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Oxidative stress is a possible mechanism by which ambient fine particulate matter (PM) exerts adverse biological effects. While multiple biological effects and reactive oxygen species (ROS) production have been observed upon PM exposure, whether the biological effects are ROS-mediated remains unclear. Secondary organic aerosols (SOA) constitute a major fraction of fine PM and can contribute substantially to its toxicity. In this work, we measured three types of cell responses (mitochondrial membrane potential (MMP), caspase 3/7 activity, and ROS) and investigated their associations upon exposure to SOA formed from anthropogenic (naphthalene) and biogenic (α-pinene) precursors. MMP and caspase 3/7 activity (an early indicator of apoptosis) are key indicators of cell health, and changes of them could occur downstream of ROS-mediated pathways. We observed a significant increase in caspase 3/7 activity after SOA exposure, suggesting that apoptosis is an important pathway of cell death induced by SOA. We further found strong associations between a decrease in MMP and increase in caspase 3/7 activity with an increase in cellular ROS level. These results suggest that cell health is largely dependent on the cellular ROS level, highlighting oxidative stress as a key mechanism for biological effects from SOA exposure. Linear regression analyses reveal greater changes of the three cellular responses with increasing carbon oxidation state (OSc) of SOA, suggesting that SOA are more toxic when they are more oxidized. Overall, our work provides critical insights into the associations between cell health and ROS level upon SOA exposure and proposes that OSc could be a suitable proxy to assess the overall SOA toxicity.

Microplastics (MPs) pollution is becoming one of the most pressing environmental issues globally. MPs in the marine, freshwater and terrestrial environments have been fairly well investigated. However, knowledge of the atmospheric-mediated deposition of MPs within rural environments is limited. Here, we present the results of bulk (dry and wet) atmospheric MPs deposition in a rural region of Quzhou County in the North China Plain (NCP). Samples of MPs in the atmospheric bulk deposition were collected for individual rainfall events over a 12-month period from August 2020 to August 2021. The number and size of MPs from 35 rainfall samples were measured by fluorescence microscopy, while the chemical composition of MPs was identified using micro-Fourier transform infrared spectroscopy (μ-FTIR). The results showed that the atmospheric MPs deposition rate in summer (892–75,421 particles/m2/day) was highest compared to 735–9428, 280–4244 and 86–1347 particles/m2/day in spring, autumn, and winter, respectively. Furthermore, the MPs deposition rates in our study were 1–2 orders of magnitude higher than those in other regions, indicating a higher rate of MPs deposition in the rural region of the NCP. MPs with a diameter of 3–50 μm accounted for 75.6 %, 78.4 %, 73.4 % and 66.1 % of total MPs deposition in spring, summer, autumn, and winter, respectively, showing that the majority of MPs in the current study were small in size. Rayon fibers accounted for the largest proportion (32 %) of all MPs, followed by polyethylene terephthalate (12 %) and polyethylene (8 %). This study also found that a significant positive correlation between rainfall volume and MPs deposition rate. In addition, HYSPLIT back-trajectory modelling showed that the farthest source of deposition MPs may have come from Russia.

Exposure to atmospheric particulate matter (PM) is a leading global health risk. Despite extensive studies, it remains unclear as to what components or characteristics of PM best account for its to...

Biological soil crusts (abbreviated as biocrusts) are composed of photoautotrophic cyanobacteria, algae, lichens, and bryophytes, growing together with heterotrophic bacteria, archaea and fungi and forming an intimate association with soil particles in the uppermost millimeters of the substrate. They occur globally in drylands, where they cover about 1/3 of the soil surface, corresponding to an area of about 18 x 106 km2. Biocrusts fix atmospheric nitrogen (N), which is needed for physiological processes and the formation of biomass. However, it recently was also shown that similar to bulk soil, N is cycled within biocrusts and major fractions of it are released as nitrous acid (HONO) and nitric oxide (NO) to the atmosphere.Based on these initial results, we investigated the biologically mediated N-cycling processes in biocrusts as related to wetting and drying events. We investigated the microbial activity at different drying stages by means of transcriptome analysis and related these results to soil nitrite and nitrate concentrations over time. In addition, we utilized catalyzed reporter deposition fluorescence in situ hybridization (CARD-FISH) to quantify the number of bacteria, archaea, and nitrite oxidizing bacteria in different strata over time.Our results revealed that within less than 30 minutes after wetting, genes encoding for all relevant N cycling processes, including N fixation, ammonification, nitrification, denitrification, and assimilatory and dissimilatory N reduction were expressed. The most abundant transcriptionally active N-transforming microorganisms belonged to the Rhodobacteraceae, Enterobacteriaceae and Pseudomonadaceae within the Alpha- and Gammaproteobacteria. The soil nitrite contents increased significantly during the desiccation process, likely serving as a precursor for NO and HONO emissions, which peaked at relatively low water contents of ~20% water holding capacity. This nitrite accumulation was likely caused by a differential expression of nitrite as compared to nitrate reductase encoding genes over the course of desiccation. Additionally, our data suggest that ammonia-oxidizing organisms may have responded to changing local oxygen conditions during drying. These mechanisms are also supported by process-based modelling, which has been conducted by us. Thus, our results show that the activity of N-cycling microorganisms, as related to the water and oxygen conditions within the substrate, determines the process rates and overall quantity of reactive nitrogen emissions.

