Atmospheric brown carbon in China haze is dominated by secondary formation.

Brown carbon (BrC) is a class of light-absorbing organic aerosols (OA) and has significant influence on atmospheric radiative forcing. However, the current limited understanding of the physicochemical properties of BrC restricts the accurate evaluation of its environmental effects. Here the optical characteristics and chemical composition of BrC during wintertime in the Yangtze River Delta (YRD) region, China were measured by using high-resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectrometry. Our results showed that BrC in PM2.5 during the campaign was dominated by water-soluble organics, which consist of less oxidized oxygenated OA (LO-OOA), more oxidized oxygenated OA (MO-OOA), fossil fuel OA (FFOA) and biomass burning OA (BBOA). MO-OOA and BBOA were the strongest light absorbing BrC at 365 nm (Abs365), followed by LO-OOA and FFOA with a mass absorption coefficient (MAC) being 0.74 ± 0.04, 0.73 ± 0.03, 0.48 ± 0.04 and 0.39 ± 0.06 m2 g-1 during the campaign, respectively. In the low relative humidity (RH < 80 %) haze periods Abs365 of LO-OOA contributed to 44 % of the total light absorption at 365 nm, followed by MO-OOA (31 %), FFOA (21 %) and BBOA (4 %). In contrast, in the high-RH (RH > 80 %) haze periods Abs365 was dominated by MO-OOA, which accounted for 62 % of the total Abs365, followed by LO-OOA (17 %), BBOA (13 %) and FFOA (8 %). Chemical composition analysis further showed that LO-OOA and MO-OOA are produced from gas-phase photooxidation of VOCs and aerosol aqueous reactions, respectively, in which ammonia significantly enhanced the formation and light absorption of BrC in the high RH haze period. On average, >75 % of the total Abs365nm in the YRD region during the haze events was contributed by LO-OOA and MO-OOA, suggesting that atmospheric BrC in China haze periods is predominantly formed by secondary reactions.

High-Performance Ir1/CeO2 Single-Atom Catalyst for the Oxidation of Toluene.

The elimination of toluene is an obligatory target with increasing VOC emission in recent years. This study successfully prepared a single-atom Ir catalyst (Ir1/CeO2) by a simple incipient wetness impregnation method, confirmed by in situ CO DRIFTS and AC-HAADF-STEM. Compared to the cluster Ir catalyst (Ir/CeO2-C), Ir1/CeO2 exhibited excellent catalytic performance, stability, and water resistance for the oxidation of toluene. By Raman, H2-TPR, O2-TPD, and XPS experiments, abundant oxygen defects and a unique Ir3+-Ov-Ce3+ structure were formed for the Ir1/CeO2 sample because it had a lower oxygen vacancy formation energy. Furthermore, the DFT results revealed that the Ir1/CeO2 sample had a lower ring-opening energy barrier and adsorption energy of the ring-opening products, which was the rate-determining step for the oxidation of toluene. This work provides instructive insights into the construction of Ir/CeO2 catalysts for the highly efficient removal of VOCs.

Emission and optical characteristics of brown carbon in size-segregated particles from three types of Chinese ships.

Brown carbon (BrC) is one of the important light absorption substances that have high light absorption ability under short wavelength light. However, limit studies have focused on the BrC emission from ships. In this study, size-segregated particulate matters (PM) were collected from three different types of ships, light absorption characteristics and size distribution of methanol-soluble BrC and water-soluble BrC in PM from ship exhausts were investigated. Results showed that four-stroke low-power diesel fishing boat (4-LDF) had the highest mass concentrations of methanol-soluble organic carbon (MSOC) and water-soluble organic carbon (WSOC), followed by 2-stroke high-power heavy-fuel-oil vessel (2-HHV), and four-stroke high-power marine-diesel vessel (4-HMV). While 2-HHV had obviously higher light absorption coefficients of methanol-soluble BrC (Abs365,M) and water-soluble BrC (Abs365,W) in unit weight of PM than the other two types of ships. The tested ships presented comparable or higher absorption efficiency of BrC in water extracts (MAE365,W) compared with other BrC emission sources. Majority of BrC was concentrated in fine particles, and the particle size distributions of both Abs365,M and Abs365,W showed bimodal patterns, peaking at 0.43-0.65 µm and 4.7-5.8 µm, respectively. However, different particle size distributions were found for MAE365,M between diesel and heavy fuel oil ships. Besides, different wavelength dependence in particles with different size were also detected. Ship exhaust could be confirmed as a non-ignorable BrC emission source, and complex influencing factor could affect the light absorption characteristics of ship emissions. Particle size should also be considered when light absorption ability of BrC was evaluated.

