in the last decade, resulting in numerous studies that characterized the different parameters affecting the composition of the atmospheric microbiome, that is, the aerobiome. However, less is known about the functional profile of the aerobiome and how it compares with other environments. Here, we describe the results of shotgun metagenome analysis conducted on a representative set of particulate matter (PM) samples taken in Israel under dusty and nondusty conditions. We compared the functional profiles of these samples to local metagenomes collected from soils, sea, and leaf surfaces and to PM collected in Saudi Arabia, in order to link between the sampled aerosols and potential sources that contribute to the aerobiome. We found that PM samples collected in Israel most resembled Saudi Arabian dust and Israeli soils in both community composition and functional genes profile. In addition, we found significant differences in the abundances of genes associated with anthropogenic activity. Specifically, the examined dust exhibited a significantly higher abundance of genes associated with the biodegradation of organic contaminants, mostly benzoate and aminobenzoate, compared with all other examined environments. These preliminary results suggest that an anthropogenic impact on the aerobiome composition and functional profile is widespread, and pave the path to understanding the role of dust storms in disseminating microorganisms in various environments, spreading various traits, and affecting humans, livestock, plants, and ecosystem health.

Observation-based and modeling studies have identified the Eastern Mediterranean and Middle East (EMME) region as a prominent climate change hotspot. While several initiatives have addressed the impacts of climate change in parts of the EMME, here we present an updated assessment, covering a wide range of timescales, phenomena and future pathways. Our assessment is based on a revised analysis of recent observations and projections and an extensive overview of the recent scientific literature on the causes and effects of regional climate change. Greenhouse gas emissions in the EMME are growing rapidly, surpassing those of the European Union, hence contributing significantly to climate change. Over the past half-century and especially during recent decades, the EMME has warmed significantly faster than other inhabited regions. At the same time, changes in the hydrological cycle have become evident. The observed recent temperature increase of about 0.45°C per decade is projected to continue, although strong global greenhouse gas emission reductions could moderate this trend. In addition to projected changes in mean climate conditions, we call attention to extreme weather events with potentially disruptive societal impacts. These include the strongly increasing severity and duration of heatwaves, droughts and dust storms, as well as torrential rain events that can trigger flash floods. Our review is complemented by a discussion of atmospheric pollution and land-use change in the region, including urbanization, desertification and forest fires. Finally, we identify sectors that may be critically affected and formulate adaptation and research recommendations toward greater resilience of the EMME region to climate change.

The health effects of exposure to secondary organic aerosols (SOAs) are still limited. Here, we investigated and compared the toxicities of soot particles (SP) coated with β-pinene SOA (SOAβPin-SP) and SP coated with naphthalene SOA (SOANap-SP) in a human bronchial epithelial cell line (BEAS-2B) residing at the airliquid interface. SOAβPin-SP mostly contained oxygenated aliphatic compounds from β-pinene photooxidation, whereas SOANap-SP contained a significant fraction of oxygenated aromatic products under similar conditions. Following exposure, genome-wide transcriptome responses showed an Nrf2 oxidative stress response, particularly for SOANap-SP. Other signaling pathways, such as redox signaling, inflammatory signaling, and the involvement of matrix metalloproteinase, were identified to have a stronger impact following exposure to SOANap-SP. SOANap-SP also induced a stronger genotoxicity response than that of SOAβPin-SP. This study elucidated the mechanisms that govern SOA toxicity and showed that, compared to SOAs derived from a typical biogenic precursor, SOAs from a typical anthropogenic precursor have higher toxicological potency, which was accompanied with the activation of varied cellular mechanisms, such as aryl hydrocarbon receptor. This can be attributed to the difference in chemical composition; specifically, the aromatic compounds in the naphthalene-derived SOA had higher cytotoxic potential than that of the β-pinene-derived SOA.

Microbially-produced ice nucleating proteins (INpro) are unique molecular structures with the highest known catalytic efficiency for ice formation. Airborne microorganisms utilize these proteins to enhance their survival by reducing their atmospheric residence times. INpro also have critical environmental effects including impacts on the atmospheric water cycle, through their role in cloud and precipitation formation, as well as frost damage on crops. INpro are ubiquitously present in the atmosphere where they are emitted from diverse terrestrial and marine environments. Even though bacterial genes encoding INpro have been discovered and sequenced decades ago, the details of how the INpro molecular structure and oligomerization foster their unique ice-nucleation activity remain elusive. Using machine-learning based software AlphaFold 2 and trRosetta, we obtained and analysed the first ab initio structural models of full length and truncated versions of bacterial INpro. The modeling revealed a novel beta-helix structure of the INpro central repeat domain responsible for ice nucleation activity. This domain consists of repeated stacks of two beta strands connected by two sharp turns. One beta-strand is decorated with a TxT amino acid sequence motif and the other strand has an SxL[T/I] motif. The core formed between the stacked beta helix-pairs is unusually polar and very distinct from previous INpro models. Using synchrotron radiation circular dichroism, we validated the β-strand content of the central repeat domain in the model. Combining the structural model with functional studies of purified recombinant INpro, electron microscopy and modeling, we further demonstrate that the formation of dimers and higher-order oligomers is key to INpro activity. Using computational docking of the new INpro model based on rigid-body algorithms we could reproduce a previously proposed homodimer structure of the INpro CRD with an interface along a highly conserved tyrosine ladder and show that the dimer model agrees with our functional data. The parallel dimer structure creates a surface where the TxT motif of one monomer aligns with the SxL[T/I] motif of the other monomer widening the surface that interacts with water molecules and therefore enhancing the ice nucleation activity. This work presents a major advance in understanding the molecular foundation for bacterial ice-nucleation activity.

Delivering medication to the lungs via nebulization of pharmaceuticals is a noninvasive and efficient therapy route, particularly for respiratory diseases. The recent worldwide severe acute respiratory syndrome coronavirus type 2 (SARS-CoV-2) pandemic urges the development of such therapies as an effective alternative to vaccines. The main difficulties in using inhalation therapy are the development of effective medicine and methods to stabilize the biological molecules and transfer them to the lungs efficiently following nebulization. We have developed a high-affinity angiotensin-converting enzyme 2 (ACE2) receptor-binding domain (RBD-62) that can be used as a medication to inhibit infection with SARS-CoV-2 and its variants. In this study, we established a nebulization protocol for drug delivery by inhalation using two commercial vibrating mesh (VM) nebulizers (Aerogen Solo and PARI eFlow) that generate similar mist size distribution in a size range that allows efficient deposition in the small respiratory airway. In a series of experiments, we show the high activity of RBD-62, interferon-α2 (IFN-α2), and other proteins following nebulization. The addition of gelatin significantly stabilizes the proteins and enhances the fractions of active proteins after nebulization, minimizing the medication dosage. Furthermore, hamster inhalation experiments verified the feasibility of the protocol in pulmonary drug delivery. In short, the gelatin-modified RBD-62 formulation in coordination with VM nebulizer can be used as a therapy to cure SARS-CoV-2.

The diversity of microbes and their transmission between ocean and atmosphere are poorly understood despite the implications for microbial global dispersion and biogeochemical processes. Here, we survey the genetic diversity of airborne and surface ocean bacterial communities sampled during springtime transects across the northwest Pacific and subtropical north Atlantic as part of the Tara Pacific Expedition. We find that microbial community composition is more variable in the atmosphere than in the surface ocean. Bacterial communities were more similar between the two surface oceans than between the ocean and the overlying atmosphere. Likewise, Pacific and Atlantic atmospheric microbial communities were more similar to each other than to those in the ocean beneath. Atmospheric community composition over the Atlantic was dominated by terrestrial and specifically, dust-associated bacteria, whereas over the Pacific there was a higher prevalence and differential abundance of marine bacteria. Our findings highlight regional differences in long-range microbial exchange and dispersal between land, ocean, and atmosphere.

This study investigates selected secondary atmospheric responses to the widely reported emission change attributed to COVID19 lockdowns in the highly polluted IndoGangetic Plain (IGP) using groundbased measurements of trace gases and particulate matter. We used a chemical boxmodel to show that production of nighttime oxidant, NO3, was affected mainly by emission decrease (average nighttime production rates 1.2, 0.8 and 1.5 ppbv hr−1 before, during and relaxation of lockdown restrictions, respectively), while NO3 sinks were sensitive to both emission reduction and seasonal variations. We have also shown that the maximum potential mixing ratio of nitryl chloride, a photolytic chlorine radical source which has not been previously considered in the IGP, is as high as 5.5 ppbv at this inland site, resulting from strong nitrate radical production and a potentially large particulate chloride mass. This analysis suggests that air quality measurement campaigns and modeling explicitly consider heterogeneous nitrogen oxide and halogen chemistry.
Plain Language Summary
The IndoGangetic Plain (IGP) is one of the most polluted regions on earth, with poor air quality affecting the majority of the Indian population. The atmospheric chemistry that transforms major regional emissions into harmful secondary pollutants is complex. Here, we quantify, for the first time, several important oxidative processes and show the potential for substantial oxidation of biogenic volatile organic compounds and the production of chlorine through unconventional chemistry in the IGP. We further show how these chemical cycles varied due to the emission reductions as a result of COVID19 lockdown, findings that will serve to define their sensitivity to future emission changes in the region.
Key Points
Atmospheric response in the IndoGangetic Plain varied according to seasonal changes and emissions reductions due to COVID19 lockdown
NO3 production was mainly affected by emission changes, while NO3 sinks were sensitive to both emissions and seasonal changes
Nitryl chloride, a photolytic chlorine radical source not previously considered in the inland IndoGangetic Plain, may be up to 5.5 ppbv

Background:Secondary organic aerosols (SOAs) formed from anthropogenic or biogenic gaseous precursors in the atmosphere substantially contribute to the ambient fine particulate matter [PM ≤2.5μm in aerodynamic diameter (PM2.5)] burden, which has been associated with adverse human health effects. However, there is only limited evidence on their differential toxicological impact.Objectives:We aimed to discriminate toxicological effects of aerosols generated by atmospheric aging on combustion soot particles (SPs) of gaseous biogenic (β-pinene) or anthropogenic (naphthalene) precursors in two different lung cell models exposed at the airliquid interface (ALI).Methods:Mono- or cocultures of lung epithelial cells (A549) and endothelial cells (EA.hy926) were exposed at the ALI for 4 h to different aerosol concentrations of a photochemically aged mixture of primary combustion SP and β-pinene (SOAβPIN-SP) or naphthalene (SOANAP-SP). The internally mixed soot/SOA particles were comprehensively characterized in terms of their physical and chemical properties. We conducted toxicity tests to determine cytotoxicity, intracellular oxidative stress, primary and secondary genotoxicity, as well as inflammatory and angiogenic effects.Results:We observed considerable toxicity-related outcomes in cells treated with either SOA type. Greater adverse effects were measured for SOANAP-SP compared with SOAβPIN-SP in both cell models, whereas the nano-sized soot cores alone showed only minor effects. At the functional level, we found that SOANAP-SP augmented the secretion of malondialdehyde and interleukin-8 and may have induced the activation of endothelial cells in the coculture system. This activation was confirmed by comet assay, suggesting secondary genotoxicity and greater angiogenic potential. Chemical characterization of PM revealed distinct qualitative differences in the composition of the two secondary aerosol types.Discussion:In this study using A549 and EA.hy926 cells exposed at ALI, SOA compounds had greater toxicity than primary SPs. Photochemical aging of naphthalene was associated with the formation of more oxidized, more aromatic SOAs with a higher oxidative potential and toxicity compared with β-pinene. Thus, we conclude that the influence of atmospheric chemistry on the chemical PM composition plays a crucial role for the adverse health outcome of emissions.

Sea spray aerosol (SSA) formation have a major role in the climate system, but measurements at a global-scale of this micro-scale process are highly challenging. We measured high-resolution temporal patterns of SSA number concentration over the Atlantic Ocean, Caribbean Sea, and the Pacific Ocean covering over 42,000 km. We discovered a ubiquitous 24-hour rhythm to the SSA number concentration, with concentrations increasing after sunrise, remaining higher during the day, and returning to predawn values after sunset. The presence of dominating continental aerosol transport can mask the SSA cycle. We did not find significant links between the diel cycle of SSA number concentration and diel variations of surface winds, atmospheric physical properties, radiation, pollution, nor oceanic physical properties. However, the daily mean sea surface temperature positively correlated with the magnitude of the day-to-nighttime increase in SSA concentration. Parallel diel patterns in particle sizes were also detected in near-surface waters attributed to variations in the size of particles smaller than ~1 µm. These variations may point to microbial day-tonight modulation of bubble-bursting dynamics as a possible cause of the SSA cycle.

The atmosphere plays an important role in transporting microorganisms on a global scale, yet the processes affecting the composition of the airborne microbiome, the aerobiome, are not fully outlined. Here we present the community compositions of bacteria and fungi obtained by DNA amplicon-sequencing of aerosol samples collected in a size-resolved manner during nine consecutive days in central Israel. The campaign captured dust events originating from the Sahara and the Arabian deserts, as well as days without dust (\u201cclear days\u201d). We found that the source of the aerosol was the main variable contributing to the composition of both fungal and bacterial communities. Significant differences were also observed between communities representing particles of different sizes. We show evidence for the significant transport of bacteria as cell-aggregates and/or via bacterial attachment to particles during dust events. Our findings further point to the mixing of local and transported bacterial communities, observed mostly in particles smaller than 0.6 μm in diameter, representing bacterial single cells. Fungal communities showed the highest dependence on the source of the aerosols, along with significant daily variability, and without significant mixing between sources, possibly due to their larger aerodynamic size and shorter atmospheric residence times. These results, obtained under highly varied atmospheric conditions, provide significant assurances to previously raised hypotheses and could set the course for future studies on aerobiome composition.

