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Light Detection And Ranging (LiDAR) technology has provided an impactful way to capture 3D environmental map. However, consistent mapping in sensing-degenerated and perceptually-limited scenes (e.g. multi-story buildings) or under high dynamic sensor motion (e.g. rotating platform) remains a significant challenge. To this end, an efficient multi-floor indoor mapping system is proposed in this paper utilizing a versatile rotating LiDAR platform. In the front end, measurements from motor, IMU and LiDAR are tightly integrated to track the fast motion state of system, based on iterative Error State Kalman Filter (ESKF). Then linear and planar features are extracted from the point cloud map voxelized with adaptive resolutions. A sliding-window-based batch optimization is performed to simultaneously optimize the states of local frames with reference to the map consistency. In the experiments, we investigated the influence of rotating speed on the mapping performance as well as the superiority of rotating mechanism when compared to standard LiDAR setup. Moreover, comparative studies with one of the SOTA work, FAST-LIO2, have shown the competitive mapping results in multi-floor indoor environments.

Black carbon (BC) in the Tibetan Plateau (TP) region has distinct climate effects that strongly depend on its mixing state. The aging processes of BC in the TP are subject to emissions from various regions, resulting in considerable variability of its mixing state and physicochemical properties. However, the mechanism and magnitude of this effect are not yet clear. In this study, field observations on physicochemical properties of BC-containing particles (PMBC) were conducted in the northeast (Xihai) and southeast (Lulang) regions of the TP to investigate the impacts of transported emissions from lower-altitude areas on BC characteristics in the TP. Large spatial discrepancies were found in the chemical composition of PMBC. Both sites showed higher concentrations of PMBC when they were affected by transported air masses outside the TP but with diverse chemical composition. Source apportionment for organic aerosol (OA) suggested that primary OA in the northeastern TP was attributed to hydrocarbon OA (HOA) from anthropogenic emissions, while it was dominated by biomass burning OA (BBOA) in the southeastern TP. Regarding secondary aerosol, a marked enhancement in nitrate fraction was observed on aged BC coating in Xihai when the air masses were brought by updrafts and easterly winds from lower-altitude areas. With the development of boundary layer, the enhanced turbulent mixing promoted the elevation of anthropogenic pollutants. In contrast to Xihai, the thickly coated BC in Lulang was mainly caused by elevation and transportation of biomass burning plumes from south Asia, showing a large contribution of secondary organic aerosol (SOA). The distinct transported emissions lead to substantial variations of both chemical composition and light absorption ability of BC across the TP. The thicker coating and higher mass absorption cross-section (MAC) of PMBC in air masses elevated from lower-altitude regions reveal the promoted BC aging processes and their impacts on the mixing state and light absorption of BC in the TP. These findings emphasize the vulnerability of plateau regions to influences of elevated emissions, leading to significant changes in BC concentration, mixing states and light absorption across the TP, all of which need to be considered in the evaluation of BC radiative effects for the TP region.

New particle formation (NPF) plays a crucial role in the atmospheric aerosol population and has significant implications on climate dynamics, particularly in climate-sensitive zones such as the Tibetan Plateau (TP). However, our understanding of NPF on the TP is still limited due to a lack of comprehensive measurements and verified model simulations. To fill this knowledge gap, we conducted an integrated study combining comprehensive field measurements and chemical transport modeling to investigate NPF events on the southeastern TP during the pre-monsoon season. NPF was observed to occur frequently on clear-sky days on the southeastern TP, contributing significantly to the cloud condensation nuclei (CCN) budget in this region. The observational evidence suggests that highly oxygenated organic molecules (HOMs) from monoterpene oxidation participate in the nucleation on the southeastern TP. After updating the monoterpene oxidation chemistry and nucleation schemes in the meteorology–chemistry model, the model well reproduces observed NPF and reveals an extensive occurrence of NPF across the southeastern TP. The dominant nucleation mechanism is the synergistic nucleation of sulfuric acid, ammonia, and HOMs, driven by the transport of anthropogenic precursors from South Asia and the presence of abundant biogenic gases. By investigating the vertical distribution of NPF, we find a significant influence of vertical transport on the southeastern TP. More specifically, strong nucleation near the surface leads to an intense formation of small particles, which are subsequently transported upward. These particles experience enhanced growth to larger sizes in the upper planetary boundary layer (PBL) due to favorable conditions such as lower temperatures and a reduced condensation sink. As the PBL evolves, the particles in larger sizes are brought back to the ground, resulting in a pronounced increase in near-surface particle concentrations. This study highlights the important roles of anthropogenic–biogenic interactions and meteorological dynamics in NPF on the southeastern TP.

New particle formation (NPF) is a major source of aerosol particles and cloud condensation nuclei in the troposphere, playing an important role in both air quality and climate. Frequent NPF events have been observed in heavily polluted urban environments, contributing to the aerosol number concentration by a significant amount. The Po Valley region in northern Italy has been characterized as a hotspot for high aerosol loadings and frequent NPF events in southern Europe. However, the mechanisms of NPF and growth in this region are not completely understood. In this study, we conducted a continuous 2-month measurement campaign with state-of-the-art instruments to elucidate the NPF and growth mechanisms in northern Italy. Our results demonstrate that frequent NPF events (66 % of all days during the measurement campaign) are primarily driven by abundant sulfuric acid (8.5×106 cm−3) and basic molecules in this area. In contrast, oxygenated organic molecules from the atmospheric oxidation of volatile organic compounds (VOCs) appear to play a minor role in the initial cluster formation but contribute significantly to the consecutive growth process. Regarding alkaline molecules, amines are insufficient to stabilize all sulfuric acid clusters in the Po Valley. Ion cluster measurements and kinetic models suggest that ammonia (10 ppb) must therefore also play a role in the nucleation process. Generally, the high formation rates of sub-2 nm particles (87 cm−3 s−1) and nucleation-mode growth rates (5.1 nm h−1) as well as the relatively low condensational sink (8.9×10-3 s−1) will result in a high survival probability for newly formed particles, making NPF crucial for the springtime aerosol number budget. Our results also indicate that reducing key pollutants, such as SO2, amine and NH3, could help to substantially decrease the particle number concentrations in the Po Valley region.

New particle formation contributes significantly to the number concentration of ultrafine particles (UFPs, d ≤ 100 nm) and has a great impact on human health and global climate. Iodine oxoacids (HIOx, including iodic acid, HIO3, and iodous acid, HIO2) have been observed in pristine regions and proved to dominate new particle formation (NPF) at some sites. However, the knowledge of HIOx in polluted urban areas is rather limited. Here, we conducted a long-term measurements of gaseous iodine oxoacids and sulfuric acid in Beijing from January 2019 to October 2021 and also in Nanjing from March 2019 to February 2020 and investigated the contribution of HIOx to UFP number concentration in both urban environments. HIO3 is highest in summer, up to 2.85 × 106 and 2.78 × 106 cm−3 in Beijing and Nanjing, respectively, and is lowest in winter by 96 % and 75 %, respectively. HIO3 exhibits more prominent variation than H2SO4 in both urban sites. HIO3 concentration shows a clear diurnal pattern at both sites with a daily maximum at around noontime, similar to the atmospheric temperature, solar radiation, and ozone (O3) levels. HIO2 concentration has the same diurnal and seasonal trend as HIO3 but is overall about an order of magnitude lower than HIO3 concentration. Back trajectory analysis suggests that the sources for inland iodine species could be a mix of marine and terrestrial origins, with both having peak iodine emission in warm seasons. While the contribution of HIO2 to particle growth is marginal in Beijing and Nanjing, our results demonstrate that HIO3 enhances the particle survival probability of sub-3 nm particles by about 40 % (median) and occasionally by more than 100 % in NPF events, suggesting HIOx are significant contributor to UFPs in polluted urban areas. As the growth contribution from HIO3 and H2SO4 is similar on a per-molecule basis, we propose that the sum of HIO3 and H2SO4 could be used to estimate sub-3 nm particle growth of inorganic acid origin in polluted atmospheres with a significant amount of HIOx.

