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The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

Iron (Fe) in aerosol particles is a major external source of micronutrients for marine ecosystems and poses a potential threat to human health. To understand the impacts of aerosol Fe, it is essential to quantify the sources of dissolved Fe and total Fe. In this study, we applied receptor modeling for the first time to apportion the sources of dissolved Fe and total Fe in fine particles collected under five different weather conditions in the Hangzhou megacity of Eastern China, which is upwind of the East Asian outflow. Results showed that Fe solubility (dissolved Fe to total Fe) was the largest on fog days (6.7 ± 3.0 %), followed by haze (4.8 ± 1.9 %), dust (2.1 ± 0.7 %), clear (1.9 ± 1.0 %), and rain (0.9 ± 0.5 %) days. Positive matrix factorization (PMF) analysis suggested that industrial emissions were the largest contributor to dissolved Fe (44.5 %–72.4 %) and total Fe (39.1 %–55.0 %, except for dust days) during haze, fog, dust, and clear days. Transmission electron microscopy analysis of individual particles showed that > 75 % of Fe-containing particles were internally mixed with acidic secondary aerosol species on haze, fog, dust, and clear days. Furthermore, Fe solubility showed significant positive correlations with aerosol acidity/total Fe and liquid water content. These results indicated that the wet surface of aerosol particles promotes heterogeneous reactions between acidic species and Fe aerosols, contributing to a high Fe solubility.

This study presents the source apportionment of PM2.5 performed by positive matrix factorization (PMF) on data presented here which were collected at urban (Institute of Atmospheric Physics – IAP) and rural (Pinggu – PG) sites in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese megacity (APHH-Beijing) field campaigns. The campaigns were carried out from 9 November to 11 December 2016 and from 22 May to 24 June 2017. The PMF analysis included both organic and inorganic species, and a seven-factor output provided the most reasonable solution for the PM2.5 source apportionment. These factors are interpreted as traffic emissions, biomass burning, road dust, soil dust, coal combustion, oil combustion, and secondary inorganics. Major contributors to PM2.5 mass were secondary inorganics (IAP: 22 %; PG: 24 %), biomass burning (IAP: 36 %; PG: 30 %), and coal combustion (IAP: 20 %; PG: 21 %) sources during the winter period at both sites. Secondary inorganics (48 %), road dust (20 %), and coal combustion (17 %) showed the highest contribution during summer at PG, while PM2.5 particles were mainly composed of soil dust (35 %) and secondary inorganics (40 %) at IAP. Despite this, factors that were resolved based on metal signatures were not fully resolved and indicate a mixing of two or more sources. PMF results were also compared with sources resolved from another receptor model (i.e. chemical mass balance – CMB) and PMF performed on other measurements (i.e. online and offline aerosol mass spectrometry, AMS) and showed good agreement for some but not all sources. The biomass burning factor in PMF may contain aged aerosols as a good correlation was observed between biomass burning and oxygenated fractions (r2= 0.6–0.7) from AMS. The PMF failed to resolve some sources identified by the CMB and AMS and appears to overestimate the dust sources. A comparison with earlier PMF source apportionment studies from the Beijing area highlights the very divergent findings from application of this method.

Carbonaceous aerosol is a dominant component of fine particles in Beijing. However, it is challenging to apportion its sources. Here, we applied a newly developed method which combined radiocarbon (14C) with organic tracers to apportion the sources of fine carbonaceous particles at an urban (IAP) and a rural (PG) site of Beijing. PM2.5 filter samples (24 h) were collected at both sites from 10 November to 11 December 2016 and from 22 May to 24 June 2017. 14C was determined in 25 aerosol samples (13 at IAP and 12 at PG) representing low pollution to haze conditions. Biomass burning tracers (levoglucosan, mannosan, and galactosan) in the samples were also determined using gas chromatography–mass spectrometry (GC-MS). Higher contributions of fossil-derived OC (OCf) were found at the urban site. The OCf / OC ratio decreased in the summer samples (IAP: 67.8 ± 4.0 % in winter and 54.2 ± 11.7 % in summer; PG: 59.3 ± 5.7 % in winter and 50.0 ± 9.0 % in summer) due to less consumption of coal in the warm season. A novel extended Gelencsér (EG) method incorporating the 14C and organic tracer data was developed to estimate the fossil and non-fossil sources of primary and secondary OC (POC and SOC). It showed that fossil-derived POC was the largest contributor to OC (35.8 ± 10.5 % and 34.1 ± 8.7 % in wintertime for IAP and PG, 28.9 ± 7.4 % and 29.1 ± 9.4 % in summer), regardless of season. SOC contributed 50.0 ± 12.3 % and 47.2 ± 15.5 % at IAP and 42.0 ± 11.7 % and 43.0 ± 13.4 % at PG in the winter and summer sampling periods, respectively, within which the fossil-derived SOC was predominant and contributed more in winter. The non-fossil fractions of SOC increased in summer due to a larger biogenic component. Concentrations of biomass burning OC (OCbb) are resolved by the extended Gelencsér method, with average contributions (to total OC) of 10.6 ± 1.7 % and 10.4 ± 1.5 % in winter at IAP and PG and 6.5 ± 5.2 % and 17.9 ± 3.5 % in summer, respectively. Correlations of water-insoluble OC (WINSOC) and water-soluble OC (WSOC) with POC and SOC showed that although WINSOC was the major contributor to POC, a non-negligible fraction of WINSOC was found in SOC for both fossil and non-fossil sources, especially during winter. In summer, a greater proportion of WSOC from non-fossil sources was found in SOC. Comparisons of the source apportionment results with those obtained from a chemical mass balance model were generally good, except for the cooking aerosol.

