Formation mechanisms of nitrous acid (HONO) during the haze and non-haze periods in Beijing, China

As an important precursor of hydroxyl radical (OH), nitrous acid (HONO) plays a significant role in atmospheric chemistry. Here, an observation of HONO and relevant air pollutants in an urban site of Beijing from 14 to 28 April, 2017 was performed. Two distinct peaks of HONO concentrations occurred during the observation. In contrast, the concentration of particulate matter in the first period (period Ⅰ) was significantly higher than that in the second period (period Ⅱ). Comparing to HONO sources in the two periods, we found that the direct vehicle emission was an essential source of the ambient HONO during both periods at night, especially in period Ⅱ. The heterogeneous reaction of NO₂ was the dominant source in period Ⅰ, while the homogeneous reaction of NO with OH was more critical source at night in period Ⅱ. In the daytime, the heterogeneous reaction of NO₂ was a significant source and was confirmed by the good correlation coefficients (R²) between the unknown sources (P_unknown) with NO₂, PM_2.5, NO₂ × PM_2.5 in period Ⅰ. Moreover, when solar radiation and OH radicals were considered to explore unknown sources in the daytime, the enhanced correlation of P_unknown with photolysis rate of NO₂ and OH ($J_{{\mathrm{NO}}_2}$ × OH) were 0.93 in period Ⅰ, 0.95 in period Ⅱ. These excellent correlation coefficients suggested that the unknown sources released HONO highly related to the solar radiation and the variation of OH radicals.     

Long-term winter observation of nitrous acid in the urban area of Beijing

The particulate matter (PM) pollution has been significantly improved by carrying out various valid emission control strategies since 2013 in China. Meanwhile the variation trend of nitrous acid (HONO) is worthy to investigate due to its vital role in the atmospheric oxidation process. In this study, field observation in the winter is conducted to investigate the concentration of HONO in an urban area of Beijing. In the winter of 2019, the mean HONO concentration is 1.38 ppbV during the whole winter. Photo-enhanced NO₂ heterogeneous reactions on the ground and aerosol surfaces were found as the possible daytime sources of HONO. Compared to O₃, photolysis of HONO dominates the primary OH sources during the winter time. To understand the HONO pollution patterns by years variation, multi-year data is summarized and finds that primary pollutants including CO and NO decreased, but secondary pollutants i.e., HONO (mostly generated via secondary process) increased. Our study highlights the requirement to mitigate secondary pollution by control HONO concentration.     

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO₂ on different surfaces play an important role in atmospheric NO_x removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO₂ uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime. However, the uptake behavior of NO₂ varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO₂ uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO₂ uptake coefficients (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions, with the measured γ varied from <10^?8 to 3.2 × 10^?7 under different humidity. A photo-enhanced uptake of NO₂ on urban grime was observed, with the obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9 × 10^?6 at 5% relative humidity (RH) and 5.8 × 10^?6 at 70% RH on urban grime, showing a positive RH dependence for both NO₂ uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO₂-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.     

Assessing outdoor air quality vertically in an urban street canyon and its response to microclimatic factors

The vertical distribution of air pollutants in urban street canyons is closely related to residents’ health. However, the vertical air quality in urban street canyons has rarely been assessed using field observations obtained throughout the year. Therefore, this study investigated the seasonal and annual concentrations of particulate matter (PM_2.5 and PM₁₀), CO, NO₂, SO₂, O₃, air quality index, and their responses to microclimatic factors at three height levels (1.5, 27, and 69 m above street level) in an urban street canyon. The PM concentration was higher at 27 m than at 1.5 m in winter, whereas the situation was reversed in other seasons. It was found that photochemical pollutants such as NO₂ and O₃ were the primary pollutants in the urban street canyon. The days on which O₃ was the primary pollutant at the height of 1.5 m accounted for 81.07% of the entire year. The days on which NO₂ was the primary pollutant at the height of 27 and 69 m accounted for 82.49% and 72.33% of the entire year, respectively. Substantially higher concentrations of NO₂ and O₃ were found at the height of 27 m than at 69 m. In-canyon concentrations of NO₂ and O₃ were strongly correlated with air temperature, wind speed, and wind direction, which played important roles in photochemical reactions and pollutant dispersion.     