Atmospheric pollution in urban regions is highly influenced by oxidants due to their important role in the formation of secondary organic aerosol (SOA) and smog. These include the nitrate radical (NO3), which is typically considered a nighttime oxidant, and the chlorine radical (Cl), an extremely potent oxidant that can be released in the morning in chloride-rich environments as a result of nocturnal build-up of nitryl chloride (ClNO2). Chloride makes up a higher percentage of particulate matter in Delhi than has been observed anywhere else in the world, which results in Cl having an unusually strong influence in this city. Here, we present observations and model results revealing that atmospheric chemistry in Delhi exhibits an unusual diel cycle that is controlled by high concentrations of NO during the night. As a result of this, the formation of both NO3 and dinitrogen pentoxide (N2O5), a precursor of ClNO2 and thus Cl, are suppressed at night and increase to unusually high levels during the day. Our results indicate that a substantial reduction in nighttime NO has the potential to increase both nocturnal oxidation via NO3 and the production of Cl during the day.

Below-cloud wet scavenging is an important pathway to remove atmospheric aerosols. The below-cloud wet-scavenging coefficient (BWSC) is the value to describe the ability of rainfall to remove aerosols. The reported BWSCs obtained from the field measurements are much higher than the theory, but the reason for this remains unclear. Based on the long-term field measurements in the Yangtze River Delta of eastern China, we find that 28 % of the rainfall events are high-BWSC events. The high-BWSC events show the sudden decrease in the particle number concentration in all size bins near the end of rainfall. By investigating the simultaneously observed changes in carbon monoxide and aerosol chemical compositions during rainfall events, the circulation patterns, and backward trajectories, we find the cause of the high-BWSC events is the air mass changing but not the wet scavenging. The change in air masses is always followed by the rainfall processes and cannot be screened out by the traditional meteorological criteria, which would cause the overestimation of BWSC. After excluding the high-BWSC events, the observed BWSC is close to the theory and is correlated with the rainfall intensity and particle number concentrations prior to rainfall. This study highlights that the discrepancy between the observed BWSC and the theoretical value may not be as large as is currently believed. To obtain reasonable BWSCs and parameterization from field measurements, the effect of air mass changing during rainfall needs to be carefully considered.

During the COVID-19 lockdown, the dramatic reduction of anthropogenic emissions provided a unique opportunity to investigate the effects of reduced anthropogenic activity and primary emissions on atmospheric chemical processes and the consequent formation of secondary pollutants. Here, we utilize comprehensive observations to examine the response of atmospheric new particle formation (NPF) to the changes in the atmospheric chemical cocktail. We find that the main clustering process was unaffected by the drastically reduced traffic emissions, and the formation rate of 1.5 nm particles remained unaltered. However, particle survival probability was enhanced due to an increased particle growth rate (GR) during the lockdown period, explaining the enhanced NPF activity in earlier studies. For GR at 1.5–3 nm, sulfuric acid (SA) was the main contributor at high temperatures, whilst there were unaccounted contributing vapors at low temperatures. For GR at 3–7 and 7–15 nm, oxygenated organic molecules (OOMs) played a major role. Surprisingly, OOM composition and volatility were insensitive to the large change of atmospheric NOx concentration; instead the associated high particle growth rates and high OOM concentration during the lockdown period were mostly caused by the enhanced atmospheric oxidative capacity. Overall, our findings suggest a limited role of traffic emissions in NPF.

Oxygenated organic molecules (OOMs) are crucial for atmospheric new particle formation and secondary organic aerosol (SOA) growth. Therefore, understanding their chemical composition, temporal behavior, and sources is of great importance. Previous studies on OOMs mainly focus on environments where biogenic sources are predominant, yet studies on sites with dominant anthropogenic emissions, such as megacities, have been lacking. Here, we conducted long-term measurements of OOMs, covering four seasons of the year 2019, in urban Beijing. The OOM concentration was found to be the highest in summer (1.6×108 cm−3), followed by autumn (7.9×107 cm−3), spring (5.7×107 cm−3) and winter (2.3×107 cm−3), suggesting that enhanced photo-oxidation together with the rise in temperature promote the formation of OOMs. Most OOMs contained 5 to 10 carbon atoms and 3 to 7 effective oxygen atoms (nOeff=nO-2×nN). The average nOeff increased with increasing atmospheric photo-oxidation capacity, which was the highest in summer and the lowest in winter and autumn. By performing a newly developed workflow, OOMs were classified into the following four types: aromatic OOMs, aliphatic OOMs, isoprene OOMs, and monoterpene OOMs. Among them, aromatic OOMs (29 %–41 %) and aliphatic OOMs (26 %–41 %) were the main contributors in all seasons, indicating that OOMs in Beijing were dominated by anthropogenic sources. The contribution of isoprene OOMs increased significantly in summer (33 %), which is much higher than those in the other three seasons (8 %–10 %). Concentrations of isoprene (0.2–5.3×107 cm−3) and monoterpene (1.1–8.4×106 cm−3) OOMs in Beijing were lower than those reported at other sites, and they possessed lower oxygen and higher nitrogen contents due to high NOx levels (9.5–38.3 ppbv – parts per billion by volume) in Beijing. With regard to the nitrogen content of the two anthropogenic OOMs, aromatic OOMs were mainly composed of CHO and CHON species, while aliphatic OOMs were dominated by CHON and CHON2 ones. Such prominent differences suggest varying formation pathways between these two OOMs. By combining the measurements and an aerosol dynamic model, we estimated that the SOA growth rate through OOM condensation could reach 0.64, 0.61, 0.41, and 0.30 µg m−3 h−1 in autumn, summer, spring, and winter, respectively. Despite the similar concentrations of aromatic and aliphatic OOMs, the former had lower volatilities and, therefore, showed higher contributions (46 %–62 %) to SOA than the latter (14 %–32 %). By contrast, monoterpene OOMs and isoprene OOMs, limited by low abundances or high volatilities, had low contributions of 8 %–12 % and 3 %–5 %, respectively. Overall, our results improve the understanding of the concentration, chemical composition, seasonal variation, and potential atmospheric impacts of OOMs, which can help formulate refined restriction policy specific to SOA control in urban areas.

The Middle East and North Africa (MENA) region has experienced more frequent and severe drought events in recent decades, leading to increasingly pressing concerns over already strained food and water security. An effective drought monitoring and early warning system is thus critical to support risk mitigation and management by countries in the region. Here we investigate the potential for assimilation of leaf area index (LAI) and soil moisture observations to improve the representation of the overall hydrological and carbon cycles and drought by an advanced land surface model. The results reveal that assimilating soil moisture does not meaningfully improve model representation of the hydrological and biospheric processes for this region, but instead it degrades the simulation of the interannual variation in evapotranspiration (ET) and carbon fluxes, mainly due to model weaknesses in representing prognostic phenology. However, assimilating LAI leads to greater improvement, especially for transpiration and carbon fluxes, by constraining the timing of simulated vegetation growth response to evolving climate conditions. LAI assimilation also helps to correct for the erroneous interaction between the prognostic phenology and irrigation during summertime, effectively reducing a large positive bias in ET and carbon fluxes. Independently assimilating LAI or soil moisture alters the categorization of drought, with the differences being greater for more severe drought categories. We highlight the vegetation representation in response to changing land use and hydroclimate as one of the key processes to be captured for building a successful drought early warning system for the MENA region.

ABSTRACT: This experiment evaluated the standard ileal digestibility (SID) of amino acids (AA) in 8 different sources of wheat fed to broilers and established prediction equations based on the chemical properties of wheat. A total of five hundred forty 1-day-old broilers were tested in 2 stages (from d 10 to 13 and from d 25 to 28). On d 13, 324 broilers were randomly assigned to 9 diets (6 replicate cages, 6 broilers per cage); on d 28, 216 broilers were randomly assigned to 9 diets (6 replicate cages, 4 broilers per cage). The 9 experimental diets included 8 test diets and 1 nitrogen-free diet. Titanium dioxide was added as an exogenous indicator at 0.5% of the diet. In 8 wheat samples, the mean values of total amino acids (TAA), dispensable amino acids (DAA), and indispensable amino acids (IAA) were 12.16% (CV 13.70%), 7.97% (CV 15.49%), and 4.20% (CV 11.47%). On d 13, the lowest SID of AA was Lys (86.71%), and the highest was Pro (97.98%). On d 28, the lowest SID of AA was His (81.31%), and the highest was Pro (96.83%). There was an effect of wheat source on the SID of AA except for Trp (P < 0.05); the broiler age had an effect on the SID of AA except for Tyr (P < 0.05); the SID of most AA were higher at d 13 compared to d 28. At d 13, the SID of AA was correlated with CP, NDF, and ST (P < 0.05). At d 28, the SID of AA was correlated with EE, Ash, ADF, and NDF (P < 0.05). The R2 value of stepwise regression equations to predict the SID of AA at d 13 was highest for Leu (R2 = 0.972), lowest for Asp (R2 = 0.785); at d 28 was highest for Gly (R2 = 0.995), lowest for His (R2 = 0.678). In conclusion, this experiment showed that the chemical properties of wheat can be used to establish accurate equations for predicting the SID of AA. This made it more efficient to obtain the SID of AA for wheat.