Cloth masks are a tool for controlling community transmission during pandemics, as well as during other outbreak situations. However, cloth masks vary in their designs, and the consequences of this variability for their effectiveness as source control have received little attention, particularly in terms of user discomfort and problematic mask-wearing behaviors. In the present studies, common design parameters of cloth masks were systematically varied to ascertain their effect(s) on the subjective discomfort and frequency of problematic mask-wearing behaviors, which detract from the effectiveness of cloth masks as source control. The type of fabric comprising a mask (flannel or twill made of 100% cotton) and the attachment-style of a mask (i.e., ear loops or fabric ties) were varied in adults (18 to 65 years) and children (ages 6 to 11 years). For adults, ear loops were less comfortable than ties (p = .035) and were associated with greater face- (p = .005) and mask-touching (p = .001). Children, however, found flannel masks to be more breathable than twill masks (p = .007) but touched their masks more frequently when wearing a mask made of flannel than twill (p = .033). Common design parameters of cloth masks not only affect user discomfort and behavior but do so differently in adults and children. To improve the effectiveness of cloth masks as source control, the present studies highlight the importance of measuring the effect(s) of design decisions on user discomfort and behavior in different populations.

Cerium oxide nanoparticles (CeNPs) have been shown to exhibit antioxidant capabilities, but their efficiency in scavenging reactive oxygen species (ROS) and the underlying mechanisms are not yet well understood. In this study, cerium dioxide nanoparticles (CeNPs) and nanorods (CeNRs) were found to exhibit much stronger scavenging activity than ·OH generation in phosphate buffered saline (PBS) and surrogate lung fluid (SLF). The larger surface area and higher defect density of CeNRs may lead to higher ·OH scavenging activity than for CeNPs. These insights are important to understand the redox activity of cerium nanomaterials and provide clues to the role of CeNPs in biological and environmental processes.

Toll-like receptor 4 (TLR4) plays a crucial role in the recognition of invading pathogens. Upon activation by lipopolysaccharides (LPS), TLR4 is recruited into specific membrane domains and dimerizes. In addition to LPS, TLR4 can be stimulated by wheat amylase-trypsin inhibitors (ATI). ATI are proteins associated with gluten containing grains, whose ingestion promotes intestinal and extraintestinal inflammation. However, the effect of ATI vs. LPS on the membrane distribution of TLR4 at the nanoscale has not been analyzed. In this study, we investigated the effect of LPS and ATI stimulation on the membrane distribution of TLR4 in primary human macrophages using single molecule localization microscopy (SMLM). We found that in unstimulated macrophages the majority of TLR4 molecules are located in clusters, but with donor-dependent variations from ∼51% to ∼75%. Depending on pre-clustering, we found pronounced variations in the fraction of clustered molecules and density of clusters on the membrane upon LPS and ATI stimulation. Although clustering differed greatly among the human donors, we found an almost constant cluster diameter of ∼44 nm for all donors, independent of treatment. Together, our results show donor-dependent but comparable effects between ATI and LPS stimulation on the membrane distribution of TLR4. This may indicate a general mechanism of TLR4 activation in primary human macrophages. Furthermore, our methodology visualizes TLR4 receptor clustering and underlines its functional role as a signaling platform.