Accurate Rayleigh scattering and absorption cross sections of atmospheric gases are essential for understanding the propagation of electromagnetic radiation in planetary atmospheres. Accurate extinction cross sections are also essential for calibrating high-finesse optical cavities and differential optical absorption spectroscopy and for accurate remote sensing. In this study, we measured the scattering and absorption cross sections of carbon dioxide, nitrous oxide, sulfur hexafluoride, oxygen, and methane in the continuous wavelength range of 307-725nm using broadband cavity-enhanced spectroscopy (BBCES). The experimentally derived Rayleigh scattering cross sections for CO2, N2O, SF6, O2, and CH4 agree with refractive index-based calculations, with a difference of (0.4±1.2)%, (-0.6±1.1)%, (0.9±1.4)%, (2.8±1.2)%, and (0.9±2.2)%, respectively. The O2-O2 collision-induced absorption and absorption by methane are obtained with high precision at the 0.8nm resolution of our BBCES instrument in the 307-725nm wavelength range. New dispersion relations for N2O, SF6, and CH4 were derived using data in the UV-vis wavelength range. This study provides dispersion relations for refractive indices, n-based Rayleigh scattering cross sections, and absorption cross sections based on more continuous and more extended wavelength ranges than available in the current literature.

In 2018, 3.8 million premature deaths were attributed to exposure to biomass burning nanoparticles from wood combustion. The objective of this study was to investigate and compare the toxic effect of wood-combustion-related biomass burning nanoparticles from three different combustion stages (i.e., flaming, smoldering, and pyrolysis) on alveolar lung cells, by studying cell proliferation, and structural and behavioral parameters. A549 lung epithelial cells were treated with 31, 62, 125, 250, and 500 µg/mL of water-soluble particulate pollutants from wood burning, and measured by means of real-time cell analysis, cell imaging, and phase imaging microscopy. At low concentrations (31 and 62 µg/mL), all three types of wood burning samples exhibited no toxicity. At 125 µg/mL, they caused decreased cell proliferation compared to the control. Exposure to higher concentrations (250 and 500 µg/mL) killed the cells. Cell physical parameters (area, optical volume, eccentricity, perimeter, and optical thickness) and behavioral parameters (migration, motility, and motility speed) did not change in response to exposure to wood burning materials up to a concentration of 125 µg/mL. Exposure to higher concentrations (250 and 500 µg/mL) changed cell perimeter, optical thickness for smoldering and flaming particles, and led to decreased migration, motility, and motility speed of cells. In conclusion, all three of the combustion water-soluble organic pollutants were identified as equally toxic by real-time cell analysis (RTCA) results. The parameters describing cell structure suggest that pyrolysis particles were slightly less toxic than others.

The composition of organic aerosol has a pivotal influence on aerosol properties such as toxicity and cloud droplet formation capability, which could affect both climate and air quality. However, a comprehensive and fundamental understanding of the chemical and physical processes that occur in nanometer-sized atmospheric particles remains a challenge that severely limits the quantification and predictive capabilities of aerosol formation pathways. Here, we investigated the effects of a fundamental and hitherto unconsidered physical property of nanoparticles-the Laplace pressure. By studying the reaction of glyoxal with ammonium sulfate, both ubiquitous and important atmospheric constituents, we show that high pressure can significantly affect the chemical processes that occur in atmospheric ultrafine particles (i.e., particles

Nitrated aromatic compounds (NACs) are toxic and allergenic airborne pollutants from both primary emissions and atmospheric reactions of aromatics with NO₂. A comprehensive investigation of NACs is challenging given their low ambient levels. By applying gas chromatography and tandem mass spectrometry coupled with an electron capture negative ionization source, this study achieved a comprehensive high-throughput and standard-independent detection of nonpolar NACs in fine particulate matter (PM_2.5) sampled over 2 years in Beijing, China. Overall, 1047 NACs were detected, among which, the elemental composition of 128 species were derived using time-of-flight mass spectrometry, and 25 species were confirmed using reference standards. In addition to mono-nitrated polycyclic aromatic hydrocarbons (NPAHs), di-nitrated PAHs and alkylated and oxygenated NPAHs were found. Cluster analysis suggested these compounds were derived from various sources particularly atmospheric reactions. We found that the annual levels of primary NPAHs decreased by 46.354.8% from 20122013 to 20162018, though the secondary species did not change significantly after normalization by PM_2.5. These results were validated by diagnostic ratios, which indicated an increasing contribution from the secondary formation including nighttime reactions. This novel method for NACs detection may provide valuable insights into the formation mechanisms of NACs in the atmosphere.

Asian dust is an important source of atmospheric ice-nucleating particles (INPs). However, the freezing activity of airborne Asian dust, especially its sensitivity to particle size, is poorly understood. In this study we report the first INP measurement of size-resolved airborne mineral dust collected during East Asian dust events. The measured total INP concentrations in the immersion mode ranged from 10(-2) to 10(2) L-1 in dust events at temperatures between 25 and 5 degrees C. The average contributions of heat-sensitive INPs at three temperatures, -10, 15, and 20 degrees C, were 81 +/- 12 %, 70 +/- 15 %, and 38 +/- 21 %, respectively, suggesting that proteinaceous biological materials have a substantial effect on the ice nucleation properties of Asian airborne mineral dust at high temperatures. The dust particles which originated from China's northwest deserts are more efficient INPs compared to those from northern regions. In general, there was no significant difference in the ice nucleation properties between East Asian dust particles and other regions in the world. An explicit size dependence of both INP concentration and surface ice-active-site density was observed. The nucleation efficiency of dust particles increased with increasing particle size, while the INP concentration first increased rapidly and then leveled, due to the significant decrease in the number concentration of larger particles. A new set of parameterizations for INP activity based on size-resolved nucleation properties of Asian mineral dust particles were developed over an extended temperature range (35 to 6 degrees C). These size-dependent parameterizations require only particle size distribution as input and can be easily applied in models.

Atmospheric iodine chemistry can significantly affect the atmospheric oxidation capacity in certain regions. In such processes, particle-phase organic iodine compounds (OICs) are key reservoir species in their loss processes. However, their presence and formation mechanism remain unclear, especially in continental regions. Using gas chromatography and time-of-flight mass spectrometry coupled with both electron capture negative ionization and electron impact sources, this study systematically identified unknown OICs in 2-year samples of ambient fine particulate matter (PM2.5) collected in Beijing, an inland city. We determined the molecular structure of 37 unknown OICs, among which six species were confirmed by reference standards. The higher concentrations for ∑37OICs (median: 280 pg m-3; range: 49.0-770 pg m-3) measured in the heating season indicate intensive coal combustion sources of atmospheric iodine. 1-Iodo-2-naphthol and 4-iodoresorcinol are the most abundant species mainly from primary combustion emission and secondary formation, respectively. The detection of 2- and 4-iodoresorcinols, but not of iodine-substituted catechol/hydroquinone or 5-iodoresorcinol, suggests that they are formed via the electrophilic substitution of resorcinol by hypoiodous acid, a product of the reaction of iodine with ozone. This study reports isomeric information on OICs in continental urban PM2.5 and provides valuable evidence on the formation mechanism of OICs in ambient particles.

Anthropogenic pollution from marine microplastic particles is a growing concern, both as a source of toxic compounds, and because they can transport pathogens and other pollutants. Airborne microplastic particles were previously observed over terrestrial and coastal locations, but not in the remote ocean. Here, we collected ambient aerosol samples in the North Atlantic Ocean, including the remote marine atmosphere, during the Tara Pacific expedition in May-June 2016, and chemically characterized them using micro-Raman spectroscopy. We detected a range of airborne microplastics, including polystyrene, polyethylene, polypropylene, and poly-silicone compounds. Polyethylene and polypropylene were also found in seawater, suggesting local production of airborne microplastic particles. Terminal velocity estimations and back trajectory analysis support this conclusion. For technical reasons, only particles larger than 5µm, at the upper end of a typical marine atmospheric size distribution, were analyzed, suggesting that our analyses underestimate the presence of airborne microplastic particles in the remote marine atmosphere.

The Negev Desert in Israel is susceptible to frequent atmospheric events of high dust loading which have been linked with negative human health outcomes, including cardiovascular and respiratory distress. Previous research suggests that the highest levels of dust over the region occur during an atmospheric pattern with a cyclone situated over the eastern Mediterranean. This Cyprus Low can bring unsettled weather and strong westerly winds over the Negev. However, while the overall pattern associated with dust events in the Negev Desert is generally well-understood, it remains unclear why days with seemingly similar weather patterns result in different levels of atmospheric dust. Thus, the goal of this study is to better differentiate the atmospheric patterns during dust events over the Negev. Using PM10 data collected in Beer Sheva, Israel, from 2000 to 2015 in concert with 72-h HYSPLIT back trajectories at three different height levels (surface, 200 m, 500 m), we examine the source region, trajectory groups using a K-Means clustering procedure, and overall synoptic pattern during dust events. Further, we use sea-level pressure data across the region to determine how cyclone strength and location impact dust events in Beer Sheva. We find that the highest levels of atmospheric dust in the Negev are associated with the Cyprus Low pattern, and air traversing Libya seems to play an especially important role, likely due to the countrys arid surface cover. Cyclone strength is also a critical factor, as lower sea-level pressure results in more severe dust events. A better understanding of the atmospheric features associated with dust events over the Negev Desert will hopefully aid in forecasting these occurrences across the region.

The composition of atmospheric aerosols is dynamic and influenced by their emission sources, organic and inorganic composition, transport pathways, chemical and physical processes, microorganisms' content and more. Characterization of such factors can improve the ability to evaluate air quality and health risks under different atmospheric scenarios. Here we investigate the microbial composition of the atmospheric particulate matter (

The possible use of organic particle emissions as indicators of smoldering fires at low temperatures (early stages,

Particulate matter (PM), an important component of air pollution, induces significant adverse health effects. Many of the observed health effects caused by inhaled PM are associated with oxidative stress and inflammation. This association has been linked in particular to the particles chemical components, especially the inorganic/metal and the organic/polycyclic aromatic hydrocarbon (PAH) fractions, and their ability to generate reactive oxygen species (ROS) in biological systems. The transcription factor NF-E2 nuclear factor erythroid-related factor 2 (Nrf2) is activated by redox imbalance and regulates the expression of phase II detoxifying enzymes. Nrf2 plays a key role in preventing PM-induced toxicity by protecting against oxidative damage and inflammation. This review focuses on specific PM fractions, particularly the dissolved metals and PAH fractions, and their roles in inducing oxidative stress and inflammation in cell and animal models with respect to Nrf2 and mitochondria.

Organic nitrates (ONs) are an important component of secondary organic aerosols that play significant roles in atmospheric chemical processes such as ozone formation and as a reservoir of nitrogen oxides (NOx). However, hindered by the availability of analytical techniques, characteristics of ON molecules remain unclear in regions influenced by anthropogenic volatile organic compounds (VOCs) and pollution. In this study, we achieved isomeric identification of particle-phase ONs in such regions. Using gas chromatography and time-of-flight mass spectrometry with an electron capture negative ionization source, we established a systematic procedure for screening unknown ONs in fine particulate matter (PM) collected in Beijing based primarily on the characteristic fragment ions of NO2 and [MNO2]−/[MNO2H2]−. We found 78 ON candidates, 12 of which were confirmed using synthesized standards. Seventy-three of these detected ONs might originate from anthropogenic VOC precursors especially alkenes. Significantly, we observed two isomers generated from straight-chain 1-alkenes, namely, 2-hydroxy-1-nitrate and 1-hydroxy-2-nitrate. The signal ratios of the two isomers suggested that these hydroxy nitrates are mainly produced photochemically rather than through nighttime reactions. This study provides a promising method for identifying ONs in atmospheric PM and elucidating their formation pathways.

Ice-binding proteins (IBPs) are found in many organisms, such as fish and hexapods, plants, and bacteria that need to cope with low temperatures. Ice nucleation and thermal hysteresis are two attributes of IBPs. While ice nucleation is promoted by large proteins, known as ice nucleating proteins, the smaller IBPs, referred to as antifreeze proteins (AFPs), inhibit the growth of ice crystals by up to several degrees below the melting point, resulting in a thermal hysteresis (TH) gap between melting and ice growth. Recently, we showed that the nucleation capacity of two types of IBPs corresponds to their size, in agreement with classical nucleation theory. Here, we expand this finding to additional IBPs that we isolated from snow fleas (the arthropod Collembola), collected in northern Israel. Chemical analyses using circular dichroism and Fourier-transform infrared spectroscopy data suggest that these IBPs have a similar structure to a previously reported snow flea antifreeze protein. Further experiments reveal that the ice-shell purified proteins have hyperactive antifreeze properties, as determined by nanoliter osmometry, and also exhibit low ice-nucleation activity in accordance with their size.

The prediction of cloud ice formation in climate models remains a challenge, partly due to the complexity of ice-related processes. Mineral dust is a prominent aerosol in the troposphere and is an important contributor to ice nucleation in mixed-phase clouds, as dust can initiate ice heterogeneously at relatively low supercooling conditions. We characterized the ice nucleation properties of size-segregated mineral dust sampled during dust events in the eastern Mediterranean. The sampling site allowed us to compare the properties of airborne dust from several sources with diverse mineralogy that passed over different atmospheric paths. We focused on particles with six size classes determined by the Micro-Orifice Uniform Deposit Impactor (MOUDI) cutoff sizes: 5.6, 3.2, 1.8, 1.0, 0.6 and 0.3 μm. Ice nucleation experiments were conducted in the Weizmann Supercooled Droplets Observation on a Microarray (WISDOM) setup, whereby the particles are immersed in nanoliter droplets using a microfluidics technique. We observed that the activity of airborne particles depended on their size class; supermicron and submicron particles had different activities, possibly due to different composition. The concentrations of ice-nucleating particles and the density of active sites (n_s) increased with the particle size and particle concentration. The supermicron particles in different dust events showed similar activity, which may indicate that freezing was dominated by common mineralogical components. Combining recent data of airborne mineral dust, we show that current predictions, which are based on surface-sampled natural dust or standard mineral dust, overestimate the activity of airborne dust, especially for the submicron class. Therefore, we suggest including information on particle size in order to increase the accuracy of ice formation modeling and thus weather and climate predictions.

Polycyclic aromatic hydrocarbons (PAHs) are toxic organic trace components in atmospheric aerosols that have impacts on climate and human health. They are bound to airborne particles and transported over long distances. Observations of their distribution, transport pathways, and degradation are crucial for risk assessment and mitigation. Such estimates would benefit from online detection of PAHs along with analysis of the carrying particles to identify the source. Typically, laser desorption/ionization (LDI) in a bipolar mass spectrometer reveals the inorganic constituents and provides limited molecular information. In contrast, two-step ionization approaches produce detailed PAH mass spectra from individual particles but without the source-specific inorganic composition. Here we report a new technique that yields the single-particle PAH composition along with both positive and negative inorganic ions via LDI. Thus, the complete particle characterization and source apportionment from conventional bipolar LDI-analysis becomes possible, combined with a detailed PAH spectrum for the same particle. The key idea of the method is spatiotemporal matching of the ionization laser pulse to the transient component distribution in the particle plume after laser desorption. The technique is robust and field-deployable with only slightly higher costs and complexity compared to two-step approaches. We demonstrate its capability to reveal the PAH-distribution on different particle types in combustion aerosols and ambient air.