The mixing states of particulate amines with different chemical components are of great significance in studying the formation and evolution processes of amine-containing particles. In this work, the mixing states of single particles containing trimethylamine (TMA) and diethylamine (DEA) are investigated using a high-performance single-particle aerosol mass spectrometer located in Nanjing, China, in September 2019. TMA- and DEA-containing particles accounted for 22.8 % and 5.5 % of the total detected single particles, respectively. The particle count and abundance of the TMA-containing particles in the total particles notably increased with enhancement of ambient relative humidity (RH), while the DEA-containing particles showed no increase under a high RH. This result suggested the important role of RH in the formation of particulate TMA. Significant enrichments of secondary organic species, including 43C2H3O+, 26CN−, 42CNO−, 73C3H5O2-, and 89HC2O4-, were found in DEA-containing particles, indicating that DEA-containing particles were closely associated with the aging of secondary organics. The differential mass spectra of the DEA-containing particles showed a much higher abundance of nitrate and organic nitrogen species during the nighttime than during the daytime, which suggested that the nighttime production of particulate DEA might be associated with reactions of gaseous DEA with HNO3 and/or particulate nitrate. In the daytime, the decrease in DEA-containing particles was observed with the enrichment of oxalate and glyoxylate, which suggested a substantial impact of photochemistry on the aging process of DEA-containing particles. Furthermore, more than 80 % of TMA- and DEA-containing particles internally mixed with nitrate, while the abundance of sulfate was higher in the DEA-containing particles (79.3 %) than in the TMA-containing particles (55.3 %). This suggested that particulate DEA existed both as nitrate and sulfate aminium salts, while the particulate TMA primarily presented as nitrate aminium salt. The different mixing states of the TMA- and DEA-containing particles suggested their different formation processes and various influencing factors, which are difficult to investigate using bulk analysis. These results provide insights into the discriminated fates of organics during the evolution process in aerosols, which helps to illustrate the behavior of secondary organic aerosols.

Oxygenated organic molecules (OOMs) are the crucial intermediates linking volatile organic compounds (VOCs) to secondary organic aerosols (SOAs) in the atmosphere, but comprehensive understanding of the characteristics of OOMs and their formation from VOCs is still missing. Ambient observations of OOMs using recently developed mass spectrometry techniques are still limited, especially in polluted urban atmospheres where VOCs and oxidants are extremely variable and complex. Here, we investigate OOMs, measured by a nitrate-ion-based chemical ionization mass spectrometer at Nanjing in eastern China, through performing positive matrix factorization on binned mass spectra (binPMF). The binPMF analysis reveals three factors about anthropogenic VOC (AVOC) daytime chemistry, three isoprene-related factors, three factors about biogenic VOC (BVOC) nighttime chemistry, and three factors about nitrated phenols. All factors are influenced by NOx in different ways and to different extents. Over 1000 non-nitro molecules have been identified and then reconstructed from the selected solution of binPMF, and about 72 % of the total signals are contributed by nitrogen-containing OOMs, mostly regarded as organic nitrates formed through peroxy radicals terminated by nitric oxide or nitrate-radical-initiated oxidations. Moreover, multi-nitrates account for about 24 % of the total signals, indicating the significant presence of multiple generations, especially for isoprene (e.g., C5H10O8N2 and C5H9O10N3). Additionally, the distribution of OOM concentration on the carbon number confirms their precursors are driven by AVOCs mixed with enhanced BVOCs during summer. Our results highlight the decisive role of NOx in OOM formation in densely populated areas, and we encourage more studies on the dramatic interactions between anthropogenic and biogenic emissions.

New particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than 4 orders of magnitude, and the reasons behind this variability are the subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments is largely driven by the formation of sulfuric acid–base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly diverse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres.

Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene (C10H16) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene (C5H8), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms – which drive particle nucleation and early growth – while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C20 and C15, respectively) are produced by termination reactions between pairs of peroxy radicals (RO2⚫) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene ∕ monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C15 dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical (OH⚫) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO2⚫ radicals that reduce C20 formation. RO2⚫ termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C20 yield, such as NO, HO2 and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.

Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ∘C compared with 25 ∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles ( nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van der Waals forces between the vapour molecules and particles and disentangle it from charge–dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %.

ClNO2 and Cl2 can affect atmospheric oxidation and thereby the formation of ozone and secondary aerosols, yet their sources and production mechanisms are not well understood or quantified. In this study we present field observations of ClNO2 and Cl2 at a suburban site in eastern China during April 2018. Persistent high levels of ClNO2 (maximum: ∼3.7 ppbv; 1 min average) were frequently observed at night, due to the high ClNO2 yield (φ (ClNO2), 0.56±0.20) inferred from the measurements. The φ (ClNO2) value showed a positive correlation with the [Cl−] / [H2O] ratio, and its parameterization was improved at low to median yields (0–0.75) by the incorporation of [Cl−] / [H2O] and the suppression effect of aerosol organics. ClNO2 and Cl2 showed a significant correlation on most nights. We show that the Cl2 at our site was more likely a co-product with ClNO2 from N2O5 uptake on acidic aerosols that contain chloride than being produced by ClNO2 uptake as previously suggested. We propose a mechanism in which NO2+ can react with Cl− to produce Cl2 and ClNO2 simultaneously. Under a new framework which regards Cl2, ClNO2, and nitrate as products of N2O5 uptake, the Cl2 yield (φ (Cl2)) was derived using ambient data. φ (Cl2) exhibited significant correlations with [Cl−] and [H+], based on which a parameterization of φ (Cl2) was developed. The derived parameterizations of φ (ClNO2) and φ (Cl2) can be used in models to evaluate the nighttime production of ClNO2 and Cl2 and their impact on the next day's photochemistry.

The concentration of cloud condensation nuclei (CCN) is an essential parameter affecting aerosol–cloud interactions within warm clouds. Long-term CCN number concentration (NCCN) data are scarce; there are a lot more data on aerosol optical properties (AOPs). It is therefore valuable to derive parameterizations for estimating NCCN from AOP measurements. Such parameterizations have already been made, and in the present work a new parameterization is presented. The relationships between NCCN, AOPs, and size distributions were investigated based on in situ measurement data from six stations in very different environments around the world. The relationships were used for deriving a parameterization that depends on the scattering Ångström exponent (SAE), backscatter fraction (BSF), and total scattering coefficient (σsp) of PM10 particles. The analysis first showed that the dependence of NCCN on supersaturation (SS) can be described by a logarithmic fit in the range SS  %, without any theoretical reasoning. The relationship between NCCN and AOPs was parameterized as NCCN≈((286±46)SAE ln(SS/(0.093±0.006))(BSF − BSFmin) + (5.2±3.3))σsp, where BSFmin is the minimum BSF, in practice the 1st percentile of BSF data at a site to be analyzed. At the lowest supersaturations of each site (SS ≈0.1 %), the average bias, defined as the ratio of the AOP-derived and measured NCCN, varied from ∼0.7 to ∼1.9 at most sites except at a Himalayan site where the bias was >4. At SS >0.4 % the average bias ranged from ∼0.7 to ∼1.3 at most sites. For the marine-aerosol-dominated site Ascension Island the bias was higher, ∼1.4–1.9. In other words, at SS >0.4 % NCCN was estimated with an average uncertainty of approximately 30 % by using nephelometer data. The biases were mainly due to the biases in the parameterization related to the scattering Ångström exponent (SAE). The squared correlation coefficients between the AOP-derived and measured NCCN varied from ∼0.5 to ∼0.8. To study the physical explanation of the relationships between NCCN and AOPs, lognormal unimodal particle size distributions were generated and NCCN and AOPs were calculated. The simulation showed that the relationships of NCCN and AOPs are affected by the geometric mean diameter and width of the size distribution and the activation diameter. The relationships of NCCN and AOPs were similar to those of the observed ones.