Comparison of acidity and chemical composition of summertime cloud water and aerosol at an alpine site in Northwest China: Implications for the neutral property of clouds in the free troposphere.

Aerosol and cloud acidity are essential to human health, ecosystem health and productivity, as well as climate effects. The main chemical composition of cloud water greatly varies in different regions, resulting in substantial differences in the pH of cloud water. However, the influences of the anthropogenic emissions of acidic gases and substances, alkaline dust components, and dicarboxylic acids (diacids) on the ground concerning the acidity of cloud water in the free troposphere of the Guanzhong Plain, China, remain clear. In this study, cloud water and PM2.5 samples were simultaneously collected in the troposphere (Mt. Hua, 2060 m a.s.l). The results indicated that the cloud water was alkaline (pH = 7.6) and PM2.5 was acidic (pH = 3.2). These results showed the neutral property of clouds collected in the heavily polluted Guanzhong Plain, although most previous studies always considered acidity as a marker of pollution. The sulfate (SO42-), nitrate (NO3-), and ammonium (NH4+) (SNA) of particulate matter and cloud water in the same period were compared. SO42- was dominant in particulate matters (accounting for 63.4 % of the total SNA) but substantially decreased in cloud water (only 30.1 % of the total SNA), whereas NO3- and NH4+ increased from 28.5 % and 8.2 % to 39.8 % and 30.2 %, respectively. This could be attributed to the complex formation mechanism and sources of SO42- and NO3- in the cloud. The results of ion balance indicated that a significant deficit of inorganic anion equivalents was observed in the cloud water samples. The high concentration of diacids in the cloud phase (1237.4 µg L-1) may facilitate the formation of salt complexes with NH4+, thus influencing the acidity of the cloud water. The pH of cloud water has increased in recent decades due to the sustained reduction of sulfur dioxide, which may also affect the acidity of future precipitation.

Elucidating the Mechanism on the Transition-Metal Ion-Synergetic-Catalyzed Oxidation of SO2 with Implications for Sulfate Formation in Beijing Haze.

Currently, atmospheric sulfate aerosols cannot be predicted reliably by numerical models because the pathways and kinetics of sulfate formation are unclear. Here, we systematically investigated the synergetic catalyzing role of transition-metal ions (TMIs, Fe3+/Mn2+) in the oxidation of SO2 by O2 on aerosols using chamber experiments. Our results showed that the synergetic effect of TMIs is critically dependent on aerosol pH due to the solubility of Fe(III) species sensitive to the aqueous phase acidity, which is effective only under pH < 3 conditions. The sulfate formation rate on aerosols is 2 orders of magnitude larger than that in bulk solution and increases significantly on smaller aerosols, suggesting that such a synergetic-catalyzed oxidation occurs on the aerosol surface. The kinetic reaction rate can be described as R = k*[H+]-2.95[Mn(II)][Fe(III)][S(IV)] (pH ≤ 3.0). We found that TMI-synergetic-catalyzed oxidation is the dominant pathway of sulfate formation in Beijing when haze particles are very acidic, while heterogeneous oxidation of SO2 by NO2 is the most important pathway when haze particles are weakly acidic. Our work for the first time clarified the role and kinetics of TMI-synergetic-catalyzed oxidation of SO2 by O2 in haze periods, which can be parameterized into models for future studies of sulfate formation.

Interannual evolution of the chemical composition, sources and processes of PM2.5 in Chengdu, China: Insights from observations in four winters.

