Effects of human activities on atmospheric nitrate (NO₃⁻) formation remain unclear, though the knowledge is critical for improving atmospheric chemistry models and nitrogen deposition reduction strategies. A potentially useful way to explore this is to compare NO₃⁻ oxidation processes in urban and rural atmospheres based upon the oxygen stable isotope composition of NO₃⁻ (Δ¹⁷O–NO₃⁻). Here we compared the Δ¹⁷O–NO₃⁻ from three-years of daily-based bulk deposition in urban (Shenyang) and forested rural sites (Qingyuan) in northeast China and quantified the relative contributions of different formation pathways based on the SIAR model. Our results showed that the Δ¹⁷O in Qiangyuan (26.2 ± 3.3‰) is significantly higher (p < 0.001) than in Shenyang (24.0 ± 4.0‰), and significantly higher in winter (Shenyang: 26.1 ± 6.7‰, Qingyuan: 29.6 ± 2.5‰) than in summer (Shenyang: 22.7 ± 2.9‰, Qingyuan: 23.8 ± 2.4‰) in both sites. The lower values in the urban site are linked with conditions that favored a higher relative contribution of nitrogen dioxide reaction with OH pathway (0.76-0.91) than in rural site (0.47-0.62), which should be induced by different levels of human activities in the two sites. The seasonal variations of Δ¹⁷O–NO₃⁻ in both sites are explained by a higher relative contribution of ozone-mediated oxidation chemistry and unfavorable conditions for the OH pathway during winter relative to summer, which is affected by human activities and seasonal meteorological condition change. Based on Δ¹⁷O, wintertime conditions led to a contribution of O₃ related pathways (NO₃ + DMS/HC and N₂O₅ hydrolysis) of 0.63 in Qingyuan and 0.42 in Shenyang, while summertime conditions led to 0.15 in Qingyuan and 0.05 in Shenyang. Our comparative study on Δ¹⁷O–NO₃⁻ between urban and rural sites reveals different anthropogenic effects on nitrate formation processes on spatial and temporal scales, illustrating different responses of reactive nitrogen chemistry to changes in human activities.

We investigate the distribution of volatile organic compounds (VOCs) over Indian subcontinent during a winter month of January 2011 combining the regional model WRF-Chem (Weather Research and Forecasting model coupled with Chemistry) with ground- and space-based observations and chemical reanalysis. WRF-Chem simulated VOCs are found to be comparable with ground-based observations over contrasting environments of the Indian subcontinent. WRF-Chem results reveal the elevated levels of VOCs (e. g. propane) over the Indo-Gangetic Plain (16 ppbv), followed by the Northeast region (9.1 ppbv) in comparison with other parts of the Indian subcontinent (1.3–8.2 ppbv). Higher relative abundances of propane (27–31%) and ethane (13–17%) are simulated across the Indian subcontinent. WRF-Chem simulated formaldehyde and glyoxal show the western coast, Eastern India and the Indo-Gangetic Plain as the regional hotspots, in a qualitative agreement with the MACC (Monitoring Atmospheric Composition and Climate) reanalysis and satellite-based observations. Lower values of RGF (ratio of glyoxal to formaldehyde <0.04) suggest dominant influences of the anthropogenic emissions on the distribution of VOCs over Indian subcontinent, except the northeastern region where higher RGF (∼0.06) indicates the role of biogenic emissions, in addition to anthropogenic emissions. Analysis of HCHO/NO₂ ratio shows a NOₓ-limited ozone production over India, with a NOₓ-to-VOC transition regime over central India and IGP. The study highlights a need to initiate in situ observations of VOCs over regional hotspots (Northeast, Central India, and the western coast) based on WRF-Chem results, where different satellite-based observations differ significantly.

Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01).

