Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to ...date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5‐laden air at the high‐elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well‐processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5–16% at the ozone peak or 11–41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground‐level ozone and haze.
Key Points
First observation of ClNO2 in the planetary boundary layer of China
Combined high‐resolution meteorological and measurement‐constrained chemical models in data analysis
ClNO2 enhances daytime ozone peak by 5‐16% in well‐processed PRD air
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
•Well-defined seasonal patterns of AOC, kOH and ROx production were found in rural Hong Kong.•kOH was dominated by oxidation of NO2 and OVOCs in later summer and of CO and OVOCs in autumn and ...winter.•Major primary ROx sources were photolysis of O3 and HONO in late summer and photolysis of O3 and HCHO in autumn and winter.
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Atmospheric oxidizing capacity (AOC), dominated by the hydroxyl radical (OH), is an important index of the self-cleaning capacity of atmosphere and plays a vital role in the tropospheric chemistry. To better understand the key processes governing the chemistry of rural atmosphere of southern China, we analyzed the oxidation capacity and radical chemistry at a regional background site in Hong Kong from 23 August to 22 December 2012, which covered the summer, autumn and winter seasons. A chemical box model built on the latest Master Chemical Mechanism (v3.3) was used to elucidate the OH reactivity and sources of ROX radicals (ROX=OH+HO2+RO2). The AOC showed a clear seasonal pattern with stronger intensity in late summer compared to autumn and winter. Reactions with NO2 (30%) and oxygenated volatile organic compounds (OVOCs) (31%) together dominated the OH loss in summer, while reactions with CO (38% in autumn and 39% in winter) and OVOCs (34% in autumn and 25% in winter) made larger contributions in autumn and winter. Photolysis of O3 (36%–47%) presented the major ROX source during all three seasons. The second largest ROx source was HONO photolysis (25%) in summer compared to HCHO photolysis in autumn (20%) and winter (21%). Besides, photolysis of other OVOCs was another important primary source of ROx radicals with average contributions of 14%, 13% and 20% for the summer, autumn and winter cases, respectively. Overall, the present study evaluates the oxidizing capacity of the rural atmosphere of South China and elucidates the varying characteristics of photochemical processes in different air masses.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Heterogeneous uptake of dinitrogen pentoxide (N2O5) and production of nitryl chloride (ClNO2) are important nocturnal atmospheric processes that have significant implications for the production of ...secondary pollutants. However, the understanding of N2O5 uptake processes and ClNO2 production remains limited, especially in China. This study presents a field investigation of the N2O5 heterogeneous uptake coefficient (γ(N2O5)) and ClNO2 production yield (ϕ) in a polluted area of northern China during the summer of 2014. The N2O5 uptake coefficient and ClNO2 yield were estimated by using the simultaneously measured ClNO2 and total nitrate in 10 selected cases, which have concurrent increases in the ClNO2 and nitrate concentrations and relatively stable environmental conditions. The determined γ(N2O5) and ϕ values varied greatly, with an average of 0.022 for γ(N2O5) (±0.012, standard deviation) and 0.34 for ϕ (±0.28, standard deviation). The variations in γ(N2O5) could not be fully explained by the previously derived parameterizations of N2O5 uptake that consider nitrate, chloride, and the organic coating. Heterogeneous uptake of N2O5 was found to have a strong positive dependence on the relative humidity and aerosol water content. This result suggests that the heterogeneous uptake of N2O5 in Wangdu is governed mainly by the amount of water in the aerosol, and is strongly water limited, which is different from most of the field observations in the US and Europe. The ClNO2 yield estimated from the parameterization was also overestimated comparing to that derived from the observation. The observation-derived ϕ showed a decreasing trend with an increasing ratio of acetonitrile to carbon monoxide, an indicator of biomass burning emissions, which suggests a possible suppressive effect on the production yield of ClNO2 in the plumes influenced by biomass burning in this region. The findings of this study illustrate the need to improve our understanding and to parameterize the key factors for γ(N2O5) and ϕ to accurately assess photochemical and haze pollution.
Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation ...processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO
) and perchloric (HClO
) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO
and HClO
. Significant levels of HClO
were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 10
molecule cm
. The increase in HClO
, concomitantly with that in HClO
, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO
and HClO
by hydroxyl radicals. HClO
and HClO
are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.
Heterogeneous reactivity of N2O5 on aerosols is a critical parameter in assessing NOx fate, nitrate production, and particulate chloride activation. Accurate measurement of its uptake coefficient ...(γN2O5) and representation in air quality models are challenging, especially in the polluted environment. With an in situ aerosol flow-tube system, the γN2O5 was directly measured on ambient aerosols at two rural sites in northern and southern China. The results were analyzed together with the γN2O5 derived from previous field studies in China to obtain a holistic picture ofN2O5 uptake and the influencing factors under various climatic and chemical conditions. The field-derived or measured γN2O5 was generally promoted by the aerosol water content and suppressed by particle nitrate. Significant discrepancies were found between the measured γN2O5 and that estimated from laboratory-determined parameterizations. An observation-based empirical parameterization was derived in the present work, which better reproduced the mean value and variability of the observedγN2O5. Incorporating this new parameterization into a regional air quality model (WRF-CMAQ) has improved the simulation of N2O5, nitrogen oxides, and secondary nitrate in the polluted regions of China.
The uptake of methanesulfonic acid (MSA) on
existing particles is a major route of the particulate MSA formation,
however, MSA uptake on different particles is still lacking in knowledge.
...Characteristics of MSA uptake on different aerosol particles were
investigated in polynya (an area of open sea water surrounded by ice)
regions of the Ross Sea, Antarctica. Particulate MSA mass concentrations, as
well as aerosol population and size distribution, were observed
simultaneously for the first time to access the uptake of MSA on different
particles. The results show that MSA mass concentration does not always
reflect MSA particle population in the marine atmosphere. MSA uptake on
aerosol particle increases the particle size and changes aerosol chemical
composition, but it does not increase the particle population. The uptake rate
of MSA on particles is significantly influenced by aerosol chemical
properties. Sea salt particles are beneficial for MSA uptake, as MSA-Na and
MSA-Mg particles are abundant in the Na and Mg particles, accounting for
0.43±0.21 and 0.41±0.20 of the total Na and Mg particles,
respectively. However, acidic and hydrophobic particles suppress the uptake
of MSA, as MSA-EC (elemental carbon) and MSA-SO42- particles account for only
0.24±0.68 and 0.26±0.47 of the total EC and SO42-
particles, respectively. The results extend the knowledge of the formation
and environmental behavior of MSA in the marine atmosphere.
Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key species in nocturnal tropospheric chemistry and have significant effects on particulate nitrate formation and the following day's ...photochemistry through chlorine radical production and NOx recycling upon photolysis of ClNO2. To better understand the roles of N2O5 and ClNO2 in the high-aerosol-loading environment of northern China, an intensive field study was carried out at a high-altitude site (Mt. Tai, 1465 m a.s.l.) in the North China Plain (NCP) during the summer of 2014. Elevated ClNO2 plumes were frequently observed in the nocturnal residual layer with a maximum mixing ratio of 2.1 ppbv (1 min), whilst N2O5 was typically present at very low levels (< 30 pptv), indicating fast heterogeneous N2O5 hydrolysis. Combined analyses of chemical characteristics and backward trajectories indicated that the ClNO2-laden air was caused by the transport of NOx-rich plumes from the coal-fired industry and power plants in the NCP. The heterogeneous N2O5 uptake coefficient (γ) and ClNO2 yield (ϕ) were estimated from steady-state analysis and observed growth rate of ClNO2. The derived γ and ϕ exhibited high variability, with means of 0.061 ± 0.025 and 0.28 ± 0.24, respectively. These values are higher than those derived from previous laboratory and field studies in other regions and cannot be well characterized by model parameterizations. Fast heterogeneous N2O5 reactions dominated the nocturnal NOx loss in the residual layer over this region and contributed to substantial nitrate formation of up to 17 µg m−3. The estimated nocturnal nitrate formation rates ranged from 0.2 to 4.8 µg m−3 h−1 in various plumes, with a mean of 2.2 ± 1.4 µg m−3 h−1. The results demonstrate the significance of heterogeneous N2O5 reactivity and chlorine activation in the NCP, and their unique and universal roles in fine aerosol formation and NOx transformation, and thus their potential impacts on regional haze pollution in northern China.