Studies on relationships between air pollutants and allergenicity of Humulus Scandens pollen collected from different areas of Shanghai

Pollen pollution and allergy are becoming prominent issues in China.However,few studies on pollinosis have been reported.As an allergen in the atmosphere,allergenic Humulus scandens pollen was collected from four districts of Shanghai,including Wusong(WS),Jiading(KD),Xujiahui(XJH) and Songjiang(SJ).The mass concentrations of SO₂,NO₂,O₃,PM₁₀,and PM_2.5(particulate matter with air dynamic diameter less than 10 and 2.5 um,respectively) near the ...     

Effects of fulvic acid and humic acid from different sources on Hg methylation in soil and accumulation in rice

Humus is often used as an organic modifier to reduce the bioaccumulation of heavy metals in plants, but the effects of different humus components from different sources on the fate of mercury (Hg) in paddy fields are still unclear. Here, fulvic acid (FA) and humic acid (HA) extracted from composted straw (CS), composted cow dung (CCD), peat soil (PM) and lignite coal (LC) were used to understand their effects on the methylation and bioaccumulation of Hg in paddy soil by pot experiments. Amendments of both FA and HA largely increased the abundance of Hg-methylating microbes and low-molecular-weight organic matters (e.g, cysteine) in paddy soil. They were also found to change the aromaticity, molecular size and Chromophoric DOM concentration of DOM, and resulted in heterogeneous effects on migration and transformation of Hg. All the FA-amended treatments increased the mobility and methylation of Hg in soil and its absorption in roots. Nevertheless, FA from different sources have heterogeneous effects on transport of Hg between rice tissues. FA-CCD and FA-PM promoted the translocation of MeHg from roots to rice grains by 32.95% and 41.12%, while FA-CS and FA-LC significantly inhibited the translocation of inorganic Hg (IHg) by 52.65% and 66.06% and of MeHg by 46.65% and 36.23%, respectively. In contrast, all HA-amended treatments reduced the mobility of soil Hg, but promoted Hg methylation in soil. Among which, HA-CCD and HA-PM promoted the translocation of MeHg in rice tissues by 88.95% and 64.10%, while its accumulation in rice grains by 28.43% and 28.69%, respectively. In general, the application of some FA and HA as organic modifiers to reduce Hg bioaccumulation in rice is not feasible.     

青岛大气中HNO3、HNO2和NH3的浓度及其影响因素

硝酸(HNO₃)、亚硝酸(HNO₂)和氨气(NH₃)是大气中重要的含氮化合物,不仅影响大气的光化学氧化能力和酸碱性,还在大气氮沉降中有重要贡献.利用2012年5月4—13日在青岛采集的denuder大气样品,分析了其中HNO₃、HNO₂和NH₃的浓度.青岛大气中HNO₃、HNO₂和NH₃浓度分别为0.88~6.15 μg·m^-3、0.07~2.02 μg·m^-3和0.47~7.87 μg·m^-3,平均分别为2.06 μg·m^-3、0.92 μg·m^-3和3.03 μg·m^-3.大气中3种气体浓度的昼夜变化均无显著性差异.平行采集的样品分析结果显示:denuder涂层的差异对HNO₃和NH₃的观测结果影响较小,但对HNO₂的影响较大,且高温天气易于造成HNO₂更大的观测误差.青岛大气中HNO₃浓度与温度呈正相关、与湿度呈负相关关系,高温低湿天气时样品中HNO₃的浓度一般较高,而高湿或降雨天气时的浓度则较低.NH₃浓度与风向呈显著相关关系,主要受局地一次排放源的影响, NH₄NO₃和NH₄NO₂分解对青岛大气中NH₃的贡献小于23%.青岛大气样品中NH₃的浓度在阵雨时以受土壤释放的影响为主,浓度较高;而连续降雨时则以受湿清除作用的影响为主,浓度较低.     