The air quality in China has improved significantly in the last decade and, correspondingly, the characteristics of PM2.5 have also changed. We studied the interannual variation of PM2.5 in Chengdu, one of the most heavily polluted megacities in southwest China, during the most polluted season (winter). Our results show that the mass concentrations of PM2.5 decreased significantly year-by-year, from 195.8 ± 91.0 µg/m3 in winter 2016 to 96.1 ± 39.3 µg/m3 in winter 2020. The mass concentrations of organic matter (OM), SO42-, NH4+ and NO3- decreased by 49.6%, 57.1%, 49.7% and 28.7%, respectively. The differential reduction in the concentrations of chemical components increased the contributions from secondary organic carbon and NO3- and there was a larger contribution from mobile sources. The contribution of OM and NO3- not only increased with increasing levels of pollution, but also increased year-by-year at the same level of pollution. Four sources of PM2.5 were identified: combustion sources, vehicular emissions, dust and secondary aerosols. Secondary aerosols made the highest contribution and increased year-by-year, from 40.6% in winter 2016 to 46.3% in winter 2020. By contrast, the contribution from combustion sources decreased from 14.4% to 8.7%. Our results show the effectiveness of earlier pollution reduction policies and emphasizes that priority should be given to key pollutants (e.g., OM and NO3-) and sources (secondary aerosols and vehicular emissions) in future policies for the reduction of pollution in Chengdu during the winter months.

Double-Edged Role of VOCs Reduction in Nitrate Formation: Insights from Observations during the China International Import Expo 2018.

Aerosol nitrate (NO3-) constitutes a significant component of fine particles in China. Prioritizing the control of volatile organic compounds (VOCs) is a crucial step toward achieving clean air, yet its impact on NO3- pollution remains inadequately understood. Here, we examined the role of VOCs in NO3- formation by combining comprehensive field measurements conducted during the China International Import Expo (CIIE) in Shanghai (from 10 October to 22 November 2018) and multiphase chemical modeling. Despite a decline in primary pollutants during the CIIE, NO3- levels increased compared to pre-CIIE and post-CIIE─NO3- concentrations decreased in the daytime (by -10 and -26%) while increasing in the nighttime (by 8 and 30%). Analysis of the observations and backward trajectory indicates that the diurnal variation in NO3- was mainly attributed to local chemistry rather than meteorological conditions. Decreasing VOCs lowered the daytime NO3- production by reducing the hydroxyl radical level, whereas the greater VOCs reduction at night than that in the daytime increased the nitrate radical level, thereby promoting the nocturnal NO3- production. These results reveal the double-edged role of VOCs in NO3- formation, underscoring the need for transferring large VOC-emitting enterprises from the daytime to the nighttime, which should be considered in formulating corresponding policies.

Different gene alterations in patients with non-small-cell lung cancer between the eastern and southern China.

Geographical differences are conspicuous in lung cancer, and the distinct molecular features of lung tumor between Western patients and Asian patients have been demonstrated. However, the etiology of non-small-cell lung cancer (NSCLC) and the distribution of associated molecular aberrations in China have not been fully elucidated. The mutational profiles of 12 lung cancer-related genes were investigated in 85 patients from eastern China and 88 patients from southern China who had been histologically confirmed NSCLC. Overall, 93.6% (162/173) of tumor samples harbored at least one somatic alteration. The most frequently mutated genes were TP53 (56.1%), EGFR (50.3%), and KRAS (14.5%). We found that EGFR mutated much more frequently (60.0% vs 40.9%, P = 0.012) and TP53 mutations had significantly lower incidence (47.1% vs 64.8%, P = 0.019) in eastern cohort than that in southern cohort. Mutational signature analysis revealed a region-related mutagenesis mechanism characterized by a high prevalence of C to T transitions mainly occurring at CpG dinucleotides in southern patients. This study reveals the difference in the mutational features between NSCLC patients in eastern and southern China. The distinct patterns of gene mutation could provide clues for the mechanism of carcinogenesis of lung cancer, offering opportunities to stratify patients into optimal treatment plans based on genomic profiles.

Secondary Formation of Atmospheric Brown Carbon in China Haze: Implication for an Enhancing Role of Ammonia.

Optical characteristics and molecular compositions of brown carbon (BrC) were investigated during winter 2019 at a rural site of China with a focus on nitro-aromatic compounds (NACs) and imidazoles (IMs). The abundance of gaseous nitrophenols relative to CO during the campaign maximized at noontime, being similar to O3, while the particulate NACs during the haze periods strongly correlated with toluene and NO2, suggesting that NACs in the region are largely formed from the gas-phase photooxidation. Strong correlations of particulate IMs in the dry haze periods with the mass ratio of EC/PM2.5 and the concentration of levoglucosan were observed, indicating that IMs during the dry events are largely derived from biomass burning emissions. However, an increase in IMs with the increasing aerosol liquid water content and pH was observed in the humid haze events, along with much lower abundances of levoglucosan and K+ relative to PM2.5, suggesting that IMs were mostly formed from aqueous reactions in the humid haze periods. These IMs exponentially increased with an increasing NH3 owing to an aqueous reaction of carbonyls with free ammonia. Our findings for the first time revealed an enhancing effect of ammonia on BrC formation in China, especially in humid haze periods.