The fine structure of isotopic peak distributions of glutathione in mass spectra is measured using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) at 12 and 15 T magnetic field, with an infinity cell and a dynamically harmonized cell (DHC) respectively. The resolved peaks in the fine structure of glutathione consist of 2H, 13C, 15N, 17O, 18O, 33S, 34S, 36S, and combinations of them. The positions of the measured fine structure peaks agree with the simulated isotopic distributions with the mass error less than 250 ppb in broadband mode for the infinity cell and no more than 125 ppb with the DHC after internal calibration. The 15 T FT-ICR MS with DHC cell also resolved around 30 isotopic peaks in broadband with a resolving power (RP) of 2 M. In narrowband (m/z 307–313), our current highest RP of 13.9 M in magnitude mode was observed with a 36 s transient length by the 15 T FT-ICR MS with the DHC and 2ω detection on the 15 T offers slightly higher RP (14.8 M) in only 18 s. For the 12 T FT-ICR MS with the infinity cell, the highest RP achieved was 15.6 M in magnitude mode with a transient length of 45 s. Peak decay was observed for low abundance peaks, which could be due to the suppression effects from the most abundant peak, as result of ion cloud Coulombic interactions (space-charge).\ud \ud

This study aims to critically evaluate the source apportionment of fine particles by multiple receptor modelling approaches, including carbon mass balance modelling of filter-based radiocarbon (14C) data, Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) analysis on filter-based chemical speciation data, and PMF analysis on Aerosol Mass Spectrometer (AMS-PMF) or Aerosol Chemical Speciation Monitor (ACSM-PMF) data. These data were collected as part of the APHH-Beijing (Atmospheric Pollution and Human Health in a Chinese Megacity) field observation campaigns from 10th November to 12th December in winter 2016 and from 22nd May to 24th June in summer 2017. 14C analysis revealed the predominant contribution of fossil fuel combustion to carbonaceous aerosols in winter compared with non-fossil fuel sources, which is supported by the results from other methods. An extended Gelencs´er (EG) method incorporating 14C data, as well as the CMB and AMS/ACSM-PMF methods, generated a consistent source apportionment for fossil fuel related primary organic carbon. Coal combustion, traffic and biomass burning POC were comparable for CMB and AMS/ACSM-PMF. There are uncertainties in the EG method when estimating biomass burning and cooking OC. The POC from cooking estimated by different methods was poorly correlated, suggesting a large uncertainty when differentiating this source type. The PM2.5 source apportionment results varied between different methods. Through a comparison and correlation analysis of CMB, PMF and AMS/ACSM-PMF, the CMB method appears to give the most complete and representative source apportionment of Beijing aerosols. Based upon the CMB results, fine aerosols in Beijing were mainly secondary inorganic ion formation, secondary organic aerosol formation, primary coal combustion and from biomass burning emissions.

Iron (Fe) in aerosol particles is a major external source of micronutrients for marine ecosystems, and poses a potential threat to human health. To understand these impacts of aerosol Fe, it is essential to quantify the sources of dissolved and total Fe. In this study, we applied a receptor modelling for the first time to apportion the sources of dissolved and total Fe in fine particles collected under five different weather conditions in Hangzhou megacity of Eastern China, which is upwind of East Asian outflow. Results showed that Fe solubility (dissolved to total Fe) was the largest in fog days (6.3 ± 2.6 %), followed by haze (4.6 ± 1.9 %), dust (2.1 ± 0.7 %), clear (1.7 ± 0.6 %), and rain (0.8 ± 0.3 %) days. Positive Matrix Factorisation (PMF) analysis suggested that industrial and traffic emissions were the two dominant primary sources of dissolved and total Fe during haze and fog days, but dust was the dominant source in dust days. About 15 % of dissolved Fe was associated with secondary sources during haze and fog days, although it was less than 5 % during dust and clear days. Transmission electron microscopy analysis of individual particles showed that approximately 76 % and 87 % of Fe-containing particles were internally mixed with acidic sulfates and nitrates in haze and fog days, respectively. Our results indicated that aqueous surface of aerosol particles promotes heterogeneous reactions between acidic species and Fe aerosol, contributing to higher Fe solubility during fog and haze days.