Criegee intermediates (CI) from ozonolysis of biogenic volatile organic compounds (BVOC) have been suggested to be important atmospheric oxidants. However, due to their low atmospheric concentrations, possible high reactivity with water vapor, and unconstrained thermal unimolecular decay rates, their impact on atmospheric oxidation of trace species such as SO2 and NO2 remains uncertain. In this study, we investigate the formation of secondary sulfate aerosols (SSA) in nocturnal power plant plumes in the Southeastern US. These plumes have large mixing ratios of SO2 and NO that make reaction with CI competitive with other pathways, such as thermal unimolecular decay and water vapor reaction. The background into which these plumes are emitted has high levels of BVOC and O-3, whose reaction produces a large source of CI. Observed nighttime power plant plume intercepts had measurable sulfate aerosol, ranging from 0.7-1.2% of the total plume sulfur (SO2 + sulfate) on a molar basis. In the absence of photochemical OH oxidation, these observed sulfate levels can be compared to calculated CI + SO2 production. We present a plume dispersion model that simulates the chemical evolution of these nighttime plumes and compare the results to observed sulfate aerosol. Thermal unimolecular decay of CI is the largest uncertainty. In the absence of thermal unimolecular CI decay, CI reactions with SO2 in the dark account for up to 41% of the total observed sulfate aerosol, with the remainder attributable to reaction of SO2 with secondary OH and direct emission. Conversely, with a thermal unimolecular decay rate for all CI of 200 s(-1), equivalent to the highest measured rate, CI reactions with SO2 accounted for only S.7% of the total SSA. A second uncertainty is the rate coefficients for larger, and as yet unmeasured, CI species. The most important CI in the modeled scenario is the C, compound, CH2OO, which accounts for up to 50% of the CIs produced from isoprene. C-4 CIs may contribute up to 40% of the CIs produced and are expected to have substantially slower thermal unimolecular decay rates and water vapor reaction rate coefficients. Therefore, the model results may be a lower limit to the CI contribution to SSA. Calculated nighttime (10 h) total SO2 oxidation was 1.8%, of which 1.1% was due to CI + SO2, and the remainder to secondary OH + SO2. This compares to daytime (14 h) SO2 oxidation rates of 4% due to photochemical OH + SO2 reaction.

Several types of natural molecules interact specifically with ice crystals. Small antifreeze proteins (AFPs) adsorb to particular facets of ice crystals, thus inhibiting their growth, whereas larger ice-nucleating proteins (INPs) can trigger the formation of new ice crystals at temperatures much higher than the homogeneous ice nucleation temperature of pure water. It has been proposed that both types of proteins interact similarly with ice and that, in principle, they may be able to exhibit both functions. Here we investigated two naturally occurring antifreeze proteins, one from fish, type-III AFP, and one from beetles, TmAFP. We show that in addition to ice growth inhibition, both can also trigger ice nucleation above the homogeneous freezing temperature, providing unambiguous experimental proof for their contrasting behavior. Our analysis suggests that the predominant difference between AFPs and INPs is their molecular size, which is a very good predictor of their ice nucleation temperature.

The second phase of the Fifth International Ice Nucleation Workshop (FIN-02) involved the gathering of a large number of researchers at the Karlsruhe Institute of Technology's Aerosol Interactions and Dynamics of the Atmosphere (AIDA) facility to promote characterization and understanding of ice nucleation measurements made by a variety of methods used worldwide. Compared to the previous workshop in 2007, participation was doubled, reflecting a vibrant research area. Experimental methods involved sampling of aerosol particles by direct processing ice nucleation measuring systems from the same volume of air in separate experiments using different ice nucleating particle (INP) types, and collections of aerosol particle samples onto filters or into liquid for sharing amongst measurement techniques that post-process these samples. In this manner, any errors introduced by differences in generation methods when samples are shared across laboratories were mitigated. Furthermore, as much as possible, aerosol particle size distribution was controlled so that the size limitations of different methods were minimized. The results presented here use data from the workshop to assess the comparability of immersion freezing measurement methods activating INPs in bulk suspensions, methods that activate INPs in condensation and/or immersion freezing modes as single particles on a substrate, continuous flow diffusion chambers (CFDCs) directly sampling and processing particles well above water saturation to maximize immersion and subsequent freezing of aerosol particles, and expansion cloud chamber simulations in which liquid cloud droplets were first activated on aerosol particles prior to freezing. The AIDA expansion chamber measurements are expected to be the closest representation to INP activation in atmospheric cloud parcels in these comparisons, due to exposing particles freely to adiabatic cooling.The different particle types used as INPs included the minerals illite NX and potassium feldspar (K-feldspar), two natural soil dusts representative of arable sandy loam (Argentina) and highly erodible sandy dryland (Tunisia) soils, respectively, and a bacterial INP (Snomax (R)). Considered together, the agreement among post-processed immersion freezing measurements of the numbers and fractions of particles active at different temperatures following bulk collection of particles into liquid was excellent, with possible temperature uncertainties inferred to be a key factor in determining INP uncertainties. Collection onto filters for rinsing versus directly into liquid in impingers made little difference. For methods that activated collected single particles on a substrate at a controlled humidity at or above water saturation, agreement with immersion freezing methods was good in most cases, but was biased low in a few others for reasons that have not been resolved, but could relate to water vapor competition effects. Amongst CFDC-style instruments, various factors requiring (variable) higher supersaturations to achieve equivalent immersion freezing activation dominate the uncertainty between these measurements, and for comparison with bulk immersion freezing methods. When operated above water saturation to include assessment of immersion freezing, CFDC measurements often measured at or above the upper bound of immersion freezing device measurements, but often underestimated INP concentration in comparison to an immersion freezing method that first activates all particles into liquid droplets prior to cooling (the PIMCA-PINC device, or Portable Immersion Mode Cooling chAmber-Portable Ice Nucleation Chamber), and typically slightly underestimated INP number concentrations in comparison to cloud parcel expansions in the AIDA chamber; this can be largely mitigated when it is possible to raise the relative humidity to sufficiently high values in the CFDCs, although this is not always possible operationally.Correspondence of measurements of INPs among direct sampling and post-processing systems varied depending on the INP type. Agreement was best for Snomax (R) particles in the temperature regime colder than 10 degrees C, where their ice nucleation activity is nearly maximized and changes very little with temperature. At temperatures warmer than -10 degrees C, Snomax (R) INP measurements (all via freezing of suspensions) demonstrated discrepancies consistent with previous reports of the instability of its protein aggregates that appear to make it less suitable as a calibration INP at these temperatures. For Argentinian soil dust particles, there was excellent agreement across all measurement methods; measures ranged within 1 order of magnitude for INP number concentrations, active fractions and calculated active site densities over a 25 to 30 degrees C range and 5 to 8 orders of corresponding magnitude change in number concentrations. This was also the case for all temperatures warmer than -25 degrees C in Tunisian dust experiments. In contrast, discrepancies in measurements of INP concentrations or active site densities that exceeded 2 orders of magnitude across a broad range of temperature measurements found at temperatures warmer than- 25 degrees C in a previous study were replicated for illite NX. Discrepancies also exceeded 2 orders of magnitude at temperatures of -20 to -25 degrees C for potassium feldspar (K-feldspar), but these coincided with the range of temperatures at which INP concentrations increase rapidly at approximately an order of magnitude per 2 degrees C cooling for K-feldspar.These few discrepancies did not outweigh the overall positive outcomes of the workshop activity, nor the future utility of this data set or future similar efforts for resolving remaining measurement issues. Measurements of the same materials were repeatable over the time of the workshop and demonstrated strong consistency with prior studies, as reflected by agreement of data broadly with parameterizations of different specific or general (e.g., soil dust) aerosol types. The divergent measurements of the INP activity of illite NX by direct versus post-processing methods were not repeated for other particle types, and the Snomax (R) data demonstrated that, at least for a biological INP type, there is no expected measurement bias between bulk collection and direct immediately processed freezing methods to as warm as -10 degrees C. Since particle size ranges were limited for this workshop, it can be expected that for atmospheric populations of INPs, measurement discrepancies will appear due to the different capabilities of methods for sampling the full aerosol size distribution, or due to limitations on achieving sufficient water supersaturations to fully capture immersion freezing in direct processing instruments. Overall, this workshop presents an improved picture of present capabilities for measuring INPs than in past workshops, and provides direction toward addressing remaining measurement issues.

Exposure to ambient fine particulate matter (PM
_2.5) is a leading risk factor for the global burden of disease. However, uncertainty remains about PM
_2.5 sources. We use a global chemical transport model (GEOS-Chem) simulation for 2014, constrained by satellite-based estimates of PM
_2.5 to interpret globally dispersed PM
_2.5 mass and composition measurements from the ground-based surface particulate matter network (SPARTAN). Measured site mean PM
_2.5 composition varies substantially for secondary inorganic aerosols (2.4-19.7 μg/m
³), mineral dust (1.9-14.7 μg/m
³), residual/organic matter (2.1-40.2 μg/m
³), and black carbon (1.0-7.3 μg/m
³). Interpretation of these measurements with the GEOS-Chem model yields insight into sources affecting each site. Globally, combustion sectors such as residential energy use (7.9 μg/m
³), industry (6.5 μg/m
³), and power generation (5.6 μg/m
³) are leading sources of outdoor global population-weighted PM
_2.5 concentrations. Global population-weighted organic mass is driven by the residential energy sector (64%) whereas population-weighted secondary inorganic concentrations arise primarily from industry (33%) and power generation (32%). Simulation-measurement biases for ammonium nitrate and dust identify uncertainty in agricultural and crustal sources. Interpretation of initial PM
_2.5 mass and composition measurements from SPARTAN with the GEOS-Chem model constrained by satellite-based PM
_2.5 provides insight into sources and processes that influence the global spatial variation in PM
_2.5 composition.

Sea spray aerosols (SSA), have a profound effect on the climate; however, the contribution of oceanic microbial activity to SSA is not fully established. We assessed aerosolization of the calcite units (coccoliths) that compose the exoskeleton of the cosmopolitan bloom-forming coccolithophore, Emiliania huxleyi. Airborne coccolith emission occurs in steady-state conditions and increases by an order of magnitude during E. huxleyi infection by E. huxleyi virus (EhV). Airborne to seawater coccolith ratio is 1:10⁸, providing estimation of airborne concentrations from seawater concentrations. The coccoliths' unique aerodynamic structure yields a characteristic settling velocity of ∼0.01 cm s^-1, ∼25 times slower than average sea salt particles, resulting in coccolith fraction enrichment in the air. The calculated enrichment was established experimentally, indicating that coccoliths may be key contributors to coarse mode SSA surface area, comparable with sea salt aerosols. This study suggests a coupling between key oceanic microbial interactions and fundamental atmospheric processes like SSA formation.

Atmospheric photooxidation of isoprene forms isoprene epoxydiols (IEPOX) and hydroxymethel-methyl-α-lactone (HMML) via hydroperoxyl radical (HO
₂) channel and NO/NO
₂ channel, respectively. Reactive uptake of these epoxides onto particles produces isoprene secondary organic aerosols (iSOA). Currently, there is little information regarding these two epoxides during iSOA formation in polluted regions. In this study, iSOA tracers from IEPOX and HMML were measured from summer to fall in the heavily polluted Pearl River Delta (PRD) region. The total concentration of the iSOA tracers ranged from 5.77 to 466 ng m
⁻³. Isoprene SOA tracers correlated well with sulfate (p 22 °C) suppresses the production of HMML, likely as a result of fast decomposition of HMML's precursor under high temperatures. Thus, the HMML-derived tracers had lower levels than the IEPOX-derived SOA tracers during the whole campaign. The ratios of the IEPOX-derived tracers to the HMML-derived SOA tracers in summer were ~3 times higher than those in fall. This seasonal trend may be explained by the relative high isoprene/NO
_x ratio, temperature, and fast heterogeneous reaction of IEPOX in summer. Our study shows that in highly polluted regions like PRD, reduction in SO
₂ emission can significantly reduce iSOA formation.

Exposure to air pollution can induce oxidative stress, inflammation and adverse health effects. To understand how seasonal and chemical variations drive health impacts, we investigated indications for oxidative stress and inflammation in mice exposed to water and organic extracts from urban fine particles/PM_2.5 (particles with aerodynamic diameter ≤ 2.5 μm) collected in Beijing, China. Higher levels of pollution components were detected in heating season (HS, winter and part of spring) PM_2.5 than in the non-heating season (NHS, summer and part of spring and autumn) PM_2.5. HS samples were high in metals for the water extraction and high in polycyclic aromatic hydrocarbons (PAHs) for the organic extraction compared to their controls. An increased inflammatory response was detected in the lung and liver following exposure to the organic extracts compared to the water extracts, and mostly in the HS PM_2.5. While reduced antioxidant response was observed in the lung, it was activated in the liver, again, more in the HS extracts. Nrf2 transcription factor, a master regulator of stress response that controls the basal oxidative capacity and induces the expression of antioxidant response, and its related genes were induced. In the liver, elevated levels of lipid peroxidation adducts were measured, correlated with histologic analysis that revealed morphologic features of cell damage and proliferation, indicating oxidative and toxic damage. In addition, expression of genes related to detoxification of PAHs was observed. Altogether, the study suggests that the acute effects of PM_2.5 can vary seasonally with stronger health effects in the HS than in the NHS in Beijing, China and that some secondary organs may be susceptible for the exposure damage. Specifically, the liver is a potential organ influenced by exposure to organic components such as PAHs from coal or biomass burning and heating.

