Atmospheric protein chemistry influenced by anthropogenic air pollutants: nitration and oligomerization upon exposure to ozone and nitrogen dioxide.

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.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in the environment - A review.

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are derivatives of PAHs with at least one nitro-functional group (-NO2) on the aromatic ring. The toxic effects of several nitro-PAHs are more pronounced than those of PAHs. Some nitro-PAHs are classified as possible or probable human carcinogens by the International Agency for Research on Cancer. Nitro-PAHs are released into the environment from combustion of carbonaceous materials (e.g. fossil fuels, biomass, waste) and post-emission transformation of PAHs. Most studies on nitro-PAHs are about air (gas-phase and particulate matter), therefore less is known about the occurrence, concentrations, transport and fate of nitro-PAHs in soils, aquatic environment and biota. Studies on partition and exchange of nitro-PAHs between adjacent environmental compartments are also sparse. The concentrations of nitro-PAHs cannot easily be predicted from the intensity of anthropogenic activity or easily related to those of PAHs. This is because anthropogenic source strengths of nitro-PAHs are different from those of PAHs, and also nitro-PAHs have additional sources (formed by photochemical conversion of PAHs). The fate and transport of nitro-PAHs could be considerably different from their related PAHs because of their higher molecular weights and considerably different sorption mechanisms. Hence, specific knowledge on nitro-PAHs is required. Regulations on nitro-PAHs are also lacking. We present an extensive review of published literature on the sources, formation, physico-chemical properties, methods of determination, occurrence, concentration, transport, fate, (eco)toxicological and adverse health effects of nitro-PAHs. We also make suggestions and recommendations about data needs, and future research directions on nitro-PAHs. It is expected that this review will stimulate scientific discussion and provide the basis for further research and regulations on nitro-PAHs.

Azaarenes in fine particulate matter from the atmosphere of a Chinese megacity.

Azaarenes (AZAs) are toxicologically relevant organic compounds with physicochemical properties that are significantly different from the well-studied polycyclic aromatic hydrocarbons (PAHs). However, little is known about their concentrations, seasonal variations, fate, and relationship with PAHs in air. This paper reports the temporal variations in the concentrations and composition patterns of AZAs in PM2.5 that was sampled once per 6 days from outdoor air of Xi'an, China from July 2008 to August 2009. The concentrations of the ∑AZAs, quinoline (QUI), benzo[h]quinoline (BQI), and acridine (ACR) in PM2.5 were 213-6441, 185-520, 69-2483, and 10-3544 pg m(-3), respectively. These concentrations were higher than those measured in urban areas of Western Europe. AZA compositional patterns were dominated by BQI and ACR. The high concentration of AZAs, high AZA/related PAH ratio, and the dominance of three-ring AZAs (BQI and ACR) in PM2.5 of Xi'an are all in contrast to observations from Western European and North American cities. This contrast likely reflects differences in coal type and the more intense use of coal in China. The PM2.5-bound concentration of AZA in winter season (W) was higher than during the summer season (S) with W/S ratios of 5.7, 1.4, 4.1, and 13, for ∑AZAs, QUI, BQI, and ACR, respectively. Despite their significantly different physicochemical properties, AZAs were significantly (p < 0.05) positively correlated with their related PAHs and pyrogenic elemental carbon. The changes in AZA concentrations were positively correlated with ambient pressure but negatively correlated with ambient temperature, wind speed, and relative humidity. This trend is similar to that observed for the related PAHs. We conclude that Xi'an and possibly other Chinese cities have higher emission of AZAs into their atmosphere because of the more pronounced use of coal. We also conclude that in spite of differences in physicochemical properties between AZAs and related PAHs, the atmospheric dynamics and relationships with meteorological factors of both compound groups are similar.

Biological soil crusts accelerate the nitrogen cycle through large NO and HONO emissions in drylands.

Reactive nitrogen species have a strong influence on atmospheric chemistry and climate, tightly coupling the Earth's nitrogen cycle with microbial activity in the biosphere. Their sources, however, are not well constrained, especially in dryland regions accounting for a major fraction of the global land surface. Here, we show that biological soil crusts (biocrusts) are emitters of nitric oxide (NO) and nitrous acid (HONO). Largest fluxes are obtained by dark cyanobacteria-dominated biocrusts, being ∼20 times higher than those of neighboring uncrusted soils. Based on laboratory, field, and satellite measurement data, we obtain a best estimate of ∼1.7 Tg per year for the global emission of reactive nitrogen from biocrusts (1.1 Tg a(-1) of NO-N and 0.6 Tg a(-1) of HONO-N), corresponding to ∼20% of global nitrogen oxide emissions from soils under natural vegetation. On continental scales, emissions are highest in Africa and South America and lowest in Europe. Our results suggest that dryland emissions of reactive nitrogen are largely driven by biocrusts rather than the underlying soil. They help to explain enigmatic discrepancies between measurement and modeling approaches of global reactive nitrogen emissions. As the emissions of biocrusts strongly depend on precipitation events, climate change affecting the distribution and frequency of precipitation may have a strong impact on terrestrial emissions of reactive nitrogen and related climate feedback effects. Because biocrusts also account for a large fraction of global terrestrial biological nitrogen fixation, their impacts should be further quantified and included in regional and global models of air chemistry, biogeochemistry, and climate.

Protein Cross-Linking and Oligomerization through Dityrosine Formation upon Exposure to Ozone.

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.

PM2.5-bound oxygenated PAHs, nitro-PAHs and parent-PAHs from the atmosphere of a Chinese megacity: seasonal variation, sources and cancer risk assessment.

Polycyclic aromatic compounds (PACs) in air particulate matter contribute considerably to the health risk of air pollution. The objectives of this study were to assess the occurrence and variation in concentrations and sources of PM2.5-bound PACs [Oxygenated PAHs (OPAHs), nitro-PAHs and parent-PAHs] sampled from the atmosphere of a typical Chinese megacity (Xi'an), to study the influence of meteorological conditions on PACs and to estimate the lifetime excess cancer risk to the residents of Xi'an (from inhalation of PM2.5-bound PACs). To achieve these objectives, we sampled 24-h PM2.5 aerosols (once in every 6 days, from 5 July 2008 to 8 August 2009) from the atmosphere of Xi'an and measured the concentrations of PACs in them. The PM2.5-bound concentrations of Σcarbonyl-OPAHs, ∑hydroxyl+carboxyl-OPAHs, Σnitro-PAHs and Σalkyl+parent-PAHs ranged between 5-22, 0.2-13, 0.3-7, and 7-387 ng m(-3), respectively, being markedly higher than in most western cities. This represented a range of 0.01-0.4% and 0.002-0.06% of the mass of organic C in PM2.5 and the total mass of PM2.5, respectively. The sums of the concentrations of each compound group had winter-to-summer ratios ranging from 3 to 8 and most individual OPAHs and nitro-PAHs had higher concentrations in winter than in summer, suggesting a dominant influence of emissions from household heating and winter meteorological conditions. Ambient temperature, air pressure, and wind speed explained a large part of the temporal variation in PACs concentrations. The lifetime excess cancer risk from inhalation (attributable to selected PAHs and nitro-PAHs) was six fold higher in winter (averaging 1450 persons per million residents of Xi'an) than in summer. Our results call for the development of emission control measures.