Epidemiological studies have consistently linked exposure to PM2.5 with adverse health effects. The oxidative potential (OP) of aerosol particles has been widely suggested as a measure of their potential toxicity. Several acellular chemical assays are now readily employed to measure OP; however, uncertainty remains regarding the atmospheric conditions and specific chemical components of PM2.5 that drive OP. A limited number of studies have simultaneously utilised multiple OP assays with a wide range of concurrent measurements and investigated the seasonality of PM2.5 OP. In this work, filter samples were collected in winter 2016 and summer 2017 during the atmospheric pollution and human health in a Chinese megacity campaign (APHH-Beijing), and PM2.5 OP was analysed using four acellular methods: ascorbic acid (AA), dithiothreitol (DTT), 2,7-dichlorofluorescin/hydrogen peroxidase (DCFH) and electron paramagnetic resonance spectroscopy (EPR). Each assay reflects different oxidising properties of PM2.5, including particle-bound reactive oxygen species (DCFH), superoxide radical production (EPR) and catalytic redox chemistry (DTT/AA), and a combination of these four assays provided a detailed overall picture of the oxidising properties of PM2.5 at a central site in Beijing. Positive correlations of OP (normalised per volume of air) of all four assays with overall PM2.5 mass were observed, with stronger correlations in winter compared to summer. In contrast, when OP assay values were normalised for particle mass, days with higher PM2.5 mass concentrations (μgm−3) were found to have lower mass-normalised OP values as measured by AA and DTT. This finding supports that total PM2.5 mass concentrations alone may not always be the best indicator for particle toxicity. Univariate analysis of OP values and an extensive range of additional measurements, 107 in total, including PM2.5 composition, gas-phase composition and meteorological data, provided detailed insight into the chemical components and atmospheric processes that determine PM2.5 OP variability. Multivariate statistical analyses highlighted associations of OP assay responses with varying chemical components in PM2.5 for both mass- and volume-normalised data. AA and DTT assays were well predicted by a small set of measurements in multiple linear regression (MLR) models and indicated fossil fuel combustion, vehicle emissions and biogenic secondary organic aerosol (SOA) as influential particle sources in the assay response. Mass MLR models of OP associated with compositional source profiles predicted OP almost as well as volume MLR models, illustrating the influence of mass composition on both particle-level OP and total volume OP. Univariate and multivariate analysis showed that different assays cover different chemical spaces, and through comparison of mass- and volume-normalised data we demonstrate that mass-normalised OP provides a more nuanced picture of compositional drivers and sources of OP compared to volume-normalised analysis. This study constitutes one of the most extensive and comprehensive composition datasets currently available and provides a unique opportunity to explore chemical variations in PM2.5 and how they affect both PM2.5 OP and the concentrations of particle-bound reactive oxygen species.

Strict seasonal emission controls are a popular measure in China for addressing severe air pollution, in particular fine particulate matter (PM2.5). Here we evaluate the efficacy of these measures, with a particular focus on the strict emission controls imposed on pollution sources in 28 cities in and around the Beijing-Tianjin-Hebei region (BTH) in autumn-winter 2017/2018. For this we use the GEOS-Chem chemical transport model and air pollutant measurements from the national and Beijing local monitoring networks, after evaluating the network data with independent measurements and correcting large biases in the bottom-up emissions inventory. The network measurements are temporally consistent (r > 0.9 for PM2.5 and r > 0.7 for gases) with the independent measurements, though with systematic differences of 5–17 % for nitrogen dioxide (NO2) and 16–28 % for carbon monoxide (CO). The average decrease in monitoring network PM2.5 in BTH in autumn-winter 2017/2018 relative to the previous year is 27 %, declining from 103 to 75 µg m−3. The regional decline in PM2.5 in the model is 20 %, exceeding the regional target of 15 %. According to the model, pollution control measures led to decline in PM2.5 precursor emissions of 0.27 Tg NOx (as NO), 0.66 Tg sulfur dioxide (SO2), 70 Gg organic carbon (OC), and 50 Gg black carbon (BC). We find though that these alone only lead to an 8 % decline in PM2.5 and that interannual variability in meteorology accounts for more than half (57 %) the decline. This demonstrates that year-on-year comparisons are misleading for assessing the efficacy of air pollution measures and should be taken into consideration when extending such measures beyond BTH.