The wavelength-dependence of the complex refractive indices (RI) in the visible spectral range of secondary organic aerosols (SOA) are rarely studied, and the evolution of the RI with atmospheric aging is largely unknown. In this study, we applied a novel white light-broadband cavity enhanced spectroscopy to measure the changes in the RI (400-650 nm) of β-pinene and p-xylene SOA produced and aged in an oxidation flow reactor, simulating daytime aging under NO_x-free conditions. It was found that these SOA are not absorbing in the visible range, and that the real part of the RI, n, shows a slight spectral dependence in the visible range. With increased OH exposure, n first increased and then decreased, possibly due to an increase in aerosol density and chemical mean polarizability for SOA produced at low OH exposures, and a decrease in chemical mean polarizability for SOA produced at high OH exposures, respectively. A simple radiative forcing calculation suggests that atmospheric aging can introduce more than 40% uncertainty due to the changes in the RI for aged SOA.

Lag Ba'Omer, a nationwide bonfire festival in Israel, was chosen as a case study to investigate the influence of a major biomass burning event on the light absorption properties of atmospheric brown carbon (BrC). The chemical composition and optical properties of BrC chromophores were investigated using a high performance liquid chromatography (HPLC) platform coupled to photo diode array (PDA) and high resolution mass spectrometry (HRMS) detectors. Substantial increase of BrC light absorption coefficient was observed during the night-long biomass burning event. Most chromophores observed during the event were attributed to nitroaromatic compounds (NAC), comprising 28 elemental formulas of at least 63 structural isomers. The NAC, in combination, accounted for 50-80% of the total visible light absorption (>400 nm) by solvent extractable BrC. The results highlight that NAC, in particular nitrophenols, are important light absorption contributors of biomass burning organic aerosol (BBOA), suggesting that night time chemistry of NO₃ and N₂O₅ with particles may play a significant role in atmospheric transformations of BrC. Nitrophenols and related compounds were especially important chromophores of BBOA. The absorption spectra of the BrC chromophores are influenced by the extraction solvent and solution pH, implying that the aerosol acidity is an important factor controlling the light absorption properties of BrC.

Yinon Rudich responded: It would be beneficial to reach out to other scientific communities and adopt new methods and technologies to atmospheric chemistry. For example, biologists have developed very sensitive tools and assays, that can help address questions relevant to the Anthropocene.

Y. Rudich remarked: About comparisons between biogenic and anthropogenic SOA, in terms of potency to have a biological effect, chamber studies suggest that anthropogenic SOA is more toxic and leads to more mortality than BSOA.1,2 Can you bridge the gap between your conclusions and these studies?1 W. Y. Tuet et al., Atmos. Chem. Phys., 2017, 17, 839853.2 V. Verma et al., Environ. Sci. Technol., 2017, 51, 31283137

Microorganisms carried by dust storms are transported through the atmosphere and may affect human health and the functionality of microbial communities in various environments. Characterizing the dust-borne microbiome in dust storms of different origins or that followed different trajectories provides valuable data to improve our understanding of global health and environmental impacts. We present a comparative study on the diversity of dust-borne bacterial communities in dust storms from three distinct origins (North Africa, Syria and Saudi Arabia) and compare them with local bacterial communities sampled on clear days, all collected at a single location: Rehovot, Israel. Storms from different dust origins exhibited distinct bacterial communities, with signature bacterial taxa. Dust storms were characterized by a lower abundance of selected antibiotic resistance genes (ARGs) compared with ambient dust, asserting that the origin of these genes is local and possibly anthropogenic. With the progression of the storm, the storm-borne bacterial community showed increasing resemblance to ambient dust, suggesting mixing with local dust. These results show, for the first time, that dust storms from different sources display distinct bacterial communities, suggesting possible diverse effects on the environment and public health.

The multi-pass photoacoustic spectrometer (PAS) is an important tool for the direct measurement of light absorption by atmospheric aerosol. Accurate PAS measurements heavily rely on accurate calibration of their signal. Ozone is often used for calibrating PAS instruments by relating the photoacoustic signal to the absorption coefficient measured by an independent method such as cavity ring down spectroscopy (CRD-S), cavity-enhanced spectroscopy (CES) or an ozone monitor. We report here a calibration method that uses measured absorption coefficients of aerosolized, light-absorbing organic materials and offer an alternative approach to calibrate photoacoustic aerosol spectrometers at 404 nm. To implement this method, we first determined the complex refractive index of nigrosin, an organic dye, using spectroscopic ellipsometry and then used this well-characterized material as a standard material for PAS calibration.

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

Anthropogenic activities are responsible for the emission of gaseous and particulate pollutants that modify atmospheric composition. Such changes are, in turn, responsible for the degradation of air quality at the regional/local scale as well as for changes of climate. Air pollution and climate change are two intimately connected environmental issues. However, these two environmental challenges are still viewed as separate issues, which are dealt with by different science communities and within different policy frameworks. Indeed, many mitigation options offer the possibility to both improve air quality and mitigate climate change but, at the same time, mitigation options that may provide benefits to one aspect, are worsening the situation in the other. Therefore, coordinated actions taking into account the air quality-climate linkages are required. These actions need to be based on strong scientific grounds, as recognised by the European Commission that in the past few years has promoted consultation processes among the science community, the policy makers and the relevant stakeholders. Here, the main fields in which such coordinated actions are needed are examined from a policy perspective.

The Surface PARTiculate mAtter Network (SPARTAN) is a long-term project that includes characterization of chemical and physical attributes of aerosols from filter samples collected worldwide. This paper discusses the ongoing efforts of SPARTAN to define and quantify major ions and trace metals found in fine particulate matter (PM_2.5). Our methods infer the spatial and temporal variability of PM_2.5 in a cost-effective manner. Gravimetrically weighed filters represent multi-day averages of PM_2.5, with a collocated nephelometer sampling air continuously. SPARTAN instruments are paired with AErosol RObotic NETwork (AERONET) sun photometers to better understand the relationship between ground-level PM_2.5 and columnar aerosol optical depth (AOD). We have examined the chemical composition of PM_2.5 at 12 globally dispersed, densely populated urban locations and a site at Mammoth Cave (US) National Park used as a background comparison. So far, each SPARTAN location has been active between the years 2013 and 2016 over periods of 2-26 months, with an average period of 12 months per site. These sites have collectively gathered over 10 years of quality aerosol data. The major PM_2.5 constituents across all sites (relative contribution±SD) are ammoniated sulfate (20%±11%), crustal material (13.4%±9.9%), equivalent black carbon (11.9%±8.4%), ammonium nitrate (4.7%±3.0%), sea salt (2.3%±1.6%), trace element oxides (1.0%±1.1%), water (7.2%±3.3%) at 35% RH, and residual matter (40%±24%). Analysis of filter samples reveals that several PM_2.5 chemical components varied by more than an order of magnitude between sites. Ammoniated sulfate ranges from 1.1μg m^-3 (Buenos Aires, Argentina) to 17μg m^-3 (Kanpur, India in the dry season). Ammonium nitrate ranged from 0.2μg m^-3 (Mammoth Cave, in summer) to 6.8 μg m^-3 (Kanpur, dry season). Equivalent black carbon ranged from 0.7μg m^-3 (Mammoth Cave) to over 8μg m^-3 (Dhaka, Bangladesh and Kanpur, India). Comparison of SPARTAN vs. coincident measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network at Mammoth Cave yielded a high degree of consistency for daily PM_2.5 (r² = 0.76, slope = 1.12), daily sulfate (r² = 0.86, slope = 1.03), and mean fractions of all major PM_2.5 components (within 6%). Major ions generally agree well with previous studies at the same urban locations (e.g. sulfate fractions agree within 4% for 8 out of 11 collocation comparisons). Enhanced anthropogenic dust fractions in large urban areas (e.g. Singapore, Kanpur, Hanoi, and Dhaka) are apparent from high Zn:Al ratios. The expected water contribution to aerosols is calculated via the hygroscopicity parameter κv for each filter. Mean aggregate values ranged from 0.15 (Ilorin) to 0.28 (Rehovot). The all-site parameter mean is 0.20±0.04. Chemical composition and water retention in each filter measurement allows inference of hourly PM_2.5 at 35% relative humidity by merging with nephelometer measurements. These hourly PM_2.5 estimates compare favourably with a beta attenuation monitor (MetOne) at the nearby US embassy in Beijing, with a coefficient of variation r² = 0.67 (n = 3167), compared to r² = 0.62 when κv was not considered. SPARTAN continues to provide an open-access database of PM_2.5 compositional filter information and hourly mass collected from a global federation of instruments.

We evaluated the impact of Saharan dust storms on the local airborne microbiome in a city in the Eastern Mediterranean area. Samples of particles with diameter less than 10 μm were collected during two spring seasons on both dusty and nondusty days. DNA was extracted, and partial 16S rRNA gene amplicons were sequenced using the Illumina platform. Bioinformatic analysis showed the effect of dust events on the diversity of the atmospheric microbiome. The relative abundance of desert soil-associated bacteria increased during dust events, while the relative abundance of anthropogenic-influenced taxa decreased. Quantitative polymerase chain reaction measurements of selected clinically significant antibiotic resistance genes (ARGs) showed that their relative abundance decreased during dust events. The ARG profiles on dust-free days were similar to those in aerosol collected in a poultry house, suggesting a strong agricultural influence on the local ambient profiles. We conclude that dust storms enrich the ambient airborne microbiome with new soil-derived bacteria that disappear as the dust settles, suggesting that the bacteria are transported attached to the dust particles. Dust storms do not seem to be an important vector for transport of probed ARGs.

Outdoor aerosol research commonly uses particulate matter sampled on filters. This procedure enables various characterizations of the collected particles to be performed in parallel. The purpose of the method presented here is to obtain a highly accurate and reliable analysis of the endotoxin and DNA content of bio-aerosols extracted from filters. The extraction of high molecular weight organic molecules, such as lipopolysaccharides, from sampled filters involves shaking the sample in a pyrogen-free water-based medium. The subsequent analysis is based on an enzymatic reaction that can be detected using a turbidimetric measurement. As a result of the high organic content on the sampled filters, the extraction of DNA from the samples is performed using a commercial DNA extraction kit that was originally designed for soils and modified to improve the DNA yield. The detection and quantification of specific microbial species using quantitative polymerase chain reaction (q-PCR) analysis are described and compared with other available methods.

The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity for a series of alkylaminium carboxylate aerosols have been measured using a hygroscopicity tandem differential mobility analyzer coupled to a condensation particle counter and a CCN counter. The particles, consisting of the mixtures of mono- (acetic, propanoic, p-toluic, and cis-pinonic acid) and dicarboxylic (oxalic, succinic, malic, adipic, and azelaic acid) acid with alkylamine (mono-, di-, and trimethylamines), represent those commonly found under diverse environmental conditions. The hygroscopicity parameter (κ) of the alkylaminium carboxylate aerosols was derived from the HGF and CCN results and theoretically calculated. The HGF at 90% RH is in the range of 1.3 to 1.8 for alkylaminium monocarboxylates and 1.1 to 2.2 for alkylaminium dicarboxylates, dependent on the molecular functionality (i.e., the carboxylic or OH functional group in organic acids and methyl substitution in alkylamines). The κ value for all alkylaminium carboxylates is in the range of 0.061.37 derived from the HGF measurements at 90% RH, 0.050.49 derived from the CCN measurements, and 0.220.66 theoretically calculated. The measured hygroscopicity of the alkylaminium carboxylates increases with decreasing acid to base ratio. The deliquescence point is apparent for several of the alkylaminium dicarboxylates but not for the alkylaminium monocarboxylates. Our results reveal that alkylaminium carboxylate aerosols exhibit distinct hygroscopic and deliquescent characteristics that are dependent on their molecular functionality, hence regulating their impacts on human health, air quality, and direct and indirect radiative forcing on climate.

Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, kappa(CCN), did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)(2)SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, kappa(HTDMA) of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.030-0.06), which was attributed to the higher degree of oxida-tion of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.Closure analysis of CCN and HTDMA data showed kappa(HTDMA) was lower than kappa(CCN) by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH4HSO4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.

Inhalation of traffic-associated atmospheric particulate matter (PM2.5) is recognized as a significant health risk. In this study, we focused on a single ("subclinical response") exposure to water-soluble extracts from PM collected at a roadside site in a major European city to elucidate potential components that drive pulmonary inflammatory, oxidative, and defense mechanisms and their systemic impacts. Intratracheal instillation (IT) of the aqueous extracts induced a 24 h inflammatory response characterized by increased broncho-alveolar lavage fluid (BALF) cells and cytokines (IL-6 and TNF-α), increased reactive oxygen species production, but insignificant lipids and proteins oxidation adducts in mouse lungs. This local response was largely self-resolved by 48 h, suggesting that it could represent a subclinical response to everyday-level exposure. Removal of soluble metals by chelation markedly diminished the pulmonary PM-mediated response. An artificial metal solution (MS) recapitulated the PM extract response. The self-resolving nature of the response is associated with activating defense mechanisms (increased levels of catalase and glutathione peroxidase expression), observed with both PM extract and MS. In conclusion, metals present in PM collected near roadways are largely responsible for the observed transient local pulmonary inflammation and oxidative stress. Simultaneous activation of the antioxidant defense response may protect against oxidative damage. (Figure Presented).

Marine viruses constitute a major ecological and evolutionary driving force in the marine ecosystems. However, their dispersal mechanisms remain underexplored. Here we follow the dynamics of Emiliania huxleyi viruses (EhV) that infect the ubiquitous, bloom-forming phytoplankton E. huxleyi and show that EhV are emitted to the atmosphere as primary marine aerosols. Using a laboratory-based setup, we showed that the dynamic of EhV aerial emission is strongly coupled to the host-virus dynamic in the culture media. In addition, we recovered EhV DNA from atmospheric samples collected over an E. huxleyi bloom in the North Atlantic, providing evidence for aerosolization of marine viruses in their natural environment. Decay rate analysis in the laboratory revealed that aerosolized viruses can remain infective under meteorological conditions prevailing during E. huxleyi blooms in the ocean, allowing potential dispersal and infectivity over hundreds of kilometers. Based on the combined laboratory and in situ findings, we propose that atmospheric transport of EhV is an effective transmission mechanism for spreading viral infection over large areas in the ocean. This transmission mechanism may also have an important ecological impact on the large-scale host-virus "arms race" during bloom succession and consequently the turnover of carbon in the ocean.