Characterization of water-soluble brown carbon in atmospheric fine particles over Xi'an, China: Implication of aqueous brown carbon formation from biomass burning.

Brown carbon (BrC) aerosols can affect not only the climate but also human health, however, the light absorption, chemical compositions, and formation mechanisms of BrC are still uncertain, which leads to uncertainties in the accurate estimation of its climate and health impacts. In this study, highly time - resolved brown carbon (BrC) in fine particles was investigated in Xi'an using offline aerosol mass spectrometer analysis. The light absorption coefficient (babs365) and mass absorption efficiency (MAE365) at 365 nm of water-soluble organic aerosol (WSOA) generally increased with oxygen-to-carbon (O/C) ratios, indicating that oxidized OA could have more impacts on BrC light absorption. Meanwhile, the light absorption appeared to increase generally with the increases of nitrogen-to-carbon (N/C) ratios and water-soluble organic nitrogen; strong correlations (R of 0.76 for CxHyNp+ and R of 0.78 for CxHyOzNp+) between babs365 and the N - containing organic ion families were observed, suggesting that the N - containing compounds are the effective BrC chromophores. babs365 correlated relatively well with BBOA (r of 0.74) and OOA (R of 0.57), but weakly correlated with CCOA (R of 0.33), indicating that BrC in Xi'an was likely to be associated with biomass burning and secondary sources. A multiple linear regression model was applied to apportion babs365 to contributions of different factors resolved from positive matrix factorization on water-soluble organic aerosols (OA) and obtained MAE365 values of different OA factors. We found that biomass-burning organic aerosol (BBOA) dominated the babs365 (48.3 %), followed by oxidized organic aerosol (OOA, 33.6 %) and coal combustion organic aerosol (CCOA, 18.1 %). We further observed that nitrogen-containing organic matter (i.e., CxHyNp+ and CxHyOzNp+) increased with the increase of OOA/WSOA and the decrease of BBOA/WSOA, especially under high ALWC conditions. Our work offered proper observation evidence that BBOA is oxidized through the aqueous formation to produce BrC in Xi'an, China.

Simultaneous stabilization of Pb, Cd, and As in soil by rhamnolipid coated sulfidated nano zero-valent iron: Effects and mechanisms.

Sulfidation effectively improves the electron transfer efficiency of nanoscale zero-valent iron (nZVI), but decreases the specific surface area of nZVI. In this study, sulfidated nZVI (S-nZVI) coated with rhamnolipid (RL-S-nZVI) was synthesized and used to stabilize Pb, Cd, and As in combined polluted soil. The stabilization efficiency of 0.3% (wt) RL-S-nZVI to water soluble Pb, Cd, and As in soil reached 88.76%, 72%, and 63%, respectively. Rhamnolipid coating inhibited the reduction of specific surface area and successfully encapsulated nZVI, thus reducing the oxidation of Fe0. The types of iron oxides in RL-S-nZVI were reduced compared to S-nZVI, but the content and strength of Fe0 iron were obviously enhanced. Furthermore, rhamnolipid functional groups (-COOH and -COO-) were also involved in the stabilization process. In addition, the stabilization efficiency of RL-S-nZVI to the bioavailable Pb, Cd, and As in soil increased by 41%, 41%, and 50%, respectively, compared with nZVI. The presence of organic acids, especially citric acid, improved the stabilization efficiency of RL-S-nZVI to the three metals. The result of BCR sequential extraction indicated that RL-S-nZVI increased the residual state of Pb, Cd, and As and reduced the acid-soluble and reducible state after 28 days of soil incubation. XRD and XPS analyses showed that the stabilization mechanisms of RL-S-nZVI on heavy metals involved in ion exchange, surface complexation, adsorption, co-precipitation, chemisorption, and redox.