Saccharides are important constituents in atmospheric aerosols but studies in northwestern China are still very limited. Here, we have measured anhydrosugars (levoglucosan, mannosan and galactosan), primary sugars (glucose, fructose, sucrose and trehalose), and sugar alcohols (arabitol, mannitol, sorbitol and inositol) in ambient PM2.5 samples during summer and winter in Xi'an city, northwestern China. The abundance of total saccharides showed no clear seasonal variation, but apparent distinctions on the levels of the three categories and individual saccharide compounds were found. Primary sugars and particularly sucrose were dominant in summer. In contrast, levoglucosan was the predominant species in winter, contributing 60% of total saccharides. Source apportionment by positive matrix factorization revealed that airborne pollen was a major source of PM2.5 associated-saccharides in summer, accounting for 35% of total saccharides; while biomass burning activities contributed to 60% of the winter saccharides. Furthermore, an increasing trend of biomass/biofuel burning contribution to winter PM2.5 was observed in comparison with previous studies in Xi'an, suggesting a change in emission sources may be underway in northwestern China.

The COVID-19 pandemic has resulted in a severe shortage of personal protective equipment. The World Health Organization (WHO) and the US Centers for Disease Control and Prevention (CDC) recommend the general public to use cloth masks as a protection for individuals and reduce the transmission of the disease. Here, we evaluated the size-dependent filtration efficiency of submicron particles and the overall filtration efficiency (total rejection of particles) of multiple commercially available materials in the size range of 17–700 nm. Single-layer samples of woven fabrics such as cotton and polyester have overall filtration efficiency of 12%−22%. Blended fabrics filter 11%−48% of particles. Products manufactured from cellulose have filtration efficiency of 29%−33%. Materials commonly found and used in hospitals remove 20%−63% of particles and filtration efficiency of filter materials ranges from 40% to 96%. Particle filtration of materials becomes more efficient when individual materials are stacked and used as multiple layers. Different combinations of woven, nonwoven, and blended fabrics were evaluated and have overall particle filtration efficiency of 38%−63%. Results in this study highlight the importance of using multiple layers in homemade masks to enhance filtration efficiency. Commercially accessible materials like Halyard sterilization wrap and blackout drapery lining show the best filtration performance among all tested single-layer materials and therefore are recommended to use as one of the layers in homemade masks. Universal mask wearing – regardless of whether an individual is infected – will help reduce transmission risk. Copyright © 2021 American Association for Aerosol Research

Interaction of water with fine particulate matter leads to the formation of reactive species (RS) that may influence the aging, properties, and health effects of atmospheric aerosols. In this study, we explore the RS yields of fine PM from remote forest (Hyytiälä, Finland) and polluted urban air (Mainz, Germany and Beijing, China) and relate these yields to different chemical constituents and reaction mechanisms. Ultrahigh-resolution mass spectrometry was used to characterize organic aerosol composition, electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping technique was used to determine the concentrations •OH, O2•−, and carbon- or oxygen-centered organic radicals, and a fluorometric assay was used to quantify H2O2 concentration. The mass-specific yields of radicals were lower for sampling sites with higher concentration of ambient PM2.5 (particles with a diameter 2O2 yields exhibited no clear trend. The abundances of water-soluble transition metals and aromatics in ambient PM2.5 were positively correlated with the relative fraction of •OH to the totally detected radicals, but negatively correlated with the relative fraction of carbon-centered radicals. Moreover, we found that the relative fractions of different types of radicals formed by ambient PM2.5 were comparable to the surrogate mixtures comprising transition metals, organic hydroperoxide, H2O2, and humic or fulvic acids. Therein humic and fulvic acids exhibited strong radical scavenging effect to substantially decrease the radical yield of mixtures comprising cumene hydroperoxide and Fe2+. The interplay of transition metals (e.g., iron), highly oxidized compounds (e.g., organic hydroperoxides), and complexing agents (e.g., humic or fulvic acids), leads to non-linear concentration dependencies of production and yields of different types of RS. Our findings show that how the composition of PM2.5 influences the amount and nature of RS produced upon interaction with water, which may explain differences in the chemical reactivity and health effects of particulate matter in clean and polluted air.

Health risks associated with exposure to ambient particulate matter (PM) are a major concern around the world. Adverse PM health effects have been proposed to be linked to oxidative stress through the generation of reactive oxygen species (ROS).