Heterogeneous neutralization reactions of ammonia and alkylamines with sulfuric acid play an important role in aerosol formation and particle growth. However, little is known about the physical and chemical properties of alkylaminium salts of organic acids. In this work we studied the thermal stability and volatility of alkylaminium carboxylate salts of short aliphatic alkylamines with monocarboxylic and dicarboxylic acids. The enthalpy of vaporization and saturation vapor pressure at 298 K were derived using the kinetic model of evaporation and the Clausius-Clapeyron relation. The vapor pressure of alkylaminium dicarboxylate salts is ∼10^-6 Pa, and the vaporization enthalpy ranges from 73 to 134 kJ mol^-1. Alkylaminium monocarboxylate salts show high thermal stability, and their thermograms do not follow our evaporation model. Hence, we inferred their vapor pressure from their thermograms as comparable to that of ammonium sulfate (∼10^-9 Pa). Further characterization showed that alkylaminium monocarboxylates are room temperature protic ionic liquids (RTPILs) that are more hygroscopic than ammonium sulfate (AS). We suggest that the irregular thermograms result from an incomplete neutralization reaction leading to a mixture of ionic and nonionic compounds. We conclude that these salts are expected to contribute to new particle formation and particle growth under ambient conditions and can significantly enhance the CCN activity of mixed particles in areas where SO₂ emissions are regulated.

Background: Over the last decade, there is growing evidence that exposure to air pollution may be associated with increased risk for congenital malformations. Objectives: To evaluate the possible association between exposures to air pollution during pregnancy and congenital malformations among infants born following spontaneously conceived (SC) pregnancies and assisted reproductive technology (ART) pregnancies. Methods: This is an historical cohort study comprising 216,730 infants: 207,825 SC infants and 8905 ART conceived infants, during the periods 1997-2004. Air pollution data including sulfur dioxide (SO₂), particulate matter

To evaluate the health impacts of particulate matter and develop effective pollutant abatement strategies, one needs to know the source contributions to the observed concentrations. The most common approach involves the collection of ambient air samples on filters, laboratory analyses to quantify the chemical composition, and application of receptor modeling methods. This approach is expensive and time consuming and limits the ability to monitor the temporal and spatial impacts from different pollutant sources. An alternative method for apportioning the sources of ambient PM is the application of microscopic chemical imaging (MCI). The MCI method involves measuring individual particle's fluorescence and source attribution is based on the individual particle analysis coupled with identification from a source library. Using this approach, the apportionment of ambient PM can be performed in near real time, which allows for the generation of temporal and spatial maps of pollutant source impacts in an urban area.

Porous glassy particles are a potentially significant but unexplored component of atmospheric aerosol that can form by aerosol processing through the ice phase of high convective clouds. The optical properties of porous glassy aerosols formed from a freeze-dry cycle simulating freezing and sublimation of ice particles were measured using a cavity ring down aerosol spectrometer (CRD-AS) at 532 nm and 355 nm wavelength. The measured extinction efficiency was significantly reduced for porous organic and mixed organic-ammonium sulfate particles as compared to the extinction efficiency of the homogeneous aerosol of the same composition prior to the freeze-drying process. A number of theoretical approaches for modeling the optical extinction of porous aerosols were explored. These include effective medium approximations, extended effective medium approximations, multilayer concentric sphere models, Rayleigh-Debye-Gans theory, and the discrete dipole approximation. Though such approaches are commonly used to describe porous particles in astrophysical and atmospheric contexts, in the current study, these approaches predicted an even lower extinction than the measured one. Rather, the best representation of the measured extinction was obtained with an effective refractive index retrieved from a fit to Mie scattering theory assuming spherical particles with a fixed void content. The single-scattering albedo of the porous glassy aerosols was derived using this effective refractive index and was found to be lower than that of the corresponding homogeneous aerosol, indicating stronger relative absorption at the wavelengths measured. The reduced extinction and increased absorption may be of significance in assessing direct, indirect, and semidirect forcing in regions where porous aerosols are expected to be prevalent.

The cytotoxicity of tungsten disulfide nano tubes (INT-WS₂) and inorganic fullerene-like molybdenum disulfide (IF-MoS₂) nanoparticles (NPs) used in industrial and medical applications was evaluated in comparison to standard environmental particulate matter. The IF-MoS₂ and INT-WS₂ reside in vesicles/inclusion bodies, suggestive of endocytic vesicles. In cells representing the respiratory, immune and metabolic systems, both IF-MoS₂ and INT-WS₂ NPs remained nontoxic compared to equivalent concentrations (up to 100 μg/mL in the medium) of silica dioxide (SiO₂), diesel engine-derived and carbon black NPs, which induced cell death. Associating with this biocompatibility of IF-MoS₂\INT- WS₂, we demonstrate in nontransformed human bronchial cells (NL-20) relative low induction of the pro-inflammatory cytokines IL-1β, IL-6, IL-8, and TNF-α. Moreover, IF-MoS₂ and INT-WS₂ activated antioxidant response as measured by the antioxidant response element (ARE) using a luciferase reporter, and induced Nrf2-mediated Phase II detoxification genes. Collectively, our findings suggest that the lower cytotoxicity of IF-MoS ₂ and INT-WS₂ NPs does not reflect general biological inertness. Rather, compared to other NP's, it likely results from decreased pro-inflammatory activation, but a comparable significant capacity to induce protective antioxidant/detoxification defense mechanisms.

We examined fungal communities associated with the PM₁₀ mass of Rehovot, Israel outdoor air samples collected in the spring and fall seasons. Fungal communities were described by 454 pyrosequencing of the internal transcribed spacer (ITS) region of the fungal ribosomal RNA encoding gene. To allow for a more quantitative comparison of fungal exposure in humans, the relative abundance values of specific taxa were transformed to absolute concentrations through multiplying these values by the sample's total fungal spore concentration (derived from universal fungal qPCR). Next, the sequencing-based absolute concentrations for Alternaria alternata, Cladosporium cladosporioides, Epicoccum nigrum, and Penicillium/Aspergillus spp. were compared to taxon-specific qPCR concentrations for A.alternata, C.cladosporioides, E.nigrum, and Penicillium/Aspergillus spp. derived from the same spring and fall aerosol samples. Results of these comparisons showed that the absolute concentration values generated from pyrosequencing were strongly associated with the concentration values derived from taxon-specific qPCR (for all four species, p0.70). The correlation coefficients were greater for species present in higher concentrations. Our microbial aerosol population analyses demonstrated that fungal diversity (number of fungal operational taxonomic units) was higher in the spring compared to the fall (p=0.02), and principal coordinate analysis showed distinct seasonal differences in taxa distribution (ANOSIM p=0.004). Among genera containing allergenic and/or pathogenic species, the absolute concentrations of Alternaria, Aspergillus, Fusarium, and Cladosporium were greater in the fall, while Cryptococcus, Penicillium, and Ulocladium concentrations were greater in the spring. The transformation of pyrosequencing fungal population relative abundance data to absolute concentrations can improve next-generation DNA sequencing-based quantitative aerosol exposure assessment.

Using shipboard and satellite measurements we explore the environmental factors affecting the number concentration of aerosols with diameter 100

Alkyl aminium sulfates have been postulated to constitute important components of nucleation and accumulation mode atmospheric aerosols. In this study we present laboratory data on the thermochemical, cloud condensation nuclei (CCN) activity, and optical properties of selected aminium sulfate compounds of atmospheric relevance (monomethyl aminium sulfate (MMAS), dimethyaminium sulfate (DMAS), trimethylaminium sulfate, monoethylaminium sulfate (MEAS), diethylaminium sulfate (DEAS), and triethylaminium sulfate (TEAS)). We found that the vapor pressure of these aminium salts is 1-3 orders of magnitude lower than that of ammonium sulfate and as such they can contribute to new aerosols and secondary aerosols formation. We infer that these species have very high CCN activity, with hygroscopicity parameter that is similar to that ammonium sulfate. Finally, between 360 and 420 nm, these aminium sulfate salts scatter light less efficiently than ammonium sulfate, and do not absorb light. These derived parameters can contribute to the better understanding and characterization of the role that these compounds play in atmospheric chemical reactions, gas-solid partitioning and their possible contribution to the microphysical and radiative effects of atmospheric aerosols.

Increased susceptibility to allergies has been documented in the Western world in recent decades. However, a comprehensive understanding of its causes is not yet available. It is therefore essential to understand trends and mechanisms of allergy-inducing agents, such as fungal conidia. In this study, we investigated the hypothesis that environmental conditions linked to global atmospheric changes can affect the allergenicity of Aspergillus fumigatus, a common allergenic fungal species in indoor and outdoor environments and in airborne particulate matter. We show that fungi grown under present-day CO₂ levels (392 ppm) exhibit 8.5 and 3.5 fold higher allergenicity compared to fungi grown at preindustrial (280 ppm) and double (560 ppm) CO₂ levels, respectively. A corresponding trend is observed in the expression of genes encoding for known allergenic proteins and in the major allergen Asp f1 concentrations, possibly due to physiological changes such as respiration rates and the nitrogen content of the fungus, influenced by the CO₂ concentrations. Increased carbon and nitrogen levels in the growth medium also lead to a significant increase in the allergenicity. We propose that climatic changes such as increasing atmospheric CO₂ levels and changes in the fungal growth medium may impact the ability of allergenic fungi such as A. fumigatus to induce allergies.

Aerosols influence the Earth's radiative budget by scattering and absorbing incoming solar radiation. The optical properties of aerosols vary as a function of wavelength, but few measurements have reported the wavelength dependence of aerosol extinction cross sections and complex refractive indices. We describe a new laboratory instrument to measure aerosol optical extinction as a function of wavelength, using cavity enhanced spectroscopy with a broadband light source. The instrument consists of two broadband channels which span the 360-390 and 385-420 nm spectral regions using two light emitting diodes (LED) and a grating spectrometer with charge-coupled device (CCD) detector. We determined aerosol extinction cross sections and directly observed Mie scattering resonances for aerosols that are purely scattering (polystyrene latex spheres and ammonium sulfate), slightly absorbing (Suwannee River fulvic acid), and strongly absorbing (nigrosin dye). We describe an approach for retrieving refractive indices as a function of wavelength from the measured extinction cross sections over the 360-420 nm wavelength region. The retrieved refractive indices for PSL and ammonium sulfate agree within uncertainty with the literature values for this spectral region. The refractive index determined for nigrosin is 1.78 (±0.03) + 0.19 (±0.08)i at 360 nm and 1.63 (±0.03) + 0.21 (±0.05)i at 420 nm. The refractive index determined for Suwannee River fulvic acid is 1.71 (±0.02) + 0.07 (±0.06)i at 360 nm and 1.66 (±0.02) + 0.06 (±0.04)i at 420 nm. These laboratory results support the potential for a field instrument capable of determining ambient aerosol optical extinction, average aerosol extinction cross section, and complex refractive index as a function of wavelength.

Cavity ring-down spectroscopy (CRD-S) is widely adapted for studying light extinction by aerosol in laboratory and field studies. The complex refractive index (RI) of an aerosol can be retrieved by finding the theoretical Mie theory curve that best fits the measured extinction efficiency for as many aerosol diameters as possible. In this study, we introduce a new retrieval approach for the complex RI of aerosols using extinction measurements at only two carefully selected size parameters. We show that for three model substances measured (ammonium sulfate, Suwannee river fulvic acid, and nigrosin) and for 22 other reanalyzed datasets, the "2-points" measurement approach enables the retrieval of complex refractive indices with comparable uncertainty to the traditional measurement and retrieval procedure. The advantages and disadvantages of the new approach are discussed.

Climate change will induce extended heat waves to parts of the vegetation more frequently. High temperatures may act as stress (thermal stress) on plants changing emissions of biogenic volatile organic compounds (BVOCs). As BVOCs impact the atmospheric oxidation cycle and aerosol formation, it is important to explore possible alterations of BVOC emissions under high temperature conditions. Applying heat to European beech, Palestine oak, Scots pine, and Norway spruce in a laboratory setup either caused the well-known exponential increases of BVOC emissions or induced irreversible changes of BVOC emissions. Considering only irreversible changes of BVOC emissions as stress impacts, we found that high temperatures decreased the de novo emissions of monoterpenes, sesquiterpenes and phenolic BVOC. This behaviour was independent of the tree species and whether the de novo emissions were constitutive or induced by biotic stress. In contrast, application of thermal stress to conifers amplified the release of monoterpenes stored in resin ducts of conifers and induced emissions of green leaf volatiles. In particular during insect attack on conifers, the plants showed de novo emissions of sesquiterpenes and phenolic BVOCs, which exceeded constitutive monoterpene emissions from pools. The heat-induced decrease of de novo emissions was larger than the increased monoterpene release caused by damage of resin ducts. For insect-infested conifers the net effect of thermal stress on BVOC emissions could be an overall decrease. Global change-induced heat waves may put hard thermal stress on plants. If so, we project that BVOC emissions increase is more than predicted by models only in areas predominantly covered with conifers that do not emit high amounts of sesquiterpenes and phenolic BVOCs. Otherwise overall effects of high temperature stress will be lower increases of BVOC emissions than predicted by algorithms that do not consider stress impacts.

The correct version of Fig. 9 is shown in this document

Simultaneously retrieving the complex refractive indices of the core and shell of coated aerosol particles given the measured extinction efficiency as a function of particle dimensions (core diameter and coated diameter) is much more difficult than retrieving the complex refractive index of homogeneous aerosol particles. Not only must the minimization be performed over a four-parameter space, making it less efficient, but in addition the absolute value of the difference between the measured extinction and the calculated extinction does not have an easily distinguished global minimum. Rather, there are a number of local minima to which almost all conventional retrieval algorithms converge. In this work, we develop a new (to our knowledge) retrieval algorithm that employs the numerical method known as simulated annealing with an innovative "temperature" schedule. This study is limited only to spherical particles with a concentric shell and to cases in which the diameter of both the core and the coated particle are known. We find that when the top ranking particle sizes according to their information content are combined from separate experiments to make up the particle size distribution, the simulated annealing retrieval algorithm is quite robust and by far superior to a greedy random perturbation approach often used.

In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols from a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (HR-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While these types of extensive BB events are not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). The average EBRI for a mixed population of aerosols dominated by open fires was m = 1.53(+/- 0.03) + 0.07i(+/- 0.03), during the smoldering phase of the fires we found the EBRI to be m = 1.54(+/- 0.01) + 0.04i(+/- 0.01) compared to m = 1.49(+/- 0.01) + 0.02i(+/- 0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.