Ammonia in urban atmosphere can be substantially reduced by vehicle emission control: A case study in Shanghai, China.

To investigate the impact of emission controls on ammonia (NH3) pollution in urban atmosphere, observation on NH3 (1 hr interval) was performed in Shanghai before, during and after the 2019 China International Import Expo (CIIE) event, along with measurements on inorganic ions, organic tracers and stable nitrogen isotope compositions of ammonium in PM2.5. NH3 during the CIIE period was 6.5±1.0 µg/m3, which is 41% and 32% lower than that before and after the event, respectively. Such a decrease was largely ascribed to the emission controls in nonagricultural sources, of which contribution for measured NH3 in control phase abated by ∼20% compared to that during uncontrol period. Molecular compositions of PAHs and hopanes further suggested a dominant role of the reduced vehicle emissions in the urban NH3 abatement during the CIIE period. Our results revealed that vehicle exhaust emission control is an effective way to mitigate NH3 pollution and improve air quality in Chinese urban areas.

Occurrence, spatial distribution, and risk assessment of brominated flame retardants in farmland soils of typical provinces in China.

In the present study, we investigated the occurrence, distribution, and potential risks of 4 brominated flame retardants in farmland soils across 18 provinces of China. The total mean concentrations of the BFRs were in order as DBDPE > BDE209 > HBB > TBB. DBDPE concentration was highest at 177.208 ng/kg, revealing its long-term use and persistence across the study areas. In parts of China, DBDPE was highest in the south (Sichuan, Shaanxi and Guangdong provinces), BDE209 was highest in the south (Sichuan province) and north (Jilin province), while HBB was highest in the south (Sichuan province) and east (Anhui and Zhejiang provinces) of China. Comparisons of the results in this study to other reported studies in different regions indicated that the studied BFRs concentrations were higher in the studied provinces of China. Pearson correlation between BFRs revealed both positive and negative associations within the BFRs groups and between BFRs and soil properties (SOM, CEC, pH, EC and PS%). The mean hazard quotients (HQ) of ecological risks ranged from 8.76 × 10-6 to 1.16 × 10-2 (HQ < 1) while non-carcinogenic human health risk evaluation for adults ranged from 7.05 × 10-7 - 7.48 × 10-4 (HQ < 1) and for children 2.99 × 10-4 - 4.30 × 10-2 (HQ < 1). Although the risk evaluations of BFRs from farmland soils in this study were low, the results serve as useful indicators of potential cumulative and long-term threats of BFR to rural areas where there is a high conversion of agricultural lands to non-agricultural use.

Progress in quantitative research on the relationship between atmospheric oxidation and air quality.

Atmospheric oxidizing capacity (AOC) is an essential driving force of troposphere chemistry and self-cleaning, but the definition of AOC and its quantitative representation remain uncertain. Driven by national demand for air pollution control in recent years, Chinese scholars have carried out studies on theories of atmospheric chemistry and have made considerable progress in AOC research. This paper will give a brief review of these developments. First, AOC indexes were established that represent apparent atmospheric oxidizing ability (AOIe) and potential atmospheric oxidizing ability (AOIp) based on aspects of macrothermodynamics and microdynamics, respectively. A closed study refined the quantitative contributions of heterogeneous chemistry to AOC in Beijing, and these AOC methods were further applied in Beijing-Tianjin-Hebei and key areas across the country. In addition, the detection of ground or vertical profiles for atmospheric OH·, HO2·, NO3· radicals and reservoir molecules can now be obtained with domestic instruments in diverse environments. Moreover, laboratory smoke chamber simulations revealed heterogeneous processes involving reactions of O3 and NO2, which are typical oxidants in the surface/interface atmosphere, and the evolutionary and budgetary implications of atmospheric oxidants reacting under multispecies, multiphase and multi-interface conditions were obtained. Finally, based on the GRAPES-CUACE adjoint model improved by Chinese scholars, simulations of key substances affecting atmospheric oxidation and secondary organic and inorganic aerosol formation have been optimized. Normalized numerical simulations of AOIe and AOIp were performed, and regional coordination of AOC was adjusted. An optimized plan for controlling O3 and PM2.5 was analyzed by scenario simulation.

Investigation into the differences and relationships between gasSOA and aqSOA in winter haze pollution on Chongming Island, Shanghai, based on VOCs observation.