Water-soluble proteinaceous matter including proteins and free amino acids (FAAs) as well as some other chemical components was analyzed in fine particulate matter (PM2.5) samples collected over a period of one year in rural Guangzhou. Annual averaged protein and total FAAs concentrations were 0.79 ± 0.47 μg m–3 and 0.13 ± 0.05 μg m–3, accounting for 1.9 ± 0.7% and 0.3 ± 0.1% of PM2.5, respectively. Among FAAs, glycine was the most abundant species (19.9%), followed by valine (18.5%), methionine (16.1%), and phenylalanine (13.5%). Both proteins and FAAs exhibited distinct seasonal variations with higher concentrations in autumn and winter than those in spring and summer. Correlation analysis suggests that aerosol proteinaceous matter was mainly derived from intensive agricultural activities, biomass burning, and fugitive dust/soil resuspension. Significant correlations between proteins/FAAs and atmospheric oxidant (O3) indicate that proteins/FAAs may be involved in O3 related atmospheric processes. Our ob...

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5–200 ppb O3, 5–200 ppb NO2, 45–96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5–25% and 0.5–7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration, but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.

Highly oxygenated molecules (HOMs) play an important role in the formation and evolution of secondary organic aerosols (SOA). However, the abundance of HOMs in different environments and their relation to the oxidative potential of fine particulate matter (PM) are largely unknown. Here, we investigated the relative HOM abundance and radical yield of laboratory-generated SOA and fine PM in ambient air ranging from remote forest areas to highly polluted megacities. By electron paramagnetic resonance and mass spectrometric investigations, we found that the relative abundance of HOMs, especially the dimeric and low-volatility types, in ambient fine PM was positively correlated with the formation of radicals in aqueous PM extracts. SOA from photooxidation of isoprene, ozonolysis of alpha- and beta-pinene, and fine PM from tropical (central Amazon) and boreal (Hyytiala, Finland) forests exhibited a higher HOM abundance and radical yield than SOA from photooxidation of naphthalene and fine PM from urban sites (Beijing, Guangzhou, Mainz, Shanghai, and Xian), confirming that HOMs are important constituents of biogenic SOA to generate radicals. Our study provides new insights into the chemical relationship of HOM abundance, composition, and sources with the yield of radicals by laboratory and ambient aerosols, enabling better quantification of the component-specific contribution of source- or site-specific fine PM to its climate and health effects.

Particulate matter (PM) exposure is a leading global human health risk. In this study, water-soluble oxidative potential (OP) and intracellular reactive oxygen and nitrogen species (ROS/RNS) production were measured for open biomass burning aerosol collected from the Brazilian Amazon. Compared to ambient samples collected from Atlanta and laboratory-generated secondary organic aerosol (SOA), biomass burning aerosol had comparable OP and induced higher levels of ROS/RNS. Compared to regressed OP ranges for biomass burning factors resolved using source apportionment in prior studies, the samples investigated in this study spanned a wider OP range, suggesting that concentration addition may not be applicable for OP measurements. The discrepancy between ROS/RNS estimated using laboratory polycyclic aromatic hydrocarbons (PAHs) solution mixtures and ROS/RNS measured for the water-soluble hydrophobic fraction of Amazon filter samples further supports this conclusion. These results have important implications as...

Amylase trypsin inhibitors (ATI) can be found in all gluten containing cereals and are, therefore, ingredient of basic foods like bread or pasta. In the gut ATI can mediate innate immunity via activation of the Toll-like receptor 4 (TLR4) on immune cells residing in the lamina propria, promoting intestinal, as well as extra-intestinal, inflammation. Inflammatory conditions can induce formation of peroxynitrite (ONOO-) and, thereby, endogenous protein nitration in the body. Moreover, air pollutants like ozone (O3) and nitrogen dioxide (NO2) can cause exogenous protein nitration in the environment. Both reaction pathways may lead to the nitration of ATI. To investigate if and how nitration modulates the immunostimulatory properties of ATI, they were chemically modified by three different methods simulating endogenous and exogenous protein nitration and tested in vitro. Here we show that ATI nitration was achieved by all three methods and lead to increased immune reactions. We found that ATI nitrated by tetranitromethane (TNM) or ONOO- lead to a significantly enhanced TLR4 activation. Furthermore, in human primary immune cells, TNM nitrated ATI induced a significantly higher T cell proliferation and release of Th1 and Th2 cytokines compared to unmodified ATI. Our findings implicate a causative chain between nitration, enhanced TLR4 stimulation, and adaptive immune responses, providing major implications for public health, as nitrated ATI may strongly promote inhalative wheat allergies (baker's asthma), non-celiac wheat sensitivity (NCWS), other allergies, and autoimmune diseases. This underlines the importance of future work analyzing the relationship between endo- and exogenous protein nitration, and the rise in incidence of ATI-related and other food hypersensitivities.