In this paper, the Chapman-Richards model is adapted to best fit three types of nonlinear curves that are generally encountered in geotechnical engineering practices, i.e. the degree of consolidation versus time factor curves in one-dimensional consolidation and plane strain consolidation under strip loading, the compressibility and permeability curves of soft clay, and the geometry parameters of geosynthetic tube versus pumping pressure curves. The methods of determining unknown parameters using the Chapman-Richards model are fully demonstrated. It is found that the Chapman-Richards model has its range of applications in geotechnical engineering and may provide unique insights into the complexity of geotechnical problems. Keywords: Mathematical modeling, Chapman-Richards model, Curve-fitting

Due to the important contribution of nitrous acid (HONO) to OH radicals in the atmosphere, various technologies have been developed to measure HONO. Among them, wet-denuder–ion-chromatography (WD/IC) is a widely used measurement method. Here, we found interferences with HONO measurements by WD/IC based on a comparison study of concurrent observations of HONO concentrations using a WD/IC instrument (Monitor for AeRosols and Gases in ambient Air, MARGA) and long-path absorption photometer (LOPAP) at the Station for Observing Regional Processes of the Earth System (SORPES) in eastern China. The measurement deviation of the HONO concentration with the MARGA instrument, as a typical instrument for WD/IC, is affected by two factors. One is the change in denuder pH influenced by acidic and alkaline gases in the ambient atmosphere, which can affect the absorption efficiency of HONO by the wet denuder to underestimate the HONO concentration by up to 200 % at the lowest pH. The other is the reaction of NO2 oxidizing SO2 to form HONO in the denuder solution to overestimate the HONO concentration, which can be increased by to 400 % in denuder solutions with the highest pH values due to ambient NH3. These processes are in particularly important in polluted east China, which suffers from high concentrations of SO2, NH3, and NO2. The overestimation induced by the reaction of NO2 and SO2 is expected to be of growing importance with the potentially increased denuder pH due to the decrease in SO2. We further established a method to correct the HONO data measured by a WD/IC instrument such as the MARGA. In case a large amount WD/IC-technique-based instruments are deployed with the main target of monitoring the water-soluble composition of PM2.5, our study can help to obtain a long-term multi-sites database of HONO to assess the role of HONO in atmospheric chemistry and air pollution in east China.

Nitrous acid (HONO), an important precursor of the hydroxyl radical (OH), has long been recognized as of significance to atmospheric chemistry, but its sources are still debated. In this study, we conducted continuous measurement of HONO from November 2017 to November 2018 at the SORPES station in Nanjing of eastern China. The yearly average mixing ratio of observed HONO was 0.69±0.58 ppb, showing a larger contribution to OH relative to ozone with a mean OH production rate of 1.16 ppb h−1. To estimate the effect of combustion emissions of HONO, the emitted ratios of HONO to NOx were derived from 55 fresh plumes (NO∕NOx > 0.85), with a mean value of 0.79 %. During the nighttime, the chemistry of HONO was found to depend on RH, and heterogeneous reaction of NO2 on an aerosol surface was presumably responsible for HONO production. The average nighttime NO2-to-HONO conversion frequency (CHONO) was determined to be 0.0055±0.0032 h−1 from 137 HONO formation cases. The missing source of HONO around noontime seemed to be photo-induced, with an average Punknown of 1.04 ppb h−1, based on a semi-quantitative HONO budget analysis. An over-determined system of equations was applied to obtain the monthly variations in nocturnal HONO sources. Besides the burning-emitted HONO (accounting for about 23 % of the total concentration), the contribution of HONO formed heterogeneously on ground surfaces to measured HONO was an approximately constant proportion of 36 % throughout the year. The soil emission revealed clear seasonal variation and contributed up to 40 % of observed HONO in July and August. A higher propensity for generating HONO on aerosol surfaces occurred in severe hazes (accounting for 40 % of the total concentration in January). Our results highlight ever-changing contributions of HONO sources and encourage more long-term observations to evaluate the contributions from varied sources.

Haze pollution caused by PM2.5 is the largest air quality concern in China in recent years. Long-term measurements of PM2.5 and the precursors and chemical speciation are crucially important for evaluating the efficiency of emission control, understanding formation and transport of PM2.5 associated with the change of meteorology, and accessing the impact of human activities on regional climate change. Here we reported long-term continuous measurements of PM2.5, chemical components, and their precursors at a regional background station, the Station for Observing Regional Processes of the Earth System (SORPES), in Nanjing, eastern China, since 2011. We found that PM2.5 at the station has experienced a substantial decrease (−9.1 % yr−1), accompanied by even a very significant reduction of SO2 (−16.7 % yr−1), since the national “Ten Measures of Air” took action in 2013. Control of open biomass burning and fossil-fuel combustion are the two dominant factors that influence the PM2.5 reduction in early summer and winter, respectively. In the cold season (November–January), the nitrate fraction was significantly increased, especially when air masses were transported from the north. More NH3 available from a substantial reduction of SO2 and increased oxidization capacity are the main factors for the enhanced nitrate formation. The changes of year-to-year meteorology have contributed to 24 % of the PM2.5 decrease since 2013. This study highlights several important implications on air pollution control policy in China.

Particulate nitrate contributes a large fraction of secondary aerosols. Despite understanding of its important role in regional air quality and global climate, long-term continuous measurements are rather limited in China. In this study, we conducted online measurement of PM2.5 (particulate matter with diameters less than 2.5 µm) nitrate for 2 years from March 2014 to February 2016 using the Monitor for AeRosols and Gases in ambient Air (MARGA) in the western Yangtze River Delta (YRD), eastern China, and investigate the main factors that influenced its temporal variations and formation pathways. Compared to other sites in China, an overall high concentration of particulate nitrate was observed, with a mean value of 15.8 µg m−3 (0.5 to 92.6 µg m−3). Nitrate on average accounted for 32 % of the total mass of water-soluble ions and the proportion increased with PM loading, indicating that nitrate is a major driver of haze pollution episodes in this region. Sufficient ammonia drove most nitrate into the particle phase in the form of ammonium nitrate. A typical seasonal cycle of nitrate was observed, with the concentrations in winter on average 2 times higher than those in summer mainly due to different meteorological conditions. In summer, the diurnal variation of particulate nitrate was determined by thermodynamic equilibrium, resulting in a much lower concentration during daytime despite a considerable photochemical production. Air masses from the polluted YRD and biomass burning region contributed to the high nitrate concentration during summer. In winter, particulate nitrate did not reveal an evident diurnal variation. Regional transport from northern China played an important role in enhancing nitrate concentration. A total of 18 nitrate episodes were selected to understand the processes that drive the formation of high concentration of nitrate. Rapid nitrate formation was observed during the pre-episode (the day before nitrate episode day) nights, and dominated the increase of total water-soluble ions. Calculated nitrate from N2O5 hydrolysis was highly correlated to and accounted for 80 % of the observed nitrate, suggesting that N2O5 hydrolysis was a major contributor to the nitrate episodes. Our results suggested that rapid formation of nitrate could be a main cause for extreme aerosol pollution events in the YRD during winter, and illustrated the urgent need to control NOx emission.

Atmospheric new particle formation (NPF) is an important phenomenon in terms of global particle number concentrations. Here we investigated the frequency of NPF, formation rates of 10 nm particles, and growth rates in the size range of 10–25 nm using at least 1 year of aerosol number size-distribution observations at 36 different locations around the world. The majority of these measurement sites are in the Northern Hemisphere. We found that the NPF frequency has a strong seasonal variability. At the measurement sites analyzed in this study, NPF occurs most frequently in March–May (on about 30 % of the days) and least frequently in December–February (about 10 % of the days). The median formation rate of 10 nm particles varies by about 3 orders of magnitude (0.01–10 cm−3 s−1) and the growth rate by about an order of magnitude (1–10 nm h−1). The smallest values of both formation and growth rates were observed at polar sites and the largest ones in urban environments or anthropogenically influenced rural sites. The correlation between the NPF event frequency and the particle formation and growth rate was at best moderate among the different measurement sites, as well as among the sites belonging to a certain environmental regime. For a better understanding of atmospheric NPF and its regional importance, we would need more observational data from different urban areas in practically all parts of the world, from additional remote and rural locations in North America, Asia, and most of the Southern Hemisphere (especially Australia), from polar areas, and from at least a few locations over the oceans.