Volatile methyl siloxanes (VMS) have been widely used in personal care products and industrial applications, and are an important component of VOCs (volatile organic compounds) indoors. They have sufficiently long lifetimes to undergo long-range transport and to form secondary aerosols through atmospheric oxidation. To investigate these silicon-containing secondary organic aerosols (Si-SOA), we collected PM

This study presents the source apportionment of PM2.5 performed by PMF on data collected at an urban (Institute of Atmospheric Physics – IAP) and a rural site (Pinggu-PG) in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese megacity (APHH-Beijing) field campaigns. The campaigns were carried out from 9th November to 11th December 2016 and 22nd May to 24th June 2017. The PMF included both organic and inorganic species, and a seven-factor output provided the most reasonable solution for the PM2.5 source apportionment. These factors are interpreted to be traffic emissions, biomass burning, road dust, soil dust, coal combustion, oil combustion and secondary inorganics. Major contributors to PM2.5 mass were secondary inorganics (22–24 %), biomass burning (30–36 %), and coal combustion (20–21 %) sources during the winter period at both sites. Secondary inorganics (48 %), road dust (20 %) and coal combustion (17 %) showed the highest contribution during summer at PG, while PM2.5 particles were mainly composed of soil dust (35 %) and secondary inorganics (40 %) at IAP. Despite this, factors that were resolved based on metal signatures were not fully resolved and indicate a mixing of two or more sources. PMF results were also compared with sources resolved from another receptor model (i.e. CMB) and PMF performed on other measurements (i.e. online and offline aerosol mass spectrometry (AMS)) and showed a good agreement for some but not all sources. The biomass burning factor in PMF may contain aged aerosols as a good correlation was observed between biomass burning and oxygenated fractions (r2 = 0.6–0.7) from AMS. The PMF failed to resolve some sources identified by the CMB and AMS, and appears to overestimate the dust sources. A comparison with earlier PMF source apportionment studies from the Beijing area highlights the very divergent findings from application of this method.

True air quality improvements during the COVID-19 lockdowns in global cities are more limited than we thought., The COVID-19 lockdowns led to major reductions in air pollutant emissions. Here, we quantitatively evaluate changes in ambient NO2, O3, and PM2.5 concentrations arising from these emission changes in 11 cities globally by applying a deweathering machine learning technique. Sudden decreases in deweathered NO2 concentrations and increases in O3 were observed in almost all cities. However, the decline in NO2 concentrations attributable to the lockdowns was not as large as expected, at reductions of 10 to 50%. Accordingly, O3 increased by 2 to 30% (except for London), the total gaseous oxidant (Ox = NO2 + O3) showed limited change, and PM2.5 concentrations decreased in most cities studied but increased in London and Paris. Our results demonstrate the need for a sophisticated analysis to quantify air quality impacts of interventions and indicate that true air quality improvements were notably more limited than some earlier reports or observational data suggested.

Fine particles were sampled from 9th November to 11th December 2016 and 22nd May to 24th June 2017 as part of the Atmospheric Pollution and Human Health in a Chinese megacity (APHH-China) field campaigns in urban Beijing, China. Inorganic ions, trace elements, OC, EC, and organic compounds including biomarkers, hopanes, PAHs, n-alkanes and fatty acids, were determined for source apportionment in this study. Carbonaceous components contributed on average 47.2 % and 35.2 % of total reconstructed PM2.5 during the winter and summer campaigns, respectively. Secondary inorganic ions (sulfate, nitrate, ammonium; SNA) accounted for 35.0 % and 45.2 % of total PM2.5 in winter and summer. Other components including inorganic ions (K+, Na+, Cl−), geological minerals, and trace metals only contributed 13.2 % and 12.4 % of PM2.5 during the winter and summer campaigns. Fine OC was explained by seven primary sources (industrial/residential coal burning, biomass burning, gasoline/diesel vehicles, cooking and vegetative detritus) based on a chemical mass balance (CMB) receptor model. It explained an average of 75.7 % and 56.1 % of fine OC in winter and summer, respectively. Other (unexplained) OC was compared with the secondary OC (SOC) estimated by the EC-tracer method, with correlation coefficients (R2) of 0.58 and 0.73, and slopes of 1.16 and 0.80 in winter and summer, respectively. This suggests that the unexplained OC by CMB was mostly associated with SOC. PM2.5 apportioned by CMB showed that the SNA and secondary organic matter were the highest two contributors to PM2.5. After these, coal combustion and biomass burning were also significant sources of PM2.5 in winter. The CMB results were also compared with results from Positive Matrix Factorization (PMF) analysis of co-located Aerosol Mass Spectrometer (AMS) data. The CMB was found to resolve more primary OA sources than AMS-PMF but the latter apportioned more secondary OA sources. The AMS-PMF results for major components, such as coal combustion OC and oxidized OC correlated well with the results from CMB. However, discrepancies and poor agreements were found for other OC sources, such as biomass burning and cooking, some of which were not identified in AMS-PMF factors.