Day-night PM10-bound PAHs were studied at an urban site of Xi’an from 20 December 2006 to 28 October 2007. The annual mean concentration of nighttime PAHs (285.0 ng m−3) was higher than that in daytime (239.4 ng m−3). A significant difference of PAH concentrations between daytime and nighttime was found in autumn with a coefficient of divergence (CD) of 0.23 (significant level 0.2). However, no distinct difference was observed in other seasons (with CD values < 0.2), although the difference of PAHs partition capacity in PM10 between daytime and nighttime was significant in the four seasons. Remarkable seasonal variations were observed in the total PAH levels, with a highest mean concentration of 344.6 ng m−3 in winter and a lowest mean concentration of 177 ng m−3 in summer. Positive matrix factorization results revealed that residential emission for heating is the major contributor of the elevated PAH levels in winter, accounting for 49% of the total PAH levels. The coal combustion including industrial and residential usage, contributed over 40% of the PAH emissions in PM10 of Xi’an during the one-year sampling period. These results can provide guidance for taking measures in reducing PAHs levels in the air.

Air pollution and climate change are potential drivers for the increasing burden of allergic diseases. The molecular mechanisms by which air pollutants and climate parameters may influence allergic diseases, however, are complex and elusive. This article provides an overview of physical, chemical and biological interactions between air pollution, climate change, allergens, adjuvants and the immune system, addressing how these interactions may promote the development of allergies. We reviewed and synthesized key findings from atmospheric, climate, and biomedical research. The current state of knowledge, open questions, and future research perspectives are outlined and discussed. The Anthropocene, as the present era of globally pervasive anthropogenic influence on planet Earth and, thus, on the human environment, is characterized by a strong increase of carbon dioxide, ozone, nitrogen oxides, and combustion- or traffic-related particulate matter in the atmosphere. These environmental factors can enhance the abundance and induce chemical modifications of allergens, increase oxidative stress in the human body, and skew the immune system toward allergic reactions. In particular, air pollutants can act as adjuvants and alter the immunogenicity of allergenic proteins, while climate change affects the atmospheric abundance and human exposure to bioaerosols and aeroallergens. To fully understand and effectively mitigate the adverse effects of air pollution and climate change on allergic diseases, several challenges remain to be resolved. Among these are the identification and quantification of immunochemical reaction pathways involving allergens and adjuvants under relevant environmental and physiological conditions.

Laboratory investigations of aerosol physico-chemical properties are usually initiated by spray-drying processes. Morphology of the generated particles may vary largely under different spray-drying conditions, which may further affect the characterization of particle properties. However, only limited data is available on the morphology of nebulized submicron particles, particularly for protein particles. To fill this gap, a centrifugal particle mass analyzer coupled with a scanning mobility particle sizer was used to analyze the effective density, an indicator of particle morphology, of nebulized protein particles (bovine serum albumin and ovalbumin) in a size range from 40 to 200 nm. Results indicate that the effective density of the protein particles generated via spray-drying processes is mainly determined by the competition between the removal of liquid water and the redistribution of the solute monomers in the sprayed droplets. Factors increasing the time needed for solute monomers redistribution (e.g. lower solution concentration and larger particle dry size) or decreasing the time needed for liquid water removal (e.g. higher drying rate) may result in a lower particle effective density, meaning a semi-solid structure or partially hollow morphology. This is also confirmed by the particle hygroscopicity measured with a nano-particle hygroscopic tandem differential mobility analyzer and a high humidity tandem differential mobility analyzer. Our results suggest that the factors affecting the morphology of particles may be complex and coupled with each other, highlighting the importance of monitoring particle effective densities in studies using aerosol particles generated via spray-drying processes.