New particle formation (NPF) provides a large source of atmospheric aerosols, which affect the climate and human health. In recent chamber studies, ion-induced nucleation (IIN) has been discovered as an important pathway of forming particles; however, atmospheric investigation remains incomplete. For this study, we investigated the air anion compositions in the boreal forest in southern Finland for three consecutive springs, with a special focus on H2SO4-NH3 anion clusters. We found that the ratio between the concentrations of highly oxygenated organic molecules (HOMs) and H2SO4 controlled the appearance of H2SO4-NH3 clusters (3 no. S 2SO4] was smaller than 30. The number of H2SO4 molecules in the largest observable cluster correlated with the probability of ion-induced nucleation (IIN) occurrence, which reached almost 100 % when the largest observable cluster contained six or more H2SO4 molecules. During selected cases when the time evolution of H2SO4-NH3 clusters could be tracked, the calculated ion growth rates exhibited good agreement across measurement methods and cluster (particle) sizes. In these cases, H2SO4-NH3 clusters alone could explain ion growth up to 3 nm (mobility diameter). IIN events also occurred in the absence of H2SO4-NH3, implying that other NPF mechanisms also prevail at this site, most likely involving HOMs. It seems that H2SO4 and HOMs both affect the occurrence of an IIN event, but their ratio ([HOMs] ∕ [H2SO4]) defines the primary mechanism of the event. Since that ratio is strongly influenced by solar radiation and temperature, the IIN mechanism ought to vary depending on conditions and seasons.

Highly oxygenated multifunctional compounds (HOMs) play a key role in new particle formation (NPF), but their quantitative roles in different environments of the globe have not been well studied yet. Frequent NPF events were observed at two flagship stations under different environmental conditions, i.e. a remote boreal forest site (SMEAR II) in Finland and a suburban site (SORPES) in polluted eastern China. The averaged formation rate of 6 nm particles and the growth rate of 6–30 nm particles were 0.3 cm−3 s−1 and 4.5 nm h−1 at SMEAR II compared to 2.3 cm−3 s−1 and 8.7 nm h−1 at SORPES, respectively. To explore the differences of NPF at the two stations, the HOM concentrations and NPF events at two sites were simulated with the MALTE-BOX model, and their roles in NPF and particle growth in the two distinctly different environments are discussed. The model provides an acceptable agreement between the simulated and measured concentrations of sulfuric acid and HOMs at SMEAR II. The sulfuric acid and HOM organonitrate concentrations are significantly higher but other HOM monomers and dimers from monoterpene oxidation are lower at SORPES compared to SMEAR II. The model simulates the NPF events at SMEAR II with a good agreement but underestimates the growth of new particles at SORPES, indicating a dominant role of anthropogenic processes in the polluted environment. HOMs from monoterpene oxidation dominate the growth of ultrafine particles at SMEAR II while sulfuric acid and HOMs from aromatics oxidation play a more important role in particle growth. This study highlights the distinct roles of sulfuric acid and HOMs in NPF and particle growth in different environmental conditions and suggests the need for molecular-scale measurements in improving the understanding of NPF mechanisms in polluted areas like eastern China.

Hybrid 2D layered perovskites are solution-processed quantum wells whose optoelectronic properties are tunable by varying the thickness of the inorganic slab. Here Blancon et al. work out a general behavior for dependence of the excitonic properties in layered 2D perovskites.

Brown carbon (BrC), a certain group of organic carbon (OC) with strong absorption from the visible (VIS) to ultraviolet (UV) wavelengths, makes a considerable contribution to light absorption on both global and regional scales. A high concentration and proportion of OC has been reported in China, but studies of BrC absorption based on long-term observations are rather limited in this region. In this study, we reported 3-year results of light absorption of BrC based on continuous measurement at the Station for Observing Regional Processes of the Earth System (SORPES) in the Yangtze River Delta, China, combined with Mie theory calculation. Light absorption of BrC was obtained using an improved absorption Ångström exponent (AAE) segregation method. The AAE of non-absorbing coated black carbon (BC) at each time step is calculated based on Mie theory simulation, together with single particle soot photometer (SP2) and aethalometer observations. By using this improved method, the variation of the AAE over time is taken into consideration, making it applicable for long-term analysis. The annual average light absorption coefficient of BrC (babs_BrC) at 370 nm was 6.3 Mm−1 at the SORPES station. The contribution of BrC to total aerosol absorption (PBrC) at 370 nm ranged from 10.4 to 23.9 % (10th and 90th percentiles, respectively), and reached up to ∼ 33 % in the open-biomass-burning-dominant season and winter. Both babs_BrC and PBrC exhibited clear seasonal cycles with two peaks in later spring/early summer (May–June, babs_BrC ∼ 6 Mm−1, PBrC ∼ 17 %) and winter (December, babs_BrC ∼ 15 Mm−1, PBrC ∼ 22 %), respectively. Lagrangian modeling and the chemical signature observed at the site suggested that open biomass burning and residential coal/biofuel burning were the dominant sources influencing BrC in the two seasons, respectively.

Aerosol optical properties (AOPs) and supporting parameters – particle number size distributions, PM2.5 mass concentrations, and the concentrations of trace gases (NOx and NOy) – were measured at SORPES, a regional background station in Nanjing, China from June 2013 to May 2015. The aerosol was highly scattering: the average scattering coefficient was σsp = 403 ± 314 Mm−1, the absorption coefficient σap = 26 ± 19 Mm−1, and the single-scattering albedo SSA = 0.93 ± 0.03 for green light. The SSA in Nanjing appears to be slightly higher than published values from several other sites in China and elsewhere. The average Ångström exponent of absorption (AAE) for the wavelength range 370–950 nm was 1.04 and the AAE range was 0.7–1.4. These AAE values can be explained with different amounts of non-absorbing coating on pure black carbon (BC) cores and different core sizes rather than contribution by brown carbon. The AOPs had typical seasonal cycles with high σsp and σap in winter and low ones in summer: the averages were σsp = 544 ± 422 and σap = 36 ± 24 Mm−1 in winter and σsp = 342 ± 281 and σap = 20 ± 13 Mm−1 in summer. The intensive AOPs had no clear seasonal cycles, the variations in them were rather related to the evolution of pollution episodes. The diurnal cycles of the intensive AOPs were clear and in agreement with the cycle of the particle number size distribution. The diurnal cycle of SSA was similar to that of the air photochemical age, suggesting that the darkest aerosol originated from fresh traffic emissions. A Lagrangian retroplume analysis showed that the potential source areas of high σsp and σap are mainly in eastern China. Synoptic weather phenomena dominated the cycle of AOPs on a temporal scale of 3–7 days. During pollution episodes, modeled boundary layer height decreased, whereas PM2.5 concentrations and σsp and σap typically increased gradually and remained high during several days but decreased faster, sometimes by even more than an order of magnitude within some hours. During the growth phase of the pollution episodes the intensive AOPs evolved clearly. The mass scattering efficiency MSE of PM2.5 grew during the extended pollution episodes from ∼ 4 to ∼ 6 m2 g−1 and the mass fraction of BCe decreased from ∼ 10 to ∼ 3 % during the growth phase of the episodes. Particle growth resulted in the backscatter fraction decreasing from more than 0.16 to less than 0.10, SSA growing from less than 0.9 to more than 0.95, and radiative forcing efficiency (RFE) changing from less than −26 W m−2 to more than −24 W m−2, which means that the magnitude of RFE decreased. The RFE probability distribution at SORPES was clearly narrower than at a clean background site which is in agreement with a published RFE climatology.

The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nanoparticle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e., in conditions in which neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.5 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.5 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.5 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.

