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The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

The impact of emissions of volatile organic compounds (VOCs) to the atmosphere on the production of secondary pollutants, such as ozone and secondary organic aerosol (SOA), is mediated by the concentration of nitric oxide (NO). Polluted urban atmospheres are typically considered to be "high-NO"environments, while remote regions such as rainforests, with minimal anthropogenic influences, are considered to be "low NO". However, our observations from central Beijing show that this simplistic separation of regimes is flawed. Despite being in one of the largest megacities in the world, we observe formation of gas- and aerosol-phase oxidation products usually associated with low-NO "rainforest-like"atmospheric oxidation pathways during the afternoon, caused by extreme suppression of NO concentrations at this time. Box model calculations suggest that during the morning high-NO chemistry predominates (95 %) but in the afternoon low-NO chemistry plays a greater role (30 %). Current emissions inventories are applied in the GEOS-Chem model which shows that such models, when run at the regional scale, fail to accurately predict such an extreme diurnal cycle in the NO concentration. With increasing global emphasis on reducing air pollution, it is crucial for the modelling tools used to develop urban air quality policy to be able to accurately represent such extreme diurnal variations in NO to accurately predict the formation of pollutants such as SOA and ozone.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

The impact of emissions of volatile organic compounds (VOCs) to the atmosphere on the production of secondary pollutants, such as ozone and secondary organic aerosol (SOA), is mediated by the concentration of nitric oxide (NO). Polluted urban atmospheres are typically considered to be "high-NO"environments, while remote regions such as rainforests, with minimal anthropogenic influences, are considered to be "low NO". However, our observations from central Beijing show that this simplistic separation of regimes is flawed. Despite being in one of the largest megacities in the world, we observe formation of gas- and aerosol-phase oxidation products usually associated with low-NO "rainforest-like"atmospheric oxidation pathways during the afternoon, caused by extreme suppression of NO concentrations at this time. Box model calculations suggest that during the morning high-NO chemistry predominates (95 %) but in the afternoon low-NO chemistry plays a greater role (30 %). Current emissions inventories are applied in the GEOS-Chem model which shows that such models, when run at the regional scale, fail to accurately predict such an extreme diurnal cycle in the NO concentration. With increasing global emphasis on reducing air pollution, it is crucial for the modelling tools used to develop urban air quality policy to be able to accurately represent such extreme diurnal variations in NO to accurately predict the formation of pollutants such as SOA and ozone.

Direct measurements of NOx, CO and aromatic volatile organic compound (VOC) (benzene, toluene, C2-benzenes and C3-benzenes) flux were made for a central area of Beijing using the eddy-covariance technique. Measurements were made during two intensive field campaigns in central Beijing as part of the Air Pollution and Human Health (APHH) project, the first in November–December 2016 and the second during May–June 2017, to contrast wintertime and summertime emission rates. There was little difference in the magnitude of NOx flux between the two seasons (mean NOx flux was 4.41 mg m−2 h−1 in the winter compared to 3.55 mg m−2 h−1 in the summer). CO showed greater seasonal variation, with mean CO flux in the winter campaign (34.7 mg m−2 h−1) being over twice that of the summer campaign (15.2 mg m−2 h−1). Larger emissions of aromatic VOCs in summer were attributed to increased evaporation due to higher temperatures. The largest fluxes in NOx and CO generally occurred during the morning and evening rush hour periods, indicating a major traffic source with high midday emissions of CO, indicating an additional influence from cooking fuel. Measured NOx and CO fluxes were then compared to the MEIC 2013 emissions inventory, which was found to significantly overestimate emissions for this region, providing evidence that proxy-based emissions inventories have positive biases in urban centres. This first set of pollutant fluxes measured in Beijing provides an important benchmark of emissions from the city which can help to inform and evaluate current emissions inventories.

Isoprene-derived secondary organic aerosol (iSOA) is a significant contributor to organic carbon (OC) in some forested regions, such as tropical rainforests and the Southeastern US. However, its contribution to organic aerosol in urban areas that have high levels of anthropogenic pollutants is poorly understood. In this study, we examined the formation of anthropogenically influenced iSOA during summer in Beijing, China. Local isoprene emissions and high levels of anthropogenic pollutants, in particular NOx and particulate SO2-4 , led to the formation of iSOA under both high- A nd low-NO oxidation conditions, with significant heterogeneous transformations of isoprene-derived oxidation products to particulate organosulfates (OSs) and nitrooxyorganosulfates (NOSs). Ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was combined with a rapid automated data processing technique to quantify 31 proposed iSOA tracers in offline PM2.5 filter extracts. The co-elution of the inorganic ions in the extracts caused matrix effects that impacted two authentic standards differently. The average concentration of iSOA OSs and NOSs was 82.5 ngm-3, which was around 3 times higher than the observed concentrations of their oxygenated precursors (2-methyltetrols and 2-methylglyceric acid). OS formation was dependant on both photochemistry and the sulfate available for reactive uptake, as shown by a strong correlation with the product of ozone (O3) and particulate sulfate (SO2-4). A greater proportion of high-NO OS products were observed in Beijing compared with previous studies in less polluted environments. The iSOA-derived OSs and NOSs represented 0.62% of the oxidized organic aerosol measured by aerosol mass spectrometry on average, but this increased to ∼ 3% on certain days. These results indicate for the first time that iSOA formation in urban Beijing is strongly controlled by anthropogenic emissions and results in extensive conversion to OS pro