Aerosols containing biological components can have a significant effect on human health by causing primarily irritation, infection and allergies. Specifically, airborne fungi can cause a wide array of adverse responses in humans depending on the type and quantity present. In this study we used chemical biomarkers for analyzing fungi-containing aerosols in the eastern Mediterranean region during the year 2009 in order to quantify annual fungal abundances. The prime marker for fungi used in this study was ergosterol, and its concentrations were compared with those of mannitol and arabitol which were recently suggested to also correlate with fungal spores concentrations (Bauer et al., 2008a). Back trajectory analysis, inorganic ions, humidity and temperature were used in an attempt to identify sources as well as the dependence on seasonal and environmental conditions. We found that the ambient concentrations of ergosterol, arabitol and mannitol range between 0 and 2.73 ng m^-3, 1.85 and 58.27 ng m^-3, 5.57 and 138.03 ng m^-3, respectively. The highest levels for all biomarkers were during the autumn, probably from local terrestrial sources, as deduced from the inorganic ions and back trajectory analysis. Significant correlations were observed between arabitol and mannitol during the entire year except for the winter months. Both sugars correlated with ergosterol only during the spring and autumn. We conclude that mannitol and arabitol might not be specific biomarkers for fungi and that the observed correlations during spring and autumn may be attributed to high levels of vegetation during spring blossoms and autumn decomposing.

This study focuses on the retrieval of the normalized mass absorption cross section (MAC) of soot using theoretical calculations that incorporate new measurements of the optical properties of organic carbon (OC) intrinsic to fresh diesel soot. Intrinsic OC was extracted by water and an organic solvent, and the complex refractive index of the extracted OC was derived at 532 and 355-nm wavelengths using cavity ring-down aerosol spectrometry. The extracted OC was found to absorb weakly in the visible wavelengths and moderately at blue wavelengths. The mass ratio of OC and elemental carbon (EC) in the collected particles was evaluated using a thermo-optical method. The measured EC/OC ratio in the soot exhibited substantial variability from measurement to measurement, ranging between 2 and 5. To test the sensitivity of the MAC to this variability, three different EC/OC ratios (2:1, 1:1, and 1:2) were chosen as representative. Particle size and spherule morphology were estimated using scanning electron microscopy, and the soot was found to be primarily in the form of aggregates with a dominant aggregate diameter mode in the range 200-250 nm. The measured refractive index of the extracted OC was used with a variety of theoretical models to calculate the MAC of internally mixed diesel soot at 532 and 355 nm. We conclude that Rayleigh-Debye-Gans theory on clusters of coated spherules and T-matrix of a solid EC spheroid coated by intrinsic OC are both consistent with previous measurements; however, Rayleigh-Debye-Gans theory provides a more realistic physical model for the calculation.

Atmospheric aerosols scatter and absorb solar radiation leading to variable effects on Earth's radiative balance. Aerosols individually comprising mixtures of different components ("internally mixed") interact differently with light than mixtures of aerosols, each comprising a different single component ("externally mixed"), even if the relative fractions of the different components are equal. In climate models, the optical properties of internally mixed aerosols are generally calculated by using electromagnetic "mixing rules", which average the refractive indices of the individual components in different proportions, or by using coated-sphere Mie scattering codes, which solve the full light scattering problem assuming that the components are divided into two distinct layers. Because these calculation approaches are in common use, it is important to validate them experimentally. In this article, we present a broad perspective on the optical properties of internally mixed aerosols based on a series of laboratory experiments and theoretical calculations. The optical properties of homogenously mixed aerosols comprised of non-absorbing and weakly absorbing compounds, and of coated aerosols comprised of strongly absorbing, non-absorbing, and weakly absorbing compounds in different combinations are measured using pulsed and continuous wave cavity ring down aerosol spectrometry (CRD-AS). The success of electromagnetic mixing rules and Mie scattering codes in reproducing the measured aerosol extinction values is discussed.

The Mediterranean region is expected to experience substantial climatic change in the next 50 years. But, possible effects of climate change on biogenic volatile organic compound (VOC) emissions as well as on the formation of secondary organic aerosols (SOA) produced from these VOC are yet unexplored. To address such issues, the effects of temperature on the VOC emissions of Mediterranean Holm Oak and small Mediterranean stand of Wild Pistacio, Aleppo Pine, and Palestine Oak have been studied in the Jülich plant aerosol atmosphere chamber. For Holm Oak the optical and microphysical properties of the resulting SOA were investigated. Monoterpenes dominated the VOC emissions from Holm Oak (97.5%) and Mediterranean stand (97%). Higher temperatures enhanced the overall VOC emission but with different ratios of the emitted species. The amount of SOA increased linearly with the emission strength with a fractional mass yield of 6.0±0.6%, independent of the detailed emission pattern. The investigated particles were highly scattering with no absorption abilities. Their average hygroscopic growth factor of 1.13 ±0.03 at 90% RH with a critical diameter of droplet activation was 100 ± 4 nm at a supersaturation of 0.4%. All microphysical properties did not depend on the detailed emission pattern, in accordance with an invariant O/C ratio (0.57(+0.03-0.1)) of the SOA observed by high resolution aerosol mass spectrometry. The increase of Holm oak emissions with temperature (20% per degree) was stronger than e.g. for Boreal tree species (-10% per degree). The SOA yield for Mediterranean trees determined here is similar as for Boreal trees. Increasing mean temperature in Mediterranean areas could thus have a stronger impact on BVOC emissions and SOA formation than in areas with Boreal forests.

Air quality transcends all scales with in the atmosphere from the local to the global with handovers and feedbacks at each scale interaction. Air quality has manifold effects on health, ecosystems, heritage and climate. In this review the state of scientific understanding in relation to global and regional air quality is outlined. The review discusses air quality, in terms of emissions, processing and transport of trace gases and aerosols. New insights into the characterization of both natural and anthropogenic emissions are reviewed looking at both natural (e.g. dust and lightning) as well as plant emissions. Trends in anthropogenic emissions both by region and globally are discussed as well as biomass burning emissions. In terms of chemical processing the major air quality elements of ozone, non-methane hydrocarbons, nitrogen oxides and aerosols are covered. A number of topics are presented as a way of integrating the process view into the atmospheric context; these include the atmospheric oxidation efficiency, halogen and HO_x chemistry, nighttime chemistry, tropical chemistry, heat waves, megacities, biomass burning and the regional hot spot of the Mediterranean. New findings with respect to the transport of pollutants across the scales are discussed, in particular the move to quantify the impact of long-range transport on regional air quality. Gaps and research questions that remain intractable are identified. The review concludes with a focus of research and policy questions for the coming decade. In particular, the policy challenges for concerted air quality and climate change policy (co-benefit) are discussed.

By emission of volatile organic compounds (VOC) which
on oxidation form secondary organic aerosols (SOA) the
vegetation is coupled to atmosphere and climate. We
investigated new particle formation from tree emissions in a
new setup: a plant chamber housing the trees coupled to a
reaction chamber for oxidizing the plant emissions and for
forming SOA (J¸lich Plant Aerosol Atmosphere Chamber,
JPAC).
Boreal, temperate Midlatitude, and Mediterranean tree
species were studied and α-pinene was used as reference
compound to characterize the specifics of JPAC and to study
humidity and OH dependence of new particle formation. The
strength and the pattern of the tree emissions were varied by
increasing the temperature for the plants, thus mimicking the
higher frequency of occurrence of warmer days in a future
climate.
Under the experimental conditions OH radicals were
essential for inducing new particle formation, although O3 (≤
80 ppb) was always present and a part of the monoterpenes
and the sesquiterpenes reacted already with ozone before OH
was generated. Formation rates of 3 nm particles were linearly
related to the carbon mixing ratios of the VOC, as were the
maximum observed volume and the condensational growth
rates. The threshold of new particle formation was lower for
the tree emissions than for α-pinene.
Hygroscopic growth factors and activation to cloud
droplets were measured to characterize climate relevant
properties of the resulting aerosols. Overall the hygroscopic
properties of the biogenic SOA from the highly mixed tree
emissions are similar to those found for individual
monoterpenes and sesquiterpenes. However, changes of
emission pattern from species to species or induced by heat
stress is reflected in the hygroscopic properties of the resulting
SOA. The biogenic SOA revealed close to ideal Kˆhler
behavior with significantly reduced surface tension at
activation compared to pure water.

The major uncertainties associated with the direct impact of aerosols on climate call for fast and accurate characterization of their optical properties. Cavity ring down (CRD) spectroscopy provides highly sensitive measurement of aerosols' extinction coefficients from which the complex refractive index (RI) of the aerosol may be retrieved accurately for spherical particles of known size and number density, thus it is possible to calculate the single scattering albedo and other atmospherically relevant optical parameters. We present a CRD system employing continuous wave (CW) single mode laser. The single mode laser and the high repetition rate obtained significantly improve the sensitivity and reliability of the system, compared to a pulsed laser CRD setup. The detection limit of the CW-CRD system is between 6.67 × 10^-10 cm ^-1 for an empty cavity and 3.63 × 10^-9 cm ^-1 for 1000 particles per cm³ inside the cavity, at a 400 Hz sampling and averaging of 2000 shots for one sample measurement taken in 5 s. For typical pulsed-CRD, the detection limit for an empty cavity is less than 3.8 × 10^-9 cm^-1 for 1000 shots averaged over 100 s at 10 Hz. The system was tested for stability, accuracy, and RI retrievals for scattering and absorbing laboratory-generated aerosols. Specifically, the retrieved extinction remains very stable for long measurement times (1 h) with an order of magnitude change in aerosol number concentration. In addition, the optical cross section (σ_ext) of a 400 nm polystyrene latex sphere (PSL) was determined within 2% error compared to the calculated value based on Mie theory. The complex RI of PSL, nigrosin, and ammonium sulfate (AS) aerosols were determined by measuring the extinction efficiency (Q _ext) as a function of the size parameter ((πD)/λ) and found to be in very good agreement with literature values. A mismatch in the retrieved RI of Suwannee River fulvic acid (SRFA) compared to a previous study was observed and is attributed to variation in the sample composition. The small system presented delivers high ability for fast measurements and accurate analysis, making it a good candidate for field aerosol optical properties studies.

A new approach to retrieve the effective broadband refractive indices (n_broad,eff) of aerosol particles by a white light aerosol spectrometer (WELAS) optical particle counter (OPC) is presented. Using a tandem differential mobility analyzer (DMA)-OPC system, the n_broad,eff are obtained for both laboratory and field applications. This method was tested in the laboratory using substances with a wide range of optical properties. With the obtained n_broad,eff, WELAS aerosol size distributions can be corrected. Therefore, this method can be used for instrument calibration in both laboratory and field measurements. The retrieved effective broadband refractive indices for the scattering aerosols were: ammonium sulfate ((NH ₄)₂SO₄, AS) n_broad,eff = 1.52(±0.01) + i0.0, glutaric acid (HOOC(CH₂)₃COOH, GA) n_broad,eff = 1.45(±0.01) + i0.0, and sodium chloride (NaCl) n_broad,eff = 1.49(±0.02) + i0.0, all within 4% of literature values. A lightly absorbing substance, Suwannee river fulvic acid (SRFA), was also measured, and its retrieved n_broad,eff is like that of a pure scatterer, with a value of n_broad,eff = 1.53(±0.01) + i0.0. The retrieved real part of n_broad,eff is in accordance with literature values and the imaginary part with the behavior of the white light spectrum of the WELAS, which is not sensitive below a wavelength of 380 nm, where SRFA mainly absorbs. For absorbing substances, nigrosine and various mixtures of nigrosine with AS and GA were measured. For nigrosine, n _broad,eff = 1.64(±0.04) + i0.20(±0.03) was retrieved, in very good agreement with values found in the literature. The n _broad,eff retrieved by this method for the mixtures was in accordance with the complex refractive index expected. The n_broad,eff retrieved by this method would be similar to the values obtained using the solar spectrum.

Surfactants often found in tropospheric aerosols, can affect the onset and development of clouds. Due to high dilution during droplet growth, the effects of surfactants on cloud microphysical processes have been mostly neglected. However, while cloud growth by coalescence conserves the combined volume of all cloud droplets, it reduces the combined surface area. This could lead to enrichment of water-insoluble surfactants (WIS) and to reduced surface tension of droplets forming in warm processes. Measurements of individual raindrops reveal the presence of water insoluble surfactants. Our field and laboratory studies as well as simple theoretical arguments suggest that by causing varying and size-dependent surface tension, WIS can affect cloud microphysics.

The concentrations of the water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), chloride (Cl-), and sulfate (SO42-), were measured from September to November 2002 at a pasture site in the Amazon Basin (Rondônia, Brazil) (LBA-SMOCC). Measurements were conducted using a semi-continuous technique (Wet-annular denuder/Steam-Jet Aerosol Collector: WAD/SJAC) and three integrating filter-based methods, namely (1) a denuder-filter pack (DFP: Teflon and impregnated Whatman filters), (2) a stacked-filter unit (SFU: polycarbonate filters), and (3) a High Volume dichotomous sampler (HiVol: quartz fiber filters). Measurements covered the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). Analyses of the particles collected on filters were performed using ion chromatography (IC) and Particle-Induced X-ray Emission spectrometry (PIXE). Season-dependent discrepancies were observed between the WAD/SJAC system and the filter-based samplers. During the dry season, when PM2.5 (Dp ≤ 2.5 μm) concentrations were ∼100 μg m-3, aerosol NH4+ and SO42- measured by the filter-based samplers were on average two times higher than those determined by the WAD/SJAC. Concentrations of aerosol NO3- and Cl- measured with the HiVol during daytime, and with the DFP during day- and nighttime also exceeded those of the WAD/SJAC by a factor of two. In contrast, aerosol NO3- and Cl- measured with the SFU during the dry season were nearly two times lower than those measured by the WAD/SJAC. These differences declined markedly during the transition period and towards the cleaner conditions during the onset of the wet season (PM2.5 ∼5 μg m-3); when filter-based samplers measured on average 40-90% less than the WAD/SJAC. The differences were not due to consistent systematic biases of the analytical techniques, but were apparently a result of prevailing environmental conditions and different sampling procedures. For the transition period and wet season, the significance of our results is reduced by a low number of data points. We argue that the observed differences are mainly attributable to (a) positive and negative filter sampling artifacts, (b) presence of organic compounds and organosulfates on filter substrates, and (c) a SJAC sampling efficiency of less than 100%.