The fast economic development of southwest China has resulted in significant increases in the concentrations of reactive nitrogen (Nr) in the atmosphere. In this study, an urban (Chengdu, CD), suburban (Shifang, SF) and agriculture (Yanting, YT) – dominated location in the Sichuan Province, southwest China, were selected to investigate the atmospheric composition of Nr, their concentrations and deposition rates. We measured Nr concentrations in precipitation (NH₄⁺, NO₃⁻ and organic N (DON)), the gas phase (NH₃ and NO₂), and the aerosol particles (PM₂.₅), and calculated their fluxes over a two year period (2014–2016). Total annual N deposition rates were 49.2, 44.7 and 19.8 kg N ha⁻¹ yr⁻¹ at CD, SF and YT, respectively. Ammonia concentrations were larger at the urban and suburban sites than the agricultural site (12.2, 14.9, and 4.9 μg N m⁻³ at CD, SF and YT, respectively). This is consistent with the multitude of larger sources of NH₃, including city garbage, livestock and traffic, in the urban and suburban areas. Monthly NO₂ concentrations were lower in warmer compared to the colder months, but seasonal differences were insignificant. Daily PM₂.₅ concentrations ranged from 7.7 to 236.0, 5.0–210.4 and 4.2–128.4 μg m⁻³ at CD, SF and YT, respectively, and showed significant correlations with fine particulate NH₄⁺ and NO₃⁻ concentrations. Ratios of reduced to oxidized N were in the range of 1.6–2.7. This implies that the control of reduced Nr especially in urban environments is needed to improve local air quality.

A total of 82 aerosol samples (PM10-2.5) were collected from June 18, 2015 to October 1, 2016 at the remote sea site, the Ieodo Ocean Research Station (IORS), in the East China Sea. Samples were analyzed for 10 elements (Al, Fe, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) as well as Pb isotopic composition to characterize temporal variations in elemental concentration levels, and to identify the potential source regions of atmospheric pollutants transported over the remote East China Sea. The results showed that the annual average element concentrations were lowest compared to those at different sites in East Asia, suggesting a very clean background area of IORS, with values ranging from 114 ng m⁻³ for Al to 0.045 ng m⁻³ for Tl. Concentrations averaged seasonally for all the elements revealed the highest levels occurring between winter and spring, and the lowest levels in summer. High enrichment factors (EF) of more than 100 for trace elements suggest that these elements originated mostly from anthropogenic sources. Coupling the Pb isotopic composition with a back trajectory analysis identified the potential source regions for each sample. Our approach identified China as a dominant contributor affecting atmospheric composition changes at IORS, the remote area of the East China Sea. As the largest anthropogenic emission source in East Asia, China contributed to almost 100% of the elemental concentration levels in winter and spring, ∼53% in summer and ∼63% in autumn. Because IORS's ambient air is sensitive to even slight changes in pollutant loading due to the significantly low pollution levels, long-term monitoring of air quality at IORS will provide invaluable information on the progress and efforts of atmospheric pollution management linked to emission controls in East Asian countries, especially China.

Common air pollutants, such as nitrogen oxides (NOₓ), emitted in diesel exhaust, and ozone (O₃), have been implicated in the decline of pollinating insects. Reductionist laboratory assays, focused upon interactions between a narrow range of flowering plant and pollinator species, in combination with atmospheric chemistry models, indicate that such pollutants can chemically alter floral odors, disrupting the cues that foraging insects use to find and pollinate flowers. However, odor environments in nature are highly complex and pollination services are commonly provided by suites of insect species, each exhibiting different sensitivities to different floral odors. Therefore, the potential impacts of pollution-induced foraging disruption on both insect ecology, and the pollination services that insects provide, are currently unknown. We conducted in-situ field studies to investigate whether such pollutants could reduce pollinator foraging and as a result the pollination ecosystem service that those insects provide. Using free-air fumigation, we show that elevating diesel exhaust and O₃, individually and in combination, to levels lower than is considered safe under current air quality standards, significantly reduced counts of locally-occurring wild and managed insect pollinators by 62–70% and their flower visits by 83–90%. These reductions were driven by changes in specific pollinator groups, including bees, flies, moths and butterflies, and coincided with significant reductions (14–31%) in three different metrics of pollination and yield of a self-fertile test plant. Quantifying such effects provides new insights into the impacts of human-induced air pollution on the natural ecosystem services upon which we depend.