Deep-seated landslides are an important and widespread natural hazard within alpine regions and can have significant impacts on infrastructure. Pore water pressure plays an important role in determining the stability of hydrologically triggered deep-seated landslides. Based on a simple tank model structure, we improve groundwater level prediction by introducing time lags associated with groundwater supply caused by snow accumulation, snowmelt and infiltration in deep-seated landslides. In this study, we demonstrate an equivalent infiltration calculation to improve the estimation of time lags using a modified tank model to calculate regional groundwater levels. Applied to the deep-seated Aggenalm landslide in the German Alps at 1000–1200 m a. s. l. , our results predict daily changes in pore water pressure ranging from −1 to 1.6 kPa, depending on daily rainfall and snowmelt, which are compared to piezometric measurements in boreholes. The inclusion of time lags improves the results of standard tank models by ∼  36 % (linear correlation with measurement) after heavy rainfall and by ∼ 82 % following snowmelt in a 1–2-day period. For the modified tank model, we introduced a representation of snow accumulation and snowmelt based on a temperature index and an equivalent infiltration method, i.e. the melted snow-water equivalent. The modified tank model compares well to borehole-derived water pressures. Changes of pore water pressure can be modelled with 0–8 % relative error in rainfall season (standard tank model: 2–16 % relative error) and with 0–7 % relative error in snowmelt season (standard tank model: 2–45 % relative error). Here we demonstrate a modified tank model for deep-seated landslides which includes snow accumulation, snowmelt and infiltration effects and can effectively predict changes in pore water pressure in alpine environments.

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3−) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Aerosol effects on low warm clouds over the Yangtze River Delta (YRD, eastern China) are examined using co-located MODIS, CALIOP and CloudSat observations. By taking the vertical locations of aerosol and cloud layers into account, we use simultaneously observed aerosol and cloud data to investigate relationships between cloud properties and the amount of aerosol particles (using aerosol optical depth, AOD, as a proxy). Also, we investigate the impact of aerosol types on the variation of cloud properties with AOD. Finally, we explore how meteorological conditions affect these relationships using ERA-Interim reanalysis data. This study shows that the relation between cloud properties and AOD depends on the aerosol abundance, with a different behaviour for low and high AOD (i.e. AOD 0.35). This applies to cloud droplet effective radius (CDR) and cloud fraction (CF), but not to cloud optical thickness (COT) and cloud top pressure (CTP). COT is found to decrease when AOD increases, which may be due to radiative effects and retrieval artefacts caused by absorbing aerosol. Conversely, CTP tends to increase with elevated AOD, indicating that the aerosol is not always prone to expand the vertical extension. It also shows that the COT–CDR and CWP (cloud liquid water path)–CDR relationships are not unique, but affected by atmospheric aerosol loading. Furthermore, separation of cases with either polluted dust or smoke aerosol shows that aerosol–cloud interaction (ACI) is stronger for clouds mixed with smoke aerosol than for clouds mixed with dust, which is ascribed to the higher absorption efficiency of smoke than dust. The variation of cloud properties with AOD is analysed for various relative humidity and boundary layer thermodynamic and dynamic conditions, showing that high relative humidity favours larger cloud droplet particles and increases cloud formation, irrespective of vertical or horizontal level. Stable atmospheric conditions enhance cloud cover horizontally. However, unstable atmospheric conditions favour thicker and higher clouds. Dynamically, upward motion of air parcels can also facilitate the formation of thicker and higher clouds. Overall, the present study provides an understanding of the impact of aerosols on cloud properties over the YRD. In addition to the amount of aerosol particles (or AOD), evidence is provided that aerosol types and ambient environmental conditions need to be considered to understand the observed relationships between cloud properties and AOD.

The volatility distribution of secondary organic aerosols that formed and had undergone aging – i.e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase – was characterized in a boreal forest environment of Hyytiälä, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40 % of the organics in particles were semi-volatile, 34 % were low-volatility organics and 26 % were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (ΔHVAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol−1 were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m∕z 43 (f43) and m∕z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when ΔHVAP = 80 kJ mol−1 was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16 % (R2) of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.

The volatility of organic aerosols remains poorly understood due to the complexity of speciation and multiphase processes. In this study, we extracted humic-like substances (HULIS) from four atmospheric aerosol samples collected at the SORPES station in Nanjing, eastern China, and investigated the volatility behavior of particles at different sizes using a Volatility Tandem Differential Mobility Analyzer (VTDMA). In spite of the large differences in particle mass concentrations, the extracted HULIS from the four samples all revealed very high-oxidation states (O : C > 0.95), indicating secondary formation as the major source of HULIS in Yangtze River Delta (YRD). An overall low volatility was identified for the extracted HULIS, with the volume fraction remaining (VFR) higher than 55 % for all the regenerated HULIS particles at the temperature of 280 °C. A kinetic mass transfer model was applied to the thermodenuder (TD) data to interpret the observed evaporation pattern of HULIS, and to derive the mass fractions of semi-volatile (SVOC), low-volatility (LVOC) and extremely low-volatility components (ELVOC). The results showed that LVOC and ELVOC dominated (more than 80 %) the total volume of HULIS. Atomizing processes led to a size-dependent evaporation of regenerated HULIS particles, and resulted in more ELVOC in smaller particles. In order to understand the role of interaction between inorganic salts and atmospheric organic mixtures in the volatility of an organic aerosol, the evaporation of mixed samples of ammonium sulfate (AS) and HULIS was measured. The results showed a significant but nonlinear influence of ammonium sulfate on the volatility of HULIS. The estimated fraction of ELVOC in the organic part of the largest particles (145 nm) increased from 26 %, in pure HULIS samples, to 93 % in 1 : 3 (mass ratio of HULIS : AS) mixed samples, to 45 % in 2 : 2 mixed samples, and to 70 % in 3 : 1 mixed samples, suggesting that the interaction with ammonium sulfate tends to decrease the volatility of atmospheric organic compounds. Our results demonstrate that HULIS are important low-volatility, or even extremely low-volatility, compounds in the organic-aerosol phase. As important formation pathways of atmospheric HULIS, multiphase processes, including oxidation, oligomerization, polymerization and interaction with inorganic salts, are indicated to be important sources of low-volatility and extremely low-volatility species of organic aerosols.

Temporal variations in aerosol optical properties were investigated at a coastal station in Hong Kong based on the field observation from February 2012 to February 2015. At 550 nm, the average light-scattering (151 ± 100 Mm−1) and absorption coefficients (8.3 ± 6.1 Mm−1) were lower than most of other rural sites in eastern China, while the single-scattering albedo (SSA = 0.93 ± 0.05) was relatively higher compared with other rural sites in the Pearl River Delta (PRD) region. Correlation analysis confirmed that the darkest aerosols were smaller in particle size and showed strong scattering wavelength dependencies, indicating possible sources from fresh emissions close to the measurement site. Particles with Dp of 200–800 nm were less in number, yet contributed the most to the light-scattering coefficients among submicron particles. In summer, both ΔBC / ΔCO and SO2 / BC peaked, indicating the impact of nearby combustion sources on this site. Multi-year backward Lagrangian particle dispersion modeling (LPDM) and potential source contribution (PSC) analysis revealed that these particles were mainly from the air masses that moved southward over Shenzhen and urban Hong Kong and the polluted marine air containing ship exhausts. These fresh emission sources led to low SSA during summer months. For winter and autumn months, contrarily, ΔBC / ΔCO and SO2 / BC were relatively low, showing that the site was more under influence of well-mixed air masses from long-range transport including from South China, East China coastal regions, and aged aerosol transported over the Pacific Ocean and Taiwan, causing stronger abilities of light extinction and larger variability of aerosol optical properties. Our results showed that ship emissions in the vicinity of Hong Kong could have visible impact on the light-scattering and absorption abilities as well as SSA at Hok Tsui.

The measurement of sub-3 nm aerosol particles is technically challenging. Therefore, there is a lack of knowledge about the concentrations of atmospheric sub-3 nm particles and their variation in different environments. In this study, the concentrations of ∼ 1–3 nm particles measured with a particle size magnifier (PSM) were investigated at nine sites around the world. Sub-3 nm particle concentrations were highest at the sites with strong anthropogenic influence. In boreal forest, measured particle concentrations were clearly higher in summer than in winter, suggesting the importance of biogenic precursor vapors in this environment. At all sites, sub-3 nm particle concentrations had daytime maxima, which are likely linked to the photochemical production of precursor vapors and the emissions of precursor vapors or particles from different sources. When comparing ion concentrations to the total sub-3 nm particle concentrations, electrically neutral particles were observed to dominate in polluted environments and in boreal forest during spring and summer. Generally, the concentrations of sub-3 nm particles seem to be determined by the availability of precursor vapors rather than the level of the sink caused by preexisting aerosol particles. The results also indicate that the formation of the smallest particles and their subsequent growth to larger sizes are two separate processes, and therefore studying the concentration of sub-3 nm particles separately in different size ranges is essential.

Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6) and amides (C1 to C6). This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of ∼ 0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb) were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.