Recent field observations suggest that ammonium salts of organic acids may be very important in accounting for aerosols' properties in many environments. In this study we present laboratory experiments and calculations on the influence of ammonia reaction with organic aerosol components and its effect upon their (1) subsaturation hygroscopic growth (HG) and (2) supersaturation cloud condensation nuclei (CCN) activity. By using adipic acid (slightly soluble), citric acid (soluble), and di(ethylene glycol) monovinyl ether (DEGMVE, nonacidic compound) aerosols we show the feasibility and importance of atmospherically relevant acid-base neutralization by ammonia for different organic species. It is suggested that the formation of ammonium salts due to reaction of ammonia with slightly soluble organic acids (such as adipic acid) can affect the CCN activity and hygroscopic growth of aerosols with a significant organic component. It is further confined that the reaction involves carboxylic groups, it requires presence of water in the aerosol, and that the effects are stronger for less soluble organic acids.

Cavity ring down aerosol extinction measurements are combined with size distribution measurements to provide a multi-parameter basis for the retrieval of the aerosol complex refractive index. We show that two distinct size distributions of small particles (

Cloud and aerosols interact and form a complex system leading to high uncertainty in understanding climate change. To simplify this non-linear system it is customary to distinguish between "cloudy" and "cloud-free" areas and measure them separately. However, we find that clouds are surrounded by a "twilight zone" - a belt of forming and evaporating cloud fragments and hydrated aerosols extending tens of kilometers from the clouds into the so-called cloud-free zone. The gradual transition from cloudy to dry atmosphere is proportional to the aerosol loading, suggesting an additional aerosol effect on the composition and radiation fluxes of the atmosphere. Using AERONET data, we find that the measured aerosol optical depth is higher by 13% ± 2% in the visible and 22% ± 2% in the NIR in measurements taken near clouds relative to its value in the measurements taken before or after, and that 30%-60% of the free atmosphere is affected by this phenomenon.

The role of biomass burning aerosols in the climate system is still poorly quantified, in part due to uncertainties regarding the optical properties of elemental and organic carbon (EC and OC, respectively), the main constituents of pyrogenic aerosols. In this study, we utilize comprehensive physical and chemical field measurements of biomass burning aerosols in Brazil to constrain the densities and refractive indices (RI) of EC and OC in these particles, by comparing their optically and chemically derived RI. The optically derived effective RI are retrieved from the measured absorption and scattering coefficients using a Mie scattering algorithm, and serve as a reference dataset, while the chemically derived effective RI are calculated from the measured chemical composition using electromagnetic mixing rules. The results are discussed in light of the observed combustion conditions, and in an effort to derive conclusions as to the chemical and optical properties of the usually less well-characterized components of biomass burning aerosols, namely, elemental carbon and organic matter. The best agreement between the optically and chemically derived RI was achieved by assigning a density of ρ_EC = 1.8 g cm^{- 3} and refractive index RI_EC = 1.87 - 0.22 i to the EC component, and ρ = 0.9 g cm^{- 3} and RI = 1.4 - 0 i to the unidentified organic matter fraction of the particles. These parameters suggest low graphitization levels for the EC, and a dominant proportion of aliphatic compounds in the unidentified organic matter. Combining the density and RI of the unidentified organic matter with the properties of the chemically characterized organic fraction yields ρ = 1.1 g cm^{- 3} and RI = 1.3 - 0 i for the total aerosol OC.

Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gas-particle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It enables a detailed description of mass transport and chemical reactions at the gas-particle interface, and it allows linking aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes. The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined and consistent rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surface-bulk transport (gas phase diffusion, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of concentration and time dependences (transient and steady-state conditions); flexible addition of unlimited numbers of chemical species and physicochemical processes; optional aggregation or resolution of intermediate species, sequential processes, and surface layers; and full compatibility with traditional resistor model formulations. The outlined double-layer surface concept and formalisms represent a minimum of model complexity required for a consistent description of the non-linear concentration and time dependences observed in experimental studies of atmospheric multiphase processes (competitive co-adsorption and surface saturation effects, etc.). Exemplary practical applications and model calculations illustrating the relevance of the above aspects are presented in a companion paper (Ammann and Pöschl, 2007). We expect that the presented model framework will serve as a useful tool and basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions. It shall help to end the "Babylonian confusion" that seems to inhibit scientific progress in the understanding of heterogeneous chemical reactions and other multiphase processes in aerosols and clouds. In particular, it shall support the planning and design of laboratory experiments for the elucidation and determination of fundamental kinetic parameters; the establishment, evaluation, and quality assurance of comprehensive and self-consistent collections of rate parameters; and the development of detailed master mechanisms for process models and derivation of simplified but yet realistic parameterizations for atmospheric and climate models.

The oxidation of organics in aerosol particles affects the physical properties of aerosols through a process known as aging. Atmospheric particles compose a huge set of specific organic compounds, most of which have not been identified in field measurements. Laboratory experiments inevitably address model systems of reduced complexity to isolate critical chemical phenomena, but growing evidence suggests that composition effects may play a central role in the atmospheric aging of organic particles. In this review we seek to address the connections between recent laboratory studies and recent field campaigns addressing the aging of organic aerosols. We review laboratory studies on the uptake of oxidants, the evolution of particle-water interactions, and the evolution of particle density with aging. Finally, we review field data addressing condensed-phase lifetimes of organic tracers. These data suggest that although matrix effects identified in the laboratory have taken a step toward reconciling laboratory-field disagreements, further work is needed to understand the actual aging rates of organics in ambient particles.

The transport of anthropogenic pollution by desert dust in the Eastern Mediterranean region was studied by analyzing major and trace element composition, organic species, and Pb isotope ratios in suspended dust samples collected in Jerusalem, Israel. Dust storms in this region are associated with four distinct synoptic conditions (Red Sea Trough (RS), Eastern High (EH), Sharav Cyclone (SC), and Cold Depression (Cyprus low, CD)) that carry dust mostly from North African (SC, CD, EH) and Arabian and Syrian (RS, EH) deserts. Substantial contamination of dust particles by Pb, Cu, Zn, and Ni is observed, while other elements (Na, Ca, Mg, Mn, Sr, Rb, REE, U, and Th) display natural concentrations. Sequential extraction of the abovementioned elements from the dust samples shows that the carbonate and sorbed fractions contain most of the pollution, yet the Al-silicate fraction is also contaminated, implying that soils and sediments in the source terrains of the dust are already polluted. We identified the pollutant sources by using Pb isotopes. It appears that before the beginning of the dust storm, the pollutants in the collected samples are dominated by local sources but with the arrival of dust from North Africa, the proportion of foreign pollutants increases. Organic pollutants exhibit behavior similar and complementary to that of the inorganic tracers, attesting to the importance of anthropogenic-pollutant addition en route of the dust from its remote sources. Pollution of suspended dust is observed under all synoptic conditions, yet it appears that easterly winds carry higher proportions of local pollution and westerly winds carry pollution emitted in the Cairo basin. Therefore, pollution transport by mineral dust should be accounted for in environmental models and in assessing the health-related effects of mineral dust.

The actual number of particles in formulations of nanoparticles (NP) is of importance for quality assurance, comprehensive physicochemical characterization, and pharmacodynamics. Some calculation methods that have been previously employed are limited because they rely on several assumptions and are not applicable for certain preparations. Currently there are no validated experimental methods for determining the particle number-concentration (N _c) of liposomal and polymeric nanoparticulate preparations (

A class of organic molecules extracted atmospheric aerosol particles and isolated from fog and cloud water has been termed HUmic-LIke Substances (HULIS) due to a certain resemblance to terrestrial and aquatic humic and fulvic acids. In light of the interest that this class of atmospheric compounds currently attracts, we comprehensively review HULIS properties, as well as laboratory and field investigations concerning their formation and characterization in atmospheric samples. While sharing some important features such as polyacidic nature, accumulating evidence suggests that atmospheric HULIS differ substantially from terrestrial and aquatic humic substances. Major differences between HULIS and humic substances, including smaller average molecular weight, lower aromatic moiety content, greater surface activity, better droplet activation ability, as well as others, are highlighted. Several alternatives are proposed that may explain such differences: (1) the possibility that mono- and di-carboxylic acids and mineral acids abundant in the atmosphere prevent the formation of large humic "supramolecular associations"; (2) that large humic macromolecules are destroyed in the atmosphere by UV radiation, O₃, and OH^- radicals; 3) that "HULIS" actually consists of a complex, unresolved mixture of relatively small molecules rather than macromolecular entities; and (4) that HULIS formed via abiotic and short-lived oxidative reaction pathways differ substantially from humic substances formed over long time periods via biologically-mediated reactions. It should also be recalled that the vast majority of studies of HULIS relate to the water soluble fraction, which would include only the fulvic acid fraction of humic substances, and exclude the humic acid (base-soluble) and humin (insoluble) fractions of humic substances. A significant effort towards adopting standard extraction and characterization method is required to develop a better and meaningful comparison between different HULIS samples.

Prior to the massive use of new oxygenated solvents, data on their multiphase reactivity must be obtained to assess their environmental fate and impact on water and air quality. For this, the kinetics and mechanisms of the photochemical and photocatalytic degradation of selected oxygenated solvents by common tropospheric oxidants (such as OH and ozone) must be characterized. We studied the oxidation kinetics of new oxygenated solvents as pure organic liquids and in an aqueous medium by ozone and by the OH radical, respectively. The studied chemicals are all unsaturated compounds, having none, one, or two ether groups. The results indicate that the OH reaction proceeds at the diffusion limit by addition to the double bond. The reactive uptake coefficients associated with the reaction initiated by ozone are of the order of 10 ^-3. The reactions of compounds with two double bonds are very fast and probably occur at the surface. This kinetic information demonstrates that organic solvents in an organic medium or in an aqueous droplet will be oxidized rapidly by these oxidation reactions. These reactions, however, are not significant sinks for ozone and OH radicals.

Biomass burning is an important source of smoke aerosol particles, which contain water-soluble inorganic and organic species, and thus have a great potential of affecting cloud formation, precipitation, and climate on global and regional scales. In this study, we have developed a new chromatographic method for the determination of levoglucosan (a specific tracer for biomass burning particles), related polyhydroxy compounds, and 2-methyl-erythritol (recently identified as isoprene oxidation product in fine aerosols in the Amazon) in smoke and in rainwater samples. The new method is based on water extraction and utilizes ion-exclusion high-performance liquid chromatography (IEC-HPLC) separation and spectroscopic detection at 194 nm. The new method allows the analysis of wet samples, such as rainwater samples. In addition, aliquots of the same extracts can be used for further analyses, such as ion chromatography. The overall method uncertainty for sample analysis is 15%. The method was applied to the analysis of high-volume and size-segregated smoke samples and to rainwater samples, all collected during and following the deforestation fires season in Rondônia, Brazil. From the analysis of size-segregated samples, it is evident that levoglucosan is a primary vegetation combustion product, emitted mostly in the 0.175-1 μm size bins. Levoglucosan concentrations decrease below the detection limit at the end of the deforestation fires period, implying that it is not present in significant amounts in background Amazon forest aerosols. The ratio of daytime levoglucosan concentration to particulate matter (PM) concentration was about half the nighttime ratio. This observation is rationalized by the prevalence of flaming combustion during day as opposed to smoldering combustion during night. This work broadens the speciation possibilities offered by simple HPLC and demonstrates the importance of multianalysis of several kinds of samples for a deeper understanding of biomass burning aerosols.

The aerosol in the Amazon basin is dominated throughout the year by organic matter, for the most part soluble in water. In this modeling study, we show how the knowledge of water-soluble organic compounds (WSOC) and the associated physical and chemical properties (e.g. solubility, surface tension, dissociation into ions) affect the hygroscopic growth and activation of the aerosol in this area. The study is based on data obtained during the SMOCC field experiment carried out in Rondônia, Brazil, over a period encompassing the dry (biomass burning) season to the onset of the wet season (September to mid-November, 2002). The comparison of predicted and measured cloud condensation nuclei (CCN) number concentration shows that the knowledge of aerosol WSOC composition in terms of classes of compounds and of their relative molecular weights and acidic properties may be sufficient to predict aerosol activation, without any information on solubility. Conversely, the lack of knowledge on WSOC solubility leads to a high overestimation of the observed diameter growth factors (DGF) by the theory. Moreover, the aerosol water soluble inorganic species fail to predict both DGFs and CCN number concentration. In fact, this study shows that a good reproduction of the measured DGF and CCN concentration is obtained if the chemical composition of aerosol, especially that of WSOC, is appropriately taken into account in the calculations. New parameterizations for the computed CCN spectra are also derived which take into account the variability caused by chemical effects (surface tension, molecular composition, solubility, degree of dissociation of WSOC).

Particles from biomass burning and regional haze were sampled in Rondônia, Brazil, during dry, transition and wet periods from September to November 2002, as part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia - Smoke, Aerosols, Clouds, Rainfall, and Climate) field campaign. Water soluble organic and inorganic compounds in bulk (High Volume and Stacked Filter Unit sampler) and size-resolved (Micro Orifice Uniform Deposit Impactor - MOUDI) smoke samples were determined by ion chromatography. It was found that low molecular weight polar organic acids account for a significant fraction of the water soluble organic carbon (WSOC) in biomass burning aerosols (C₂-C₆ dicarboxylic acids reached up to 3.7% and one-ring aromatic acids reached up to 2% of fine fraction WSOC during burning period). Short dicarboxylic (C₂-C₆) acids are dominated by oxalic acid followed by malonic and succinic acids. The largest ionic species is ammonium sulfate (60-70% of ionic mass). It was found that most of the ionic mass is concentrated in submicrometer-sized particles. Based on the size distribution and correlations with K⁺, a known biomass burning tracer, it is suggested that many of the organic acids are directly emitted by vegetation fires. Concentrations of dicarboxylic acids in the front and back filters of high volume sampler were determined. Based on these measurements, it was concluded that in the neutral or slightly basic smoke particles typical of this region, dicarboxylic acids are mostly confined to the particulate phase. Finally, it is shown that the distribution of water soluble species shifts to larger aerosols sizes as the aerosol population ages and mixes with other aerosol types in the atmosphere.