We examine the street-scale variation of NOx, NO3, O3 and PM2.5 concentrations in Beijing during the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-China) winter measurement campaign in November-December 2016. Simulations are performed using the urban air pollution dispersion and chemistry model ADMS-Urban and an explicit network of road source emissions. Two versions of the gridded Multi-resolution Emission Inventory for China (MEIC v1.3) are used: the standard MEIC v1.3 emissions and an optimised version, both at 3 km resolution. We construct a new traffic emissions inventory by apportioning the transport sector onto a detailed spatial road map. Agreement between mean simulated and measured pollutant concentrations from Beijing's air quality monitoring network and the Institute of Atmospheric Physics (IAP) field site is improved when using the optimised emissions inventory. The inclusion of fast NOx-O3 chemistry and explicit traffic emissions enables the sharp concentration gradients adjacent to major roads to be resolved with the model. However, NO2 concentrations are overestimated close to roads, likely due to the assumption of uniform traffic activity across the study domain. Differences between measured and simulated diurnal NO2 cycles suggest that an additional evening NOx emission source, likely related to heavy-duty diesel trucks, is not fully accounted for in the emissions inventory. Overestimates in simulated early evening NO2 are reduced by delaying the formation of stable boundary layer conditions in the model to replicate Beijing's urban heat island. The simulated campaign period mean PM2.5 concentration range across the monitoring network (∼15 µg m-3) is much lower than the measured range (∼40 µg m-3). This is likely a consequence of insufficient PM2.5 emissions and spatial variability, neglect of explicit point sources, and assumption of a homogeneous background PM2.5 level. Sensitivity studies highlight that the use of explicit r

We examine the street-scale variation of NOx, NO3, O3 and PM2.5 concentrations in Beijing during the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-China) winter measurement campaign in November-December 2016. Simulations are performed using the urban air pollution dispersion and chemistry model ADMS-Urban and an explicit network of road source emissions. Two versions of the gridded Multi-resolution Emission Inventory for China (MEIC v1.3) are used: the standard MEIC v1.3 emissions and an optimised version, both at 3 km resolution. We construct a new traffic emissions inventory by apportioning the transport sector onto a detailed spatial road map. Agreement between mean simulated and measured pollutant concentrations from Beijing's air quality monitoring network and the Institute of Atmospheric Physics (IAP) field site is improved when using the optimised emissions inventory. The inclusion of fast NOx-O3 chemistry and explicit traffic emissions enables the sharp concentration gradients adjacent to major roads to be resolved with the model. However, NO2 concentrations are overestimated close to roads, likely due to the assumption of uniform traffic activity across the study domain. Differences between measured and simulated diurnal NO2 cycles suggest that an additional evening NOx emission source, likely related to heavy-duty diesel trucks, is not fully accounted for in the emissions inventory. Overestimates in simulated early evening NO2 are reduced by delaying the formation of stable boundary layer conditions in the model to replicate Beijing's urban heat island. The simulated campaign period mean PM2.5 concentration range across the monitoring network (∼15 µg m-3) is much lower than the measured range (∼40 µg m-3). This is likely a consequence of insufficient PM2.5 emissions and spatial variability, neglect of explicit point sources, and assumption of a homogeneous background PM2.5 level. Sensitivity studies highlight that the use of explicit r

Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidized multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes, and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside volatile organic compounds (VOCs) and trace-gas data from a campaign in June 2017, in Beijing. Many gas-phase HOMs have been characterized and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a degree of oxidation comparable to that seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2 center dot terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C-5 and C-10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH center dot chemistry in the formation of HOMs, as O-3 tends to be lower on days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulfuric acid vapours, suggesting that the nucleation process is sulfuric-acid-dependent, with

Atmospheric NH3 plays a vital role not only in the environmental ecosystem but also in atmosphere chemistry. To further understand the effects of NH3 on the formation of haze pollution in Beijing, ambient NH3 and related species were measured and simulated at high resolutions during the wintertime Air Pollution and Human Health-Beijing (APHH-Beijing) campaign in 2016. We found that the total NHx (gaseous NH3+particle NH4+) was mostly in excess of the SO42--NO3--NH4+-water equilibrium system during our campaign. This NHx excess made medium aerosol acidity, with the median pH value being 3.6 and 4.5 for polluted and nonpolluted conditions, respectively, and enhanced the formation of particle phase nitrate. Our analysis suggests that NH4NO3 is the most important factor driving the increasing of aerosol water content with NO3- controlling the prior pollution stage and NH4+ the most polluted stage. Increased formation of NH4NO3 under excess NHx, especially during the nighttime, may trigger the decreasing of aerosol deliquescence relative humidity even down to less than 50% and hence lead to hygroscopic growth even under RH conditions lower than 50% and the wet aerosol particles become better medium for rapid heterogeneous reactions. A further increase of RH promotes the positive feedback "aerosol water content-heterogeneous reactions" and ultimately leads to the formation of severe haze. Modeling results by Nested Air Quality Prediction Monitor System (NAQPMS) show the control of 20% NH3 emission may affect 5-11% of particulate matter PM2.5 formation under current emissions conditions in the North China Plain.

Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidized multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes, and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside volatile organic compounds (VOCs) and trace-gas data from a campaign in June 2017, in Beijing. Many gas-phase HOMs have been characterized and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a degree of oxidation comparable to that seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2 center dot terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C-5 and C-10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH center dot chemistry in the formation of HOMs, as O-3 tends to be lower on days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulfuric acid vapours, suggesting that the nucleation process is sulfuric-acid-dependent, with