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4-C11) and perfluorosulfonates (PFSAs, C4, C6-C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(-)ESI-MS/MS). The concentrations of total PFAAs (Sigma PFAAs) ranged from 3.0 to 52 ng L-1, with an average of 19 12 ng L-1. The highest concentrations of Sigma PFAAs were detected in the surface water of the Dong Jiang tributary (17-52 ng L-1), followed by the main stream (13-26 ng L-1) and the Sha Wan stream (3.0-4.5 ng L-1). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of EPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs. (C) 2013 Elsevier Ltd. All rights reserved.

Dry and wet deposition of atmospheric particles is a dominant pathway for PAHs to the coastal environments. Very few studies have been conducted to quantify the contribution of atmospheric deposition to PAH levels in the coastal regions. In this study, PAHs were analyzed in samples collected during a year-round campaign using atmospheric (gas and particle) and depositional samples at a coastal site South China. The average PAH particle deposition fluxes observed calculated 260 ± 190 ng m−2 d−1. Remarkable seasonal variations were recorded in the total PAH deposition fluxes, with higher deposition fluxes in the dry seasons and lower fluxes in the wet seasons. The temporal trend of deposition fluxes was influenced by PAH concentration in the aerosols and changes in meteorological parameters, such as temperature, rainfall, and wind speed etc. Dry deposition velocities of individual PAH compound ranged from 0.02 to 1.03 cm s−1, and there was a decrease pattern in dry deposition velocity with increasing molecular weight of PAHs. The annual mean washout ratio, defined as the ratio between the particle-associated concentrations of PAHs in precipitations and aerosols, was 3.4 × 105 in this study. Washout ratios decreased with increasing rainfall frequency and reached a consistent level afterward. The contribution of atmospheric deposition to PAH concentrations in the sediments was estimated to be 30%–40% in the coastal regions of South China.

Due to the unique characteristics, such as intensive radiation, high altitude and low humidity, plateau climate importantly affects the airborne organic contaminants' behavior in the environment. In this study, USEPA priority polycyclic aromatic hydrocarbons (PAHs) and benzo[e]pyrene were detected in the air samples collected at two suburban sites in Lhasa city. The total concentrations of USEPA priority fifteen PAHs (except naphthalene) in the particulate phase ranged from 4.4 to 60 ng/m 3 , while in the gas phase from 79 to 350 ng/m 3 . Integrated results of the multiple diagnostic ratios indicated that the major potential sources of PAHs in Lhasa city were local incomplete combustion of wood and cow dung cake. Particulate and gaseous PAH levels in this study displayed two clear and different diurnal and nocturnal concentration patterns, however, no distinct diurnal and nocturnal variation was observed for the total suspended particles (TSP) concentrations. No significant correlation was found between TSP concentrations and particle-bound PAHs, meaning physicochemical processes play an important role in diurnal and nocturnal variations of PAHs in the atmosphere except emission sources in this study. Based on the diurnal and nocturnal changes of the percentage of particulate phase PAHs in total PAHs, it suggested that gas–particle partitioning driven by temperature makes a great contribution to the variations of PAHs concentrations. The most susceptible to transformation between gas and particle phase chemicals are PHE, ANT, FLA, PYR, BaA and CHR. In addition, our observation suggested that atmospheric reaction and photolytic degradation also exert an important impact on the variations of PAHs in both phases in the atmosphere of Lhasa city.

Chemical modifications such as nitration and cross-linking may enhance the allergenic potential of proteins. The kinetics and mechanisms of the underlying chemical processes, however, are not yet well understood. Here, we present a size-exclusion chromatography/spectrophotometry method (SEC-HPLC-DAD) that allows a simultaneous detection of mono-, di-, tri-, and higher protein oligomers, as well as their individual nitration degrees (NDs). The ND results of proteins from this new method agree well with the results from an alternative well-established method, for the analysis of tetranitromethane (TNM)- and nitrogen dioxide and ozone (NO2/O3)-nitrated protein samples. Importantly, the NDs for individual oligomer fractions can be obtained from the new method, and also, we provide a proof of principle for the calculation of the concentrations for individual protein oligomer fractions by their determined NDs, which will facilitate the investigation of the kinetics and mechanism for protein tyrosine nitration and cross-linking.