Highly oxidized multifunctional compounds (HOMs) have been demonstrated to be important for atmospheric secondary organic aerosols (SOA) and new-particle formation (NPF), yet it remains unclear which the main atmospheric HOM formation pathways are. In this study, a nitrate-ion-based chemical ionization atmospheric-pressure-interface time-of-flight mass spectrometer (CI-APi-TOF) was deployed to measure HOMs in the boreal forest in Hyytiälä, southern Finland. Positive matrix factorization (PMF) was applied to separate the detected HOM species into several factors, relating these “factors” to plausible formation pathways. PMF was performed with a revised error estimation derived from laboratory data, which agrees well with an estimate based on ambient data. Three factors explained the majority (> 95 %) of the data variation, but the optimal solution found six factors, including two nighttime factors, three daytime factors, and a transport factor. One nighttime factor is almost identical to laboratory spectra generated from monoterpene ozonolysis, while the second likely represents monoterpene oxidation initiated by NO3. The exact chemical processes forming the different daytime factors remain unclear, but they all have clearly distinct diurnal profiles, very likely related to monoterpene oxidation with a strong influence from NO, presumably through its effect on peroxy radical (RO2) chemistry. Apart from these five “local” factors, the sixth factor is interpreted as a transport related factor. These findings improve our understanding of HOM production by confirming current knowledge and inspiring future research directions and provide new perspectives on using factorization methods to understand short-lived atmospheric species.

Biomass burning is a main source for primary carbonaceous particles in the atmosphere and acts as a crucial factor that alters Earth's energy budget and balance. It is also an important factor influencing air quality, regional climate and sustainability in the domain of Pan-Eurasian Experiment (PEEX). During the exceptionally intense agricultural fire season in mid-June 2012, accompanied by rapidly deteriorating air quality, a series of meteorological anomalies was observed, including a large decline in near-surface air temperature, spatial shifts and changes in precipitation in Jiangsu province of East China. To explore the underlying processes that link air pollution to weather modification, we conducted a numerical study with parallel simulations using the fully coupled meteorology–chemistry model WRF-Chem with a high-resolution emission inventory for agricultural fires. Evaluation of the modeling results with available ground-based measurements and satellite retrievals showed that this model was able to reproduce the magnitude and spatial variations of fire-induced air pollution. During the biomass-burning event in mid-June 2012, intensive emission of absorbing aerosols trapped a considerable part of solar radiation in the atmosphere and reduced incident radiation reaching the surface on a regional scale, followed by lowered surface sensible and latent heat fluxes. The perturbed energy balance and re-allocation gave rise to substantial adjustments in vertical temperature stratification, namely surface cooling and upper-air heating. Furthermore, an intimate link between temperature profile and small-scale processes like turbulent mixing and entrainment led to distinct changes in precipitation. On the one hand, by stabilizing the atmosphere below and reducing the surface flux, black carbon-laden plumes tended to dissipate daytime cloud and suppress the convective precipitation over Nanjing. On the other hand, heating aloft increased upper-level convective activity and then favored convergence carrying in moist air, thereby enhancing the nocturnal precipitation in the downwind areas of the biomass-burning plumes.

New particle formation (NPF) has been investigated intensively during the last 2 decades because of its influence on aerosol population and the possible contribution to cloud condensation nuclei. However, intensive measurements and modelling activities on this topic in urban metropolitan areas in China with frequent high-pollution episodes are still very limited. This study provides results from a comprehensive modelling study on the occurrence of NPF events in the western part of the Yangtze River Delta (YRD) region, China. The comprehensive modelling system, which combines the WRF-Chem (the Weather Research and Forecasting model coupled with Chemistry) regional chemical transport model and the MALTE-BOX sectional box model (the model to predict new aerosol formation in the lower troposphere), was shown to be capable of simulating atmospheric nucleation and subsequent growth. Here we present a detailed discussion of three typical NPF days, during which the measured air masses were notably influenced by either anthropogenic activities, biogenic emissions, or mixed ocean and continental sources. Overall, simulated NPF events were generally in good agreement with the corresponding measurements, enabling us to get further insights into NPF processes in the YRD region. Based on the simulations, we conclude that biogenic organic compounds, particularly monoterpenes, play an essential role in the initial condensational growth of newly formed clusters through their low-volatility oxidation products. Although some uncertainties remain in this modelling system, this method provides a possibility to better understand particle formation and growth processes.

Aerosol particles play important roles in regional air quality and global climate change. In this study, we analyzed 2 years (2011–2013) of measurements of submicron particles (6–800 nm) at a suburban site in the western Yangtze River Delta (YRD) of eastern China. The number concentrations (NCs) of particles in the nucleation, Aitken and accumulation modes were 5300 ± 5500, 8000 ± 4400, 5800 ± 3200 cm−3, respectively. The NCs of total particles are comparable to those at urban/suburban sites in other Chinese megacities, such as Beijing, but about 10 times higher than in the remote western China. Long-range and regional transport largely influenced number concentrations and size distributions of submicron particles. The highest and lowest accumulation-mode particle number concentrations were observed in air masses from the YRD and coastal regions, respectively. Continental air masses from inland brought the highest concentrations of nucleation-mode particles. New particle formation (NPF) events, apparent in 44 % of the effective measurement days, occurred frequently in all the seasons except winter. The frequency of NPF in spring, summer and autumn is much higher than other measurement sites in China. Sulfuric acid was found to be the main driver of NPF events. The particle formation rate was the highest in spring (3.6 ± 2.4 cm−3 s−1), whereas the particle growth rate had the highest values in summer (12.8 ± 4.4 nm h−1). The formation rate was typically high in relatively clean air masses, whereas the growth rate tended to be high in the polluted YRD air masses. The frequency of NPF events and the particle growth rates showed a strong year-to-year difference. In the summer of 2013, associated with a multi-week heat wave and strong photochemical processes, NPF events occurred with larger frequency and higher growth rates compared with the same period in 2012. The difference in the location and strength of the subtropical high pressure system, which influences the air mass transport pathways and solar radiation, seems to be the cause for year-to-year differences. This study reports, up to now, the longest continuous measurement records of submicron particles in eastern China and helps to achieve a comprehensive understanding of the main factors controlling the seasonal and year-to-year variation of the aerosol size distribution and NPF in this region.

Measurements of the hygroscopicity of 15–145 nm particles in a boreal forest environment were conducted using two Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) systems during the Pan-European Gas-Aerosols-climate interaction Study (PEGASOS) campaign in spring 2013. Measurements of the chemical composition of non-size segregated particles were also performed using a high-resolution aerosol mass spectrometer (HR-AMS) in parallel with hygroscopicity measurements. On average, the hygroscopic growth factor (HGF) of particles was observed to increase from the morning until afternoon. In case of accumulation mode particles, the main reasons for this behavior were increases in the ratio of sulfate to organic matter and oxidation level (O : C ratio) of the organic matter in the particle phase. Using an O : C dependent hygroscopic growth factor of organic matter (HGForg), fitted using the inverse Zdanovskii–Stokes–Robinson (ZSR) mixing rule, clearly improved the agreement between measured HGF and that predicted based on HR-AMS composition data. Besides organic oxidation level, the influence of inorganic species was tested when using the ZSR mixing rule to estimate the hygroscopic growth factor of organics in the aerosols. While accumulation and Aitken mode particles were predicted fairly well by the bulk aerosol composition data, the hygroscopicity of nucleation mode particles showed little correlation. However, we observed them to be more sensitive to the gas phase concentration of condensable vapors: the more sulfuric acid in the gas phase, the more hygroscopic the nucleation mode particles were. No clear dependence was found between the extremely low-volatility organics concentration (ELVOC) and the HGF of particles of any size.