Epidemiological studies have consistently linked exposure to PM2.5 with adverse health effects. The oxidative potential (OP) of aerosol particles has been widely suggested as a measure of their potential toxicity. Several acellular chemical assays are now readily employed to measure OP, however, uncertainty remains regarding the atmospheric conditions and specific chemical components of PM2.5 that drive OP. A limited number of studies have simultaneously utilised multiple OP assays with a wide range of concurrent measurements and investigated the seasonality of PM2.5 OP. In this work, filter samples were collected in winter 2016 and summer 2017 during the atmospheric pollution and human health in a Chinese megacity (APHH-Beijing) campaign, and PM2.5 OP was analysed using four acellular methods; ascorbic acid (AA), dithiothreitol (DTT), 2-7-dichlorofluoroscin/hydrogen peroxidase (DCFH) and electron paramagnetic resonance spectroscopy (EPR). Positive correlations of OP normalised per volume of air of all four assays with overall PM2.5 mass was observed, with stronger correlations in the winter compared to the summer. In contrast, when OP assay values were normalised for particle mass, days with higher PM2.5 mass concentrations (μg m−3) were found to have lower intrinsic mass-normalised OP values as measured by AA and DTT. This indicates that total PM2.5 mass concentrations alone might not always be the best indicator for particle toxicity. Univariate analysis of OP values and an extensive range of additional measurements, 107 in total, including PM2.5 composition, gas phase composition and meteorological data, provides detailed insight into chemical components or atmospheric processes that determine PM2.5 OP variability. Multivariate statistical analyses highlighted associations of OP assay responses with varying chemical components in PM2.5 for both mass- and volume-normalised data. Variable selection was used to produce subsets of measurements indicative of PM2.5 sources, and used to model OP response; AA and DTT assays were well predicted by small panels of measurements, and indicated fossil fuel combustion processes, vehicle emissions and biogenic SOA as most influential in the assay response. Through comparative analysis of both mass- and volume-normalised data we demonstrate the importance of also considering mass-normalised OP when correlating with particle composition measurements, which provides a more nuanced picture of compositional drivers and sources of OP compared to volume-normalised analysis, and which may be more useful in temporal and site comparative contexts.

Wintertime urban air pollution in many global megacities is characterised by episodic rapid increase in particulate matter concentrations associated with elevated relative humidity-so-called haze episodes, which have become characteristic of cities such as Beijing. Atmospheric chemistry within haze combines gas-and condensed-phase chemical processes, leading to the growth in secondary species such as sulphate aerosols. Here, we integrate observations of reactive gas phase species (HONO, OH, NOx) and time-resolved aerosol composition, to explore observational constraints on the mechanisms responsible for sulphate growth during the onset of haze events. We show that HONO abundance is dominated by established fast gas-phase photochemistry, but the consideration of the additional formation potentially associated with condensed-phase oxidation of S species by aqueous NO2 leading to NO2- production and hence HONO release, improves agreement between observed and calculated gas-phase HONO levels. This conclusion is highly dependent upon aerosol pH, ionic strength and particularly the parameterisation employed for S(iv) oxidation kinetics, for which an upper limit is derived. This journal is

This study aimed to characterize PM

Size distributions of inorganic and organic components in particulate matter (PM) provide critical information on its sources, fate and pollution processes. Here, ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in size-resolved (9 stages) PM were analyzed during one year in a typical northern Chinese industrial megacity (Tianjin). We found that the concentrations of organic carbon fraction OC3, NO3− (or SO42−) and the sum of crustal elements were the highest in the pseudo-ultrafine ( 2.1 μm) modes, respectively. The diagnostic ratios of organic components consistently suggest that the traffic influence was stronger during summer and coal combustion during winter. Nitrate and high molecular weight PAHs were concentrated in the fine mode during winter, while nitrate and low molecular weight PAHs showed bimodal distributions especially during summer due to repartitioning. Long-chain n-alkanes showed a peak in the coarse mode during spring and summer, indicating a relatively stronger vegetation source and resuspended dust. Furthermore, we found a major difference in the size distribution of aerosol components during heavy pollution episodes (PM10 > 233 μg m−3) in different seasons: in spring, OC fractions, 4- and 5-ring PAHs, hopanes and C18–C33 n-alkanes were enhanced at 1.1–3.3 μm, implying that they may arise from local combustion sources which emit relatively large particles; in summer PM mass, SO42−, NH4+, Al, and C26–C33 n-alkanes were enhanced mainly in the coarse mode, peaking at 5.8–9.0 μm, indicating a large contribution from resuspended dust or heterogeneous reactions on dusts; in the winter and autumn, NO3− was significantly enhanced followed by SO42−, NH4+, OC and EC with their peaks shifting from 0.43–0.65 μm to 0.65–2.1 μm, indicating strong atmospheric processing. These results reveal that the size distributions of inorganic and organic aerosol components are dependent on the seasons and pollution levels as a result of the differing sources and physicochemical processes.

