Environmental Science-Nano
·
2018
·Vol. 5
·期 8
·1821-1833
·
IF 6.087
Tao Wang,Yangyang Liu,Yue Deng,Hongbo Fu,Liwu Zhang,Jianmin Chen
Sulfate compounds formed on mineral dust nanoparticles contribute significantly to severe haze events. Atmospheric particles are complex mixtures that comprise various species and little is known about the heterogeneous conversion of sulfur dioxide (SO2) on multi-composition nanoparticles. In this study, the heterogeneous reaction of SO2 on hematite–alumina mixtures is investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Reactions in the presence of SO2 (polluted period) and its subsequent absence (clean period) are included. It is found that sulfite and sulfate species are the dominant products on alumina and hematite-containing mixtures, respectively. Since the uptake coefficients calculated using both Brunauer–Emmett–Teller (BET) surface area and geometric surface area present similar ‘S’ shape uptrends with increasing hematite proportion, a logistic regression model is employed for further predictions. Sulfate formation still occurs during the clean period, which can be attributed to the physical adsorption of SO2 during the polluted period. In both the periods, hematite-rich mixtures exhibit higher sulfate yields compared to their corresponding theoretical values based on the contribution of each individual component, whereas alumina-rich mixtures present an opposite trend, implying synergistic and antagonistic effects, respectively. A simplified mechanism is demonstrated and the environmental implications are discussed.
研究领域:
大气化学
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环境科学
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纳米材料化学
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表面反应动力学
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气溶胶科学
✓ 已验证
DOI
高影响因子
npj Climate and Atmospheric Science
·
2025
·Vol. 8
·期 1
·1-12
·
IF 8.4
Liu Yangyang,Li Xiao,Ge Qiuyue,Fang Xiaozhong,Wang Tao,You Wenbo,Wang Wei,Xie Lifang,Li Kejian,Gong Kedong,Yang Le,Wang Runbo,Wang Jilun,Wang Licheng,Ma Minglu,Huang Tingting,Fu Hongbo,Chen Jianmin,Dong Xinyi,Zhang Liwu
Carbonate radical anion ( \({{\rm{CO}}}_{{3}^{.-}}\) ) is generally considered as a marginal intermediate that rarely regulates atmospheric-relevant reactions of significance. Unexpectedly, in this work, employing a suit of the in-field measurements, lab-based validations, improved kinetic numerical calculations, and chemical transport modeling, we demonstrate that \({{\rm{CO}}}_{{3}^{.-}}\) gives a significantly overlooked contribution (~54.4%) to overall secondary sulfate formation during dust storm-relevant episodes and ~236.3% increase of SO 2 uptake over mineral dust pathway during haze-relevant periods. GEOS-Chem modeling results further emphasize the important position of this radical ion in dust-driven SO 2 oxidation chemistry. Our finding leaves this active intermediate no longer a marginal oxidant currently prevailing in the framework of the atmospheric science community. More importantly, after considering this rapid dust-driven sulfate formation channel mediated by carbonate radicals during pollution episodes, this study provides a clear indication that high priority should be given to reducing alkaline soil dust emissions to achieve benefits for air quality.
研究领域:
大气科学
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Sciences
·
2022
·
IF 6.796
Lanxiadi Chen,Chao Peng,Jingchuan Chen,Jie Chen,Wenjun Gu,Xiaohong Jia,Zhijun Wu,Qiyuan Wang,Mingjin Tang
Mineral dust is an important type of ice nucleating particles in the troposphere; however, the effects of heterogeneous reactions on ice nucleation (IN) activities of mineral dust remain to be elucidated. A droplet-freezing apparatus (Guangzhou Institute of Geochemistry Ice Nucleation Apparatus, GIGINA) was developed in this work to measure IN activities of atmospheric particles in the immersion freezing mode, and its performance was validated by a series of experimental characterizations. This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust (ATD) particles before and after heterogeneous reaction with NO 2 (10±0.5 ppmv) at 40% relative humidity. The surface coverage of nitrate, θ (NO 3 − ), increased to 3.1±0.2 for feldspar after reaction with NO 2 for 6 hr, and meanwhile the active site density per unit surface area ( n s ) at -20°C was reduced from 92±5 to <1.0 cm −2 by about two orders of magnitude; however, no changes in nitrate content or IN activities were observed for further increase in reaction time (up to 24 hr). Both nitrate content and IN activities changed continuously with reaction time (up to 24 hr) for ATD particles; after reaction with NO 2 for 24 hr, θ (NO 3 − ) increased to 1.4±0.1 and n s at -20°C was reduced from 20±4 to 9.7±1.9 cm −2 by a factor of ∼2. Our work suggests that heterogeneous reaction with NO 2 , an abundant reactive nitrogen species in the troposphere, may significantly reduce IN activities of mineral dust in the immersion freezing mode.