Aerosol optical properties were measured with a seven-wavelength aethalometer and a three-wavelength nephelometer at the suburban site SORPES in Nanjing, China, in September 2013–January 2015. The aethalometer compensation parameter k, calculated with the Virkkula et al. (2007) method depended on the backscatter fraction, measured with an independent method, the integrating nephelometer. At λ = 660 nm the daily averaged compensation parameter k &approx; 0.0017 ± 0.0002 and 0.0042 ± 0.0013 when backscatter fraction at λ = 635 nm was in the ranges of 0.100 ± 0.005 and 0.160 ± 0.005, respectively. Also, the wavelength dependency of the compensation parameter depended on the backscatter fraction: when b(λ = 525 nm) was less than approximately 0.13 the compensation parameter decreased with wavelength and at larger b it increased with wavelength. This dependency has not been considered in any of the algorithms that are currently used for processing aethalometer data. The compensation parameter also depended on the single-scattering albedo ω0 so that k decreased with increasing ω0. For the green light (λ = 520 nm) in the ω0 range 0.870 ± 0.005, the average (± standard deviation) k &approx; 0.0047 ± 0.006 and in the ω0 range 0.960 ± 0.005, k &approx; 0.0028 ± 0.0007. This difference was larger for the near-infrared light (λ = 880 nm): in the ω0 range 0.860 ± 0.005, k &approx; 0.0055 ± 0.0023 and in the ω0 range 0.960 ± 0.005, k &approx; 0.0019 ± 0.0011. The negative dependence of k on ω0 was also shown with a simple theoretical analysis.

Nitrous acid (HONO) plays a key role in atmospheric chemistry by influencing the budget of hydroxyl radical (OH). In this study, a two-month measurement of HONO and related quantities were analyzed during a biomass burning season in 2012 at a suburban site in the western Yangtze River delta, eastern China. An overall high HONO concentration with the mean value of 0.76 ppbv (0.01 ppbv to 5.95 ppbv) was observed. During biomass burning (BB) periods, both HONO concentration and HONO/NO2 ratio were enhanced significantly (more than a factor of 2, p < 0.01) compared with non-biomass burning (non-BB) periods. A correlation analysis showed that the HONO in BB plumes was more correlated with nitrogen dioxide (NO2) than that with potassium (a tracer of BB). Estimation by the method of potassium tracing suggests a maximum contribution of 17 ± 12% from BB emission to the observed HONO concentrations, and the other over 80% of the observed nighttime HONO concentrations during BB periods were secondarily produced by the heterogeneous conversion of NO2. The NO2-to-HONO conversion rate (CHONO) in BB plumes was almost twice as that in non-BB plumes (0.0062 hr−1 vs. 0.0032 hr−1). Given that the residence time of the BB air masses was lower than that of non-BB air masses, these results suggest BB aerosols have higher NO2 conversion potentials to form HONO than non-BB aerosols. A further analysis based on comparing the surface area at similar particle mass levels and HONO/NO2 ratios at similar surface area levels suggested larger specific surface areas and higher NO2 conversion efficiencies of BB aerosols. A mixed plume of BB and anthropogenic fossil fuel (FF) emissions was observed on 10 June with even higher HONO concentrations and HONO/NO2 ratios. The strong HONO production potential (high HONO/NO2 to PM2.5 ratio) was accompanied with a high sulfate concentration in this plume, suggesting a promotion of mixed aerosols to the HONO formation. In summary, our study suggests an important role of BB in atmospheric chemistry by affecting the HONO budget. This can be especially important in eastern China, where agricultural burning plumes are inevitably mixed with urban and industrial pollution.

The influence of air pollutants, especially aerosols, on regional and global climate has been widely investigated, but only a very limited number of studies report their impacts on everyday weather. In this work, we present for the first time direct (observational) evidence of a clear effect of how a mixed atmospheric pollution changes the weather with a substantial modification in the air temperature and rainfall. By using comprehensive measurements in Nanjing, China, we found that mixed agricultural burning plumes with fossil fuel combustion pollution resulted in a decrease in the solar radiation intensity by more than 70%, a decrease in the sensible heat by more than 85%, a temperature drop by almost 10 K, and a change in rainfall during both daytime and nighttime. Our results show clear air pollution–weather interactions, and quantify how air pollution affects weather via air pollution–boundary layer dynamics and aerosol–radiation–cloud feedbacks. This study highlights cross-disciplinary needs to investigate the environmental, weather and climate impacts of the mixed biomass burning and fossil fuel combustion sources in East China.

This work presents an overview of 1 yr measurements of ozone (O3) and fine particular matter (PM2.5) and related trace gases at a recently developed regional background site, the Station for Observing Regional Processes of the Earth System (SORPES), in the western part of the Yangtze River Delta (YRD) in eastern China. Ozone and PM2.5 showed strong seasonal cycles but with contrast patterns: O3 reached a maximum in warm seasons but PM2.5 in cold seasons. Correlation analysis suggests a VOC-sensitive regime for O3 chemistry and a formation of secondary aerosols under conditions of high O3 in summer. Compared with the National Ambient Air Quality Standards in China, our measurements report 15 days of O3 exceedance and 148 days of PM2.5 exceedance during the 1 yr period, suggesting a severe air pollution situation in this region. Case studies for typical O3 and PM2.5 episodes demonstrated that these episodes were generally associated with an air mass transport pathway over the mid-YRD, i.e., along the Nanjing–Shanghai axis with its city clusters, and showed that synoptic weather played an important role in air pollution, especially for O3. Agricultural burning activities caused high PM2.5 and O3 pollution during harvest seasons, especially in June. A calculation of potential source contributions based on Lagrangian dispersion simulations suggests that emissions from the YRD contributed to over 70% of the O3 precursor CO, with a majority from the mid-YRD. North-YRD and the North China Plain are the main contributors to PM2.5 pollution in this region. This work shows an important environmental impact from industrialization and urbanization in the YRD region, and suggests an urgent need for improving air quality in these areas through collaborative control measures among different administrative regions.

Heterogeneous processes on dust particles are important for understanding the chemistry and radiative balance of the atmosphere. This paper investigates an intense Asian dust storm episode observed at Mount Heng (1269 m a.s.l.) in southern China on 24–26 April 2009. A set of aerosol and trace gas data collected during the study was analyzed to investigate their chemical evolution and heterogeneous photochemistry as the dust traveled to southern China. Results show that the mineral dust arriving at Mt. Heng experienced significant modifications during transport, with large enrichments in secondary species (sulfate, nitrate, and ammonium) compared with the dust composition collected at an upwind mountain top site (Mount Hua). A photochemical age "clock" (−Log10(NOx/NOy)) was employed to quantify the atmospheric processing time. The result indicates an obvious increase in the abundance of secondary water-soluble ions in dust particles with the air mass atmospheric processing time. Based on the observations, a 4-stage evolution process is proposed for carbonate-containing Asian dust, starting from fresh dust to particles coated with hydrophilic and acidic materials. Daytime-enhanced nitrite formation on the dust particles was also observed, which indicates the recent laboratory result of the TiO2 photocatalysis of NO2 as a potential source of nitrite and nitrous acid.

This paper presents the first results of the measurements of trace gases and aerosols at three surface sites in and outside Beijing before and during the 2008 Olympics. The official air pollution index near the Olympic Stadium and the data from our nearby site revealed an obvious association between air quality and meteorology and different responses of secondary and primary pollutants to the control measures. Ambient concentrations of vehicle-related nitrogen oxides (NOx) and volatile organic compounds (VOCs) at an urban site dropped by 25% and 20–45% in the first two weeks after full control was put in place, but the levels of ozone, sulfate and nitrate in PM2.5 increased by 16%, 64%, 37%, respectively, compared to the period prior to the full control; wind data and back trajectories indicated the contribution of regional pollution from the North China Plain. Air quality (for both primary and secondary pollutants) improved significantly during the Games, which were also associated with the changes in weather conditions (prolonged rainfall, decreased temperature, and more frequent air masses from clean regions). A comparison of the ozone data at three sites on eight ozone-pollution days, when the air masses were from the southeast-south-southwest sector, showed that regional pollution sources contributed >34–88% to the peak ozone concentrations at the urban site in Beijing. Regional sources also contributed significantly to the CO concentrations in urban Beijing. Ozone production efficiencies at two sites were low (~3 ppbv/ppbv), indicating that ozone formation was being controlled by VOCs. Compared with data collected in 2005 at a downwind site, the concentrations of ozone, sulfur dioxide (SO2), total sulfur (SO2+PM2.5 sulfate), carbon monoxide (CO), reactive aromatics (toluene and xylenes) sharply decreased (by 8–64%) in 2008, but no significant changes were observed for the concentrations of PM2.5, fine sulfate, total odd reactive nitrogen (NOy), and longer lived alkanes and benzene. We suggest that these results indicate the success of the government's efforts in reducing emissions of SO2, CO, and VOCs in Beijing, but increased regional emissions during 2005–2008. More stringent control of regional emissions will be needed for significant reductions of ozone and fine particulate pollution in Beijing.