Volatile methyl siloxanes (VMS) have been widely used in personal care products and industrial applications, and are an important component of VOCs (volatile organic compounds) indoors. They have sufficiently long lifetimes to undergo long-range transport and to form secondary aerosols through atmospheric oxidation. To investigate these silicon-containing secondary organic aerosols (Si-SOA), we collected PM2.5 samples during 8th-21st August 2018 (summer) and 3rd-23rd January 2019 (winter) at an urban site of Beijing. As the oxidation of VMS mainly results in hydrophilic polar semi-volatile and non-volatile oxidation products, the differences between total water-soluble Si and total water-soluble inorganic Si were used to estimate water-soluble organic Si, considered to be secondary organic Si (SO–Si). The average concentrations of SO–Si during the summer and winter campaigns were 4.6 ± 3.7 and 13.2 ± 8.6 ng m−3, accounting for approximately 80.1 ± 10.1% and 80.2 ± 8.7% of the total water-soluble Si, and 1.2 ± 1.2% and 5.0 ± 6.9% of total Si in PM2.5, respectively. The estimated Si-SOA concentrations were 12.7 ± 10.2 ng m−3 and 36.6 ± 23.9 ng m−3 on average in summer and winter, which accounted for 0.06 ± 0.07% and 0.16 ± 0.22% of PM2.5 mass, but increased to 0.26% and 0.92% on certain days. We found that net solar radiation is positively correlated with SO–Si levels in the summer but not in winter, suggesting seasonally different formation mechanisms.

The “Campaign on Atmospheric Aerosol Research” network of China (CARE-China) is a long-term project for the study of the spatio-temporal distributions of physical aerosol characteristics as well as the chemical components and optical properties of aerosols over China. This study presents the first long-term data sets from this project, including 3 years of observations of online PM2.5 mass concentrations (2012–2014) and 1 year of observations of PM2.5 compositions (2012–2013) from the CARE-China network. The average PM2.5 concentration at 20 urban sites is 73.2 µg m−3 (16.8–126.9 µg m−3), which was 3 times higher than the average value from the 12 background sites (11.2–46.5 µg m−3). The PM2.5 concentrations are generally higher in east-central China than in the other parts of the country due to their relatively large particulate matter (PM) emissions and the unfavourable meteorological conditions for pollution dispersion. A distinct seasonal variability in PM2.5 is observed, with highs in the winter and lows during the summer at urban sites. Inconsistent seasonal trends were observed at the background sites. Bimodal and unimodal diurnal variation patterns were identified at both urban and background sites. The chemical compositions of PM2.5 were analysed at six paired urban and background sites located within the most polluted urban agglomerations – North China Plain (NCP), Yangtze River delta (YRD), Pearl River delta (PRD), North-east China region (NECR), South-west China region (SWCR) – and the cleanest region of China – the Tibetan Autonomous Region (TAR). The major PM2.5 constituents across all the urban sites are organic matter (OM, 26.0 %), SO42- (17.7 %), mineral dust (11.8 %), NO3- (9.8 %), NH4+ (6.6 %), elemental carbon (EC) (6.0 %), Cl− (1.2 %) at 45 % RH and unaccounted matter (20.7 %). Similar chemical compositions of PM2.5 were observed at background sites but were associated with higher fractions of OM (33.2 %) and lower fractions of NO3- (8.6 %) and EC (4.1 %). Significant variations of the chemical species were observed among the sites. At the urban sites, the OM ranged from 12.6 µg m−3 (Lhasa) to 23.3 µg m−3 (Shenyang), the SO42- ranged from 0.8 µg m−3 (Lhasa) to 19.7 µg m−3 (Chongqing), the NO3- ranged from 0.5 µg m−3 (Lhasa) to 11.9 µg m−3 (Shanghai) and the EC ranged from 1.4 µg m−3 (Lhasa) to 7.1 µg m−3 (Guangzhou). The PM2.5 chemical species at the background sites exhibited larger spatial heterogeneities than those at urban sites, suggesting different contributions from regional anthropogenic or natural emissions and from long-range transport to background areas. Notable seasonal variations of PM2.5-polluted days were observed, especially for the megacities in east-central China, resulting in frequent heavy pollution episodes occurring during the winter. The evolution of the PM2.5 chemical compositions on polluted days was consistent for the urban and nearby background sites, where the sum of sulfate, nitrate and ammonia typically constituted much higher fractions (31–57 %) of PM2.5 mass, suggesting fine-particle pollution in the most polluted areas of China assumes a regional tendency, and the importance of addressing the emission reduction of secondary aerosol precursors including SO2 and NOx. Furthermore, distinct differences in the evolution of [NO3-]/[SO42-] ratio and OC∕EC ratio on polluted days imply that mobile sources and stationary (coal combustion) sources are likely more important in Guangzhou and Shenyang, respectively, whereas in Beijing it is mobile emission and residential sources. As for Chongqing, the higher oxidation capacity than the other three cities suggested it should pay more attention to the emission reduction of secondary aerosol precursors. This analysis reveals the spatial and seasonal variabilities of the urban and background aerosol concentrations on a national scale and provides insights into their sources, processes and lifetimes.