To investigate the formation of secondary organic aerosol (SOA) under current atmospheric conditions, we conducted a field observation of SOA precursors in the downwind region of the Yangtze River Delta (YRD) in winter 2019 using a variety of offline and online instruments. During the entire observation period, the averaged fine particulate SOA was 7.9 ± 2.3 µg m-3, with precursor concentrations of 31 ± 11 ppbv for the measured volatile organic compounds (VOCs) and 16 ± 12 ppbv for NOx. Compared to those on the clean days, SOA on the haze days increased by a factor of 1.6, while the VOC and NOx increased by a factor of 1.3 and 2.0, respectively. Aerosol liquid water content (ALWC) and oxygenated VOCs (OVOCs, including acetaldehyde, formic acid, acetone, acetic acid, methyl ethyl ketone, and methylglyoxal) relationships suggested that the gasSOA and aqSOA occurred simultaneously on Chongming Island in winter. The gasSOA was primarily formed by the oxidation of aromatics and NOx at low RH (RH < 80%) conditions. In contrast, the aqSOA was formed under higher RH (RH > 80%) conditions via a combination of daytime photochemical aqueous phase processes of water-soluble OVOCs and nocturnal dark aqueous phase processes of primary emissions from biomass. The inversed higher mass ratio of NACs to (benzene + toluene) and nitrogen oxidation ratio (NOR) in the daytime during the gasSOA-dominated haze periods indicated that gasSOA could be transformed to aqSOA at high NOx levels. Our results also suggested the importance of NOx and VOC reduction measures in directly mitigating gasSOA and indirectly mitigating aqSOA during winter haze pollution.

Increasing role of phenolic oxidative branch in daytime oxidation process of aromatics in Chinese haze period.

To understand the photooxidation mechanisms of aromatic compounds in the NOx-rich atmosphere, gaseous aromatics and their oxidization products (i.e., methyl glyoxal (MGLY), and nitrated phenols (NPs) including nitrophenols (NPhs) and methylnitrophenols (MNPs)) were measured with a 1-h time resolution on Chongming Island, a downwind region of the Yangtze River Delta (YRD) metropolitans of China in winter 2019 by using a proton-transfer-reaction mass spectrometer (PTR-MS). During the entire observation period, concentrations of the measured VOCs were 9.6 ± 7.1 ppbv for aromatics, 118 ± 59 pptv for MGLY, 36 ± 10 pptv for NPhs, and 9.3 ± 2.8 pptv for MNPs, respectively. Secondary NPs (SNPs) accounted for only 19-24 % of the total nitrated phenols during the clean and transition periods but increased to 44 % of the total on the hazy days. Moreover, the daytime mixing ratios of SNPs increased along with an increasing NO2 concentration during the clean and transition periods, but in the haze period the daytime SNPs first increased along with the increasing NO2 levels and then increased much more sharply when NO2 was >25 ppbv. Such highly proportional and sharply increased daytime SNPs in the haze period indicated an enhanced phenolic oxidation under the high NOx conditions. In addition, the lack of correlations between aromatics and MGLY, increased MGLYaro (MGLY produced by aromatics), and sharply increased ΔSNPs / Δ(benzene + toluene) further suggested that such an increasing role of the phenolic oxidative branch in the daytime oxidation process of aromatics during the YRD haze period was caused by the strong atmospheric oxidation capacity and the high level of NOx.

Significant coal combustion contribution to water-soluble brown carbon during winter in Xingtai, China: Optical properties and sources.

To understand the characteristics of atmospheric brown carbon (BrC), daily PM2.5 samples in Xingtai, a small city in North China Plain (NCP), during the four seasons of 2018-2019, were collected and analyzed for optical properties and chemical compositions. The light absorption at 365 nm (absλ=365 nm) displayed a strong seasonal variation with the highest value in winter (29.0±14.3 M/m), which was 3.2∼5.4-fold of that in other seasons. A strong correlation of absλ=365 nm with benzo(b)fluoranthene (BbF) was only observed in winter, indicating that coal combustion was the major source for BrC in the season due to the enhanced domestic heating. The mass absorbing efficiency of BrC also exhibited a similar seasonal pattern, and was found to correlate linearly with the aerosol pH, suggesting a positive effect of aerosol acidity on the optical properties and formation of BrC in the city. Positive matrix factorization (PMF) analysis further showed that on a yearly basis the major source for BrC was biomass burning, which accounted for 34% of the total BrC, followed by secondary formation (26.7%), coal combustion (21.3%) and fugitive dust (18%). However, the contribution from coal combustion was remarkably enhanced in winter, accounting for ∼40% of the total. Our work revealed that more efforts of "shifting coal to clean energy" are necessary in rural areas and small cities in NCP in order to further mitigate PM2.5 pollution in China.