Metaproteomic analysis of air particulate matter provides information about the abundance and properties of bioaerosols in the atmosphere and their influence on climate and public health. We developed and applied efficient methods for the extraction and analysis of proteins from glass fiber filter samples of total, coarse, and fine particulate matter. Size exclusion chromatography was applied to remove matrix components, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was applied for protein fractionation according to molecular size, followed by in-gel digestion and LC-MS/MS analysis of peptides using a hybrid Quadrupole-Orbitrap MS. Maxquant software and the Swiss-Prot database were used for protein identification. In samples collected at a suburban location in central Europe, we found proteins that originated mainly from plants, fungi, and bacteria, which constitute a major fraction of primary biological aerosol particles (PBAP) in the atmosphere. Allergenic proteins were found in coarse and fine particle samples, and indications for atmospheric degradation of proteins were observed. Graphical abstract Workflow for the metaproteomic analysis of atmospheric aerosol samples Electronic supplementary material The online version of this article (doi:10.1007/s00216-016-9747-x) contains supplementary material, which is available to authorized users.

Filter samples of total suspended particle (TSP) collected during a cruise campaign over the northern South China Sea (SCS) from September to October 2013 were analyzed for non-polar organic compounds (NPOCs) as well as organic carbon (OC), elemental carbon (EC) and water-soluble ions. A total of 115 NPOCs species in groups of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), iso-/antiso-alkanes, hopanes, steranes, methylalkanes, branched alkanes, cycloalkanes, alkenes and phthalates were detected. The characteristics of NPOCs in marine TSP samples were investigated to understand the sources from the Asian continent and other regions. The concentrations of total NPOCs ranged from 19.8 to 288.2 ng/m(3) with an average of 87.9 ng/m(3), which accounted for 0.8-1.7% (average 1.0%) of organic matter (OM). n-Alkanes was the predominant group, accounting for 43.1-79.5%, followed by PAHs (5.5-44.4%) and hopanes (1.6-11.4%). We found that primary combustion (biomass burning/fossil fuel combustion) was the dominant source for the majority of NPOCs (89.1%). Biomass burning in southern/southeastern China via long-range transport was proposed to be a major contributor of NPOCs in marine aerosols over the northern SCS, suggested by the significant correlations between nss-K(+) and NPOCs groups as well as the analysis of air mass back-trajectory and fire spots. For the samples with strong continental influence, the strong enhancement in concentrations of n-alkanes, PAHs, hopanes and steranes were attributed to fossil fuel (coal/petroleum) combustion. In addition, terrestrial plants waxes were another contributor to NPOCs.

We present a new method to quantify NOx emissions and corresponding atmospheric lifetimes from OMI NO2 observations together with ECMWF wind fields without further model input for sources located in polluted background. NO2 patterns under calm wind conditions are used as proxy for the spatial patterns of NOx emissions, and the effective atmospheric NOx lifetime is determined from the change of spatial patterns measured at larger wind speeds. Emissions are subsequently derived from the NO2 mass above background integrated around the source of interest. Lifetimes and emissions are estimated for 17 power plants and 53 cities located in non-mountainous regions across China and the US. The derived lifetimes for non-mountainous sites are 3.8 ± 1.0 h on average with ranges of 1.8 to 7.5 h. The derived NOx emissions show generally good agreement with bottom-up inventories for power plants and cities. Global inventory significantly underestimated NOx emissions in Chinese cities, most likely due to uncertainties associated with downscaling approaches.

Air pollution is a potential driver for the increasing prevalence of allergic disease, and post-translational modification by air pollutants can enhance the allergenic potential of proteins. Here, the kinetics and mechanism of protein oligomerization upon ozone (O3) exposure were studied in coated-wall flow tube experiments at environmentally relevant O3 concentrations, relative humidities and protein phase states (amorphous solid, semisolid, and liquid). We observed the formation of protein dimers, trimers, and higher oligomers, and attribute the cross-linking to the formation of covalent intermolecular dityrosine species. The oligomerization proceeds fast on the surface of protein films. In the bulk material, reaction rates are limited by diffusion depending on phase state and humidity. From the experimental data, we derive a chemical mechanism and rate equations for a kinetic multilayer model of surface and bulk reaction enabling the prediction of oligomer formation. Increasing levels of tropospheric O3 in the Anthropocene may promote the formation of protein oligomers with enhanced allergenicity and may thus contribute to the increasing prevalence of allergies.

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32–55% for BSA, ∼10–21% for OVA) were substantially higher than those for the other identified amino acids (∼5–12% for BSA, ∼4–6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals. Electronic supplementary material The online version of this article (doi:10.1007/s00216-017-0188-y) contains supplementary material, which is available to authorized users.