This research apportioned size-resolved particulate matter (PM) contributions in a megacity in northern China based on a full year of measurements of both inorganic and organic markers. Ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in 9 p.m. size fractions were analyzed. High molecular weight PAHs concentrated in fine PM, while most other organic compounds showed two peaks. Both two-way and three-way receptor models were used for source apportionment of PM in different size ranges. The three-way receptor model gave a clearer separation of factors than the two-way model, because it uses a combination of chemical composition and size distributions, so that factors with similar composition but distinct size distributions (like more mature and less mature coal combustion) can be resolved. The three-way model resolved six primary and three secondary factors. Gasoline vehicles and coal and biomass combustion, nitrate and high relative humidity related secondary aerosol, and resuspended dust and diesel vehicles (exhaust and non-exhaust) are the top two contributors to pseudo-ultrafine ( 2.1 μm) PM, respectively. Mass concentration of PM from coal and biomass combustion, industrial emissions, and diesel vehicle sources showed a bimodal size distribution, but gasoline vehicles and resuspended dust exhibited a peak in the fine and coarse mode, separately. Mass concentration of sulphate, nitrate and secondary organic aerosol exhibited a bimodal distribution and were correlated with temperature, indicating strong photochemical processing and repartitioning. High relative humidity related secondary aerosol was strongly associated with size shifts of PM, NO3− and SO42− from the usual 0.43–0.65 μm to 1.1–2.1 μm. Our results demonstrated the dominance of primary combustion sources in the

Research is restricted regarding impacts of biomass burning (BB) on fine aerosol (PM2.5), due mainly to lack of specific BB tracers. This study aims to characterize the variability, distributions, and contributions of BB and fungal spores as sources of PM2.5 using a multiple organic tracer approach. PM2.5 samples were collected at four representative sites in Yangtze River Delta (YRD), China every 6 days for one year. In the laboratory, samples were analyzed for three anhydrides (levoglucosan, mannosan, and galactosan), two sugar alcohols (arabitol and mannitol), water-soluble inorganic ions, and elemental/organic carbon (EC/OC). Levoglucosan was the most abundant BB tracer (mean concentration = 81 ng/m3), and fungal spore tracers arabitol and mannitol had similar abundances (5.6 and 5.7 ng/m3, respectively). Anhydrides and sugar alcohols had high within-group correlations, indicating their respective common sources. Concentrations of tracers displayed large temporal variations but small spatial variations, suggesting strong seasonality in BB and fungal spore sources. BB sources were burning of grass, pine needles, hardwood and crop straw, which were originated from transboundary/cross-region transport and local fire spots. PCA analyses revealed that the common sources of fine aerosols in YRD were secondary inorganic aerosols, soil dust, BB and fungal spores.

Three monosaccharide anhydrides (MAs: levoglucosan, mannosan, and galactosan) and sugar alcohols (arabitol and mannitol) are widely used as organic tracers for source identification of aerosols emitted from biomass burning and fungal spores, respectively. In the past, these two types of organic tracer have been measured separately or conjointly using different analytical techniques, with which a number of disadvantages have been experienced during the application to environmental aerosol samples, including organic solvent involved extraction, time-consuming derivatization, or poor separation efficiency due to overlapping peaks, etc. Hence, in this study a more environment-friendly, effective and integrated extraction and analytical method has been developed for simultaneous determination of the above mentioned organic tracers in the same aerosol sample using ultrasonication and high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The ultrasonication assisted extraction process using ultrapure water can achieve satisfactory recoveries in the range of 100.3 ± 1.3% to 108.4 ± 1.6% for these tracers. All the parameters related to LC and MS/MS have been optimized to ensure good identification and pronounced intensity for each compound. A series of rigorous validation steps have been conducted. This newly developed analytical method using ultrasonication and HPLC-MS/MS has been successfully applied to environmental aerosol samples of different pollution levels for the simultaneous measurement of the above mentioned five organic tracers from biomass burning and fungal spores.

To investigate the seasonal and spatial variations of ion chemistry of fine particles in Northern Zhejiang Province (NZP), China, one year-long field sampling was conducted at four representative sites (two urban, one suburb, and one rural sites) in both cities of Hangzhou and Ningbo from December 2014 to November 2015. Twelve water soluble inorganic ions (WSII) were characterized in this comprehensive study. The annual average of PM2.5 concentration in NZP as overall was 66.2 ± 37.7 μg m−3, and urban sites in NZP were observed with more severe PM2.5 pollution than the suburban and rural sites. The annual average concentration of total WSII at four sampling sites in NZP was 29.1 ± 19.9 μg m−3, dominated by SO42− (10.3 μg m−3), and followed by NO3− (8.9 μg m−3), NH4+ (6.6 μg m−3), Cl− (1.3 μg m−3) and K+ (0.7 μg m−3). Among all cations, NH4+ was the predominant neutralizing ion with the highest neutralization factor (NF), while the remaining cations showed limited neutralization capacity. The highest and lowest sulfur oxidation ratio (SOR) values in this region were found in summer and winter, respectively; while the seasonal patterns for nitrogen oxidation ratio (NOR) were opposite to that of SOR. Principal component analysis (PCA) showed that the significant sources of WSII in NZP were industrial emissions, biomass burning, and formation of secondary inorganic aerosols. In addition, contribution from transboundary transport of polluted aerosols was also confirmed from the assessment through air mass backward trajectory analysis.