研究领域:
大气科学
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环境化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
·
2023
·Vol. 128
·期 24
·e2023JD039971
·
IF 4.4
Lanxiadi Chen,Soleil E. Worthy,Wenjun Gu,Allan K. Bertram,Mingjin Tang
Mineral dust is one of the most abundant types of ice nucleating particles in the atmosphere. During atmospheric transport, mineral dust particles can become coated with inorganic and organic solutes, which can impact their ice nucleation activity. Aminium cations formed from amines are one type of organic solute that can coat mineral dust particles in the atmosphere, but their effects on the ice nucleation activity of mineral dust have not been studied. We investigated the effects of primary, secondary, and tertiary aminium cations with methyl and ethyl groups, as well as ammonium cations, on the ice nucleation activity of K-feldspar, an important type of mineral dust, in the immersion freezing mode at low cation concentrations (0.2–20 mM) using a droplet-freezing apparatus. Ammonium cations substantially increased the ice nucleation activity of K-feldspar, consistent with previous studies. In contrast, primary aminium cations significantly reduced K-feldspar ice nucleation activity, and secondary and tertiary aminium cations had no significant effect (the effect was less than the uncertainty of our measurements). Our combined results are consistent with the following mechanisms: ammonium cations undergo ion exchange with K-feldspar, providing exposed N–H groups for hydrogen bonding with ice; primary aminium cations undergo ion exchange with K-feldspar, exposing a hydrophobic tail that is not effective at nucleating ice; secondary and tertiary aminium cations do not undergo ion exchange with K-feldspar due to steric effects caused by the multiple hydrophobic groups on the cation. Key Points Ammonium cations significantly increased the ice nucleation activity of K-feldspar Primary aminium cations substantially reduced the ice nucleation activity of K-feldspar Secondary and tertiary aminium had limited effects on the ice nucleation activity of K-feldspar due to their inability for ion exchange Plain Language Summary Ice nucleating particles are particles in the atmosphere that can initiate the formation of ice in liquid clouds, impacting cloud properties, precipitation, and climate. Mineral dust is a dominant type of ice nucleating particles in the atmosphere. During atmospheric transport, aminium cations, formed from amine gases which can be abundant in the atmosphere, can coat mineral dust particles altering their ability to nucleate ice. However, the effect of aminium cations on the ice nucleation ability of mineral dust particles has not been studied. We investigated the effects of aminium and ammonium cations on the ice nucleation ability of K-feldspar, an important type of mineral dust and ice nucleating particles in the atmosphere. Our results show that secondary and tertiary aminium cations have no effect on the ice nucleating ability of K-feldspar, but primary aminium cations greatly reduce the ice nucleating ability of K-feldspar. This has possible implications for predicting cloud formation in the atmosphere. We also present a mechanism related to ion exchange that can explain our ice nucleation results.
研究领域:
大气科学
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环境化学
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物理化学
·
气候学
✓ 已验证
产品关联
DOI
高影响因子
ACS Earth and Space Chemistry
·
2021
·
IF 3.475
Xiaozhong Fang,Yangyang Liu,Kejian Li,Tao Wang,Yue Deng,Yiqing Feng,Yang Yang,Hanyun Cheng,Jianmin Chen,Liwu Zhang
The carbonate radical (CO3•–) has been proved to be of great significance in the water environment. However, a few studies concerned with its contribution to atmospheric heterogeneous chemistry. Here, we report the pathway for the first time for CO3•– generation by interfacial photogenerated hole/hydroxyl radical (•OH) transfer between the photoactive component and (bi)carbonate (CO32–/HCO3–) of mineral dust under atmospherically relevant actinic irradiation. By combining laboratory simulation, nanosecond transient absorption spectroscopy (NTAS), and field observation, we demonstrate that (bi)carbonate in the atmosphere not only has a pH buffering effect in the uptake of NO2 but more importantly directly participates in the photochemical reactions by generating CO3•– under irradiation. CO3•– can play an important role by facilitating nitrite transformation to nitrate, especially under a lower light intensity (15 mW/cm2) and a higher humidity (60% RH). Diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) was used to detect the surface species generated on simulated mineral dust. Under irradiation, the time-dependent reactive uptake coefficient for the first-order reaction of NO2 uptake on simulated mineral dust was found to be 2.817 × 10–8 × e–t/6559. These results highlight the important role of CO3•– in atmospheric photochemistry, which could act as a reactive radical and influence secondary aerosol formation.
研究领域:
大气化学
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环境科学
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光化学
✓ 已验证
产品关联
DOI
高影响因子
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