Effects of NO2 and RH on secondary organic aerosol formation and light absorption from OH oxidation of ο-xylene.

Ο-xylene is an important aromatic volatile organic compound (VOC) in the atmosphere over urban areas. In this work, the effect of nitrogen dioxide (NO2) concentration and relative humidity (RH) on the mass concentration of secondary organic aerosols (SOA) formed from ο-xylene OH oxidization was investigated in a photooxidation chamber. The ο-xylene SOA mass concentration increased from 54.2 µg m-3 to 127.2 µg m-3 during dry conditions, but decreased from 177.7 µg m-3 to 146.5 µg m-3 during high RH conditions when the initial NO2 concentration increased form 0 ppbv to about 900 ppbv. An increase in the ratio of [NO3-]/[Org] and a decrease in the oxidation state of carbon (OSC) of SOA suggested that acid-catalyzed heterogeneous reaction was responsible for enhancing SOA formation with increasing NO2 concentrations in dry conditions. In contrast, in humid conditions, the high molecular diffusion capacity of SOA could promote the reactivity of OH towards the interior of SOA, and the enhancement of nitrous acid (HONO) formation under high NO2 conditions could promote the SOA aging processes and be responsible for the decreasing trend of SOA formation with NO2. Light absorption by SOA was also measured, and both NO2 and RH enhanced the mass absorption coefficient (MACλ = 365 nm) value for the optical properties of ο-xylene SOA. The highest MACλ = 365 nm value of ο-xylene SOA was 0.89 m2 g-1, observed during humid conditions with an initial NO2 concentration of 862 ppbv, which was 3.9 times higher than in the experiment conducted in the absence of NO2 under dry conditions. The formation of nitrogen-containing organic compounds (NOCs) and humic-like substances (HULIS) were responsible for the increased MACλ = 365 nm values of ο-xylene derived SOA. This study provides new insight into the effect of NO2 on SOA formation through the change in ο-xylene photooxidation under different RH conditions, and the complex effect of multiple environmental factors on SOA formation was also important and should not be ignored.

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in wintertime aerosols of Northwest China.

Dicarboxylic acids are one of the important water-soluble organic compounds in atmospheric aerosols, causing adverse effects to both climate and human health. More attention has therefore been paid to organic acids in aerosols. In this study, the molecular distribution and diurnal variations of wintertime dicarboxylic acids in a rural site of Guanzhong Plain, Northwest China, were explored. Oxalic acid (C2, day: 438.9 ± 346.8 ng m-3, night: 398.8 ± 392.3 ng m-3) is the most abundant compound followed by methylglyoxal (mGly, day: 207.8 ± 281.1 ng m-3, night: 222.9 ± 231.0 ng m-3) and azelaic (C9, day: 212.8 ± 269.1 ng m-3, night: 211.4 ± 136.7 ng m-3) acid. The ratios of C9/C6 and C9/Ph indicating that atmospheric dicarboxylic acids in winter in the region mainly come from biomass burning. Furthermore, secondary inorganic ions (NO3-, SO42-, and NH4+), relative humidity, liquid water content, and in-situ pH of aerosols are highly linearly correlated with C2, suggesting that liquid phase oxidation is an important pathway for the formation of dicarboxylic acids. The δ13C analysis of C2 suggested that lighter carbon isotope compositions tend to be oxidized to form aqueous-phase secondary organic aerosols (aqSOA), leading to the decay of 13C in aqSOA products rather than aerosol aging. This study provides a theoretical basis for the mechanism of formation of dicarboxylic acid.

A comparative and modeled approach for three biochar materials in simultaneously preventing the migration and reducing the bioaccessibility of heavy metals in soil: Revealing immobilization mechanisms.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%-64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals' remediation.