Due to the rapid industrialization of the Yangtze River Delta (YRD) region in China, heavy air pollution episodes have occurred frequently over the past five years which are of great concern due to their environmental and health impacts. To investigate the chemical characteristics of the highly polluted aerosols in this region, a sampling campaign had been conducted in Ningbo from 3 December 2012 to 27 June 2013, during which a month long high pollution episode had been captured. Daily average PM2.5 concentrations during high and low pollution periods were 111 μg m−3 and 53 μg m−3, respectively. The most polluted day was 8 January 2013 with a PM2.5 concentration up to 175 μg m− 3. To understand the origin of the highly polluted aerosols, meteorological conditions, air mass backward trajectories, distribution of fire spots in surrounding areas and various categories of aerosol pollutants were analyzed, including trace metals, inorganic species, PAHs and anhydrosugars. Total metal concentrations were 3.8 and 1.6 μg m−3 for the high and low pollution episodes, respectively, accounting for 3.4% and 3.1% of the total PM2.5 mass. Total concentrations of ionic species accounted for more than 50.0% of the PM2.5 by mass, with dominant ions (nitrate, sulfate, ammonium) accounting for over 42.0% of the PM2.5 mass concentrations in both periods. During the high pollution episode, enhanced Cd–Pb and biomarker (levoglucosan, mannosan) levels indicated the contributions from coal combustion, traffic and biomass burning to fine aerosol PM2.5. The average diagnostic ratio of Fla/(Fla + Pyr) was 0.54 in high pollution episode, which was intermediate between that for wood (> 0.50) and coal combustion (0.58). BaP/Bpe was 0.49 and 0.30 for the highly and lightly polluted aerosols respectively, associated with the significant non-traffic emissions (< 0.60). In addition, stagnant weather conditions during the high pollution period and long-range transport of air masses from heavy industries and biomass burning from northern China to Ningbo could be considered as the main factors for the formation of the aerosols during high pollution period.

Analysing wastewater samples is an innovative approach that overcomes many limitations of traditional surveys to identify and measure a range of chemicals that were consumed by or exposed to people living in a sewer. catchment area. First conceptualised in 2001, much progress has been made to make wastewater analysis (WWA) a reliable and robust tool for measuring chemical consumption and/or exposure. At the moment, the most popular application of WWA, sometimes referred as sewage epidemiology, is to monitor the consumption of illicit drugs in communities around the globe, including China. The approach has been largely adopted bylaw enforcement agencies as a device to monitor the temporal and geographical patterns of drug consumption. In the future, the methodology can be extended to other chemicals including biomarkers of population health (e.g. environmental or oxidative stress biomarkers, lifestyle indicators or medications that are taken by different demographic groups) and pollutants that people are exposed to (e.g. polycyclic aromatic hydrocarbons, perfluorinated chemicals, and toxic pesticides). The extension of WWA to a huge range of chemicals may give rise to a field called sewage chemical-information mining (SCIM) with unexplored potentials. China has many densely populated cities with thousands of sewage treatment plants which are favourable for applying WWA/SCIM in order to help relevant authorities gather information about illicit drug consumption and population health status. However, there are some prerequisites and uncertainties of the methodology that should be addressed for SCIM to reach its full potential in China. (C) 2014 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

Recurrent smoke-haze episodes that occur in Southeast Asia (SEA) are of much concern because of their environmental and health impacts. These haze episodes are mainly caused by uncontrolled biomass and peat burning in Indonesia. Airborne particulate matter (PM) samples were collected in the southwest coast of Singapore from 16 August to 9 November in 2009 to assess the impact of smoke-haze episodes on the air quality due to the long-range transport of biomass and peat burning emissions. The physical and chemical characteristics of PM were investigated during pre-haze, smoke-haze, and post-haze periods. Days with PM2.5 mass concentrations of ≥35 μg m−3 were considered as smoke-haze events. Using this criterion, out of the total 82 sampling days, nine smoke-haze events were identified. The origin of air masses during smoke-haze episodes was studied on the basis of HYSPLIT backward air trajectory analysis for 4 days. In terms of the physical properties of PM, higher particle surface area concentrations and particle gravimetric mass concentrations were observed during the smoke-haze period, but there was no consistent pattern for particle number concentrations during the haze period as compared to the non-haze period except that there was a significant increase at about 08:00, which could be attributed to the entrainment of PM from aloft after the breakdown of the nocturnal inversion layer. As for the chemical characteristics of PM, among the six key inorganic water-soluble ions (Cl−, NO3 −, nss-SO4 2−, Na+, NH4 +, and nss-K+) measured in this study, NO3 −, nss-SO4 2−, and NH4 + showed a significant increase in their concentrations during the smoke-haze period together with nss-K+. These observations suggest that the increased atmospheric loading of PM with higher surface area and increased concentrations of optically active secondary inorganic aerosols [(NH4)2SO4 or NH4HSO4 and NH4NO3] resulted in the atmospheric visibility reduction in SEA due to the advection of biomass and peat burning emissions.