Oceans cover over 71% of the Earth's surface and play crucial roles in regulating the global climate. In the marine boundary layer, the levels of volatile organic compounds (VOCs) have been shown to ...have positive relations with the marine algal biomass, indicating that the marine biological activities can be an important biogenic VOCs (BVOCs) source. The emitted BVOCs will enhance the formation of secondary organic aerosols, and perturb the radiative forcing, which ultimately affects the climate. To date, knowledge on the emission processes (i.e., synthesis processes and emission rates) of BVOCs from marine phytoplankton is still lacking compared to the more well-known BVOCs released from terrestrial plants. In this review, we focus on the BVOCs emissions from the marine phytoplankton. Based on the available literature from field and laboratory studies, we listed the types of BVOCs being emitted by different marine phytoplankton species, summarized the diversity of BVOCs related to phytoplankton taxonomy and physiology and abiotic factors affecting their emissions in various marine environments, and discussed the biosynthesis and ecological function of important marine VOCs such as DMS, terpenoids and VHCs from phytoplankton. Finally, we highlighted the existing gaps in the current knowledge and the needs of future study for better understanding the physiological and ecological roles of BVOCs emission from marine phytoplankton.
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•The emission of VOCs related to phytoplankton taxonomy and physiology are summarized.•Effects of abiotic factors on VOCs released from phytoplankton are discussed.•Biosynthesis and ecological function of main VOCs from phytoplankton are reviewed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key species in nocturnal tropospheric chemistry and have significant effects on particulate nitrate formation and the following day's ...photochemistry through chlorine radical production and NOx recycling upon photolysis of ClNO2. To better understand the roles of N2O5 and ClNO2 in the high-aerosol-loading environment of northern China, an intensive field study was carried out at a high-altitude site (Mt. Tai, 1465 m a.s.l.) in the North China Plain (NCP) during the summer of 2014. Elevated ClNO2 plumes were frequently observed in the nocturnal residual layer with a maximum mixing ratio of 2.1 ppbv (1 min), whilst N2O5 was typically present at very low levels (< 30 pptv), indicating fast heterogeneous N2O5 hydrolysis. Combined analyses of chemical characteristics and backward trajectories indicated that the ClNO2-laden air was caused by the transport of NOx-rich plumes from the coal-fired industry and power plants in the NCP. The heterogeneous N2O5 uptake coefficient (γ) and ClNO2 yield (ϕ) were estimated from steady-state analysis and observed growth rate of ClNO2. The derivedγ and ϕ exhibited high variability, with means of 0.061 ± 0.025 and 0.28 ± 0.24, respectively. These values are higher than those derived from previous laboratory and field studies in other regions and cannot be well characterized by model parameterizations. Fast heterogeneous N2O5 reactions dominated the nocturnal NOx loss in the residual layer over this region and contributed to substantial nitrate formation of up to 17 µg m-3. The estimated nocturnal nitrate formation rates ranged from 0.2 to 4.8 µg m-3 h-1 in various plumes, with a mean of 2.2 ± 1.4 µg m-3 h-1. The results demonstrate the significance of heterogeneous N2O5 reactivity and chlorine activation in the NCP, and their unique and universal roles in fine aerosol formation and NOx transformation, and thus their potential impacts on regional haze pollution in northern China.
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