The crystals formed at 293 K by aerosol particles composed of SO ₄^2-, NO ₃^-, NH ₄⁺, and H ⁺ are determined by aerosol flow tube infrared spectroscopy. An innovative experimental protocol is employed to restore water content to the aerosol particles and thus remove the ambiguity of their physical state after exposure to low relative humidity. The six crystals formed include (NH ₄) ₂SO ₄, (NH ₄) ₃H(SO ₄) ₂, NH ₄HSO ₄, NH ₄NO ₃, 2NH ₄NO ₃·(NH ₄) ₂SO ₄, and 3NH ₄NO ₃·(NH ₄) ₂SO ₄. The dependence of which crystals form on aqueous chemical composition is reported. The infrared signatures of these crystals are determined. The infrared spectra of 2NH ₄NO ₃·(NH ₄) ₂SO ₄, and 3NH ₄NO ₃·(NH ₄) ₂SO ₄ and their formation in aerosol particles are reported for the first time. The formation of NH ₄HSO ₄ and NH ₄NO ₃ in initially homogeneous aerosol particles is also reported for the first time: crystallization occurs only after another crystal has already formed, indicating that heterogeneous nucleation is necessary for their formation. For some chemical compositions, in a fraction of the aerosol particles, metastable crystals that form at low relative humidity reconstruct to thermodynamically stable crystals at higher relative humidity. An externally mixed aerosol results. Contact ion pairs are apparent in the infrared spectra of aerosol particles that do not crystallize even at 1% relative humidity. Taken together, our findings suggest a more diverse array and more frequent occurrence of crystalline SO ₄^2--NO ₃^--NH ₄₊-H ₊ aerosol particles in the troposphere than currently considered in the literature.

Changes in aerosol composition associated with a cold front passage were examined during a field experiment in Tel Aviv, Israel (2-15 Dec, 2000). In addition to monitoring aerosol scattering and optical thickness, aerosol samples were collected for detailed chemical analyses. Data were compared to simultaneous measurements made at Sde Boker, a semi-remote site in the Negev Desert, to help determine what changes were due to local pollution as opposed to regional phenomena. During the pre-frontal period (2-7 Dec) both sites were influenced by air masses containing a relatively high content of sulphate and dust, originating from neighbouring regions of the Middle East. A steady build-up of local pollution was then observed in Tel Aviv due to vehicular emissions/industrial activities, as indicated by increasing concentrations of black carbon, organic carbon, V, Cu, Ni, Zn, Br, Pb, NO₃^- and PAHs. Identification of a number of organic biomass burning tracers (e.g., levoglucosan) indicates that smoke also contributed to the pollution build-up in Tel Aviv, while a range of sugars/sugar alcohols point to a microbial/bioaerosol component. Locally emitted pollutants tended to exhibit higher nighttime concentrations due to trapping of pollution under a nocturnal inversion. Fine aerosol iodine was the only element exhibiting higher daytime concentrations, hinting at a photochemical source. Post-frontal measurements (12-15 Dec) revealed a significant decrease in all pollutants due to dispersal of the haze by the cold front (8-9 Dec), with the air initially being dominated by marine aerosol. Concentrations of pollutants then began to increase, with backward trajectories indicating a possible contribution from Eastern Europe. Overall, the study identified a range of useful tracers for monitoring the contribution of different sources to the aerosol over Israel. Crown

[1] We investigated nucleation scavenging of aerosols by cloud drops during the passage of a shallow cold front at a mountain station in northern Israel. The chemical composition and size of the aerosols were measured during and following the passage of the front. Analysis of the air mass trajectories show that, prior to the frontal passage, the air originated from the north, bringing with it pollution particles from sources in Eastern Europe. Following the frontal passage, the air originated from the east, bringing with it some mineral dust particles. The results show that sulfate, nitrate, and ammonium were the dominant compounds in the particles. Of the total sulfate-containing particles, 65% nucleated cloud drops. We found nucleation scavenging of aerosols to be correlated with the size of the aerosols. Aerosols smaller than 0.14 mum were not significantly affected by nucleation scavenging, while the number concentration of particles larger than 0.14 mm decreased in correspondence to the increase in droplet concentrations. During the time that the cloud covered the measuring site, 80% of the particles in the size range 0.3-1 mum were scavenged. The concentrations of the particles with diameter smaller than 1 mm returned to their original values after the cloud dissipated.

Rate coefficients for the reaction of OH radical with eleven C₃-C₆ hydroxyalkyl nitrates and with two C₄ hydroxy nitrates containing a double bond were determined at atmospheric pressure and 296 ± 2 K. The rate coefficients were measured in a photochemical reactor by the relative rate technique, employing solid-phase microextraction (SPME) coupled to gas chromatography (GC) for detection of the organic reactions. Hydroxyalkyl nitrates react faster than alkyl nitrates with the OH radical. The rate coefficients increase with increasing chain length and separation between the hydroxyl and the nitrooxy groups. By including different loss processes such as photolysis, gas-phase reactions, and solubility, the tropospheric lifetime of C₃-C₆ hydroxyalkyl nitrates is estimated to range between 0.5 and 4.5 days. Due to their higher reactivity and solubility, hydroxyalkyl nitrates have a shorter atmospheric lifetime than alkyl nitrates.

Applications of new retrieval methods to old satellite data allowed us to study the effects of smoke from the Kuwait oil fires in 1991 on clouds and precipitation. The properties of smoke-affected and smoke-free clouds were compared on the background of the dust-laden desert atmosphere. Several effects were observed: (1) clouds typically developed at the top of the smoke plume, probably because of solar heating and induced convection by the strongly absorbing aerosols; (2) large salt particles from the burning mix of oil and brines formed giant cloud condensation nuclei (CCN) close to the source, which initiated coalescence in the highly polluted clouds; (3) farther away from the smoke source, the giant CCN were deposited, and the extremely high concentrations of medium and small CCN dominated cloud development by strongly suppressing drop coalescence and growth with altitude; and (4) the smaller cloud droplets in the smoke-affected clouds froze at colder temperatures and suppressed both the water and ice precipitation forming processes. These observations imply that over land the smoke particles are not washed out efficiently and can be transported to long distances, extending the observed effects to large areas. The absorption of solar radiation by the smoke induces convection above the smoke plumes and consequently leads to formation of clouds with roots at the top of the smoke layer. This process dominates over the semidirect effect of cloud evaporation due to the smoke-induced enhanced solar heating, at least in the case of the Kuwait fires.

The heterogeneous reaction between ozone and oleic and linoleic acids, prevalent components of both marine and urban organic aerosol, were studied in a flow reactor using electron impact and chemical ionization mass spectrometry. Liquids and frozen liquids were used as proxies for atmospheric aerosol. The reactive uptake coefficients, γ, were determined to be (8.3 ± 0.2) × 10^-4 and (1.2 ± 0.2) × 10^-3 for liquid oleic and linoleic acid respectively and (5.2 ± 0.1) × 10^-5 and (1.4 ± 0.1) × 10^-4 for frozen oleic and linoleic acid, respectively. Although, the reacto-diffusive length is estimated to be rather small in the liquid experiments,

The reactive uptake of the NO₃ radical by liquid and frozen organics was studied in a rotating wall flow tube coupled to a White cell. The organic liquids used included alkanes, alkenes, an alcohol, and carboxylic acids with conjugated and nonconjugated unsaturated bonds. The reactive uptake coefficients, γ, of NO₃ on n-hexadecane, l-octadecene, l-hexadecene, cis + trans 7-tetradecene, n-octanoic acid, 2,2,4,4,6,8,8 heptamethyl nonane, l-octanol, cis, trans 9,11 and 10,12 octadecadienoic acid, cis-9, cis-12 octadecadienoic acid were determined. The reactive uptake coefficients measured with the organic liquids varied from 1.4 × 10^-3 to 1.5 × 10^-2. The uptake coefficients of NO₃ by n-hexadecane and n-octanoic acid decreased by a factor of ∼5 upon freezing. This behavior is explained by reaction occurring in the bulk of the organic liquid as well as on the surface. For the rest of the compounds the change in values of γ upon freezing of the liquids was within the experimental uncertainty. This is attributed to predominant uptake of NO₃ by the top few molecular surface layers of the organic substrate and continuous replenishment of the surface layer by evaporation and/or mobility of the surface. These conclusions are corroborated by estimation of the diffuso-reactive length and solubility constant of NO₃ in these liquids. The reactivity of NO₃ with the organic surfaces is shown to correlate well with the known gas-phase chemistry of NO₃. The effect on the atmospheric chemistry of the NO₃ radical due to its interaction with organic aerosols is studied using an atmospheric box model applying realistic atmospheric scenarios. The inclusion of NO₃ uptake on organic aerosol can decrease the NO₃ lifetime by 10% or more.

Individual mineral dust particles collected in a dust storm over Israel were analyzed by a scanning electron microscopy and energy-dispersed system (SEM-EDS). The analysis shows that the particles were mostly aggregates of varying mineralogical composition rather than pure minerals. It is also shown that sulfur (not associated with gypsum) and, to a lesser extent, iron tended to reside on the particles' surface, while Ca, Mg, K, Al, and Si were all an integral part of the particles. The lack of NaCl and sulfuric acid aerosols in the sample indicates that the air mass did not interact with marine air or with clouds. This conclusion is further supported by back trajectory calculations. These findings suggest that the sulfur in the aerosols did not result from atmospheric processes but rather originated from processes in the source region. Black residue, surrounding some of the particles, suggests the possible existence of organic matter in the sample, probably originating from biological activity in the soil at the source of the particles. The method of individual particle analysis provides important information about the composition and morphology of the particles, information that otherwise cannot be obtained by bulk analysis methods.

A technique for identifying trace amounts of semivolatile organic compounds in atmospheric aerosols and in the NIST Urban Dust standard (SRM1649a) is presented. The technique is based on direct sample introduction (DSI) of small samples followed by thermal desorption in a conventional GC injector. The method enables injection of both solid and liquid samples. Validation of the method, including quantitative determination of EPA-targeted polycyclic aromatic hydrocarbons (PAHs), as well as the reproducibility and recovery efficiency tests are presented. The advantages of using aluminum foil as sampling filter are also discussed. Determination of different classes of compounds such as quinolines, methylquinoline isomers, PAHs, and n-monocarboxylic acids in the ambient size-segregated aerosol sample is also performed. The method was directly applied to the determination of C₆-C₁₆ n-monocarboxylic acids, eliminating the need for a complex sample preparation procedure. The small quantities needed for the analysis as well as the lack of complicated sample preparation steps enable fast characterization of semivolatile organic species present in time-resolved or size-segregated aerosol samples. Thus, this method can potentially be employed for air quality monitoring and field measurements as well as for fast screening of the organic content of ambient particles.

Gas-phase and surface-bound products were determined for the reaction of ozone with self assembled monolayers of alkanes and terminal alkenes serving as proxies for atmospheric organic aerosols. The organic surfaces were characterized using infrared (IR) spectroscopy (direct absorption and attenuated total reflection) as well as contact angle measurements with water before and after the reaction with ozone. The contact angle of the organic surfaces was reduced by ∼20° owing to the reaction. Following the reaction, IR absorption due to the presence of carbonyls and carboxylic acids was observed on the surface. Gas-phase products were determined using infrared spectroscopy immediately above the reaction surface. Under dry conditions, gas-phase formaldehyde yields of 0.5±0.1 for organic monolayers of allyltrichlorosilane (C₃⁼) and octenyltrichlorosilane (C₈⁼) terminal alkenes were observed, in good agreement with the yields observed for gas phase ozonolysis of terminal alkenes. Surfaces of n-octane (C₈) as well as processed alkene surfaces were nonreactive toward ozone. The reaction mechanism of ozone with the surface alkenes is discussed. Finally, the possible implications for the chemistry of organic aerosols are discussed and studied using a box model and realistic atmospheric scenarios.

The interaction between water and organic substances is of extreme importance in physical, biological, and geological chemistries. Understanding the interactions between water and organic interfaces is one of the earliest chemical quandaries. In this research, self-assembled monolayers (SAMs) were used as a tool to investigate the interaction between water molecules and hydrophobic surfaces. Real-time adsorption and desorption kinetics of water on hydrophobic SAM surfaces was monitored using a new type of field effect transistor (FET)-like device called MOCSER (molecular controlled semiconductor resistor) coated with SAMs. A quartz crystal microbalance (QCM) was used as a complementary technique to give an estimate of total water mass adsorbed. It is shown that water adsorption depends on relative humidity and is reversible. The amount of adsorbed water increased with surface corrugation. The measurements suggest that adsorption takes place as small water clusters, originating on irregularities on the surface organic layer. Molecular dynamics simulations were carried out to study the interactions of water and hydrophobic surfaces as well. These simulations also suggest the formation of water microdroplets on hydrophobic surfaces, and indicate a strong correlation between increased surface corrugation and adsorption. This paper examines the possible consequences of these interactions on the properties of organic aerosols in the troposphere.

Organic nitrates form via the photodegradation of hydrocarbons in the troposphere in the presence of NO and NO₂. This process competes with the chemical cycle leading to ozone production since it sequesters both nitrogen oxides and organic radicals. Hydroxy nitrates form via the atmospheric reactions of alkanes and alkenes and are thought to be an important nitrogen oxides reservoir. In this study, new synthetic methods to produce β-, γ-, and δ-hydroxy nitrates of atmospheric interest were developed. NMR and IR spectroscopies were used to characterize these compounds. Henry's law coefficients of C₄ and C₅ hydroxy nitrates at 291 ± 2 K were measured using a dynamic equilibrium system. The solubility decreases with the organic chain length and increases with increasing distance between the nitrooxy and hydroxy groups. Due to their large Henry's law coefficients these species will partition into droplets in the presence of clouds and fogs. Measurements of the OH reaction and photolysis rate coefficients are needed for an accurate assessment of the atmospheric lifetimes of these compounds.

The rate coefficient of the CH₃C(O)O₂ + NO gas-phase reaction was measured over the temperature range of 218-370 K and total pressure of 2-5 Torr, using chemical ionization mass spectrometry detection of the CH₃C(O)O₂ radical. The temperature-dependent expression for the rate coefficient was determined to be k(T) = (6.0 ± 1.1) 10_-12 exp{(320 ± 40)/T} cm³ molecule^-1 s^-1, and a 298 K rate constant k₂₉₈ = (1.8 ± 0.3) 10^-11 cm³ molecule^-1 s^-1 was found. These results quell some of the ambiguity presented by previous studies of this reaction and validate the recommended value to be used in tropospheric chemistry models.