Atmospheric oxidizing capacity in autumn Beijing: Analysis of the O3 and PM2.5 episodes based on observation-based model

Atmospheric oxidizing capacity (AOC) is the fundamental driving factors of chemistry process (e.g., the formation of ozone (O₃) and secondary organic aerosols (SOA)) in the troposphere. However, accurate quantification of AOC still remains uncertainty. In this study, a comprehensive field campaign was conducted during autumn 2019 in downtown of Beijing, where O₃ and PM_2.5 episodes had been experienced successively. The observation-based model (OBM) is used to quantify the AOC at O₃ and PM_2.5 episodes. The strong intensity of AOC is found at O₃ and PM_2.5 episodes, and hydroxyl radical (OH) is the dominating daytime oxidant for both episodes. The photolysis of O₃ is main source of OH at O₃ episode; the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) plays important role in OH formation at PM_2.5 episode. The radicals loss routines vary according to precursor pollutants, resulting in different types of air pollution. O₃ budgets and sensitivity analysis indicates that O₃ production is transition regime (both VOC and NO_x-limited) at O₃ episode. The heterogeneous reaction of hydroperoxy radicals (HO₂) on aerosol surfaces has significant influence on OH and O₃ production rates. The HO₂ uptake coefficient (γHO₂) is the determining factor and required accurate measurement in real atmospheric environment. Our findings could provide the important bases for coordinated control of PM_2.5 and O₃ pollution.     

Overview of key operation factors and strategies for improving fermentative volatile fatty acid production and product regulation from sewage sludge

In recent years,volatile fatty acid(VFA) production through anaerobic fermentation of sewage sludge,instead of methane production,has been regarded as a high-value and promising roadmap for sludge stabilization and resource recovery.This review first presents the effects of some essential factors that influence VFA production and composition.In the second part,we present an extensive analysis of conventional pretreatment and co-fermentation strategies ultimately addressed to improving VFA produc...     

Effects of iodoacetic acid drinking water disinfection byproduct on the gut microbiota and its metabolism in rats

Iodoacetic acid(IAA) is an unregulated disinfection byproduct in drinking water and has been shown to exert cytotoxicity, genotoxicity, tumorigenicity, and reproductive and developmental toxicity. However, the effects of IAA on gut microbiota and its metabolism are still unknown, especially the association between gut microbiota and the metabolism and toxicity of IAA. In this study, female and male Sprague–Dawley rats were exposed to IAA at 0 and 16 mg/kg bw/day daily for 8 weeks by oral gavage....     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

Decomposition of Al13 promoted by salicylic acid under acidic condition: Mechanism study by differential mass spectrometry method and DFT calculation

Decomposition of the polycation Al₁₃O₄(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) promoted by ligand is a vital subject to advance our understanding of natural and artificial occurrence and evolution of aluminum ions, especially in the case of acidic condition that dissolved Al³⁺ species can be released from the Al-bearing substances. However, the microscopic pathway of synchronous proton-promoted and ligand-promoted decomposition process for Al₁₃ is still in the status of ambiguity. Herein, we applied differential mass spectrometry method and DFT calculation to study the initial detailed process of Al₁₃ decomposition under the presence of proton and salicylic acid (H₂Sal). Mass results showed that the mononuclear Al³⁺-H₂Sal complexes dominated the resulting Al species, whereas the monodentate complex Al₁₃HSal⁶⁺ was not observed in the spectra. The difference of decomposition levels between the ligand/Al ratio 0.2 and 0.5 cases revealed that proton and ligand performed synergistic effect in initial Al₁₃ decomposition process, and the proton transfer determined the ring closure efficiency. The ring closure reaction is the prerequisite for the collapse of Al₁₃ structure and detachment of the mononuclear complex. DFT calculations reveal that hydrogen bond plays an important role in inducing the formation of chelated complex accompanying proton transfer. Attachment of protons at the bridging OH⁻ can elongate and weaken the critical bond between targeted Al³⁺ and µ₄-O^2- resulting from delocalization of electron pairs in the oxygen atom. These results demonstrate the detailed mechanism of Al₁₃ composition promoted by ligand and proton, and provide significant understanding for further application and control of Al₁₃.