The stomatal compensation point of ammonia (χs) is a key factor controlling plant-atmosphere NH3 exchange, which is dependent on the nitrogen (N) supply and varies among plant species. However, knowledge gaps remain concerning the effects of elevated atmospheric N deposition and ozone (O3) on χs for forest species, resulting in large uncertainties in the parameterizations of NH3 incorporated into atmospheric chemistry and transport models (CTMs). Here, we present leaf-scale measurements of χs for hybrid poplar clone ‘546’ (Populusdeltoides cv. 55/56 x P. deltoides cv. Imperial) growing in two N treatments (N0, no N added; N50, 50 kg N ha−1 yr−1 urea fertilizer added) and two O3 treatments (CF, charcoal-filtered air; E-O3, non-filtered air plus 40 ppb) for 105 days. Our results showed that χs was significantly reduced by E-O3 (41%) and elevated N (19%). The interaction of N and O3 was significant, and N can mitigate the negative effects of O3 on χs. Elevated O3 significantly reduced the light-saturated photosynthetic rate (Asat) and chlorophyll (Chl) content and significantly increased intercellular CO2 concentrations (Ci), but had no significant effect on stomatal conductance (gs). By contrast, elevated N did not significantly affect all measured photosynthetic parameters. Overall, χs was significantly and positively correlated with Asat, gs and Chl, whereas a significant and negative relationship was observed between χs and Ci. Our results suggest that O3-induced changes in Asat, Ci and Chl may affect χs. Our findings provide a scientific basis for optimizing parameterizations of χs in CTMs in response to environmental change factors (i.e., elevated N deposition and/or O3) in the future.

Real time chemical characterization of non-refractory submicron aerosols (NR-PM1) was carried out during post monsoon (September–October) via Aerosol Mass Spectrometer (AMS) at a polluted urban location of Kanpur, India. Organic aerosol (OA) was found to be the dominant species with 58% contribution to total NR-PM1 mass, followed by sulfate (16%). Overall, OA was highly oxidized (average O/C = 0.66) with the dominance of oxidized OAs (60% of total OA) as revealed by source apportionment. Oxidized nature of OA was also supported by very high OC/EC ratios (average = 8.2) obtained from simultaneous offline filter sampling. High and low OA loading periods have very dramatic effects on OA composition and oxidation. OA O/C ratios during lower OA loading periods were on average 30% higher than the same from high loading periods with significant changes in types and relative contribution from oxidized OAs (OOA). Comparison of OA sources and chemistry among post monsoon and other seasons revealed significant differences. Characteristics of primary OAs remain very similar, but features of OOAs showed substantial changes from one season to another. Winter had lowest OOA contribution to total OA but similar overall O/C ratios as other seasons. This reveals that processing of primary OAs, local atmospheric chemistry, and regional contributions can significantly alter OA characteristics from one season to another. This study provides interesting insights into the seasonal variations of OA sources and evolution in a very polluted and complex environment.

A characterization of the physical–chemical composition of the atmospheric PM adsorbed to airborne pollen was performed. Airborne pollen was sampled using a Hirst-type volumetric spore sampler and observed using a Field Emission Electron Probe Microanalyser for PM analysis. A secondary electron image was taken of each pollen grain and EDS spectra were obtained for individually adsorbed particles. All images were analysed and the size parameters of the particles adsorbed to pollen was determined. The measured particles’ equivalent diameter varied between 0.1 and 25.8 μm, mostly in the fine fraction. The dominant particulates identified were Si-rich, Organic-rich, SO-rich, Metals & Oxides and Cl-rich. Significant daily differences were observed in the physical–chemical characteristics of particles adsorbed to the airborne pollen wall. These differences were correlated with weather parameters and atmospheric PM concentration. Airborne pollen has the ability to adsorb fine particles that may enhance its allergenicity.

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model – Master Chemical Mechanism (MCM) model – to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.